![a) General stereolithography (SLA). b1,b2) Bottom‐up and top‐down digital light processing (DLP) configurations. Reproduced with permission.[³⁸] Copyright 2022, Springer Nature. c) Schematic of the printing platform for continuous liquid interface production (CLIP). Reproduced with permission.[⁴⁰] Copyright 2015, AAAS. d1) The representation of the volumetric computed axial lithography (CAL) printing platform and the d2) manufacturing mechanism. Reproduced with permission.[⁴⁶] Copyright 2019 AAAS. e1) Two‐photo polymerization (TPP) examples of using a single laser split into multiple points with e2) simulation of the laser splitting up to three times covering most of the model. Reproduced with permission.[⁴⁷] Copyright 2019, Springer Nature. f) Multi‐photopolymerization (MPP) with possible multiple resin vats in a rotary stage set for high resolution and scalable 3D printing.[⁴⁸] Copyright 2012, Elsevier.](https://www.researchgate.net/publication/372718635/figure/fig2/AS:11431281253915970@1718970453274/a-General-stereolithography-SLA-b1-b2-Bottom-up-and-top-down-digital-light_Q320.jpg)
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REVIEW
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3D Printing-Enabled Design and Manufacturing Strategies
for Batteries: A Review
Nathan Fonseca, Sri Vaishnavi Thummalapalli, Sayli Jambhulkar,
Dharneedar Ravichandran, Yuxiang Zhu, Dhanush Patil, Varunkumar Thippanna,
Arunachalam Ramanathan, Weiheng Xu, Shenghan Guo, Hyunwoong Ko, Mofe Fagade,
Arunchala M. Kannan, Qiong Nian, Amir Asadi, Guillaume Miquelard-Garnier,
Anna Dmochowska, Mohammad K. Hassan, Maryam Al-Ejji, Hassan M. El-Dessouky,
Felicia Stan, and Kenan Song*
Lithium-ion batteries (LIBs) have significantly impacted the daily lives, finding
broad applications in various industries such as consumer electronics, electric
vehicles, medical devices, aerospace, and power tools. However, they still face
issues (i.e., safety due to dendrite propagation, manufacturing cost, random
porosities, and basic & planar geometries) that hinder their widespread
applications as the demand for LIBs rapidly increases in all sectors due to
their high energy and power density values compared to other batteries.
Additive manufacturing (AM) is a promising technique for creating precise
and programmable structures in energy storage devices. This review first
summarizes light, filament, powder, and jetting-based 3D printing methods
with the status on current trends and limitations for each AM technology. The
paper also delves into 3D printing-enabled electrodes (both anodes and
cathodes) and solid-state electrolytes for LIBs, emphasizing the current
state-of-the-art materials, manufacturing methods, and
properties/performance. Additionally, the current challenges in the AM for
electrochemical energy storage (EES) applications, including limited
materials, low processing precision, codesign/comanufacturing concepts for
complete battery printing, machine learning (ML)/artificial intelligence (AI) for
processing optimization and data analysis, environmental risks, and the
potential of 4D printing in advanced battery applications, are also presented.
N. Fonseca, S. V. Thummalapalli, D. Ravichandran, Y. Zhu, D. Patil,
V. Thippanna, A. Ramanathan, S. Guo, H. Ko, K. Song
Manufacturing Engineering
School of Manufacturing Systems and Networks (MSN)
Ira A. Fulton Schools of Engineering
Arizona State University (ASU)
Mesa, AZ 85212, USA
E-mail: kenan.song@asu.edu
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202302718
© 2023 The Authors. Small published by Wiley-VCH GmbH. This is an
open access article under the terms of the Creative Commons Attribution
License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited.
DOI: 10.1002/smll.202302718
1. Introduction
Electrochemical energy storage (EES) refers
to the procedure and method of convert-
ing chemical energy into electric energy
via an electrochemical oxidation-reduction
reverse reaction. The EES devices have
been widely used in portable electronics
and electric vehicles (EVs) as renewable en-
ergy due to their enormous potential to
reduce carbon footprint and mitigate en-
ergy challenges with fossil fuel depletion
while promoting an eco-friendly environ-
ment. These EES systems include batter-
ies, fuel cells, and supercapacitors. Batter-
ies are the most popular among these de-
vices due to their fast-charging rates, long
cyclability/lifetime, mechanical durability,
higher energy efficiency than fuel cells,
and better specific energy than superca-
pacitors. With the advances in materials
and manufacturing, newer battery applica-
tions have emerged, such as wearable elec-
tronics, micro/smart sensors, medical de-
vices, the Internet of Things (IoT), and
electric transportation.[1,2 ] However, the
S. Jambhulkar, W. Xu, S. Guo, H. Ko, K. Song
Systems Engineering
School of Manufacturing Systems and Networks (MSN)
Ira A. Fulton Schools of Engineering, Arizona State University (ASU),
Mesa, AZ 85212, USA
M. Fagade
Mechanical Engineering
School of Engineering for Matter
Transport and Energy (SEMTE)
Ira A. Fulton Schools of Engineering
Arizona State University
Tempe, AZ 85281, USA
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demand for batteries in various applications is challenging
to meet since they require a prolonged lifetime, survivability
in harsh environments, size reduction, packing compatibility,
biodegradability, and higher energy and power densities.
Conventional manufacturing methods for energy materials
and rigid packaging or assembly requirements have significantly
limited current battery dimensions (e.g., cylindrical, prismatic,
pouch, and coin cells) and functionalities. As a new manufac-
turing technique, additive manufacturing (AM), or 3D printing,
is a series of processes making 3D objects layer-by-layer based
on light-monomer, heat-filament, laser-powder, or mechanical
shear-ink interactions via digital modeling software. Compared
to traditional subtractive manufacturing, AM has shown exten-
sive versatility with better design freedom, and design versatil-
ity along with more efficient design/deposition systems. AM is
becoming increasingly popular due to its rapid prototyping ca-
pabilities, cost- and time-efficiency, and a broad range of raw
feedstocks. Among many different utilizations, the AM used for
EES has facilitated new materials to be synthesized/fabricated,
A. M. Kannan
Fuel Cell Laboratory
The Polytechnic School (TPS)
Ira A. Fulton Schools of Engineering
Arizona State University
Mesa, AZ 85212, USA
Q. Nian
School of Engineering for Matter
Transport and Energy (SEMTE)
Arizona State University
Tempe, AZ 85287, USA
A. Asadi
Department of Engineering Technology and Industrial Distribution
(ETID)
Texas A&M University
College Station, TX 77843, USA
G. Miquelard-Garnier, A. Dmochowska
Laboratoire PIMM
Arts et Métiers Institute of Technology
CNRS, Cnam
HESAM Universite
151 Boulevard de l’Hopital, Paris 75013, France
M. K. Hassan, M. Al-Ejji
Center for Advanced Materials
Qatar University
P.O. BOX 2713, Doha Qatar
H. M. El-Dessouky
Physics Department
Faculty of Science
Galala University
Galala City 43511, Egypt
H. M. El-Dessouky
Physics Department
Faculty of Science
Mansoura University
Mansoura 35516, Egypt
F. Sta n
Center of Excellence Polymer Processing & Faculty of Engineering
Dunarea de Jos University of Galati
47 Domneasca Street, Galati 800008, Romania
K. Song
Mechanical Engineering
University of Georgia
302 E. Campus Rd, Athens, Georgia 30602, United States
creative structures to be designed, and new applications to be
targeted.[3,4 ] In addition, the AM for battery processing and pack-
aging has benefits to i) flexibly include different material types
(e.g., polymers, ceramics, metals, or their composites), ii) quickly
tune microstructures or even nanoscale features (e.g., porosity,
tortuosity, volume-to-surface ratio), iii) promptly design complex
architectures or hierarchies (e.g., surface patterning or layers in
packaging), iv) potentially maximize energy efficiency (e.g., mass
loading of active materials), and (v) rapidly finish the life cycle
assessment (e.g., on fly manufacturing, in-situ monitoring, data
analytics for quality control).[4–7]
In modern energy-focused technologies, the AM field has
pushed for higher energy density, strict safety characteristics, bet-
ter interface with human beings, and enhanced sustainability in
energy storage devices to meet design, manufacturing, cost, and
environmental demands.[8,9 ] Most review papers in the 3D print-
ing fields for energy storage devices (Table 1) fall into the follow-
ing categories.
•Various 3D printing-compatible materials for electrochemical
energy applications[6,10–12 ]
•3D printing-enabled microstructures for energy
applications[5,13–15 ]
•Main-stream 3D printing methods to compare different elec-
trochemical performances[16–19 ]
•Different 3D printing-enabled solid-state energy stor-
age devices focusing on supercapacitors and battery
components[7,11,20 ]
•3D printing-facilitated design and prototyping trends to pro-
cess or manufacture electrodes and electrolytes[2,8,9,21–23 ]
•Methods in modeling, simulation, and data analytics regard-
ing their role in 3D printing and the general manufacturing of
energy devices[24–26 ]
However, a comprehensive summary of different 3D printing
mechanisms for designing and manufacturing of energy stor-
age applications based on each battery component (i.e., anode,
cathode, and electrolyte) has been rarely reported. Therefore, un-
like other literature papers in Table 1, we have focused on differ-
ent 3D printing techniques for electrochemical energy applica-
tions, including the electrodes and solid-state electrolytes (SSEs),
featuring the role of 3D printing in energy storage device de-
velopment and their applications. Specifically, this review will
first summarize currently available 3D printing methodologies
such as light-based printing (i.e., stereolithography (SLA), digital
light processing (DLP), continuous liquid interface production
(CLIP), computed axial lithography (CAL), and two-/multi-photo
polymerization (TPP/MPP)) as shown in Figure 1a1, filament-
based (i.e., fused deposition modeling (FDM), and direct ink writ-
ing (DIW)) in Figure 1a2, powder-based (i.e., powder bed fusion
(PBF)-based printing of selective laser sintering (SLS), and selec-
tive laser melting (SLM)) in Figure 1a3, and jetting-based printing
(i.e., PolyJet, MultiJet, and Binder jetting) displayed in Figure 1a4
with their state-of-the-art trends, current challenges, and future
mitigations. Section two will briefly summarize 3D printing plat-
forms and their processing principles. Section three will cover the
electrodes (i.e., cathode and anode), emphasizing the materials,
manufacturing, and properties/performance. Similarly, section
four covers the materials and 3D printing pathways for different
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Tabl e 1 . Recent literature review papers in the field of advanced manufacturing of batteries (2015 onwards).
Year Title Focus Refs.
2023 Application of 2D MXene in Organic Electrode
Materials for Rechargeable Batteries: Recent
Progress and Perspectives
Application of MXene in organic electrode materials for rechargeable batteries.
Looking into organic polymers and the advantages of organic electrode
materials. In addition to future perspectives focused on boosting stability of
MXene, increasing the varieties and new fabrication strategies of MXene while
developing surface chemistry in the battery application
[27]
2023 Material–structure–property integrated additive
manufacturing of batteries
Package-level and material-structure-property applications with an emphasis on
additive manufacturing of batteries. Material processing and integrated
manufacturing approaches enable improvements in rechargeable batteries.
Conversely, the difficulties and drawbacks of battery materials while also
providing suggestions for improvements
[5]
2023 A non-academic perspective on the future of
lithium-based batteries
Key metrics and challenges in addition to performance aspects when developing
new technologies in the battery industry. Hence, an analysis of the supply chain,
sustainability of materials, and system-level cost for the battery industry in
addition to the latest developments with perspectives on the challenges and
prospects of various technologies in the battery industry
[28]
2022 A focus review on 3D printing of wearable energy
storage devices
Fundamentals of 3D printing inks used in wearable electrochemical systems such
as batteries and supercapacitors with an emphasis on optimizing strategies in
improving the mechanical and electrochemical properties
[4]
2022 Emerging application of 3D-printing techniques in
lithium batteries: From liquid to solid
The working principles, advantages, and limitations for solid-state batteries via 3D
printing methods with a focus on the modifications to raise the electrochemical
performance of the electrodes and electrolytes
[17]
2022 Dry electrode technology, the rising star in
solid-state battery industrialization
Review of the dry battery electrode techniques with an analysis of the superiorities,
protocols, scientific principles, and potential attempts to improve the
performance and production efficiency for industrialization
[18]
2021 Design Strategies of 3D Carbon-Based Electrodes
for Charge/Ion Transport in Lithium-ion Battery
and Sodium Ion Battery
The operating mechanism of charge/ion transport in 3D carbon-based electrodes
with a focus on architectural analogies, such as porosity and tortuosity for
higher capacity and fast transport
[21]
2021 3D Printing for Solid-State Energy Storage Recent advances in 3D-printed solid-state energy storage devices, including
solid-state batteries and solid-state supercapacitors
[20]
2021 3D printing for rechargeable lithium metal batteries Recent advances in 3D printing rechargeable lithium metal batteries with
fundamental principles, printing techniques, applications, design rationales, and
practical challenges
[29]
2021 3D printing of advanced lithium batteries: a
designing strategy of electrode/electrolyte
architectures
Development trends of electrodes and electrolyte designs via 3D printing
technologies, as well as prospects and challenges of 3D-printed lithium batteries
[9]
2021 3D printing-enabled advanced electrode architecture
design
Recent studies on 3D-printed electrodes with advanced interdigitated structures,
through-thickness aligned structures, hierarchical porous structures, and fiber
and fabric structures of electrodes. Hence, novel advancements in electrode
architecture are generated and optimized by computational simulation and
machine learning
[8]
2021 Design and Manufacturing of 3D-Printed Batteries Introduction to unique features of 3D printing techniques for battery modules and
general approach to making them printable. Examining prominent roles of
printing design in the module architectures battery configuration and effective
solutions. Hence, a guide for further research direction on functional materials,
advanced printing technologies, and new designs
[2]
2021 Hierarchically porous membranes for lithium
rechargeable batteries: Recent progress and
opportunities
Mechanisms for membranes with hierarchically porous frameworks or ordered
channels can be employed as electrodes, separators interlayers, electrolyte
transport, and charger transfer. In addition to future prospects of optimizing
membrane development for advanced battery applications
[22]
2020 Evolution of 3D Printing Methods and Materials for
Electrochemical Energy Storage
Materials and method requirements for 3D printable batteries as well as
supercapacitors with future perspectives for printable energy-storage materials,
casings, and direct printing electrodes and electrolytes
[11]
2020 3D printing of structured electrodes for rechargeable
batteries
Materials, technologies, and structures for 3D printing. Optimization strategies for
batteries, along with challenges and critical directions toward 3D printing
electrodes/electrolytes
[12]
2020 3D Printing for Electrochemical Energy Applications Overview of the motivation for 3D printing electrochemical energy storage
applications and how they are affected by various 3D-printing technologies and
post-modification techniques. In addition to future perspectives
[3]
(Continued)
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Tabl e 1 . (Continued).
Year Title Focus Refs.
2020 Additive Manufacturing of Batteries Significant achievements in 3D printing batteries, along with challenges and
potential research frontiers in developing 3D printing techniques and materials
for batteries
[10]
2020 Recent advances and future challenges in printed
batteries
Recent advances in 3D-printed batteries are separated by lithium-ion batteries,
Zn/MnO2batteries, and other battery types. In addition to future challenges in
the area of printed batteries
[30]
2019 3D Printing for Electrocatalytic Applications 3D printing benefits, potential, limitations, and current development trends for
electrocatalytic applications. The future perspective of electrodes is based on
size, printing resolution, and cost. In addition to future perspectives and
developments for electrocatalytic applications
[31]
2019 3D printed electrochemical energy storage devices Design on printed materials, printing process, and electrochemical performance of
printed devices as well as an overview of future designs
[6]
2017 Emerging 3D-Printed Electrochemical Energy
Storage Devices: A Critical Review
Recent advantages of the sandwich-type and in-plane architectures for energy
storage devices. In addition to future perspectives with unique challenges and
important directions
[23]
2017 3D printing of components and functional devices
for energy and environmental applications
Recent advances regarding the implementation of 3D printing for energy and
environmental applications
[32]
2017 Progress in 3D Printing of Carbon Materials for
Energy-Related Applications
Recent developments in 3D printing energy-related applications, electronic
circuits, and thermal-energy applications at high temperatures, in addition to
future designs and developments
[19]
types of solid electrolytes, including oxide-solid electrolytes
(OSEs), solid-polymer electrolytes (SPEs), and composite-solid
electrolytes (CSEs). Each section focuses on material choices,
design trends, process rationale and optimization, and system
performance. Lastly, section five of the review provides new in-
sights and perspectives for advanced manufacturing energy stor-
age device studies. To this end, we cover some current chal-
lenges in discovering new feedstock materials for AM, as shown
in Figure 1b1. Figure 1b2highlights the lack of printing resolu-
tion for microporous patterning and complex hierarchies in the
current 3D printing methods. Figure 1b3brings attention to new
methods of co-design and co-manufacturing concepts to fabri-
cate a complete battery in a single step. Figure 1b4brings a call to
action of incorporating uncertainty prediction through machine
learning (ML) and artificial intelligence (AI) for optimization and
data analysis while navigating around the risks in Figure 1b5
through implementing recycling methods for batteries. Addi-
tionally, the current challenges in the AM for electrochemical
energy storage (EES) applications, including limited materials,
low processing precision, co-design/co-manufacturing concepts
for complete battery printing, machine learning (ML)/artificial
intelligence (AI) for processing optimization and data analysis,
environmental risks, the potential of4D printing as shown in
Figure 1b6, a lack of rare metals, and further development of
advanced computer technology in advanced battery applications,
are also presented.
2. Additive Manufacturing Methods
2.1. Light-Based Printing
2.1.1. Stereolithography (SLA)
SLA utilizes a light source to polymerize a photocurable resin
(i.e., photoinitiator and monomer) and create delicate printable
structures. SLA has diverged with many different mechanisms
and uses (i.e., scanning, projection, continuous, and volumetric),
diversifying the SLA systems with continuous improvements for
the 3D printing resolutions and processing rates.[33] Depending
on the platform elevation direction, there are two approaches
when depositing one layer of cure resin on another, i.e., top-
down and bottom-up.[33] The bottom-up method is more advan-
tageous than the top-down method due to the faster printing
speed and non-sealed environment, which can prevent oxygen in-
hibition during photopolymerization, as presented in Figure 2a.
Resin curing-based 3D printing is particularly attractive for a
few reasons: high levels of building resolution (μm and better),
good z-axis strength due to chemical bonding between layers, and
the ability to print transparent objects.[34] Critical parameters for
the SLA include the machine parameters (e.g., light wavelength,
typically ultraviolet light (UV), light-resin interactions), material
parameters (e.g., photoinitiator, quenchers, inhibitors, diluents,
rheology, solvents, monomer types, surface tension, particle ad-
ditives), and printing parameters (e.g., scan speed, spot size, ex-
posure duration, layer thickness, patterns of masks or scans).
Over the years, SLA printing has evolved and expanded its tech-
nological capabilities by drawing inspiration from its original
roots. This has led to the emerging of various new types of print-
ers. Henceforth, the following subsections will cover DLP, CLIP,
CAL, and TPP/MPP technologies, summarized in a systematic
order (from older to newest) with updated trends, limitations, and
perspectives.
2.1.2. Digital Light Processing (DLP)
While DLP works similarly to SLA, the main difference is that
DLP uses a digital micromirror device (DMD) projector instead
of a raster laser, allowing it to print an entire layer simultane-
ously. As a result, DLP is useful for sequential processes aiming
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Figure 1. Additive manufacturing (AM) techniques for batteries, including a1) light-based printing, a2) filament-based printing, a3) powder-based print-
ing, and a4) jetting-based printing, depicted with their respective subtypes. The schematic also illustrates future advancements to b1) expand the feed-
stock of printers via new materials, b2) improve the printing resolution, (b3) adopt co-design and co-manufacturing methods, b4) incorporate machine
learning (ML) and artificial intelligence (AI) for optimized in-situ fabrication methods, b5) navigate around the risks through implementing recycling
methods for batteries, and b6) enable 4D printing of energy storage devices.
to minimize trial and error. This concept was developed in 1997
by Texas Instruments,[35] shortly after the SLA technology was
introduced. It should be noted that DLP technology operates at
a different wavelength and exhibits major differences in terms
of rheology, which makes it faster and more adaptable than SLA
technology. For example, one of the major and most distinctive
differences between DLP and SLA is the printing platforms. As
previously mentioned, DLP uses a DMD scanner that creates 2D
images of light and dark pixels, generating desirable XY-plane
resolution and allowing it to print faster by virtue of layer print-
ing versus dot printing in general SLA. In addition, DLP can print
in a bottom-up shown in Figure 2b1or top-down in Figure 2b2
configuration, similar to the general SLA. The bottom-up prints
are inverted on the build head, and that light will come from the
bottom to the top. Conversely, the top-down configuration prints
from the top of the vat, meaning the exposure to light will come
from the top to the bottom. Furthermore, DLP is not limited to
photosensitive resins and shows high flexibility to print ceramic-
and metal-loaded suspensions with post-processing (i.e., debind-
ing and sintering) techniques. Moreover, DLP can be fused with
other printing platforms, such as DIW[36] and binder jet print-
ing (BJP),[37] to print multiple materials at once, opening new
applications, such as dental implants, bone scaffolds, and inno-
vative biomaterials, soft robotics, smart wearables, and microflu-
idic devices.[38,39 ]
2.1.3. Continuous Liquid Interface Production (CLIP)
To further improve the light-based 3D printing, DeSimone et al.
designed and assembled a new 3D printing method called CLIP,
which used an oxygen-permeable window below the ultraviolet
(UV) light source as a “dead zone” for the persistent liquid in-
terface and layerless processing shown in Figure 2c.[40] This plat-
form allows for photopolymerization at a high rate of hundreds
of millimeters per hour, showing a significantly improved print-
ing speed with acceptable processing resolutions. The unique ad-
vantages of CLIP are the quick curing speed, layer-less printing,
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Figure 2. a) General stereolithography (SLA). b1,b2) Bottom-up and top-down digital light processing (DLP) configurations. Reproduced with
permission.[38] Copyright 2022, Springer Nature. c) Schematic of the printing platform for continuous liquid interface production (CLIP). Reproduced
with permission.[40] Copyright 2015, AAAS. d1) The representation of the volumetric computed axial lithography (CAL) printing platform and the d2)
manufacturing mechanism. Reproduced with permission.[46] Copyright 2019 AAAS. e1) Two-photo polymerization (TPP) examples of using a single
laser split into multiple points with e2) simulation of the laser splitting up to three times covering most of the model. Reproduced with permission.[47]
Copyright 2019, Springer Nature. f) Multi-photopolymerization (MPP) with possible multiple resin vats in a rotary stage set for high resolution and
scalable 3D printing.[48] Copyright 2012, Elsevier.
and high accuracy. As a result, CLIP supports various produc-
tion materials, such as cross-linkable monomers, rigid ceram-
ics, and biological materials.[41,42 ] However, CLIP has still been
slower than conventional methods, such as injection molding or
mold casting. Therefore, in 2022 DeSimone et al. enhanced the
CLIP design to the injection continuous liquid interface produc-
tion (iCLIP), where a direct injection into the “dead zone” alle-
viates suction forces to accelerate printing speed up to five to
ten folds over CLIP.[43] As an additional benefit, the iCLIP al-
lows for multi-material printing due to the direct injection of
photopolymerization materials. Ongoing research in CLIP has
been focused on new materials and geometries with superior me-
chanical and electrical properties for intelligent systems (e.g., 4D
printing) and on developing better predictive models for multi-
material printing.[44,45 ]
2.1.4. Computed Axial Lithography (CAL)
CAL is based on tomography reconstruction inspired by com-
puted tomography (CT), typically used in medical imaging.[46]
Using photosensitive liquid in a volumetric rotational stage, the
projected 2D images are displayed through light energy as the
printing stage rotates and reconstructs the 2D images into 3D
printable objects, as shown in Figure 2d1,d2.Thisnewmanu-
facturing method does not need layer-by-layer deposition as in
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DLP or CLIP, thus enabling exceptionally smooth surfaces and
rapid fabrication. Besides, it does not require support structures,
even with overhanging features or separate parts.[46] In addition,
CAL allows for new highly viscous photopolymer materials to
be printed, whereas traditional SLA or other conventional pho-
topolymerization methods could not. Therefore, the usability of
CAL can be extended in general photopolymers and their com-
posites containing reasonable loading of glasses, ceramics, and
metal powders.[45,46,49 ]
2.1.5. Two-/Multiphoto Polymerization (T/MPP)
Another AM method with ultrafast nanofabrication was devel-
oped by Geng et al. using a TPP process in conjunction with a
DMD scanner.[47] The DMD allows for a single-focus or multi-
focus hologram generation laser scanning, enabling the laser to
split into multiple focal points for an ultrafast print without com-
promising the pattern resolution illustrated in Figure 2e1,e2.It
is worth noting that the total printing time remains constant
regardless of the sequence or complexity. Henceforth, the TPP
equipped with the ultrafast random-access DMD scanner gives
a precise 3D printing process with complex structures through
advanced photonic resin for nanoscale applications.
The MPP can create small features in a photosensitive mate-
rial without the need for complex optical systems or photomasks.
This method relies on the multi-photon absorption process in a
transparent material, using a laser to create patterns. By scanning
and modulating the laser, a chemical change, typically polymer-
ization, occurs at the focal spot, allowing for the creation of 3D
patterns.[48] However, high-resolution printing using MPP often
comes at the cost of slower printing speeds and limited scalabil-
ity. One possible solution is to combine MPP with other tech-
niques, such as hybridization with multiple resin vats as shown
in Figure 2f.[48] This approach enables sequential printing of dif-
ferent materials, allowing for the creation of multi-material struc-
tures. It is important to note that MPP is commonly employed in
DLP configurations due to the flexibility and versatility it offers.
MPP holds great potential in the 3D printing industry, particu-
larly in terms of enhancing the mechanical, optical, electrical, and
biological properties of printed objects.
2.2. Filament-Based 3D Printing
2.2.1. Fused Deposition Modeling (FDM)
FDM is a popular 3D printing technique known for its layer-by-
layer deposition of mostly thermoplastic polymers (i.e., polylactic
acid (PLA), acrylonitrile butadiene styrene (ABS), polyethylene
terephthalate (PET), polyether ether ketone (PEEK), polypheny-
lene sulfide (PPS), polycaprolactone (PCL)). FDM printers typi-
cally come in Cartesian and delta models.[50,51 ] The main differ-
ence between these two is the movement linearity of the print
beds. Precisely, the Cartesian model moves linearly via Cartesian
coordinates, while the delta model moves circularly with its print
bed featuring a circular motion. Standard features for these mod-
els include a heated nozzle to soften/melt filaments. For exam-
ple, two stepper motors connected to the extruder head facilitate
pushing the filament by gripping the filament wire to prevent
slippage and depositing it into the substrate. Generally, the sub-
strate will move in the x/y (Cartesian model) or radial/tangent
(delta model) directions while the nozzle/extrusion mechanism
moves in the z-direction. With a similar goal for 3D structural
control, the printhead can also be based on a mechanism to move
along the in-plane (i.e., x/y-direction or rotational) while the sub-
strate moves along the out-of-plane (i.e., z-direction).
It is worth noting that the FDM mechanism is reliant on the
deposited layer to cure/harden and build upon the previous layer
to achieve complex structures. One of the tradeoffs for FDM is
the printing resolution, which decreases as the printing speed
increases. To rectify this issue, introducing multi-material/multi-
nozzle printing allows for faster feedstock deposition without sac-
rificing the printing speed. Figure 3a1–a4show printing setups
with different printhead configurations for individual or multiple
feedstocks to be extruded via one or more printheads. Multifila-
ment mono-extruder printing, represented in Figure 3a1, utilizes
a filament selector, similar to the mono-filament, but selects a
single filament to print and can change to a different filament
without the need for any human interference (e.g., Ultimaker S
model). Alternatives can be multifilament through multiple in-
dependent (Figure 3a2, e.g., Flashforge) dual extruder FDM as
shown in Figure 3a5or dependent printing nozzles (Figure 3a3,
e.g., Createbot). Mono-filament extrusion, shown in Figure 3a4,
is a neat feature that uses an individual feedstock that is either
single-phased or may combine multiple materials to create a
mono-filament layer through the extruder.
While independent extruders are available in the market, hav-
ing more than two is not expected due to the difficulty of calibra-
tion, the complexity of nozzle movement, and conflicts of tem-
perature control, as viewed in Figure 3a2. For example, the de-
pendent multi-extruder-based printhead in Figure 3a3is a unique
configuration where the extruders are all on the same axis and
are not free to move and deposit feedstocks independently.[52]
Further manufacturing features to consider during 3D print-
ing may include i) material factors (i.e., melting tempera-
tures, viscosity behaviors, solidification rates), ii) machine fac-
tors (i.e., nozzle sizes, fiber supply), iii) process parameters
(i.e., feed rate/printing speed, raster width/gap/angle, contour
width/thickness, layer thickness/orientations), and iv) environ-
mental factors (i.e., the temperature of the nozzle/bed/chamber,
humidity degrees, oxygen content).
2.2.2. Direct Ink Writing (DIW)
DIW is the most versatile technique due to its broad range of
printing feedstocks in colloids, solutions, and gels. Any poly-
mers and powders can be used if the fluidic ink meets rheologi-
cal requirements/behavior.[53,54] Generally, the inks should expe-
rience shear thinning when extruding, behave as a yield-stress-
decreasing fluid during ejection, and recover their elastic proper-
ties after printing.[53-55 ] Most inks require a post-treatment heal-
ing process after printing (i.e., liquid evaporation, gelation, ther-
mal treatment, and solvents for etching/debinding materials).[54]
The printing platform consists of an ink depositor/dispenser (i.e.,
syringe pump, delivery path), an extruder nozzle with tunable
sizes, a substrate, and printable ink, as shown in Figure 3b1.The
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Figure 3. a1–a4) Schematic illustrations of the different multi-material fused deposition modeling (FDM) configurations. a1) Monoextruder with selective
feedstock from multifilament setting, a2) multi-extruder multifilament with independent printheads, a3) multi-extruder multifilament with dependent
printheads, a4) mono-extruder setting with a concept multi-material print, and a5) an example of multifilament multi-extruder 3D printing platform,
i.e., Flashforge multimaterial printer with a dual-extruder-based setup having independently controlled printheads. b1) Direct ink writing (DIW) concept
with a 3D spiral pattern printed on a hemispherical substrate with b2) an example of DIW platform, i.e., Hyrel 3D printer with a customized printhead
connected with high-pressure dispensers for designing and processing cellular solids.
simplicity of the mechanism allows structural freedom, environ-
mental stability, biological multifunctionality, and cost-effective
manufacturing methods. In addition to being highly platform-
customizable, the DIW also allows it to be more multi-material
versatile. Figure 3b2shows an example of a Hyrel 3D printer used
as a DIW with modular printing accessories and tunable hierar-
chies. It is also worth noting that the freedom to print directly in
3D substrates is superior to other mechanisms (e.g., flat or non-
flat printing substrate, as in Figure 3b1). However, DIW has been
limited by liquid-based inks (e.g., solutions, suspensions, gels)
that require strict curing or hardening strategies.[54] Besides, the
scalability and safety of ink design/preparation remain a concern
regarding hazardous materials. For example, limited nonconduc-
tive materials (e.g., macromolecules) must be added to the active
materials to increase printability and maintain good electrochem-
ical performance for energy storage devices. Some typical addi-
tives include stabilizers, surfactants, and viscosity modifiers.[54]
These additives allow for fine tunability to printability but should
be washed through high temperatures after printing.
2.3. Powder Bed Fusion (PBF)-Based 3D Printing
2.3.1. Selective Laser Sintering (SLS)
SLS involves feeding powders and rapidly heating them to fuse
the powder surfaces via neck formations or phase changes for
specific shapes, sizes, and structures as shown in Figure 4a.
Unlike the FDM, which fuses continuous filaments, the SLS
fuses noncontinuous particles for complex solid-state dimen-
sions. Based on the state of the sintered phases, the sintering pro-
cess can be categorized either as a solid-state shown in Figure 4b1,
more common in SLS, or a liquid phase with binder coatings or
mixtures, as viewed in Figure 4b2. Compared to the particle fus-
ing in solid-state, the liquid-state sintering would rely on binders
to display liquid-like behaviors upon heating and gluing parti-
cles together. SLS powder bed can be composed of a single mate-
rial or multi-materials with binders.[56] However, SLS primarily
uses semicrystalline thermoplastic polymer and, in some cases,
amorphous polymer powders.[42,57-59 ] Characteristics for the
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Figure 4. a) Schematic of the manufacturing platform of powder-bed-fusion-based 3D printing, i.e., selective laser sintering (SLS) & selective laser
melting (SLM) representing their close similarities in the manufacturing tools. Representation of the main difference printing method for SLS in b1)
solid-state sintering (SS), where powders are compressed and heated under pressure to create a solid mass. In contrast, b2) liquid-phase sintering
involves the addition of a small amount of liquid to the powder mixture before sintering. Schematic of the printing difference for the SLM in both c1)
partial melting, where a portion of the material gets melted, and c2) full melting, where the entire material is melted.
feedstock powder quality include size, distribution, shape, flowa-
bility/viscosity, surface tension, surface charges, and transition
temperatures of powders, each of which will influence the prod-
uct quality, e.g., particle packing factor, surface roughness, or de-
fect density.[60] Although SLS has shown advanced capabilities
to process polymer and ceramic particles, further improvements
over material candidates and manufacturing precisions are still
needed. For example, many SLS platforms face challenges in un-
derperforming and need to improve to match traditional manu-
facturing methods, such as high surface roughness or a lack of
mass production capabilities. Besides, powder aggregation due
to electrostatic forces and heterogeneity from the particle synthe-
sis in the powder feedstock are vital factors negatively affecting
printed product performance. Additionally, the SLS manufactur-
ing process is more expensive and complex to operate than the
conventional processing of casting, molding, or other smaller-
footprint printers (e.g., FDM, SLA).
2.3.2. Selective Laser Melting (SLM)
SLM has a similar setup to the SLS and works with approximately
the same procedures. The main difference is in the materials,
as SLS uses primarily metal particles, which leads to SLS fusing
particles thermally, while SLM uses the complete melting of ma-
terials. SLM was developed to produce fully dense objects (i.e.,
smaller layer thickness, smaller pores) with higher mechanical
properties, in addition to the benefit of avoiding prolonged post-
processing cycles typically seen in SLS.[61] There are two different
degrees of melting, for example, partial melting, typically seen
when a partial section turns into a liquid state through melting,
represented in Figure 4c1. As the name suggests, complete melt-
ing is when an entire area is intended to melt completely, which is
often the case in metallic SLM, represented in Figure 4c2.How-
ever, “partial melting” and “full melting” are ambiguous, espe-
cially when the intention is to have near-full densified parts.[61]
It is worth noting that both polymers and metals are compati-
ble with SLM. Nonetheless, it is more commonly seen in metal
3D printing, where there are different configurations for metal-
based 3D printing, such as single component/single powder and
single component/multiple alloyed powder particles. Generally,
the powder particles range from 20 to 50 μm in diameter, and
a single layer thickness ranges from 20 to 100 μm.[62] For those
with a laser beam of a bandwidth smaller than 40 μm (e.g., lasers
of Nd:YAG, fiber, CO2), a layer thickness of less than 10 μmanda
particle size of less than 10 μm would be formed to be considered
aμ-SLM.[62]
2.4. Jetting-Based 3D Printing
2.4.1. Inkjet-Based 3D Printing of PolyJet and MultiJet
Inkjet-based printers deposit and solidify polymer powders layer
by layer through a jetting head, followed by built-in UV irra-
diation, heat transfer, or chemical reaction. The MultiJet (from
3D Systems) and PolyJet (from Stratasys) are currently the ma-
jor commercialized 3D printers based on a material jetting (MJ)
mechanism.[63,64 ] The printer heads would jet liquid resins or par-
ticles through tiny needles selected from many linearly aligned
nozzles during the MJ shown in Figure 5a. In this way, the jetting
droplets will disperse with highly complex geometries and high
surface smoothness. As a result, surface finishing is not manda-
tory since layer dimensions at the microscale are possible.[64]
Commercial companies provide proprietary jetting inks, from
rigid plastics to flexible urethane-acrylate. These inks are imme-
diately UV/thermally cured and solidified upon jetting to build
the 3D structure during crosslinking or fusing as responses to
external energies represented in Figure 5a. For example, cur-
ing reactions can be performed by dispersing two reactive com-
ponents using alternative nozzles induced by heat or UV light
(e.g., UV curing of photoresponsive monomers, and the nanopar-
ticle (NPs) may require thermal curing or annealing). In ad-
dition to these sprayable or injectable inks, support materials
are often used during the printing process to form overhangs
that are removable through solvent dissolution or mechanical
means such as peeling or scraping. The layer deposition repeats
can be spatially designated to create structures with spatially
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Figure 5. Examples of jetting-based 3D printing techniques. a) Illustration of inkjet-based 3D printing process utilizing a double ultraviolet (UV)
irradiation-facilitated curing process on a stack cube model. The ink droplets are deposited and cured layer by layer to create the 3D structure.
b) Schematic of binder jetting-based 3D printing process with a powder bed, leveling roller, and two different platforms for powder supply and printing.
The binder is selectively deposited to bind the powder particles layer by layer, forming the 3D object.
varying or graded features. Functionally graded designs are also
manufacturable by depositing materials with different ratios or
chemistries (e.g., methacrylate or acrylate).[65] Inkjet-based 3D
printing can process vendor-sold colloids and in-house prepared
monomers, polymer solutions, or NP dispersions.
2.4.2. Binder Jetting-Based 3D Printing
Binder jetting-based printing deposits a binding material onto
one powder layer and forms 3D structures to repeat this
process.[66] As a result, binder jetting-based 3D printing involves
powders and adhesive binders without external energies, illus-
trated in Figure 5b. In comparison, PBF 3D printing also involved
similar powder materials.[66] However, PBF depends on material
sintering and melting from laser sources as extra energy con-
tributions. Besides, this binder jetting technology allows multi-
material processing, including multi-colored printing across the
whole color spectrum. Binder jetting in powders gives access to
a broader range of materials, including polymers, ceramics, met-
als, and combinations, to manipulate their physical, mechanical,
and chemical properties.[67‒69 ]
3. 3D-Printing Electrodes
Conventional LIBs with thin film electrodes face many chal-
lenges related to poor ionic conductivity, energy density, safety,
and cycling stability. The mass loading of active materials per
footprint is typically low due to the trade-off between energy and
power density, increasing the inactive material ratio (current col-
lectors and separators).[70,71 ] Therefore, the primary goal of im-
proving battery performance is to reduce the proportion of inac-
tive materials while increasing the percentage of active materi-
als to optimize energy storage capacity. Thick electrodes would
decrease the use of current collectors and separators and in-
crease the active material ratio. In effect, the transport distance
of Li-ions and electrons increases with thick electrodes, result-
ing in declined rate performance due to the slow charge transfer
kinetics.[71] With the capability of desirable layer deposition, 3D-
printing technology can design and process directionally ordered
pores within the electrodes to mitigate this risk. Tables 2 and 3list
the 3D printing methods that are commonly used for anode and
cathode electrodes and show trends in processing techniques and
printing materials. For example, FDM and DIW are popular in
3D printing due to the easy use of filaments/inks.[53,54 ] Printing
feedstock-wise, the anodes are primarily comprised of lithium ti-
tanium oxide (LTO), with the cathodes dominant of lithium iron
phosphate (LFP). LTO has high rate capability, long cycle life,
and stability, due to its ability to intercalate the Li-ions, making it
a suitable electrode for high-power applications. Ni–Sn & SnO2
are also commonly used for higher theoretical capacity. Similarly,
AgNP@CC is known for its high electrical conductivity, while GO
has a high surface area and can be used for energy storage and
conversion devices requiring high cycles. Henceforth, this sec-
tion will systematically discuss different AM techniques for an-
ode and cathode materials. The specific details for the LIB appli-
cation regarding the material types, manufacturing procedures,
and cell-assembly characteristics will be discussed.
3.1. 3D-Printing Anode Materials
3.1.1. Light-Based 3D Printing for Anodes
SLA printing is a well-established AM technique that has gained
prominence in ESS, particularly in the field of anodes and solid
electrolytes. For example, Golodnitsky et al. developed a quasi-
solid rechargeable 3D microbattery via SLA 3D printing.[72] One
of the main challenges that batteries face is the low power and
capacity, which the short ion-diffusion path could mitigate. In-
creasing the thickness can achieve a better capacity, but it may
also hinder ionic kinetics by increasing the current path and
reducing power density. Therefore, more complex 3D architec-
tures are necessary, which convert the entire thin-film battery
into a network placed on a small footprint (e.g., Figure 6a1).[72]
Figure 6a2,a3illustrates the cross-section of the full cell with the
juxtapose film layers on the nickel (Ni)-current collector, cath-
ode, polymer membrane as the separator, and LTO-contained an-
ode. As a result, the fabrication of 3D microarrays in the form
of cylinders with Cartesian coordinate grid holes was conducted.
However, the microarray morphology was not limited to
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Tabl e 2 . Examples of AM methods for anodes used in LIB. See terminology below and also in Section 6 (AgNPs, silver nanoparticles; AgNWs, silver nanowires; CC, carbon cloth; CMC, carbon methyl
cellulose; DIW, direct ink writing; DLP, digital light processing; FDM, fused deposition modeling; GO, graphene oxide; Gr, graphene; Gt, graphite; KB, ketjenblack; LAGP, Li1.5 Al0.5Ge1.5 P3O12;LFP,
lithium iron phosphate; Li0.7PAA, lithium poly(lactic acid); LiM, lithium metal; LMO, lithium manganese oxide; LNMO, lithium nickel manganese oxide; LTO, lithium titanium oxide; Mg, magnesium;
MWCNT, multiwalled carbon nanotube; N/A, not applicable; NaOH, sodium hydroxide; Ni, nickel; Pd, palladium; PEDOT:PSS, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate; PF, phenolic
resin; PLA, polylactic acid; PVP, poly(vinylpyrrolidone); Si, silicon; SiNP, silicon nanoparticles; SiO, silicon monoxide; SLA, stereolithography; SLS, selective laser sintering; Sn, tin; SnO2,tin(IV)
oxide; WPF, pinewood powder; Zn, zinc).
Manufacturing Materials Properties Refs.
Anode Method Print
diameter
[μm]
Speed
[mms−1]
Layer
Number
Post-treatment Particles Additives Cell assembly Specific capacity Voltage Cycles
SLA 20 – 1 Air drying etching LTO Li0.7PAA Full-Cell
(LTO/LAGP/LFP)
400–500 (μAh cm−2) 1.9–3.2 200 [72]
15 – 1,2,3 Etching Ni–Sn photoresist
(AZ9260) (III)
and Ni
Half-cell
(LMO/Ni–Sn)
– 0.0–3.2 200 [74]
DLP 0.0018 – 1 N/A Zn GO Symmetric-cell
(3DGr@Zn)
3.76 and 3.13 (mAh cm−2) 0.12–0.27 500 [75]
40-60 ≈0.28 40 Debinding
Sintering
SnO2Camphor
quinone
Full-Cell (Sn/Ni) 100-1000 (mAh g−1) 1-2.5 50 [73]
FDM 1.4–1.75 – ≈1-2 Vacuum drying LTO PLA Half-cell (LTO/LiM) 80 (mAh g−1) 2.6–3.8 100 [76]
1.75 40 ≈1 Air drying LTO Gt, PLA Half-cell (LTO/LiM) 3.34-4.84 (mAh cm−3) 2-3 100 [77]
1.75 0–200 1 N/A Gt PLA Half-cell (Gt/LiM) 200 (mAh g−1)–6[78]
1.75 30 – Chemical (NaOH) Gr PLA Half-cell (Gr/LiM) 500 (mAh g−1) 0.01–3 60 [79]
––≈5 N/A Gr PLA Half-cell (Gr/LiM) 40 (mAh g−1) 0.01–3 3-120 [80]
DIW 100 5 6 Freeze-drying LTO GO Half-cell (LTO/LiM) 169 (mAh g−1) 2–4 20 [81]
205 2 10 Freeze-drying LTO GO, AgNWs Half-Cell (LTO/LiM) 4.74 (mAh g−1) 1–2.5 100 [82]
100 – 16 N/A LTO KB, PVP Full-cell (LTO/LFP) 4.45 (mAh cm−1) 1–2.6 2 [83]
60-100 4–8 6,12,18 Freeze-drying LTO CMC, acetylene
black
Half-cell (LTO/LiM) 4.8 4.45 (mAh cm−1) 1.2–2.4 100 [84]
210 4–8 4,8,12 Freeze-drying LTO KB, MWCNT Half-cell (LTO/LiM) 145 (mAh g−1) 1–2.5 100 [71]
100 1 7 Vacuum drying Gt SiO2Full-cell (Gt-(Gt-
SiO)/LNMO)
3.52 (mAh cm−2) 3.5–4.85 120 [85]
SLS 10.5 <1 20 Etching, purifying,
drying
Gr Ni/sucrose – – – – [86]
10 – 1 N/A Mg Mg2Cu MgCu2Half-Cell (Mg/LiM) 250 (mAh g−1) 0.005–1.5 10 [87]
100 2500 1 Vacuum drying Carbon PF, WPF – – – – [88]
Inkjet – – 25 N/A Si PEDOT: PSS Half-cell (SiNP/LiM) 1714 and 961 (mAh g−1) 0.01–0.25 100 [89]
80 50 8 N/A Gr Ethyl-cellulose Half-Cell (Gr/LiM) 942 (mAh g−1) 0.01–3.0 100 [90]
60 – 47.7 Annealed AgNP@CC Carbon Half-Cell
(AgNP@CC/Zn)
184 (mAh g−1) -0.3–- 1.0 1200 [91]
Binder
Jetting
100 – 3 De-powdering
impregnation of
Pd
GO Phosphoric acid – 430 (mF cm−2) 0.0–1.0 1000 [92]
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Tabl e 3 . Summary and comparison of 3D printed cathodes for LIB. See terminology below and also in Section 6 ( Al, aluminum; CNT, carbon nanotubes; ITO, indium tin oxide; LMFP, lithium
manganese iron phosphate; NCA, lithium nickel cobalt aluminum; NMP, N-Methyl-2-Pyrrolidone; PC, propylene carbonate; PEI, polyethylenimine; PVDF, polyvinylidene fluoride; PVDF-co-HFP,
poly(vinylidene fluoride)-co-hexafluoropropylene; SCMC, sodium carboxymethyl cellulose; Se, selenium; SY LEP, super yellow light-emitting polymer; THF, tetrahydrofuran; ZnO, zinc oxide).
Cathode Manufacturing Materials Properties Refs.
Method Print
diameter
(μm)
Speed
(mm/s)
Layer
Number
Post-Treatment Particles Additives Cell Assembly Specific Capacity Voltage Cycles
SLA 15 – 1,2,3 Etching LMO Photoresist
(AZ9260) (III)
and Ni
Full-cell
(LMO/Si-Np)
– 0.0–3.2 200 [74]
20 – 1 Air drying etching LFP – Full-cell
(LTO/LAGP/LFP)
400–500 (μAh cm−2) 1.9–3.2 200 [72]
FDM 1.75 – ≈4 N/A LFP PLA Half-cell (LFP/LiM) 15 (mAh g−1) 2.6–3.8 10 [94]
1.4–1.75 – ≈1-2 Vacuum drying LFP PLA Half-cell (LFP/LiM) 60, 50, 20 [mAh g−1] 2.6–3.8 100 [76]
150–200 5,6 2,5,10 Freeze-drying Se CNT Half-cell (Se-x/LiM) 538.1 (mAh g−1) 0.8–3 200 [95]
1.75 40 100 Air drying LMO MWCNT, PLA Half-cell (LMO/LiM) 6.99–8.1 (mAh cm−3) 3.3–4 100 [77]
DIW 100 5 6 Freeze-drying LFP GO Half-cell (LFP/LiM) 170 (mAh g−1) 2–4 20 [81]
100 – 16 N/A LFP KB, PVP Full-cell (LFP/LTO) 4.45 (mAh cm−1) 1–2.6 2 [83]
250 2
2,4,8,10,12
Freeze-drying LFP PEDOT: PSS Half-cell (LFP/LiM) 5.63 (mAh cm−1) 2–4 100 [96]
60 1–30 150–550 Calcination LMFP PVDF Half-cell
(LMFP/LiM)
150.21 (mAh g−1) 2–4.5 1000 [97]
SLS 0.4–1.0 17,21,25 100 N/A NCA – – 167.7 ±7.6 (mAh g−1) – – [98]
0.4–1.0 17,21,25 100 N/A NCA – – 167.7 ±7.6 (mAh g−1) – – [98]
Inkjet 50 – 1 Sintering ITO (Al:ZnO:PEI)
ITO/(Al:ZnO:PEI)/SY
LEP/DEDOT: PSS
– – – [99]
20 – 1 Vacuum drying LFP CB and SCMC Half-cell (LFP/LiM) 134.7 and 129.9 (mAh g−1) 2.0–4.0 9 [100]
1.4 – 1 Air drying MnO2PC, (PVDF-HFP),
THF
N/A 270 (mAh g−1) 0.5–1.7 – [101]
Aerosol 80 – 1 Calendering LFP Carbone, NMP Half-cell (LFP/LiM) 140 [mAh g−1] 2.5-4.0 100 [102]
170 – 1 Vacuum drying LFP Carbone, Kynar
1800, NMP
Half-cell (LFP/LiM) 105 to 151 (mAh g−1) 3.4 50 [103]
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Figure 6. a1) Photos of the SLA-printed polymer-based substrates for electrode applications. a2–a3) Cross-sectional view of the nickel (Ni)-based current
collector as the substrate, the cathode, the polymer membrane, and the anode contact points. Reproduced with permission.[72] Copyright 2018, Elsevier.
b1) DLP diagram of SnO2-based porous anode electrode with b2) round holes, b3) hexagonal holes, and b4) square holes in configuration. b5,b6) Photos
illustrating the printed electrodes before and after the debinding and sintering processes with different porous configurations for anodes. Reproduced
with permission.[73] Copyright 2023, Elsevier. c1) FDM printing for graphene (Gr)-based electrodes with the c2) casing configuration and the correspond-
ing c3) charge/discharge cycles with the specific capacity. Reproduced with permission.[80] Copyright 2017, Scientific Reports. d1) DIW manufacturing
method of an entirely 3D printed LIB (e.g., cathode, separator, anode, and packaging seal) with corresponding d2) current versus voltage (C–V)graphand
d3) areal capacity showing C–V relationship as a function of the cycle number for the fully 3D printed battery. Reproduced with permission.[83] Copyright
2018, Wiley-VCH. e1) Schematic representation of the 3D printed Gr foams via SLS with e2) the comparison between different computer design models
before and after printing, showing consistent processability. Scale bars are 5 mm. Reproduced with permission.[86] Copyright 2017, American Chemical
Society. f1–f4) Representation of processing 3D printable silicone NPs via an Inkjet printer. f5) Example of the “Western University” logo printed on a
copper foil in addition to optical images and scanning electron microscope (SEM) images of f6) poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
(PEDOT: PSS), f7) poly(vinylpyrrolidone) (PVP), f8) carbon methyl cellulose (CMC), and f9) Na-alginate. Scale bars red, white, and black represent 3 cm,
5 cm, and 500 nm, respectively. Reproduced with permission.[89] Copyright 2017, Elsevier. g) Schematic illustration of the binder-jetting technique by
first introducing thermally reduced graphene oxide (TRGO) powders, then dispersing them in a capillary consolidation powder to spread onto a feed
bed. After the binder injection to create 3D-printed disks, the impregnation of nano palladium (Pd) is implemented to improve the performance of the
electrode. Reproduced with permission.[92] Copyright 2017, Elsevier.
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honeycomb, triangular, or cylindrical shaped holes, providing
more freedom in tuning the density of the models as well as
the mechanical strength. Figure 6a1shows an example of a 3D-
printed anode later tested into a full-cell configuration. The elec-
trochemistry characterization showed acceptable cyclability with
an areal capacity of 400 to 500 μAh cm−2tested at a rate from 0.1
to 4C. In addition, when comparing the model for a silicon (Si)
chip, it has at least one order of magnitude higher in areal ca-
pacity than the commercial system. In contrast, the model with
the 3D printed polymer substrate is three times larger by volume
than the planar thin-film batteries.[72]
DLP is another method used in light-monomer interactive
printing. For example, Chen et al. used DLP and fabricated zinc-
ion battery electrodes with circular, hexagonal, and square holes
(Figure 6b1). As shown in Figure 6b2–b4, these porous chan-
nels had different inner diameters of 1.5 mm, 2 mm, and 1 mm,
keeping all the heights constant at 1.5 mm.[73] Figure 6b1il-
lustrates the general fabrication of the SnO2-based porous an-
ode in a three-step process (i.e., mixing, printing, and debind-
ing/sintering). It is worth noting that the debinding/sintering
process shrank the printed anodes, as shown in Figure 6b5,b6.
To minimize the shrinkage, the anode was doped with Sb2O3
at 0.5, 3, 6, and 9 wt%, which caused an average shrinkage of
26.6, 26.8, and 32.3%, respectively, while keeping a relative den-
sity of 73.5%.[73] Compared with traditional fabrication methods,
these DLP printed anodes showed a 1/25 reduced charge trans-
fer impedance, better cycle stability and rate performance, and
improved capacity retention by ≈29%. Hence, this work demon-
strated the potential of using DLP as a manufacturing method to
improve high-load porous, thick electrodes used for batteries.
3.1.2. Filament-Based 3D Printing for Anodes
FDM is known for its simplicity and rapid prototyping of anodes
of any shape and size, using filaments and a heated nozzle for de-
position. For example, Banks et al. demonstrated an FDM print-
able electrode via graphene (Gr)-based PLA filaments, as shown
in Figure 6c1.[80] Though the output/performance of the half-cell
assembly shown in Figure 6c2,c3was not highly competitive com-
pared to previous literature, this method did not require a metal-
lic current collector for the LIB, which could reduce the manufac-
turing cost. Similarly, Golodnitsky et al. 3D printed a complete
microbattery via FDM.[76] For the anode material, the LTO and
PLA were synthesized into printable discs, spiral, and double-
spiral shaped composites. While the results only used about 50 to
60% of the theoretical capacity, they proved the capability of print-
ing a biodegradable electrode for the LIB application. Further-
more, Wiley et al. demonstrated the FDM printability of LTO/PLA
electrodes.[77] Their work showed a printable profile for a full bat-
tery, with a high loading of active fillers into the polymer (i.e., a
maximum of 30%). Due to the constraint of low active material in
the PLA, the performance was about two magnitudes lower than
the LTO and LMO electrodes.[77] Maurel et al. also demonstrated
FDM printable graphite (Gt)/PLA electrodes.[78] In their studies,
the Gt load was used as high as possible to increase electrochem-
ical performance, while the amount of plasticizer was optimized
to be at a 40% ratio of the PLA to increase ductility and decrease
stiffness.[78] Most recently, Banks et al. used the same material
composition of Gr/PLA via FDM manufacturing.[79] However,
they introduced a new post-treatment method using NaOH to
create micro-porous within the electrode matrix while maintain-
ing its 3D structure. More importantly, the pre-treatment signif-
icantly enhanced the charge and discharge profiles by a 200-fold
increase in the specific capacity.[79]
Similarly, DIW can be helpful for 3D printable anodes when
the filaments are not feasible. For example, Hu et al. DIW
printed graphene oxide (GO) in electrodes featuring a fully 3D-
printed battery.[81] GO was used in the LTO electrode as an an-
ode in 6, 12, and 18 layers for the thick electrodes. The GO-
based inks showed excellent rheological properties maintaining
high apparent viscosities and shear thinning behavior, benefit-
ing DIW printing. The performance validation was done in a
half-cell configuration with a capacity of 171 mAh g−1after 10
cycles, indicating a stable charge transfer and good electrochem-
ical conductivity, as shown in Table 2.[81] Likewise, carbon black
(CB) and carbon nanotubes (CNTs) are compatible with DIW
printable inks and can also increase the electrical conductivity
in electrodes. For example, Lewis et al. used conductive ket-
jen (KB) carbon with a mixture between lithium salts (lithium
bistrifluoromethane sulfonamide (LiTFSI)) and propylene car-
bonate (PC) to stabilize the active particles.[83] With optimized
compositions, the square-based 3D printed battery, as shown
in Figure 6d1, displayed complex hierarchical structures poten-
tial for wearable electronics, sensors, and other complex geome-
tries. Figure 6d2,d3shows the areal capacity plots as a function
of cycle numbers, while also displaying the current versus volt-
age profiles for the DIW 3D printed battery. Also, Chen et al.
used highly conductive KB carbon and multi-walled carbon nan-
otubes (MWCNTs) to improve electronic conductivity.[71] Addi-
tionally, they focused on finding the effects of electrode designs
(i.e., porosity, active material particle diameter, thickness, line
width, and pore size) on their electrochemical performance. The
study showed that introducing vertically aligned pores and in-
creasing their porosity alleviated the trade-off between energy
and power density at rates below 1.0C.[71] Nonetheless, when the
discharge rate was over 2.0 C, the 3D-printed thick electrodes
notably decreased their energy and power density. Hence, the
application for their electrodes may be used in areas requiring
a high energy density below 1.0C but not at a discharge rate
over 2.0 C. Another example is Chen et al., who 3D printed
porous electrodes with a high LTO concentration via DIW.[84] The
unique curing process involved maintaining the printing cham-
ber below −7°C and storing the printed electrodes in a refriger-
ator at −20 °C for over 12 h.[84] They could print 6, 12, and 18
layer-LTO electrodes with exceptional values of ≈4.8 mAh cm−2
at a rate of 0.2C. After increasing the charge/discharge rate to
2.0 C, it maintained above ≈3.6 mAh cm−2.[84] It also retained
excellent cyclability in specific capacities after 100 cycles. How-
ever, their thick electrodes were more susceptible to degradation
at higher charge/discharge rates of up to 5.0C and relatively slow
kinetics of electrochemical reactions at higher rates due to the na-
ture of the thick electrodes that slowed the ionic transportation.
Most recently, Chen et al. developed a DIW printable gel for thick
electrodes.[82] Using silver nanowires (AgNWs), Gr, and LTO as
functional ink, they showed the electrodes capable of retaining
95.5% of their original capacity after 100 cycles.[82] Hence, their
rate capability, areal capacity, mechanical strength, and conduc-
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tivity showed competitive values in Table 2. Yet, Zhang et al. in
2021 decreased the swelling of the electrodes while preventing
degradation and improving the ionic kinetics after extensive cy-
cling by 3D printing a multilayer “biscuit” structure electrode.[85]
Using Gt as the first gradient pattern followed by a mixture of
Gt and silicon dioxide (SiO2) in a 4:1 mass ratio known as (GS),
they were able to achieve a multilayer biscuit structure via DIW
deposition. The concept behind the biscuit structure was to con-
strain the volume expansion of the GS with two outer layers com-
posed of Gt. Their unique structure improved ionic transporta-
tion while limiting the volume expansion of the electrode. Fur-
thermore, their full cell (3D Gt@GS/lithium nickel manganese
oxide (LNMO)) delivered a high reversible capacity of 5.3 mAh
cm−2at 1.8 mA cm−2and good cycling stability (i.e., a reversible
capacity of 3.52 mAh cm−2at 3.6 mA cm−2after 120 cycles).[85]
3.1.3. PBF-Printed Anodes
SLS is typically known for 3D printing metals. However, ceram-
ics and polymers are also compatible with the SLS. For example,
Tour et al. demonstrated the ability to print Gr foams via SLS
by manually placing sucrose powder and Ni together to process
in the SLS platform.[86] The sucrose powder acted as the solid
carbon source while the sintered Ni metal served as the cata-
lyst/template for the Gr to take shape. Figure 6e1shows the in-
situ synthesis of 3D Gr foams starting with the Ni powder (parti-
clesize2–3μm) and sucrose powder over the Ni particles. After-
ward, the CO2laser around 10.6 μm in diameter fused/sintered
the materials allowing the Gr/Ni to take the first layer shape.
Then another coat of Ni/sucrose was added with the process be-
ing repeated. After the desired shape was achieved, the etching
of Ni and purification was needed while drying and solidifying
the material. Figure 6e2shows the comparison of the computer
design before and after printing, allowing the Gr formation to
take place. While no characterization was performed for the LIB,
the material was used as an anode in batteries. However, some
preliminary work for the battery application was done using the
same SLS method at the same year but added MWCNTs as a
reinforcing bar which showed some improvements in the ther-
mostability, storage modulus (290.1 kPa) and conductivity (21.82
Scm
−1).[93] It also showed a stable performance as an anode with
an energy density of 32 Wh kg−1with a 78% energy retention after
500 cycles of testing at high current densities of 6.50 mA cm−2.[93]
This work further paved the way for battery manufacturing via
SLS 3D printing. Similarly, Hong et al. focused on magnesium
(Mg) matrix anode via SLS 3D printing for LIBs.[87] Printing at
50 W with a laser size of 70 μm and without the need for CB or
binders, the results showed particles being columnar crystals cov-
ering the entire surface of the printed area. This behavior was due
to the instant vaporization and cooling deposition of the material
during the SLS printing. The resulting nanostructure increased
the surface area, providing greater access to lithium ions’ inser-
tion and extraction.[87] The porosity of the microstructure also
helped with the expansion after charging and discharging, which
prolonged the battery’s cycle life. Due to the laser heat, a thin
film of low-resistance intermetallic compound between the cop-
per and Mg composed of Mg2Cu and MgCu2was formed. This
thin layer increased the bonding capability between the Mg and
Cu substrate, buffered the expansion of the active materials, and
increased the battery’s cycle life. This study showed a stable SLS-
made anode with a capacity exceeding 150 mAh g−1after 10 cy-
cles under a 0.1C current rate. Moreover, the anode showed high
thermal stability, e.g., when the temperature increased to 55°C,
the capacity increased to 250 mAh g−1after 10 cycles under a 0.1C
current rate.[87]
3.1.4. Ink-Based 3D Printing for Anodes
Inkjet printing is mostly used for homes and offices with recent
applications in printing electrode materials for energy storage
devices. For example, Sun et al. demonstrated the printability
of thin film Si anodes via inkjet printing for LIBs while com-
paring four different types of polymer binders to achieve good
electrochemical performance.[89] Figure 6f1shows the mixture
of binder polymers in water with silicone nanoparticles (SiNPs)
and CB. The mixture was then sonicated for 3 hours before it was
ready to be transferred into a cell-cleaned HP 61 cartridge to be
printed, as shown in Figure 6f2–f4. Note that the printing sheet
was copper where the electrode was deposited (Figure 6f5)where
the “Western University” logo was demonstrated. The print-
ability and performance were compared between four different
conductive polymers. Figure 6f5–f9show these polymer-based
printing (i.e., poly(3,4-ethylenedioxythiophene) polystyrene sul-
fonate (PEDOT:PSS), poly(vinylpyrrolidone) (PVP), CMC, and
Na-alginate conductive polymers, respectively) on the copper sub-
strate. Among them, PEDOT:PSS binder had superior durabil-
ity and performance, with a capacity retention over 1000 cycles
at a discharge of 1000 mAh g−1when compared to other con-
ductive polymer binders. The anode displayed high capacities of
over 1700 mAh g−1for 100 cycles, which contributed to the rapid
transfer of SiNPs as well as the flexibility to accommodate for
large volume expansion during high charge and discharge rates.
Another example of inkjet printing for anode electrodes in LIBs
is from Gupta et al., who most recently fabricated a continuous
graphene film on different substrates (i.e., glass and copper) via
inkjet printing to demonstrate its versatility.[90] Thegrapheneink
was composed of graphene and ethyl cellulose to be printed be-
fore being thermally annealed at 350 °C in an argon gas atmo-
sphere for 1.5 h. It was found that the resistance decreased with
the increased number of layers (8 layers to reach a low value of
≈0.15 kΩsq−1). Looking at the electrochemical performance and
behavior, the reversibility and cycling stability was excellent for
the electrode, retaining ≈87% of the delithiation capacity after
100 cycles.
Binder jetting is another form of ink-based printing not as
common as inkjet in energy applications. For example, Pope
et al. fabricated thick graphene-based electrodes for supercapac-
itors demonstrating the capabilities and new avenues for en-
ergy storage, conversion, and sensing applications.[92] Figure 6g
shows the general process for 3D printing GO anode electrode
by first dispersing the powder in a capillary consolidation to
have a homogenous distribution across the build bed. Then the
binder-injected samples containing >90% water, 8% glycerol,
and 2% other humectants were applied at 8-bit grayscale color-
map distribution.[92] The ink was then 3D printed as a GO disk
around 300 μm in thickness, which was then depowered, dried,
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and impregnated with palladium (Pd) to improve the perfor-
mance of the electrode. Compared to conventional mechanical
pressing, the binder jetting showed a more porous microstruc-
ture leading to an interconnected pore structure that facilitated
ion kinetics. The impregnation of Pd helped the contact resis-
tance from powder agglomerates while improving the gravimet-
ric conductivity by a factor of two and the areal capacitance by a
factor of seven.[92] Furthermore, the supercapacitor showed a ca-
pacity retention of 80% >100 cycles, demonstrating potential of
binder jet printable anodes for battery applications.
3.2. 3D-Printing Cathode Materials
3.2.1. Light-Based 3D Printing for Cathodes
Light-based 3D printing for cathode materials is very limited due
to their complex composition, structure higher melting point,
and brittleness than anode materials. However, Ning et al. fo-
cused on developing microbatteries via SLA 3D printing.[74] Com-
bining lithography and conventional photolithography allowed
for a fine tunability of the internal mesostructures. Figure 7a1
shows the overall process for printing microbattery mesostruc-
tured hierarchies. The first step was the fabrication of the holo-
graphic lattice on the indium tin oxide (ITO) substrate and then
filling the lattice with SU-8 (10 μm thick) before exposing it to
four interfering laser beams arranged in an umbrella geome-
try for 0.5 s. After drying, the infiltration of positive photoresist
AZ9260 was photopatterned using the SLA printer. Then the elec-
troplating of Ni was done, followed by removing the polymer tem-
plate, leaving an interdigitated 3D Ni structure before etching the
free ITO. The final step was the electroplating of active materi-
als, such as cathode (LMO) and anode (Ni–Sn), in an interdigi-
tated pattern (Figure 7a2). As a result, a high energy density of
6.5 μWcm
−2μm−1for the microbattery was achieved that pos-
sessed supercapacitor-like power at the peak of 3600 μWcm
−2
μm−1.[74] Figure 7a3plotted the voltage and current over time at
different cycles. The results showed that the 10 μm thick electrode
at 200 cycles had a 12% capacity fade for the lithium-ion micro-
battery. The internal structure of the design shows the relation
between the width of the active materials and the gap (15 μm).
The gap allows faster Li-ion kinetics to transfer back and forth,
producing high power and energy typically seen in lithium-ion
supercapacitors. Moreover, the capacity was measured against
the electrode digit width at different C-rates from 1 to 1000.[74]
The trend showed that the cell with the lowest tortuosity (largest
porous) had the best power performance.
3.2.2. Filament-Based 3D Printing for Cathodes
Filament-based 3D printing has gotten a lot of attention for en-
ergy storage applications. Table 3 offers a detailed comparison be-
tween filament-based 3D printable cathodes. For example, Golod-
nitsky et al. made 3D printable microbatteries using the LTO as
the anode and the cathode of the LFP conductive materials via
FDM.[76] With the unique shape of having an interlaced electrode,
it was hypothesized to alleviate the continuous volume changes
during the charge and discharge cycles of the battery. However,
it was found that only about 50% of the theoretical capacity was
used for the LFP. Hence, further optimization of the active ma-
terial, composition, morphology, compatibility, and printability
is necessary to achieve a higher-performance battery. They also
suggested looking into new hierarchies for a more continuous
charge/discharge volumetric change while operating as a multi-
material system.[76] Wiley et al. also demonstrated a completely
3D-printed LIB via FDM.[77] However, they decided to use LMO as
the main cathode material while adding PLA and MWNTs for im-
proved printability and robustness. While their studies focused
on finding the relationships between filler loading, conductiv-
ity, charge storage capacity, and printability. They found that the
maximum load of conductive filler into the polymer must be less
than 30% by volume to maintain acceptable printability.[77] This
is reflected in lower performance when compared to the conven-
tional LIBs using LTO and LMO. For future work, they suggested
that wrapping the active materials with conductive filler before
mixing them into the polymer chains could potentially improve
the electrical contact when present at low concentrations in the
polymer.[77] Hence, Maurel et al. not long after demonstrating a
3D printable anode in 2018 developed both cathode (LFP/PLA)
and separator (SiO2/PLA) materials to be printable via FDM, as
shown in Figure 7b1,b3.[78,94 ] A max load of 52 wt% of active ma-
terials were used for the cathode while still maintaining print-
able parameters. A pool of thermal, electrical, and electrochem-
ical analyses was done to arrive at an optimal filament for both
the cathode and the separator. Hence, using their previous 3D-
printed anode,[78] they were able to create a fully 3D-printed bat-
tery via the FDM method. With the freedom to tune the separator
thickness, they could balance the cell to improve the performance
of the LIBs illustrated in Figure 7b4for their specific capacity
versus the cycle number at different C-rates.[94] Shortly after,
Sun et al. FDM-printed a selenium(Se)-based cathode contain-
ing CNTs with mechanical blockage and dendritic penetration.[95]
Note that the Se had a high load of 20 mg cm−2that generated an
areal capacity of 12.99 mA h cm−2at a high current density of
3mAcm
−2. This is the highest reported areal capacity for quasi-
solid-state lithium–Se batteries.[95]
3D-printing electrodes were introduced by Lewis et al. via DIW
for both LTO and LFP electrodes.[104] Then, Hu et al. 3D printed
a complete battery using GO-based electrodes using LTO as the
anode and LFP as the cathode.[81] Both cathode and anode con-
tained GO in their matrix, but the LFP-GO cathode performed
better than the LTO-GO anode due to the smaller NPs, which
shortened the Li+transportation distance.[81] Another considera-
tion was that the LTO-GO had lower electrical conductivity, mak-
ing the capacity more susceptible to decay.[81] Another example
is from Pan et al., who developed 3D printable LiMn0.21Fe0.79 PO4
(lithium-iron-manganese-phosphate (LMFP)) nanocrystal cath-
odes achieving one of the highest rate LMFP-battery capabilities
(i.e., 150.21 and 140.67 mAh g−1after 1000 cycles at 10C and
20C, respectively) and high reversible capacity performance.[97]
The LMFP material is not the limiting factor for the battery; in-
stead, it is a combination of electrolyte diffusion factors (i.e., effi-
cient porosity, electrode thickness, and diffusion coefficient) that
need to be optimized for higher rate performance. In 2020, Liang
et al. 3D printed highly conductive thick electrodes via DIW us-
ing AgNWs, GO, and LTO as the cathode for a symmetrical cell
configuration.[82] Figure 7c1shows the synthesis process in four
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Figure 7. a1) Representation of the 6 steps for microbattery production using SLA. a2) Cross-sectional SEM image of the interdigitated electrode with the
alternating lithium manganese oxide (LMO) cathode (red) and nickel–tin (Ni–Sn) (blue) anode. a3)(V–C) versus time profile for the 1st, 100th ,and200
th
cycle. Reproduced with permission.[74] Copyright 2015, National Academy of Science. b) Filament production for lithium iron phosphate (LFP)/graphite
(Gt) electrode: b1) mixing components into a solvent to be spread out by doctor blading to create films. b2) Films are introduced into an extruder and
spooled into a filament. b3) Filament is introduced into an FDM 3D printer. b4) Capacity retention plot at different C-rates for a completely 3D printed
battery with a Hilbert curved pattern separator at 70% infill and layer thickness of 50 μm and a second separator at 100% infill density and thickness
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steps. The printable electrodes are then tested at different thick-
nesses ranging from 150 to 1500 μm as viewed in Figure 7c2.
The areal capacity versus the cycle life at the maximum thick-
ness for the electrodes was tested with and without the AgNWs
at 0.2C, as shown in Figure 7c3. The results showed a capability of
121 mAh g−1at 10C, a high areal capacity of up to 4.47 mAh cm−2,
and a capacity retention of ≈95.5% after 100 cycles.[82] LTO i s a
typical anode electrode, but in this configuration, it acted as the
cathode electrode (Figure 7c4).
Shortly after, Cui et al. fabricated a new LFP cathode using ad-
ditives in pursuit of higher energy density and areal capacity.[96]
The use of PEDOT: PSS nanofibers, carbon methyl cellulose
(CMC), and super-P were successful to create printable (i.e., LFP-
PEDOT-CMC) inks.[96] The cathode inks demonstrated high con-
ductivity due to the interconnected network, providing high ionic
kinetics throughout the charge and discharge cycles. Note that
the LFP-PEDOT-CMC had a high-capacity retention of 92% af-
ter 100 cycles at 0.2C for a 1.43 mm thick electrode.[96] Any
other electrode bigger than 1.43 mm significantly decreased the
discharge capacity rate and cycle capability. As previously men-
tioned, the transport distance increases with the thickness which
hinders the Li+and electrons transportation. Nonetheless, the
work described above illustrated the potential for researchers to
mitigate current challenges.
3.2.3. PBF-Based 3D Printing for Cathodes
Powder-based 3D printing can be useful for processing cathodes.
As demonstrated by Schoenung et al., lithium nickel cobalt alu-
minum (NCA) oxide cathode could be 3D printed via SLS.[98]
Figure 7d1illustrates the major components of SLS printing
as well as the pulse width and frequency to further tune the
printability (Figure 7d2–d5). However, finding the optimal laser
beam diameter to print cathodes was their research objective.
Figure 7d5shows the relative working distance in mm versus the
laser beam diameter in mm distribution to experimentally deter-
mine the laser beam profile. For example, the laser scan speed
and laser beam diameter could influence the morphology of the
single tracks, as shown in Figure 7d2. Therefore, the volumetric
energy density was varied from 50 to 150 J mm−3for the laser
beam profile while keeping constant the laser beam diameters
(0.85, 0.75, 0.65, 0.55, and 0.47 mm). It was found that discon-
tinuous printing happened below 75 J mm−3while continuous
printing suffered from extensive cracking when the beam is be-
low 0.65 mm in diameter.[98] Figure 7d3,d4shows an example of
the printed NCA cathode on a coin for reference while exposing
the surface porosity (2–3 μm grains) and the internal porosity
with gas pores and a lack of fusion pores within the SEM mi-
crographs. Hence, this study focused on optimizing the print-
ability parameters of the SLS with binder-free NCA with micron-
sized grains and pores. Further characterization and cell assem-
bly need to be done to determine the practicality and performance
of battery applications. Nonetheless, it shows potential for pro-
cessing advanced 3D-printed cathodes in LIBs.
3.2.4. Ink-Based 3D Printing for Cathodes
Inkjet printing has been primarily applied to text and graphic
processing. However, Gu et al. studied the physical and chemi-
cal properties of LFP aqueous-based cathode fabricated via inkjet
printing with different initial pH values.[100] To begin, the cath-
ode powder was mixed with the conductive agent and binder as
well as with different pH solutions (i.e., pH of 3, 5, 7, 9, and 10) to
determine the ionic concentration based on the initial pH values
versus the aging time relationships. Their results showed that the
pH values of different samples reached identical final values of
around 9.13 after 1 h, regardless of the initial pH value. For the
pH to change, it must consume active materials (LFP) and intro-
duce impurities. In other words, samples below 9.13 pH needed
to consume protons to raise their pH value, while samples above
9.13 needed to consume hydroxide to lower their pH value. They
also found that the particles of LFP decreased in size when initial
pH values were below 9.13. On the other hand, the particle size
increased with aging when the initial pH was above 9.13 with
less amount of oxygen. Hence the electrochemical performance
is still poor due to the impurities (LiAlO2and AlPO4) between
the Al current collector and active materials. However, there was
a strong attraction between CNT and active materials confirmed
via SEM. Ultra-thin film nano-MnO2cathode was also developed
using an inkjet printer. For example, the morphology, voltam-
metry, and electrochemical impedance were studied by Jiang et
al. As a result, the discharge capacity of the cathode film was
found to be 270 mAh g−1at the current density of 4.01 A g−1
(Table 3).[ 101] The ink synthesis was using nanosized MnO2,PC,
binder poly(vinylidene fluoride-co-hexafluoropropylene), and sol-
vent tetrahydrofuran (THF).[101 ] One of the unique features of
printing via inkjet was preventing agglomeration due to the chal-
lenges of maintaining homogenous suspensions/emulsions and
achieving the same average size of particles from the commercial
NPs. Hence, the average thickness of the printed electrode was
1.4 μm with a high discharge rate of 14.4C, showing the potential
for micro-thin film batteries via inkjet printing.
of 100 μm referred to as “One-shot battery.” Reproduced with permission.[94] Copyright 2019, Scientific Reports. c1) Schematic illustration of the 3D
printing process via DIW for the graphene oxide (GO)-AgNWs-LTO ink. c2) Image of the 3D printed electrodes with different thicknesses (e.g., 150,
300, 600, 900, 1050, and 1500 μm) after lyophilization. c3) Areal capacity and Coulombic efficiency for the GO-AgNWs-LTO and GO-LTO of 1050 μm
thickness at 0.2C for 100 cycles. c4) Illustration of the ion and electron transportation during the discharging process for the GO-AgNW-LTO electrode.
Reproduced with permission.[82] Copyright 2020, Elsevier. d1) SLS schematic with the pulse profile for the sintering process. d2) Optical micrographs
of single tracks as a function of volumetric energy density and laser beam diameter at 0.85, 0.75, 0.65, 0.55, and 0.47 mm. d3,d4) photograph and SEM
micrograph revealing the surface porosity as well as the internal porosity showing lack of fusion pores and gas pores in the cross-sectional area of the
sample. d5) Laser beam profile as a function of relative working distance and laser beam diameter. Reproduced with permission.[98] Copyright 2021,
Elsevier. e1,e2) SEM microscopy image of LFP cathode fabricated via tape casting in comparison with e3,e4) aerosol jet printing. e5) Average discharge
capacities versus cycle number for “Print A” (average discharge capacity for two battery samples) and “Print B” (average discharge capacity for three
battery samples). e6) Voltage versus discharge capacity for aerosol jet printed LFP cathode at a) C/15, b) C/10, c) C/5, d) C/2, and e) 1C. Reproduced
with permission.[103 ] Copyright 2019, Wiley-VCH.
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Aerosol jet printing of cathode electrodes for LIBs focuses
on conductive ink being deposited onto a substrate through an
aerosol stream. For example, Deiner et al. showed the print-
ability of cathode-based electrodes manufactured via aerosol jet
printing.[103 ] What they found when looking at the microstruc-
tures were aligned needles that are several hundred microns
long and ≈50 μm wide, as shown in Figure 7e1,e2. Whereas
Figures 7e3,e4are the microscopy images of the tape casting us-
ing a conventional LFP cathode. Interestingly, aerosol jet printed
cathode had more than three times porosity in the range of
1.7 nm to 300 nm than the conventional tape casting method.[103 ]
Figure 7e5shows the average discharge capacities which are sta-
ble during the 50 cycles of charge/discharge from varying C-rates
of C/5, C/2 to 1C. Additionally, the batteries showed promising
capacity retention of 93% for the first five cycles. Figure 7e6illus-
trates the voltage versus the discharge capacity for the aerosol jet
printer. It was found that the discharge capacity is 151 mAh g−1at
0.32 mA for the C/15 rate. When the C-rate increased to C/10, the
specific capacity decreases to 145 mAh g−1, which can be seen as
the trend that increasing the C-rate would cause a decrease in the
specific discharge capacity.[103] Yet, the overall performance sug-
gests that aerosol jet is a promising technique for the fabrication
of high capacity and rate capability in ESS applications.
4. 3D-Printing Electrolytes
LIBs have demonstrated enormous potential as a primary en-
ergy storage technology in various applications, including EVs,
portable electronics, and grid energy storage systems. However,
the liquid electrolytes used in LIBs can pose significant safety
concerns due to their potential to leak, leading to fires and dis-
tortions in the battery’s internal structure during swelling. Con-
sequently, researchers have focused on developing SSEs as a
promising alternative to liquid electrolytes, offering improved
safety, performance, and durability. SSEs can function as a sepa-
rator in the battery, making it less flammable, non-volatile, non-
corrosive, and thermally stable (Table 4). In recent years, 3D-
printing technology has emerged as a promising approach to pro-
ducing customized SSEs with precise microstructure and nanos-
tructure designs (Table 4). This approach allows for creating com-
plex geometries, improving the battery’s performance, and re-
ducing its weight. 3D printing also enables the production of
SSEs with controlled porosity, which can enhance their electro-
chemical performance. 3D printable SSEs include the following
categories.
•Oxide solid electrolytes (OSEs) typically comprise lithium-
containing oxides, which provide high ionic conductivity and
electrochemical stability. Researchers have developed various
printing methods for OSEs, including light- and extrusion-
based printing. These methods allow for the precise deposi-
tion of OSE ink onto a substrate, creating customized SSEs
with desired properties.
•Solid polymer electrolytes (SPEs) are another type of SSE
that has received considerable attention in 3D printing re-
search. SPEs offer several advantages, including high flex-
ibility, good adhesion, and excellent mechanical properties.
Extrusion-based printing for SPEs is the most common, allow-
ing for complex geometries with high-resolution control.
•Composite solid electrolytes (CSEs), which combine the ad-
vantages of OSEs and SPEs, have also been developed using
3D-printing technology. CSEs offer improved electrochemi-
cal properties and mechanical strength compared to single-
component SSEs. In addition, researchers have developed vari-
ous CSEs via AM, including nanocomposites, microfibers, and
microspheres.
4.1. 3D Printing Strategies for Oxide Solid Electrolytes (OSEs)
SSEs have attracted considerable attention in energy storage
due to their high energy density, longer lifetime, and im-
proved safety characteristics compared to conventional liquid
electrolytes.[2,17,29 ] In addition, among various types of SSEs,
OSEs have shown great potential due to their high ionic con-
ductivity, thermal stability, and compatibility with different elec-
trode materials.[106 ] As a result, OSEs have been extensively re-
searched for their potential applications in solid-state batteries,
fuel cells, and other electrochemical devices. To further enhance
the production and performance of OSEs, researchers have ex-
plored various strategies, including 3D printing mechanisms. 3D
printing is a promising OSE processing technique for fabricating
complex structures with high precision, reproducibility, and flex-
ibility. Different 3D printing techniques have been explored to
produce OSEs, including inkjet printing, extrusion-based print-
ing, SLA, and laser-based techniques. However, the current AM
of OSEs is still limited to only a few printing techniques, which
restricts the diversity and complexity of structures that can be
fabricated. Moreover, researchers have only explored a limited
number of OSE materials, such as lithium lanthanum zirconium
oxide (LLZO), lithium aluminum titanium phosphate (LATP),
and lithium garnet oxide (LGO), to fabricate high-performance
OSEs.[122 ] LLZO, for example, has demonstrated high ionic con-
ductivity and stability against moisture and air, making it an at-
tractive candidate for use in solid-state batteries. LATP has shown
high ionic conductivity and excellent chemical stability, making it
suitable for high-temperature applications. LGO has also demon-
strated high ionic conductivity and stability, making it a promis-
ing candidate for use in fuel cells.
Ceramic lithium-ion conductors have drawn much atten-
tion for their potential in next-generation batteries. However,
their brittle nature and high resistance at grain boundaries
have posed challenges to their practical application. Further-
more, conventional manufacturing techniques cannot achieve
the required thin microstructures, limiting their effectiveness.
In response to these challenges,[122 ] Bruce et al. proposed a
3D printing method via SLA to create microarchitectures us-
ing sacrificial materials (Figure 8a1– a4).[105 ] Specifically, tem-
plates such as cubes, gyroids, diamonds, and bijel-derived struc-
tures were produced, as shown in Figure 8a5–a8.[105] The use
of light-based 3D printing enabled the creation of finer struc-
tures (Figure 8a9–a12) through the use of light instead of phys-
ical nozzles. Therefore, after the template was 3D printed, the ce-
ramic lithium-ion conductor (Li1.4Al0.4 Ge1.6(PO4)3(LAGP)) was
filled and then calcinated/sintered to extract the sacrificial ma-
terial while filled with non-conductive polypropylene (PP) or
epoxy polymer (Figure 8a1–a4).[105 ] To check the electrochemical
characteristics, the change in resistance (R: total resistance, R1:
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Tabl e 4 . Summary and comparison of the materials, manufacturing techniques, and performance of 3D printed electrolytes for LIBs. See terminology below and also in Section 6 (ADP, ammo-
nium dihydrogen phosphate; ANN, aluminum nitrate nanohydrate; BAPO, phenylbis(2,4,6-trimethyl-benzoyl)phosphine oxide; BBP, benzyl butyl phthalate; BMITFSI, 1-butyl-3-methylimidazolium
bis(trifluoromethyl sulfonyl)imide; CSE, composite-solid electrolyte; EMI-TFSI, 1-ethyl-3-methyl imidazolium bis(trifluoromethanesulfonyl)imide; ESL 441, proprietary texanol-based composition;
ETPTA, ethoxylated trimethylolpropane triacrylate; IBoA, isobornyl acrylate; JA-UPy, jeffamine with quadruple-hydrogen bonds; LCO, lithium cobalt oxide; LiDFOB, lithium difluoro(oxalato)borat;
LiNO3, Lihtium nitrate; LiTFSI, Lithium bis(trifluoromethanesulfonyl)imide; LiTriflate, lithium trifluoromethanesulfonate; LLZO, Li7La3Zr2O12; MEG, ethylene glycol; NMC, lithium nickel-manganese-
cobalt oxide; OSE, oxide-solid electrolyte; PDMS, polydimethylsiloxane; PEGDMA, poly(ethylene glycol) dimethylether; PEG-UPy, polyethylene glycol with quadruple-hydrogen bonds; PEO, polyethy-
lene oxide; PEO-CTA, poly(ethylene oxide) macro-chain-transfer agent (macro-CTA); POEGMEA, poly(oligoethylene glycol methyl ether acrylate); PVB, polyvinyl butyral; SPE, solid-polymer electrolyte;
TMOS, tetramethyl orthosilicate; TMPTA, trimethyl propane triacrylate; TPO, diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide).
Electrolytes Manufacturing features Materials Properties Refs.
Method Features
[μm perlayer]
Speed
[mm s−1]
Layer
number
Particles Additives Cell assembly Capacity Electrical
conductivity
[mS cm−1]
OSE SLA 67 – ≈18 LAGP MEG, LiNO3, ANN,
ADP
Symmetric cell (LiM|OSE|LiM) 0.5 (mAh cm−2) 0.16 [105]
DIW 12.5, 25, 125 0–500 1–2 LLZO PVB,BBP, ESL 441 Symmetric cell (LiM|OSE|LiM) – 0.05 [106]
SPE SLA 0.05 0.01 100 LiClO4BAPO, Sudan I,
PEGDMA
Full-cell (LFP|SPE|LTO) 0.0014 (mAh g−1)
@1.5–4.2 V
4.8 @25 °C [107]
SLA 100 – 1–2 LiTFSI BAPO, PEGDMA Half-cell (LiM|SPE|LFP) 166 (mAh g−1) @ 0.1C 0.37 @25 °C [108]
DLP 50 3 7,11,15 BMITFSI PEO-CTA, IBoA,
TMPTA
Symmetric cell (carbon/PVDF|
SPE|carbon/PVDF)
–0.3@22°C [109]
DLP 11 15 s/layer ≈5 BMITFSI POEGMEA, IBoA,
TMPTA, TPO
N/A – 1.2 @ 30 °C [110]
FDM 1750 0–150 ≈2 LiTFSI PEO N/A – 2.18 @90°C [111]
FDM 1400–1700 – ≈1 LiTFSI-Pyr14TFSI PLA-PEO Symmetric cell (LiM|SPE|LiM) – 0.2 @60 °C [112]
FDM 330 10 4 LiTFSI JA-UPy PEG-UPy N/A – 10−7–10−9@80 °C [113]
DIW 200 – 1 LiTFSI ETPTA, PDMS, LiPF6Full-cell (NMC111/SPE/LTO) >120 mAh g−1– [114]
InkJet 800 – – Pyr13-Li-TFSI TMOS Full-cell (LFP/SPE/LTO) 300 μAh cm−2– [115]
CSE DIW 100 5 6,12,18 PVDF-co-HFP Al2O3Full-cell (LFP/CPE/LTO) 150 –[81]
DIW 200 2 5 EMI-TFSI SiO2Half-cell (LCO/CSE/LiM) 100 (mAh g−1) @ 0.1 C 2.9 @25 °C [116]
DIW 250–840 5–20 1–2 PVDF Al2O3Half-cell (LFP/CSE/LiM) 154 ±2 (mAh g−1)@0.2
C 101 ±5 (mAh g−1)
@5.0 C
0.82 [117]
DIW 150 5 1 PVDF-co-HFP TiO2Full-cell (LTO/CSE/LFP) 148 (mAh g−1)@16mA
g−1
0.78 [118]
FDM 330 – 6 LITFSI, PEG-UPy SiO2N/A – 0.032 [119]
FDM 200 – 1 LiTFSI Al2O3/SiO2, PLA, PEO Full-cell (LTO/CSE/LFP) – 0.03 @ 120°C [120]
Aerosol 10–50 – 60,35, 25 LiDFOB Al2O3, PEO Half-cell (LFO/CSE/LiM) 162 mAh g−10.5 @ 55 °C [121]
Aerosol 200–300 – ≈240 LiTriflate Al2O3, PEO Half-cell (LFO/CSE/LiM) 41 mAh g−10.7 @ 85 °C [121]
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Figure 8. a1–a4) SLA illustration of the Li1.5 Al0.5Ge1. 5P3O12 (LAGP)–polymer electrolyte, including SEM of the 3D printed templates for a5)cube,a
6)
gyroid, a7) diamond, and a8) bijel-derived with a9–a12) the zoomed-in SEM for each template at a scale of 100 μm. Resistance versus cycle number for
a13) LAGP-pellet and a14 ) gyroid-LAGP-epoxy as well as the cell voltage versus cell capacity for a15) LAGP pellet and a16 ) Gyroid-LAGP-epoxy. Reproduced
with permission.[105 ] Copyright 2018, Royal Society of Chemistry. b1) 3D printed LLZO schematic via DIW on an LLZO tape substrate, with SEM for the
conformal ink configuration for b2)lines,b
3)grids,andb
4) column patterns. b5–b7) Respective patterns with the self-supporting ink behavior. Rheology
characterization for the shear stress versus shear rate for the b8) self-supporting inks and conformal inks, and the b9) solvent fraction to control the ink
viscosity. b10) DC cycling profile for the symmetric cell at varying current densities. b11) Schematic grid structure used in the symmetric cell with the Li
metal filling the 3D printed LLZO pores. Reproduced with permission.[106 ] Copyright 2018, Wiley-VCH.
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intragrain, R2: intergrain, R3: interphase layer, R4: Li-LaGP inter-
face) was measured concerning the cycle number for the LAGP-
pellet and gyroid LAGP-epoxy as shown in Figure 8a13,a14 ,re-
spectively. It was found that the structured pellet had an in-
crease in interface resistance from the 10th cycle onwards.[105 ] In
addition, Figure 8a15,a16 illustrates the galvanostatic cycling for
LAGP pellet and gyroid structure at a voltage range of 12 V and
capacity range of 0.3 mAh cm−2. The gyroid LAGP-epoxy per-
forms better at retaining a gradual increase in voltage polariza-
tion while the pellet electrolyte increases rapidly during the 30
cycles.[105 ] The study shows the potential of printing OSEs while
maintaining good ionic conductivity and improving mechanical
properties.[105 ]
As another example, Wachsman et al. investigated the feasi-
bility of 3D printing OSE based on ceramics. Specifically, they
studied the printing of LLZO solid electrolytes using the DIW
method.[106 ] Figure 8b1illustrates the general printing of multi-
ple layers on an LLZO tape substrate to be sintered and create
a 3D LLZO scaffold ready to impregnate electrodes. This study
reported two types of printable inks for different structural pur-
poses. By tuning the printable inks with binders and plasticizers,
a “conformal ink” shown in (Figure 8b2–b4) and “self-supporting
ink” (Figure 8b5–b7) demonstrated the capability to print lines,
grids, and columns for both configurations. The tunability of
inks can be viewed through the rheology characterization of the
solvent fraction as shear stress versus shear rate concerning the
overall self-supporting ink and conformal ink (Figure 8b8,b9). It
is worth noting that an atomic layer deposition (ALD) was applied
on electrolytes to facilitate the wettability of the lithium metal
(LiM) to the LLZO scaffold.[106 ] The results showed a low area-
specific resistance (ASR) of 20 Ωcm−2during cycling, demon-
strating the high and stable conductivity in Figure 8b10 of the 3D-
printed LLZO electrolyte. The data presented in Figure 8b11 sug-
gests that the connections between the 3D-printed LLZO layers
and the Li metal were continuous without any noticeable defects.
However, additional investigations are required to optimize and
carefully examine the impedance of the cell, mechanical robust-
ness, and the 3D architectures of the printed components.
4.2. 3D Printing Strategies for Solid Polymer Electrolytes (SPEs)
Light-based printing is more common for SPEs and most notable
for being transparent or stretchable, depending on their material
properties. For example, Chen et al. successfully 3D printed an
SPE for a lithium-ion micro battery via SLA.[107 ] The electrolyte
was printed in a zig-zag pattern using UV-cured polyethylene gly-
col (PEG)-based polymer and sandwiched between the LFP and
LTO active materials. The zig-zag print was carefully considered
further to increase the contact between the electrodes and elec-
trolytes and decrease internal resistance. Another example can
be seen in Figure 9a1, where Liu et al. 3D printed SPEs using
PEO and lithium salts via SLA with an Archimedean spiral struc-
ture to shorten the Li-ion transport pathway between the elec-
trode and electrolyte.[108 ] Figure 9a2–a3demonstrates the spiral
structure with interdigitated patterns (Archimedean spiral struc-
ture) to increase the contact area between the electrode and elec-
trolyte and decrease internal resistance.[108 ] Figure 9a4,a5shows
the cross-sectional SEM images of the 3D-printed SPE with the
interface between the electrolyte and electrode, while Figure 9a6
shows the electrolyte flexibility and transparency. Hence, the per-
formance shows a higher specific capacity of 166 mAh g−1with
an improved capacity retention of 77% after 250 cycles at 50 °C
than structure-free SPEs.[108 ]
Using a different AM method, such as DLP, to print
SPE was demonstrated by Boyer et al., who developed a
reversible addition–fragmentation chain transfer (RAFT)-
based polymerization-induced microphase separation (PIMS)
system to fabricate SPE with tunable nanoscale morpho-
logical features, as shown in Figure 9b1,b2.[ 109] Using 1-
Butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
(BMITFSI) as the liquid electrolyte and varying the load be-
tween 40, 50, and 60 wt% did not affect the inhibition period
or the overall reaction rate.[109 ] Figure 9b3shows the storage
modulus in relation to temperature for the current SPE com-
positions. Also, it was found that varying the BMITFSI content
or poly(ethylene oxide) macrochain-transfer agent (macro-CTA)
(PEO-CTA) slightly reduced the shear modulus. Still, the me-
chanical properties of the SPEs in response to the temperature
had no notable change. Schematic of the symmetric carbon cell
assembly in Figure 9b2–b4displays the high Columbic efficiency
and excellent long-term cycling behavior from 100 to 3000 cycles.
In addition, EMITFSI and EMIBF4were tested to substitute the
BMITFSI liquid electrolyte. However, PEO-CTA was not soluble
in EMIBF4, and instead, the EMITFSI gave excellent printable
SPE with robust mechanical strength and ionic conductivity
(G’=180 MPa, 𝜎=9.0 ×10−5Scm
−1).[109 ] This work shows
the printable SPE with enhanced mechanical and conductive
properties.
FDM is another AM technique that has shown the ability
to 3D print SPE. For example, Binder et al. studied the effects
of three different telechelic polymer quadruple-hydrogen bonds
(UPy) to tune the printability of CSE used in LIBs, as shown in
Figure 9c1.[123] It was found that the JA-900-UPy was most suited
for easy self-healing showing amorphous elastic and transpar-
ent properties, illustrated by the optical images in Figure 9c2,c3.
Compositions with too little salt concentrations were found to
be too crystalline and unsuitable for testing during the rheology
characterization. Figure 9c4shows that the PEG-1500-UPy with
a molar EO/Li ratio of 10:1 and 5:1 was too sticky and viscous.
Thus, using specific ratios from EO/Li 20:1, 10:1, to 5:1, the rhe-
ological profile can be tuned for printable filaments. Figure 9c5
shows the ionic conductivity profile concerning frequency at tem-
peratures of 0, 25, and 80 °C for the JA-900-UPy-12 set, demon-
strating that lithium ions weakened the UPy-bonds and reduced
the crystallinity of the polyethylene oxide (PEO) units.[123 ] There-
fore aside from the melt-rheology, lithium salt, and polymer crys-
tallinity, it adds an additional toolbox to tune the printability of
electrolytes via FDM. Note that more examples of filament-based
printing can be found in Table 4.
Displaying the capabilities of 3D printing SPE via the DIW
method is another avenue that offers a greater range of ma-
terials to be produced. For example, Chung et al. fabricate a
complete LIB via DIW (Figure 9d1) by tuning the rheology inks
for the LTO and LFP cathodes, silver (Ag) and carbon current
collector, UV-cured SPEs and polydimethylsiloxane (PDMS) for
packing the battery.[114] Figure 9d2,d3shows microbattery arrays
(4×3) in 10 mm by 10 mm and the structure of a single LIB in
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Figure 9. a1) Illustration of the manufacturing process via SLA for the solid-polymer electrolyte (SPE) and cell assembly. Schematic representation
between the a2) interdigitated structure with improved interface adhesion versus the a3) conventional contact interface with weak adhesion prone to
have low conductivity. a4) Optical image of the top view for the spiral-interdigitated SPE and a5) SEM cross-sectional view of the interface between
the electrolyte and cathode material. a6) Flexibility and transparency of the 3D printed SPE. Scale bars are 300 mm, 50 μm, and 1 cm for a4–a6.
Reproduced with permission.[108 ] Copyright 2020, American Chemical Society. b1) DLP 3D printed of the SPE with high modulus, conductivity, and
transparency. b2) Symbolic representation of the symmetric cell assembly using carbon/polyvinylidene fluoride (PVDF) as electrodes and stainless
steel as current collectors on two sides of the 3D printed SPEs. b3) Shear modulus with respect to temperature for the SPE at varying 1-butyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide (BMITFSI) concentrations of 40, 50, and 60 wt% while keeping a constant 2 wt% diphenyl(2,4,6-
trimethylbenzoyl)phosphine oxide (TPO) concentration. (b4) Ionic conductivity and shear modulus at ambient temperature with different BMITSI con-
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addition to a side-by-side comparison of printed letters with con-
ventional SPE (right) and the 3D printed GPE (left). As a demon-
stration of the charge and discharge cycles at different mass load-
ings (Black: 6.67 mg cm−2, Red: 9.83 mg cm−2, Blue: 10.9 mg
cm−2), Figure 9d4,d5shows that the increase in mass loading had
small polarization changes.
Furthermore, inkjet printing was demonstrated by Bideau et
al., who worked on silica-based electrolytes using ionogels’ sol
precursors and solvent evaporation, as shown in Figure 9e1.To
determine the feasibility of the 3D printed SPE, Figure 9e2shows
the galvanostatic cycling on a half-cell composed of tape-casting
LFP cathode, 3D printed SPE, and the LiM as the counter elec-
trode at a C/30 rate in ambient temperature with voltage profile
from 2.0 to 4.0 V.[ 124] The half-cell test showed low polarization
due to the difference between the oxidation and reduction poten-
tial, which is around 100 mV. Furthermore, using an LFP cath-
ode and LTO anode for a full-cell assembly was done to study the
mass capacity and surface capacity with the charge and discharge
cycles shown in Figure 9e3at a C/10 rate in ambient temperature.
This study showed a surface capacity of 300 μAh cm−2up to 100
cycles, which is competitive compared to microbatteries based on
conventional manufacturing, such as PVD.[124 ]
4.3. 3D Printing Strategies for Composite Solid Electrolytes
(CSEs)
The CSEs are widely recognized for their ceramic filler, primar-
ily Al2O3and SiO2. For the AM of FDM, Golodnitsky et al. 3D
printed PLA:PEO:LiTFSI with ceramic fillers to compare SiO2
and Al2O3.Figure 10a1,a2shows the extrusion mechanism with
different coils, springs, and similar shapes. While proposing a
new co-axial printing method via FDM, the focus of the paper is
characterizing the CSE with different ceramic fillers. Figure 10a3
shows the 3D-printed semitransparent CSE with a diameter of
19 mm and thickness of 200 μm.[120 ] First, the optical SEM im-
ages were taken of PLA:PEO:LiTFSI: SiO2(59:20:20:1%) and of
PLA:PEO:LiTFSI: Al2O3(59:20:20:1%) (Figure 10a4,a5), respec-
tively, to determine the thickness of the electrolytes. The silica-
based electrolyte was around 210 to 220 μm while the aluminum-
based was around 102 to 108 μm. The ionic conductivity measure-
ments compared with conventional cast neat PEO-based elec-
trolytes showed a lower conductivity value for printed electrolytes
possibly due to the incomplete mixture of polymers/ceramic
fillers.[120 ] Hence further optimization is needed for the FDM
print on CSE.
DIW has shown versatility in printing SPEs and CSEs. For ex-
ample, Durstock et al. focused on establishing an approach to 3D
print electrolytes with controlled porosity via DIW (Figure 10b1)
using a dry phase inversion (PI) method and comparing the
structure and performance (Figure 10b2,b3) with and without
CSEs (Figure 10b4–b7).[117] With acceptable durability and pro-
cessability (Figure 10b8,b9), Al2O3as nanosized fillers with the
PI method-processed CSE (Figure 10b10–b12 ) enabled uniform
sub-micrometer pore formation with nanofillers impregnated in
the pores. Note that the rheology characterization in Figure 10b9
indicates that the CPE has a higher shear thinning behavior
than other electrolyte compositions. However, adding ceramic
fillers in the PI method allowed high flexibility of the electrolyte
(Figure 10b8). The results in this study gave a high current rate
of 5C with improved thermal stability and better wetting char-
acteristics between the electrolyte and electrode (Figure 10b2,b3)
for the cross-sectional SEM images and the specific capacity ver-
sus cycle number at different C-rates. Not to mention that the PI
method was also applied to the electrode inks, improving the elec-
trochemical properties and better flexibility, which is beneficial to
non-planar device surfaces by using AM.[117 ]
Another example from Hu et al. showed the 3D printing for a
complete GO-based battery via DIW.[81] During the primary focus
and novelty rest on 3D printing GO-based electrodes, they have
also 3D-printed their CSE using poly(vinylidene fluoride)-co-
hexafluoropropylene (PVDF-co-HFP) as their polymer electrolyte
while adding Al2O3as their ceramic nanofillers. The 3D-printed
CSE functioned as an electrically insulated separator. However,
LiPF6as a common liquid electrolyte and the 3D-printed CSE
were injected into the cell to achieve a higher and more stable
ionic conductivity. The full 3D-printed cell exhibited initial charge
and discharge capacities of 117 and 91 mAh g−1with good cycling
stability.[81] While no data was reported on ionic conductivity, the
capability of 3D printing a complete battery using interdigitated
structures was displayed to demonstrate the versatility of AM.
Note that PVD has been found to have good compatibility with
LiTFSI, which is a lithium salt. The compatibility is due to the
fact that PVDF has been observed to improve the movement of
charged particles (ions) through the material. This is why LiTFSI
is often included in battery formulation, as indicated in Table 4.
Aerosol jet printing further expands the AM methods for
CSEs for the solid-state EES. For instance, Deiner et al. printed
two distinct types of CSE using lithium difluoro(oxalate)borate
(LiDFOB) and lithium trifluoromethanesulfonate (LiTriflate) as
the main electrolytes. Each electrolyte was mixed with PEO
and ceramic filler (Al2O3). Figure 10c1,c2shows the SEM cross-
sectional area of the PEO/LiDFOB/Al2O3and PLA:PEO:LiTFSI:
centrations. Reproduced with permission.[109 ] Copyright 2022, Wiley-VCH. c1) Electrolyte mixture of telechelic, polyethylene glycol (PEG-1500-UPy),
and bivalent (2-ureido-4-pyrimidinone) Jeffamine (JA-x00-UPy) with lithium bistrifluoromethane sulfonamide (LiTFSI) for 3D printable SEP via FDM.
c2) Illustrates the transparent 3D printed JA-900-Upy for a grid-like SPE structure as well as the c3) stretchability after 4 h. c4) Rheology characteriza-
tion of the JA-900-UPy concerning viscosity as a function of the shear rate at varying temperatures to determine printing profiles of 200 to 2000 Pa s.
c5) Ionic conductivity profile with respect to the frequency at temperatures of 0, 25, and 80 °C for the JA-900-UPy 12 set. Reproduced with permission.[123 ]
Copyright 2022, Wiley-VCH. d1) Schematic illustration for a complete battery manufacturing process via DIW. d2) Example of a 3D printed microbattery
on fingertip with letters as d3) Seoul National University (SNU) at the Korean Institute of Science and Technology (KIST). d4) S, N, U battery assembly
and the d5) voltage of the complex cells in series at a C-rate of 0.2C. Reproduced with permission.[114 ] Copyright 2023, Elsevier. e1) Inkjet printing
representation for the SPEs. e2) Mass capacity versus cycling at C/10 rate and room temperature of a full cell composed of LFP cathode and LTO as
the anode electrodes. e3) Galvanostatic cycling of half-cell with LFP/SPE/LiM from 2.0 to 4.1 V at C/30 rate and room temperature showing the mass
capacity as a function of the cycle. Reproduced with permission.[124 ] Copyright 2015, Elsevier.
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Figure 10. a1) Optical image of FDM 3D printing using a filament-based extrusion with different a2) schematic designs. a3) Example of the transparent
3D printed spiral disk composite solid electrolyte containing polylactic acid (PLA): polyethylene oxide (PEO):LiTFSI and ceramic fillers, such as SiO2
or Al2O3, at the following concentrations (50:20:20:1% w/w). a4) SEM cross-sectional images of PLA:PEO:LiTFSI: SiO2(59:20:20:1%) electrolyte and
a5) PLA:PEO:LiTFSI: Al2O3(59:20:20:1%) electrolyte. Reproduced with permission.[120 ] Copyright 2020, The Electrochemical Society. b1)Schematicrep-
resentation of the electrolyte printed directly on top of the electrode via DIW. b2) SEM images of the composite-solid electrolyte (CSE) interface with the
LFP cathode from the b3) rate performance (top image) and cycling performance (bottom image) at 0.2C. b4–b7) Schematic and photos of the printed
electrolyte composition and corresponding dried films. b8) Flexible CPE-phase inversion (PI) membrane at a 6 cm diameter disk. b9) Rheology studies
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Al2O3, where the interface between the electrolyte and cath-
ode (LFP) could be compared (Figure 10c3,c4). More interest-
ingly, the PEO/LiDFOB/Al2O3(EO:Li =10:1) had better con-
ductivity than the LiTFSI-based electrolyte at >1×10−5Scm
−1at
45 °C (Figure 10c5). Looking at the rheology characterization
in Figure 10c6concerning viscosity versus shear rates, the
PEO/LiDFOB/Al2O3(EO: Li =10:1) showed a slight increase in
viscosity as the shear rate increased that did not impact the print-
ability significantly. Thus, the production via aerosol jet printing
opens a new path for higher resolution control than often used
FDM or SLS in fabricating solid-state LIBs compared to other 3D
printing methods.
5. Current Challenges and Future Perspectives
The demand for versatile energy storage devices requires quick
tunability, customization, and cost/time efficient production
that is highly possible through 3D printing. However, to meet
a wide range of needs (i.e., microbatteries, transparent, flex-
ible/wearable, biocompatible, high-energy, high-power density,
porous, and lightweight), a few challenges must be addressed.
Henceforth, this section will cover essential topics to improve
the next generation of LIBs via AM techniques. First, expand-
ing newer materials is necessary as rising applications, man-
ufacturing methods, and industry demands grow. Second, 3D
printing resolution is also limited due to specific AM process-
ing characteristics that may hinder the 3D printed microstruc-
ture and overall performance. Third, many AM techniques strug-
gle to incorporate complex designs (e.g., porous structures) in
flexible manufacturing (e.g., submicron scales) on time, mak-
ing them unsuitable for scalable applications, though accom-
modating mass customization is not problematic for 3D print-
ing nowadays. Thus, we would need new manufacturing tech-
nology that promises to print complete battery components in a
single step or on the same platform with possible comanufac-
turing techniques applicable to the EES. Fourth, we highlight
a few challenges that have hindered uncertainty prediction in
ML and AI for the in-situ examination/optimization and data
analysis. In addition, we address the environmental challenges
related to the reuse and recycling of battery materials. Further-
more, we provide a concise overview of 4D printing, which em-
ploys various stimuli sources, as a promising approach for inno-
vative energy storage devices. Additionally, it is crucial to explore
alternative materials, including rare metals, considering the fi-
nite availability of lithium storage on Earth. Finally, we empha-
size the importance of advancing computer technologies, such
as artificial intelligence and machine learning, to enhance mod-
eling, prediction, and validation capabilities in the field of energy
storage.
5.1. Expand Feedstock Types via Newer Material Synthesis
Exploring new materials for the AM methods is needed to im-
prove the performance of current EES devices. Various printing
principles demand materials that are compatible with different
AM techniques. For example, a new concept of manufacturing
transparent LIBs with flexible, stretchable, and optical proper-
ties will require different feedstock formats via complex process-
ing procedures (e.g., possibly a combination between 3D print-
ing and conventional manufacturing).[125,126 ] Carbon nanomate-
rials (i.e., CNT, graphene, fullerene) have been preferable due
to their fabrication flexibility, transparency at low loadings, and
excellent electrical and mechanical properties.[127 ] For instance,
Niederberger et al. developed transparent, flexible thin films and
hybrid supercapacitors for energy storage devices through micro-
molded patterns.[128 ] They used an ordered mesoporous carbon
and nickel-iron-oxide@reduced GO as a high-power anode for a
lithium-ion capacitor with a hexagonal grid structure to optimize
the transparency. The grid shape pattern strongly influenced the
transparency due to the light transmission through the micro-
molded patterns could enable.[128 ] The ability to bend to a radius
of 3 mm without losing electrochemical properties over 1000 cy-
cles showed an EES with high transparency and flexibility. In
contrast, 3D printing can not only rapidly prototype printed pat-
terns but also use a broader range of materials in addition to the
nanoscale carbons.
Similarly, many other materials have been developed for en-
ergy applications with multiple functionalities. For example, Cui
et al. fabricated a flexible, grid-structure electrode with 78, 60,
and 30% transparency with an energy density of 5, 10, and
20 Wh L−1, respectively.[129] The electrode was primarily us-
ing 90% active materials, either LMO or LTO with 7% CB and
3% aqueous binder to be fabricated by a microfluidic-assisted
method. Later, Taylor et al. used single-walled carbon nanotubes
(SWCNT) and vanadium pentoxide (V2O5) nanowires for an-
ode and cathode electrodes, respectively, to achieve a transparent
(>87% transmittance) energy storage device via spin-spray layer-
by-layer assembly.[130] This concept required transparent current
collectors and electrolytes to complete a functional battery. Thus,
they used three Celgard separators in between the electrodes,
which showed a capacity retention of ≈5mAhcm
−2over 100 cy-
cles and proved the concept of a fully transparent battery. With
higher processing autonomy similar to industry, Salot et al. fab-
ricated a grid-structured thin-film solid-state battery using pho-
tolithography and etching processes.[131 ] Their work showed su-
periority over previous literature in their discharge capacities
ranging from 0.15 to 0.6 mAh at transmittances between 60%
and 20% while offering good cyclability over 100 cycles with an
average capacity loss of 0.08% per cycle.[131 ] Achieving these flex-
ible electrochemical devices through various processes requires
with the viscosity as a function of shear rates for several electrolyte composites (i.e., PE, PE-PI, CPE, CPE-PI). Schematic illustration of the b10) polymer
electrolyte with PI (i.e., PE-PI), b11) composite electrolyte with ceramic fillers (i.e., CPE), and b12 ) composite electrolytes with PI (i.e., CPE-PI). Reproduced
with permission.[117 ] Copyright 2017, Wiley-VCH. SEM images of the aerosol jet printed c1) PEO/lithium difluoro(oxalato)borate (LiDFOB)/Al2O3(ethy-
lene oxide monomer:lithium ion (EO:Li) =10:1), c2) (EOS:Li =16:1), c3) PEO/lithium trifluoromethanesulfonate (LiTriflate)/Al2O3(EO:Li =10:1), and
c4)(EO:Li =16:1), respectively. c5) Temperature-dependent conductivity graph with PEO/LiDFOB/Al2O3(squares) and PEO/LiTriflate/Al2O3(circles).
c6) Rheology characterization with the viscosity versus shear rate plots for different electrolyte compositions from supporting information. Reproduced
with permission.[121 ] Copyright 2019, Wiley-VCH.
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Tabl e 5 . Materials potentially used in AM technology for EES. Section terminology in Section 6 (ACT, silver/titanium/chromium; CMC, carboxymethyl-
cellulose; GaInSnZn, gallium-indium-tin; LiPON, lithium phosphorus oxynitride; PAN, polyacrylonitrile; PBuPy, poly(1-pyrenebutyl methacry-
late); PBuPyMAA, poly(1-pyrenebutyl methacrylate-co-methacrylic acid); PDHBQS, poly (2,5-dihydroxyl-1,4- benzoquinonyl sulfide); PDI, 3,4,9,10-
perylenetetracarboxylic diimide; PEC, poly(ethylene carbonate); PMA, poly(N-methyl-malonic amide); PPC, polypropylene carbonate; Pt, platinum;
PTMC, poly(trimethylene carbonate); SWCNTs, single-walled CNTs; Ti, titanium; Ti3C2, titanium carbide; ZTO, zinc doped tin(IV) oxide).
Categories Materials Compatible AM methods New applications but
not limited to
Current collector ITO,[ 133] Ti/Pt[ 131] SLA, FDM, DIW Transparent LIBs
Cathodes LFP,[133,134 ] LCO,[131 ] LMO,[129 ] SLA, FDM, DIW, inkJet
Anodes Si,[129,131 ] (ZTO/ACT/ZTO),[133 ] LTO [ 129] SLA, FDM, DIW, inkJet
Electrolytes LiPON,[131,133 ] PVDF-HFP[129 ] SLA, FDM, DIW
LLZO,[106 ] LLZTO[135 ] SLA, FDM, DIW Garnet-type LIBs
PVDF,[136] CMC, PBuPy,[137] PBuPyMAA,[ 137] PDHBQS-SWCNTs,[138 ] PDI[125,138 ] SLA, FDM, DIW, SLS/SLM, InkJet Flexible LIBs
PEO,[139 ] Poly(ester), nitrile, PVDF-HFP,[140 ] PMA, polyimide, PEC,[141 ] PTMC,
PPC, PAN[125 ]
FDM, DIW, SLS/SLM, InkJet
General electrodes 2D and 3D MXene/Ti3C2,[ 142] GaInSnZn, Si[ 125,137] SLA, FDM, DIW, SLS/SLM
CNT,[143-146 ] Gr,[147,148] MXene hydrogels and aerogels[ 149] 2D and 3D
MXene/Ti3C2,[142,150 ] GaInSnZn, Si[125,137 ]
SLA, FDM, DIW, SLS/SLM 4D Printed LIBs
multistep fabrications. Therefore, additively manufacturing
transparent, flexible, and lightweight batteries may take this
concept to a new level for electrochemical devices. Expanding
current EES materials in 3D printing and combining different
nano/micro-sized features with fast customization will lead to
better cost and time-efficient production.
Conventional manufacturing can process more battery materi-
als than 3D printing since the latter methods are still primal (e.g.,
a lack of quick customization on delicate structures, defect den-
sity, ink tunability, and feedstock size/shape control). Besides,
material innovation has hindered the expansion of 3D printable
battery development. As a brief summary, the materials intro-
duced in Table 5 have been used for different battery compo-
nents that must be tunable for different AM platforms. For ex-
ample, the oxide powders (e.g., ITO, LLZO, LLZTO) are usually
above the microscale, causing problems in fine-resolution print-
ing. In comparison, the nanoscale carbons (e.g., Gr) of metal car-
bide/carbonitride (e.g., MXenes) are more flexible with proper
pre-processing, such as colloid dispersion or mixing with fluidic
monomers.[132 ] Polymers, on the other hand, are compatible with
the majority of 3D printing mechanisms. As the feedstock of elec-
trolytes, polymers can exist in dissolved solutions, dispersed par-
ticles in curable monomers, melts to disperse powders, and as
binders in laser-printing techniques. However, the light source in
lithography-based printing (e.g., SLA or DLP) must adjust these
materials to be photo-curable, while the inks must be prepared to
accommodate the AM rheology requirements. Though DIW can
extrude any material if it meets the rheology parameters, clogging
has been a common processing issue. Thus, the new materials-
3D printing interaction is an urgent issue to study for battery and
other energy-relevant applications.[133 ]
5.2. Increase 3D Printing Resolutions via Novel Processing
Mechanisms
Efficient design and manufacturing of high power-density and
energy-density batteries (especially micro-batteries and other mi-
crosystem energy devices) will need precise feature control.
The printing resolution of specific AM techniques is limited by
their manufacturing principles (Sections 1 and 2), especially for
complex hierarchical designs (e.g., porous microstructures, lay-
ered hierarchies, nanoscale architectures). For example, light-
monomer interaction-based printing (e.g., SLA, DLP, CLIP, CAL,
TPP/MPP) has shown a printing capability with a satisfactory res-
olution on the nano-to-micro scale due to either light wavelength
or resin monomer design control. Figure 11a1is an example of
μSLA printing using a projection method where the images are
sliced and projected to show to the subsequent layer in minutes
with features ranging from 10 to 500 μm.[151 ] Still, the particle
distribution and size play a role in the resolution of the prints,
but most importantly, the material must be photopolymerizable
to print. Figure 11a2compares light-based printing methods con-
cerning price and feature size. Generally, the smaller the feature
size, the more expensive and time-consuming the manufactur-
ing methods. Therefore, there is room to optimize printing the
submicron and micron scale in a cost and time-efficient man-
ner. Nonetheless, light-based printing can accommodate various
materials (e.g., polymers, ceramics, glass, and metals, as men-
tioned in Section 2.1). Yet, printing specific energy storage ma-
terials is limited, and most require tunability and post-printing
techniques to achieve desired printing resolutions or hierarchies
(e.g., Figure 11a3). Further optimization of light-based printing
platforms for a higher processing precision and a broader range
of materials is still needed.
For the filament base printing method, the 3D printing reso-
lution of the FDM machines is dependent on to the nozzle sizes,
printing parameters, and material characteristics. For example,
most printers will have a nozzle inner diameter of 0.1 mm to
0.8 mm based on nozzle types, and materials, object size, design
complexity, and machine specifics that could also limit 3D print-
ing resolutions.[152,153 ] Similarly, the DIW is also constrained to
the nozzle diameter, typically found in conventional syringes or
needles that can be custom-made.[154 ] Hence, the printing res-
olution for the filament-based method is primarily constrained
to the nozzle diameters, particle sizes, and feedstock rheologies.
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Figure 11. Comparing printing resolutions from different 3D printing techniques. a1) Schematic of projection μSLA with the capability of producing
ultralight, ultrahigh-stiffness, stretch-dominated micro-latices with a resolution of ≈5μm. Reproduced with permission.[151 ] Copyright 2014, AAAS.
a2) Comparison chart of different light-based printers with price versus feature size. Reproduced with permission.[161 ] Copyright 2021, IEEE. a3) Demon-
stration of solid electrolyte printed via light-based printing for a zig-zag patterning, with 500 μm scale bars. Reproduced with permission.[107 ] Copyright
2017, The Electrochemical Society. b1,b2) DIW of a 250 μm×250 μm woodpile structure in addition to hollow-woodpile design with resolutions of up
to 1 μm. Reproduced with permission.[155 ] Copyright 2006, Wiley-VCH. b3,b4) Example of DIW printed solid electrolyte in (b3) conformal configuration
and (b4) self-supporting configuration. Reproduced with permission.[106 ] Copyright 2018, Wiley-VCH. c1,c2) Electrohydrodynamic (EHD) Jet-based 3D
printing with a gold-coated glass microcapillary nozzle (2 μm internal diameter) c3) comparing the pulsating jet mode versus the stable jet mode during
printing (e.g., an image of c4) Hypatia printed using polyurethane ink with a 500 nm internal diameter nozzle), at a 5 μm scale bar. Reproduced with
permission.[162 ] Copyright 2007, Springer Nature. d1) EHD representation using electrostatic jet deflection. d2–d4) SEM micrographs for 3D cylindri-
cal PEO microstructures, with 200 μm, 5 μm, and 1 μm scale bars in (d2–d4), respectively. d5) SEM micrograph of a PEO fiber. The scale bar is 2μm.
d6,d7) SEM and zoom-in micrographs of a PEO-(Ag) cylindrical structure. Scale bars are 5 μmand1μm. Reproduced with permission.[ 160] Copyright 2020,
Springer Nature. e1,e2) Aerosol jet printing of LFP cathode with “pore superhighway’’ versus the tape cast electrode. Reproduced with permission.[102 ]
Copyright 2021, American Chemical Society.
Moreover, complex structures in the macro-nano scale are help-
ful for battery processing, but more delicate architectural re-
quirements can negatively affect the printing speed. This trade-
off makes extrusion-based printing advantageous for submicron
composition and physics design. For example, most ink-writing-
based 3D printing methods have a limit of nozzle sizes that usu-
ally leads to a deposition feature of tens of microns. However,
Ellis et al. demonstrated the ability to print high-resolution lat-
tices of up to 1 μm, as shown in Figure 11b1,b2, for the 250
by 250 μm woodpile structure to achieve a microcapillary noz-
zle of a diameter of 0.5 to 5.0 μm.[155] Wachsman et al. also
demonstrated the ability to print exceptionally fine resolutions
via the DIW method, as shown in Figure 11b3,b4for the LLZO
SSEs in both “conformal” and “self-supporting” configurations,
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respectively.[106] The ability to have multiple nozzles working si-
multaneously to print complete or large geometries to speed
up the battery printing process is also worth mentioning. How-
ever, the calibration and coordination of multiple nozzles become
more complex, which can lag the manufacturing process or re-
quire additional machine coding/data analytics. Besides, the con-
trol of thermodynamics and kinetics is significantly affected in
printing large-format systems compared to small-scale parts.[156 ]
In contrast, PBF-based 3D printing (e.g., SLS and SLM) may
rely on layer sizes, powder types, and laser-powder interactions
to determine the manufacturing sizes. As a result, achieving
ultrafine-size powders in the micro to the nanoscale is often
labor-intensive and expensive, requiring multistep processes for
breaking down the particle sizes. For example, the PBF pro-
duction via SLS to print Gr, Ni, CNTs, GO, and similar 3D
carbon materials show enormous potential to be used for bat-
tery application but requires the particle size to be in the sub-
micron scale and have a uniform distribution to be printable
in the submicron to micron scale.[86,157 ] Hence, the nature of
the materials in a powder form often hinders the quick tun-
ability of the feedstocks due to the rigorous process (mechan-
ical milling, ultrasonication, sieving, and laser/thermal abla-
tion) of synthesizing in each iteration. It is often common to
see rougher surface finishes after printing, which requires post-
processing (i.e., polishing, etching, coating), typically due to the
particle size, distribution, shape regularity, diffusion of particles
with the neighboring ones, and fluidity affecting the smooth-
ness and thickness of the layer.[158] Generally, these 3D printing
methods for batteries mostly produce a dot or line size above
10 μm and may lose the resolution below a single-digit micron
size.
Conventionally, ink jet-based 3D printing has broad applica-
tions in quickly processing microscale energy devices. However,
ink-based printers, commonly known as PolyJet or MultiJet, can-
not print submicrometer dimensions, especially for energy ap-
plications involving powder particles. Figure 11c1,c2show the
new jet-based 3D printing, electrohydrodynamic (EHD) jet print-
ing, which uses microcapillary nozzles that are turned from a
pushing jet mode as compared with a stable jet mode, as shown
in Figure 11c3, which allows printing dimensions as small as
1μm, as presented in Figure 11c4with an image of Hypatia
as an example. EHD printing has broad material compatibility
with insulating and conducting polymers, SiNPs, and SWCNTs.
For example, Steiner et al. used EHD to print CNTs with res-
olutions as low as 50–80 μm.[159 ] Similarly, Cabot et al. devel-
oped an ultrafast EHD with submicron features using electro-
static jet deflection, as shown in Figure 11d1. The team printed
PEO and Ag nanoparticles with features in the submicron scale
displayed in Figure 11d2–d7, further proving the potential for
micro-nano battery manufacturing.[160 ] Another high-resolution
3D printer capable of high-resolution printing, aerosol jet, uti-
lizes microcapillary nozzles that allow the resolutions to be in
microns and nanometer size. For instance, Rottmayer et al.
printed polymer composite electrolytes for SSB applications us-
ing aerosol jet printing capable of submicron scales.[121 ] Ro-
driguez et al. also printed LFP cathodes via the jet printer and
demonstrated superior cycling performance due to the dual-pore
network, otherwise referred to as “pore super highway,” as shown
in Figure 11e1,e2.[102]
5.3. Embed Codesign Concept via Integrated Comanufacturing at
the System Level
While most of the papers in the AM for LIBs have focused on
active materials, there has been a lack of focus on the materials
used for battery packaging design, current collectors, and non-
active materials. Regarding 3D printing, most literature investi-
gations have focused on printing a single nonactive component
before integrating the entire battery. For example, Bruce et al.
created a template using SLA to introduce only solid ceramic-
polymer electrolyte structures, with a focus on achieving reso-
lutions of up to 250 μm, a high resolution as the advantage.[163]
Another example from Rapp et al. showed a 3D printable hous-
ing device for batteries before being used in microcontrollers for
microfluidic sensors.[164 ] In an assembly, Kar et al. used carbon
fibers to overlay the cathode, SPE, anode, and current collector
through electrophoretic deposition and dip-coating methods in
wearable electronics.[165 ] Also, Zhang et al. focused on fabricating
Si/carbon nanofibers as a high-energy anode for LIBs via coax-
ial electrospinning as a facile and effective method to fabricate
1D free-standing nanofibers.[166 ] The resulting anode displayed
a high storage capacity of 762.0 mAh g−1at a specific current
of 0.1 A g−1after 100 cycles. Though with high performances,
most of these studied battery components have focused on the
single component fabrications before mechanically assembling
them for practical devices, similar to practices in the industry.
3D printing as a supply chain disrupter can process many differ-
ent materials for rapid prototyping, showing massive potential in
fabricating and assembling individual components during man-
ufacturing.
Those focused on manufacturing complete LIBs require mul-
tiple steps and pre/post-fabrication processes to achieve system-
level batteries. However, not many studies reported the entire
manufacturing and assembly of batteries via 3D printing to in-
corporate battery design, processing, and packaging.[71,77,83,104,118 ]
To solve this problem, a few research groups have studied coax-
ial printing for batteries where the cathode, anode, electrolyte,
and packaging can all be manufactured in a single print.[120,167 ]
As one trial, coaxial printing, typically composed of an outer
and an inner needle, allows for printing multi-material poten-
tially useful for assembling multiple battery components dur-
ing fabrications.[168 ] For example, Golodnitsky et al. fabricated
all-SSEs sandwiched between electrodes and their core compo-
nent of current collectors using a coaxial fabrication method,
as shown in Figure 12a1.[120] While their primary focus was on
the electrolyte composed of LiTFSI, PEO, and PLA for enhanced
mechanical properties, they carried out characterization meth-
ods through SEM, mass spectroscopy, and differential scanning
calorimetry (DSC), with the electrochemical impedance spec-
troscopy (EIS) and charge and discharge cycles demonstrated in
Figure 12a2,a3. They found that adding PLA in the FDM-printed
electrolyte enhanced the mechanical properties of the PEO, but
it also served as a Li-ion conductor. The corresponding bulk ionic
conductivity showed a 3 ×10−5Scm
−1at 90 ○C and 156 Ωcm−2
SEI resistance that paved the way for free-form-factor flexible ge-
ometries for the all-solid-state batteries through coaxial printing.
Similarly, the same strategy via layering multiple materials
can transfer to ink-based direct writing. Most recently, Ding
et al. reported a universal coaxial 3D-printing strategy in 2022
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Figure 12. Representation of the co-design and co-manufacturing techniques. a1) Schematic of the printhead design for FDM printing capable of
multi-coaxial-cable battery processing, designed with different nozzle configurations for the flexible coaxial battery. a2) Nyquistic plot of the composite
solid-state electrolyte (SSE) and a3) the charge and discharge profiles at consecutive 10 cycles. Reproduced with permission.[120 ] Copyright 2020, The
Electrochemical Society. b1) DIW for the coaxial printing of fibrous batteries with flexible straight lines, mosquito coils, and square coils. b2,b3)The
electrochemical performances of the coaxial LIBs. Reproduced with permission.[167 ] Copyright 2022, Elsevier. c1) Schematic of the multiphase direct
ink writing (MDIW) with an intricate design of the unique 3D printhead showing the multiplying procedure capable of splitting multiple feedstocks,
restacking them along different directions, and recombining them along the deposition direction. c2,c3) The MDIW-printed multiplied layers (i.e., 4, 8,
16, 64, 256, 512) showed distinct layers up to 256 layers (a resolution of 5 μm for sublayer features), while the 512 layers showed layer disruption due
to the larger particle sizes than sublayer width. Reproduced with permission.[169 ] Copyright 2021, Elsevier. d1) Voxalated architectures using the single,
1D multinozzle array and 2D multinozzle array, respectively. d2) Schematic illustrates the printhead operation to print (d3) up to four materials in a
single deposition. Reproduced with permission.[170 ] Copyright 2019, Springer Nature. d4–d7) Photos show the preliminary results of printing multiple
materials in a single deposition for battery applications via extrusion-based 3D printing. Reproduced with permission.[171] Copyright 2022, HAL.
to fabricate the all-in-one fibrous LIBs in one step, as shown in
Figure 12b1.[167] Using LTO and LFP as the active materials with
the separator filament via DIW, they fabricated straight lines,
mosquito coils, and square coils. For example, the LIBs displayed
a high-storage capacity as 510 mAh g−1and a long cyclability of
100 cycles which can be seen in Figure 12b2and the potential
versus the capacity plot in Figure 12b3.[167] It is worth noting that
their work also focused on sodium-ion batteries (SIBs) and aque-
ous zinc-ion batteries (AZIBs), demonstrating the ability of coax-
ial printing to assemble/test different batteries through a single
fabrication process quickly.
Coaxial printing has paved a new way for the battery appli-
cation to facilitate and optimize the fabrication process cost-
effectively and timely. Still, this technology needs further opti-
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mization in the interlayers between the separator and active ma-
terials for higher performances since the current coaxial printing
mechanism has a limit of structural parameters (e.g., the layer
thickness or the sublayer numbers). Ravichandran et al. recently
reported in the year of 2022 an alternative manufacturing tech-
nique, i.e., multiphase direct ink writing (MDIW), as shown in
Figure 12c1.[169] The MDIW could deliver feedstock materials A
and B simultaneously before multiplying them in the order of
2n+1to print in the range of 4, 8, 16, 64, 256, and 512 layers
(Figure 12c2,c3). During the multiplying mechanism, the feed-
stocks were injected into two channels, split along the vertical
direction, and re-stacking along the horizontal direction to main-
tain a good layer resolution (Figure 12c1). The maximum number
of layers from a single deposition could experimentally go up to
1024 sublayers with proper material selections, corresponding to
an individual layer thickness as high as ≈44 nm. The structural
robustness was demonstrated using polyvinyl alcohol (PVA) and
CNTs, showing much-improved modulus, strength, and tough-
ness. Via the same method, a few more polymers (i.e., thermo-
plastic polyurethane with varying polymer chain sizes and stiff-
ness values) and NPs (i.e., iron oxide) were also incorporated for
intelligent devices. The dual actuation in the printed composites
showed high actuation efficiency responsive to thermal and mag-
netic fields. Thus, the potential to use the co-manufacturing tech-
nology in energy-relevant applications can apply to electrode fab-
rication or supercapacitor assembly.
Another unique technique is the multi-material multi-nozzle
3D (MM3D) printing method, where the design and materials
are translated into a voxel design displayed in Figure 12d1.The
configuration of the MM3D printer can have a single nozzle, a
1D multi-nozzle array, or a 2D multi-nozzle array. Figure 12d2
shows the printhead mechanism where the voltage is applied
and changed to affect the deposition pressure with printable
origami structures, soft-robotic walkers, and voxelated facilities
while reducing the printing speed. It is worth noting that this
method could implement up to four materials, as shown in
Figure 12d3, and get perplexing patterning and structures. More
importantly, it brought attention to the capability of printing mul-
timaterial batteries in a single deposition that can be cost- and
time-efficient. As a result, Figure 12d4–d7demonstrated the pre-
liminary results of printing a complete cube lattice battery via
FDM as a multimaterial method similar to the voxelated MM3D
printer. It is worth noting that these methods with co-design and
co-manufacturing capabilities are mostly extrusion-based, which
needs further expansion in other printing mechanisms, better
material form capability, and energy storage applications. In sum,
the features of the co-design and co-manufacturing techniques
will allow for faster customization, tunability, and integration of
different energy storage devices.
5.4. Improve Uncertainty Prediction and In Situ Quality
Examination Using Data Science
Current 3D printing for processing new materials or tuning
printing parameters (e.g., ink rheologies or optimizing structure
designs) has been done through empirical and trial-and-error
methodology, which is expensive and time-consuming. The rapid
development of advanced data analytics with ML and Artificial In-
telligence (AI) allows fast research and development in battery 3D
printing. These data analytics methods are based on powerful ML
and AI algorithms (e.g., Bayesian analysis and deep neural net-
work algorithms) facilitated by combining them with in situ mon-
itoring via creative tooling engineering (e.g., 4D scanners, micro-
CT, high-rate cameras, and on-platform optical microscopes).[172]
ML and AI techniques have demonstrated tremendous promise
in mining 3D printing data. Emerging research now seeks to
find ML-driven solutions that can make anticipatory predictions
and achieve born-qualified products beyond how traditional in-
situ monitoring and control and ex situ evaluation have been
done.[173 ] On the one hand, the datasets in the battery materials
are relatively small, with multiple variables. The scarcity of data
is one of the biggest problems. Future researchers should adopt
multimodal in-process sensors to collect in situ measurements
for numerous variables in real-time to address these limitations.
The in-situ monitoring sensors measure various process signa-
tures representing the links between process control and final
part quality. Process signatures measure real-time dynamic char-
acteristics of physical properties during 3D printing operations
and give process physics and part quality information.[174,175 ] Ex-
amples of the process signatures are data measuring the real-
time evolution of 2D or 3D part geometries and temperature dur-
ing a build.[176 ] Such process signature data enable ML studies to
understand better the mechanisms of 3D printing dynamics, e.g.,
thermo-dynamics, hydro-dynamics, fluid-dynamics, or chemical
reactions.[177 ] In addition, data augmentation using advanced ML
approaches, such as generative adversarial networks, can be con-
sidered to increase data availability.[178]
On the other hand, the lack of formal methodologies and stan-
dardized frameworks defining the model and experimental vari-
ables and parameters further delays the data acquisition for ML
and AI modeling; a significant challenge for ML in 3D printing
today is that data acquisition is still ad-hoc.[173 ] This challenge
hinders the systematic adoption of advanced ML and AI in bat-
tery 3D printing. The variability of batteries with their shapes,
sizes, materials, and applications comes with different relation-
ship predictions and experiments and, therefore, other variables
and parameters at multiple scales. Predictive ML using the vari-
ables and parameters entails the acquisition of data of interest,
which needs to be guided by physics knowledge used in formulat-
ing ML and experimental requirements for battery 3D printing.
In this sense, 3D printing data must be associated with physics
knowledge about the batteries and their printing processes me-
thodically. Such an association enables the systematic acquiring
battery and 3D printing data from actual, physical, or simulated
virtual 3D printing systems and extracting the data features rep-
resenting the variables and parameters in terms of battery 3D
printing.[179 ] By doing so, ML can be consistently based on the
physical meanings of measurable quantities in iterations using
associated mathematical relations.
Finally, the lack of model interpretation is also a challenge in
ML due to the complexity and usability of the model when it
comes to materials research.[180 ] It is crucial to overcome these
challenges to increase in situ optimization and on-the-fly battery
manufacturing. To address the challenge, studies in battery 3D
printing need to adopt explainable AI (XAI), especially for deep
learning methods.[181 ] Pursuing XAI, the interpretation must
represent the findings of casual relationships in predictions from
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Figure 13. a) An overall framework for ML-driven process–structure–property (PSP) analytics in AM ({𝑝1,𝑝2,…, 𝑝𝑛}, {𝑝𝑠1,𝑝𝑠2,…, 𝑝𝑠𝑛}, {𝑠1,𝑠2,…, 𝑠𝑛}, and
{𝑝𝑟1,𝑝𝑟2,…, 𝑝𝑟𝑛} are sets of entities of process parameters, process signatures, structures, and properties, respectively). Reproduced with permission.[175]
Copyright 2023, Elsevier. b) A process of learning PSP causality using physics-guided data acquisition and ML to improve the quality of 3D printing. A
and B represent raw data sets. 𝛀and 𝚽represent PSP features extracted from A and B, respectively. T represents aligned data sets.
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Tabl e 6 . Current challenges in the recovery and recycling of LIB with corresponding descriptions.
Challenges Descriptions Refs.
Safety and hazards LIBs contain highly flammable and reactive materials, such as lead, cadmium, mercury, and lithium, requiring
specialized equipment and protocols for safety
[206]
Collecting and sorting
complexity
Batteries comprise a complex mix of (i) materials, including metals, plastics, and electrolytes; (ii) material
physics and chemistry (e.g., sizes, shapes, compositions); and (iii) end-of-life stages, requesting advances
in autonomous sorting and processing tools
[183]
Degradation Degradation during the battery’s initial use and subsequent recycling processes makes the performance
standards challenging to meet, requesting new material synthesis and processing design
[207]
Scalability Battery recycling involves complex processes (e.g., disassembly, crushing, and chemical treatment), which
require specialized scalability
[183]
Economic viability Direct recycling is still more expensive than mining and refining new materials due to the high cost of
equipment, labor, and energy required to recover the valuable materials, making it difficult for the recycling
industry to compete
[208]
ML in structured relationships.[182 ] Such techniques help pro-
vide the independence of the knowledge extracted from the ML
models, which is expected to offer new opportunities to improve
a priori physics knowledge.[182 ] Physics-informed (or -guided)
ML for Process-Structure-Property (PSP) causal analytics can ad-
vance the interpretation of the models in battery 3D printing. The
PSP approach can associate the XAI approaches with the critical
causal linkages between process mechanisms and part character-
istics in battery 3D printing processes. The physics-informed ML
approaches can fuse physics equations with real-world data to en-
hance the interpretation of predictions resulting from ML about
the physical meaning of 3D printing processes and battery char-
acteristics in extracting the PSP causal linkages. The PSP link-
ages can be advantageous when they include the process signa-
tures supporting monitoring constant dynamic changes during
battery 3D printing processes, which helps better understand the
dynamics of the printing processes. Figure 13ashowsaframe-
work driven by physics-guided ML for PSP causal analytics in
3D printing, consisting of three tiers: 1) knowledge of predictive
PSP models and physics, 2) PSP features of interest, and 3) raw
3D printing data (Figure 13b) showing a process of learning PSP
causality for 3D printing based on the framework.
5.5. Mitigate Environmental Risks via Battery Recovery
As demand increases, the material recovery from used batteries is
crucial for developing more environmentally benign, chemistry-
green, and cost-efficient batteries. However, battery recycling is a
complex process that involves several technical, economic, and
environmental challenges (Table 6). First, the recovery and re-
cycling of metal salts and cathodes have three primary meth-
ods, which involve hydrometallurgical, pyrometallurgical, and di-
rect recycling, as illustrated in Figure 14a.[183,184 ] Hydro and py-
rometallurgical methods are preferred for recovering metals (i.e.,
lithium, cobalt, Ni, manganese, and aluminum) due to their well-
established protocols and widely used instruments. Due to its
ecotechnological advantages, direct recycling is preferred to con-
ventional pyro and hydrometallurgical processes. Also, direct re-
cycling is based on thermal or acid solution treatments for re-
lithiation that allow the recyclability of primary electrodes, met-
als, and plastics. Categories under direct recycling consist of nu-
merous methods (i.e., solid-state, electrochemical, ionic liquids,
eutectic and solution-based) as shown in Figure 14b1–b5.
The first step in general battery recycling is electrolyte treat-
ment, which involves extracting CO2and organic solvent from
the electrolytes to be reused. However, recycling electrolytes is
challenging due to i) the solvent’s volatility ii) the Li salts’ insta-
bility, iii) and the high processing cost of recycling electrolytes.
Thus, electrolyte recycling may better adapt as all-solid-state bat-
teries emerge in 3D printable batteries involving SSEs in poly-
mers, ceramics, or composites. For example, Zhang et al. at-
tempted to recycle garnet-type batteries for the c-LLZTO elec-
trolyte demonstrated in Figure 14c.[185] Using ball-milling and
sintering to purify the LLZTO SSE and then adding fresh LLZTO,
they were able to obtain a relative density of 95.9%, close to the
original garnet electrolyte. However, the reused particles of the
LLZTO were not as stable as the new particles after they were
sintered, causing weak grain fusion during sintering.[185 ] While
the performance of the recycled SSE did not achieve the desired
performance, it still showed the capability to be used as a sac-
rificial powder typically seen in synthesizing LLZO. It is worth
noting that the manufacturing process of garnet-type electrolytes
is often expensive, and finding a way to reuse the materials can
bring the cost of the overall material and manufacture down.
After the separation of electrolytes, the electrode is processed
for recycling. Direct recycling techniques have been the main-
stream processing for recycling many electrodes (i.e., LFP, LCO,
NCA).[183,186 ] For example, Cheng et al. developed a new method
for directly recycling cathode material LFP using lithium salt
(i.e., 3,4-dihydroxy benzonitrile dilithium salt, Li2DHBN).[187]
The lithium salt allowed for the Fe(III) purification, responsible
for the capacity fades of the LFP cathode. Figure 14d1shows the
crystal structure comparison for the degraded and restored LFP
cathode using organic lithium salts, as shown in Figure 14d2
for comparing organic versus inorganic lithium salts. The salts
created an amorphous carbon layer coat in the LFP while puri-
fying the LFP cathode enabling good cycling stability and low-
temperature performance for the restored cathode material, as
shown in Figure 14d3.[187 ] According to the techno-economic
analysis performed in the EverBatt2022 model, this study showed
a higher potential financial benefit than many other recycling
methods, further enabling a new recycling method that is both
cost and time efficient. Moreover, there are a few selectively
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Figure 14. Different LIB recycling with a) four conventional battery recycling methods. Reproduced with permission.[184 ] Copyright 2021, American
Chemical Society. Illustration of the direct recycling techniques of b1) solid-state sintering (SS), b2) electrochemical relithiation (ECR), b3) ionother-
mal relithiation (IR), (b4) solution relithiation (SR), and b5) eutectic relithiation (ER). Reproduced with permission.[183 ] Copyright 2023, Wiley-VCH.
c) Schematic representation of the recycling of ceramic-based tantalum doped, lithium lanthanum zirconium oxide (LLZTO) electrolyte. Reproduced
with permission.[185 ] Copyright 2023, Elsevier. Regeneration of cathodes using lithium salts d1) comparing the degraded and restored crystal structure
for the LFP cathode. d2) General recycling processes for the LFP comparing both the inorganic and organic lithium salts. d3) Discharge capacity profile
versus cycle number comparing the regenerated cathode and the degraded LFP. Reproduced with permission.[187] Copyright 2023, Spring Nature. Selec-
tive leaching methods for lithium metal (LiM) e1) from cathode-based LFP materials with acetic acid and H2O2versus e2) persulfate and e3) from lithium
nickel-manganese-cobalt oxide (NMC) cathode using an electrochemical method. Reproduced with permission.[192 ] Copyright 2021, Royal Society of
Chemistry.
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leaching techniques when it comes to recycling LiM. For exam-
ple, Sun et al. selectively recovered lithium from LFP cathode
material using acetic acid and H2O2, showing a facile method of
recycling lithium, as shown in Figure 14e1.[188] Similarly, Wang
et al. leached lithium from an LFP cathode using persulfate, as
shown in Figure 14e2.[189 ] Also, Goodenough et al. used similar
materials, such as H2SO4and H2O2. However, Sun et al. used hy-
drothermal treatment to selectively leach lithium from lithium
nickel-manganese-cobalt oxide (NMC) cathode material.[190,191 ]
Figure 14e3further shows the leaching of lithium from the NMC
electrode but using an electrochemical method.[190,192 ]
The separation of materials is essential, and when it comes
to polymer recycling, it is not as common as the active materi-
als from a battery. In 2016, Jiangnan Graphene Research Insti-
tute filed a patent for a new method of recycling separator mate-
rial of LIBs using organic solvent and ultrasonic washing, which
promises efficient recycling of separators in a resourceful, cost,
and economical manner.[193] In 2020, Aravindan et al. focused on
regenerating polyolefin separators from secondary LIBs through
cleansing and washing methods using only deionized water.[194]
Through characterization techniques, including tensile strength,
differential scanning calorimetry, ionic conductivity, electrolyte
uptake, and interfacial resistance, they concluded that the recy-
cled separator works as efficiently as the virgin material.[194 ]
Several companies are focusing on recycling polymers from
batteries. Li-Cycle uses a process called “spoke and hub” recy-
cling, while Retriev Technologies uses a hydrometallurgical pro-
cess to recycle batteries.[195,196 ] Similarly, Umicore uses a com-
bination of pyrometallurgical and hydrometallurgical processes
to recover metals primarily from batteries, but also plastics and
other materials from the batteries.[197 ] Fortum also uses a hy-
drometallurgical process to recycle batteries. In addition to these
companies, many have expressed interest in recycled batteries for
EVs. General Motors has announced plans to build a factory in
Ohio to produce battery cells for its EVs, with a focus on sus-
tainability and recycling.[198 ] BMW has partnered with recycling
companies to create a closed loop for its EV batteries, while Tesla
aims to become a “closed loop” company, meaning it wants to re-
cycle its own batteries and reuse the materials.[199-201 ] Nissan has
a program called “LEAF to Home,” which allows Nissan LEAF
owners in Japan to use their car batteries to power their homes
during peak electricity usage hours. After a certain number of
years, the batteries are returned to Nissan for recycling.[202 ] Fur-
thermore, research groups and universities are also working on
developing new and innovative methods for recycling batteries.
While presenting future outlooks and state-of-the-art recycling
methods, the battery recycling industry remains deficient, facing
many challenges (Table 6).
(i) Safety and Hazards—Recycling facilities need robust safety
measures and protocols to prevent exposure to these haz-
ardous materials.
(ii) Collecting and sorting complexity—Identifying, separating,
purifying, and reusing materials is challenging to be cost-
efficient and environmentally friendly.
(iii) Degradation—New material synthesis (e.g.,
biometallurgy[203 ] or processing electrochemically[204,205 ])
will benefit the material robustness in recycling.
(iv) Scalability—Developing efficient and cost-effective recy-
cling technologies and instruments that can handle large
volumes of batteries is necessary to ensure the sustainable
use of materials.
(v) Economic viability—The economics of battery recycling de-
pends on the market prices of the materials, which requires
collaboration between various stakeholders, including gov-
ernment, industry, and academic researchers.
3D printable batteries and other electronics have shown enor-
mous potential to revolutionize many industry fields, and the re-
cycling of printed devices should be considered before similar
contamination issues in conventional manufacturing appear.
5.6. Diversify Device Intelligence via 4D Printing
AM of intelligent/innovative dynamic structures, i.e., 4D print-
ing, has primarily been composed of shape memory alloys
(SMAs) and shape memory polymers (SMPs), which are smart
materials capable of changing size, shape, or color under the
influence of external stimuli (i.e., pressure, heat, light, water,
pH, electrical or magnetic fields).[209-211 ] The potential applica-
tions of 4D printing are diverse and include self-assembling
robots, medical implants that can adapt to the body’s chang-
ing conditions, and building structures that can adjust to chang-
ing environmental conditions. For example, 3D printable PLA
inks as SMP from direct writing retained excellent shape after
UV-curing (Figure 15a1) with thermal responsiveness.[212] Dif-
ferent structures rapidly prototyped from the 3D printing proce-
dures, e.g., the spiral, wavy, and flower-like, exhibited high flex-
ibility in changing their shapes upon heating and efficiently re-
covered to their original sizes upon cooling (Figure 15a2–a4).[212]
Foldable assembly via 3D printing (Figure 15b) could also be
susceptible to thermal stimuli that can act as a robotic gripper
upon heating or cooling.[213 ] SMP is useful in 4D printing, with
Figure 15c demonstrating the capability to print living materi-
als, such as S.boulardii-TRP1 and LEU2, which grew upon ap-
propriate biochemical stimuli.[214 ] Figure 15d1–d4also shows a
4D-printed hand that accurately opens upon radiation, such as in-
frared light.[215 ] The functionality is not restricted to just the grip-
per but can also be used as a triggered alarm system. Figure 15d5–
d8shows an example of a dual-motor triggering alarm system
that used 4D printing to be stimulated via radiation to switch to
the alarm system.
Although 4D printing is still a relatively new technology being
developed and refined, it opens new avenues for electrochemical
applications, such as energy storage devices (e.g., batteries, ca-
pacitors, fuel cells, and sensors). Using innovative materials that
can change their properties in response to external stimuli, 4D
printing can create electrochemical devices that adapt to chang-
ing conditions or perform multiple functions. For example, 4D
printing batteries can accommodate the volume change from the
electrodes by changing their shape from outside stimuli, espe-
cially in soft packaging materials. Hu et al. designed a simple and
scalable extrusion-based 3D printing on DIW for fiber-shaped
LIBs.[216 ] The 3D-printed anode and cathode electrodes shown in
Figure 15e1,e2showed the merits of 3D printing with high man-
ufacturing customizability and cost efficiency. More importantly,
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Figure 15. Schematic diagram of different 4D printing techniques for printing/assembling stimuli-responsive objects and their relationship to energy
devices. a1) 4D active shape-changing architecture through ultraviolet (UV) cross-linkable PLA-based ink and a2–a4) shape-morphing structures (i.e.,
the micro spiral pattern through heat stimuli in images (i–iii), waviness-like shape in images (iv–vi), and flower-like configuration in images (vii–ix).
Reproduced with permission.[212 ] Copyright 2017 American Chemical Society. b) 4D printable, reversible, and self-holdable micro grippers in response
to the thermal fields (i.e., temperature-responsive). Reproduced with permission.[213 ] Copyright 2015, American Chemical Society. c) Schematic of a
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the extruded anode/cathode composites were automatically as-
sembled and packaged within the fibers. The packaging of fibers
showed excellent surface smoothness and continuous length,
with initial charge/discharge capacities of 141.3 and 110 mA h
g−1, respectively. Most recently, Qi et al. 4D printed fiber rein-
forcement composites via DIW for self-morphing structures ac-
tivated through thermal stimulation.[217 ] Figure 15f1,f2illustrates
the 4D printing process where a photocurable polymer is mixed
with the glass fiber and fumed silica to be extruded via DIW and
cured through UV light. The printed structure was then exited
thermally, which evaporated the solvents and caused structural
morphing. Hence, merging the fiber structure via 4D printing-
based batteries for wearable electronics is another avenue with
newer applications and functionalities.
Similarly, 4D printing has created self-folding origami-
inspired fuel cells that can change shapes and sizes to maxi-
mize energy output. These fuel cells are made of a smart ma-
terial that can respond to changes in temperature or pH and
can be printed with complex geometries that would be diffi-
cult to achieve with traditional manufacturing methods. Goel
et al. reported that the inkjet printed a portable microbial fuel
cell as an origami array (Figure 15g1–g4).[218] A tabletop PCB
inkjet printer was used to customize the electrode design, and
the node was further modified with synthesized MnO2NPs be-
fore the entire cell was formed by folding the paper along pre-
defined edges. Figure 15g5–g8shows the different iterations of
bioelectrode materials (e.g., carbon and MnO2) to determine
the morphological and structural optimization. The higher the
MnO2loading, the higher the performance reaching a maximum
power density of 15.9 μWcm
−2and current density of 130 μA
cm−2at an open-circuit potential for two connected MFCs of
0.534 V.[ 218] Such a 4D printing-enabled origami array was from
simple electrode manufacturing and modification, showing po-
tential in energy management, data monitoring, and Internet-
of-Things. Additionally, 4D printing electrolytes can selectively
create a pathway to a specific ion leading to faster charge and
discharge cycles for electrode additives to serve as insulators or
promote higher ionic conductivity. 4D printing is built upon 3D
printing by virtue, and therefore one must thoroughly scruti-
nize the 3D printing capabilities while promoting 4D printing.
First, the design of 4D LIBs with flexible shapes will need to
fit the surface of many desirable targets, one of the most sig-
nificant features of flexible/stretchable devices compared with
their rigid counterparts. Second, new materials and device struc-
tures must be created for enhanced energy/power density to
balance processing costs and feasibility. Overall, 4D printing
has the potential to revolutionize ESS, enabling new function-
alities and capabilities impossible in conventional manufactur-
ing.
5.7. Explore beyond Lithium-Ion Batteries in Additive
Manufacturing
Our focus on lithium-relevant batteries (e.g., lithium-ion,
lithium-sulfur, and lithium-solid state batteries) in this review
served as an illustrative example to elucidate the significance of
3D printing and related manufacturing techniques in the battery
domain. However, we recognize that designing, processing, and
utilizing lithium-ion batteries present their own set of challenges
and limitations. The development of sodium-ion batteries, zinc-
ion batteries, metal batteries, flow batteries, and other alterna-
tive battery technologies in recent years has been rapid. These
emerging battery systems face distinct challenges and problems
that set them apart from lithium-relevant batteries. The following
lists some of the key challenges associated with these alternative
battery technologies.
The first challenge is the low electrochemical performance.
Sodium-ion, zinc-ion, metal, flow, and other batteries often ex-
hibit lower energy density and specific capacity than lithium-ion
batteries. Achieving comparable or superior electrochemical per-
formance, including capacity, cycling stability, and rate capability
is a significant challenge for these alternative systems. On the
other hand, Li’s availability is limited and its extraction is chal-
lenging as compared to Na, Zn, and certain metals used in alter-
native batteries. Still, sodium ions and zinc ions are larger than
lithium ions, resulting in lower mobility within the electrode ma-
terials and electrolytes. Furthermore, the depletion of oxygen and
subsequent exposure frequently pose challenges, resulting in ox-
idation and decreased efficiency for battery performance. Over-
coming these limitations to achieve efficient ionic conductivity
and diffusion is a critical aspect of enhancing the performance of
these battery systems.
As discussed in the electrode materials and their design in
Sections 5.1 to 5.3, developing suitable electrode materials that
exhibit good electrochemical activity, stability, and compatibility
with the specific chemistry of sodium-ion, zinc-ion, metal, and
flow batteries is a challenge. Designing and synthesizing mate-
rials with high capacity, long cycle life, and good electrochem-
ical reversibility remains an active area of research and devel-
opment. Besides, the selection and optimization of electrolyte
compositions for alternative battery systems can be challeng-
ing. Finding electrolyte formulations in the design phase that
offer high ionic conductivity, good compatibility with electrode
3D printed bilayer composed of two engineered S. boulardii mutants with the top layer printed as stripes and the bottom layer as a flat sheet, show-
ing the normal bending and Gaussian curvature upon growth for biomedical and biological applications. Reproduced with permission.[214 ] Copyright
2022, Wiley-VCH. d1–d4) Infrared-triggered thermoplastic polyurethane (TPU)/carbon nanotubes (CNT) shape memory hands with the ability to fully
recover for motion control and sensing/actuating purposes. d5–d8) The ability to print a dual-motor triggered alarm system, where (d6) is the circuit
diagram while (d7) shows a green light for indicating a safe state as opposed to (d8). Reproduced with permission.[215 ] Copyright 2022, Wiley-VCH.
e1,e2) 3D printed carbon fibers, such as CNTs used in the cathode (LFP) fiber and anode (LTO) fiber-based materials for textile batteries. Reproduced
with permission.[216 ] Copyright 2017, Wiley-VCH. f1,f2) 4D printing of crystalline fibers with photocurable polymers and fumed silica as fiber-reinforced
composites via DIW and stimulated through the heat to create shape-shifting structures. Reproduced with permission.[217 ] Copyright 2021, American
Chemical Society. g1–g4) The schematic representation of the folded structures and the final origami-array structure. g5–g8) 4D printed via inkjet to
fabricate a portable microbial fuel cell as an origami array using custom carbon cathodes and transition metal oxide MnO2nanomaterial. Reproduced
with permission.[218 ] Copyright 2021, Elsevier.
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materials, and long-term stability is crucial for achieving opti-
mal battery performance and safety. At the same time, all bat-
tery systems experience some level of degradation over time, im-
pacting their cycle life and overall performance. Issues such as
electrode/electrolyte degradation, side reactions, and the forma-
tion of passivating layers can affect the stability and longevity of
these batteries. As a result, the safety of alternative battery tech-
nologies is a significant concern due to their diminishing prop-
erties over time and the potential for accidents. Addressing chal-
lenges like dendrite formation,[219,220 ] which can cause short cir-
cuits and thermal runaway,[221] is crucial for improving the safety
of sodium-ion batteries, zinc-ion batteries, metal-based, and flow
batteries.
More importantly, developing scalable and cost-effective man-
ufacturing processes for alternative battery systems is a chal-
lenge. Transitioning from laboratory-scale demonstrations to
mass production while maintaining consistent performance and
quality requires overcoming various technical and logistical hur-
dles. Therefore, the application of 3D printing technology in
these alternative battery systems has proven instrumental in ad-
dressing specific problems and driving notable advancements.
First, 3D printing enables rapid prototyping and iterative de-
sign iterations, reducing development time and costs. This ca-
pability promotes faster innovation cycles, facilitating the explo-
ration and optimization of novel materials, electrode geometries,
and electrolyte formulations for sodium-ion batteries, zinc-ion
batteries, metal-based batteries, and flow batteries. Second, 3D
printing enables the fabrication of complex and intricate struc-
tures with high precision. This capability allows for the cus-
tomization of battery components and the design of optimized
architectures, leading to enhanced performance and unique
characteristics[222-224 ] in sodium-ion, zinc-ion, metal, and flow
batteries. Third, 3D printing facilitates the integration of various
battery components into compact and space-efficient designs.
This is particularly valuable in applications where size and weight
constraints are critical, such as wearable devices or miniaturized
electronics, expanding the battery applications. Fourth, facilitated
by structural design and data analytics, 3D printing techniques
can be employed to create well-defined electrode structures with
tailored properties, such as specific porosity, surface area, and hi-
erarchical architectures.[225-227 ] This level of control aids in opti-
mizing electrochemical performance, including capacity, cycling
stability, and rate capability.[10] Fifth, 3D printing techniques ac-
commodate a wide range of materials, including advanced elec-
trode materials and novel electrolyte formulations. This capabil-
ity expands the material options for alternative battery systems
and allows for the exploration of new compositions and combi-
nations, ultimately contributing to the development of more effi-
cient and sustainable energy storage technologies.[228,229 ] Last but
not least, 3D printing controls processing parameters with high
autonomy and achieves consistent performance characteristics,
such as capacity, voltage, and cycle life.[230]
By leveraging 3D printing technology in the context of sodium-
ion batteries, zinc-ion batteries, metal batteries, flow batter-
ies, and related systems, researchers and engineers have made
significant strides in addressing specific challenges, improv-
ing performance parameters, and advancing the state-of-the-art
in alternative battery technologies. Considering more abundant
and cost-efficient metals (e.g., potassium-ion,[231,232 ] magnesium-
ion,[233,234 ] and aluminum-ion[235,236 ] batteries) and a lack of their
applications in advanced manufacturing, the continued explo-
ration and integration of 3D printing techniques hold great
promise for further advancements and the realization of practical
applications in the field of energy storage.
5.8. Leverage Advanced Computer Technology in 3D Printable
Batteries
The transformation and upgrading of 3D-printed batteries
through advanced computer technology offer significant poten-
tial for enhancing the entire battery lifecycle, including design,
manufacturing, and recycling. Here’s how advanced computer
technology can be leveraged in each stage.
During the design stage, computational modeling and simu-
lations can aid in the design and optimization of battery mate-
rials (cathode,[237-239 ] anode,[240 ] and SSE.[241-243 ]). It allows for ex-
ploring various material compositions, structures, and properties
to improve performance characteristics, such as energy density,
stability, and conductivity. For example, First-principle methods,
such as density functional theory (DFT), enable the calculation
of electronic structure and properties of materials from funda-
mental physical principles.[244 ] They can provide insights into the
atomic-level behavior of battery materials, including their elec-
tronic structure, stability, and reaction mechanisms. Molecular
dynamics (MD) simulations simulate the motion and interac-
tions of atoms and molecules over time. They can provide in-
formation about the behavior and dynamics of materials at the
atomic scale.[245 ] MD simulations are often used to study dif-
fusion processes, phase transitions, and ion transport in bat-
tery materials. The finite element method (FEM) is a numerical
technique for solving partial differential equations by dividing
the domain into smaller elements.[246] In the context of battery
materials, FEM can be used to model and optimize the electro-
chemical processes, heat transfer, and stress distribution within
battery electrodes and cells. It aids in predicting performance
characteristics and optimizing designs for improved efficiency
and durability. The boundary element method (BEM) is a nu-
merical method used to solve boundary value problems by dis-
cretizing the boundaries instead of the entire domain.[247 ] BEM
can be employed in battery design to model the electrostatic po-
tential distribution and electric fields within the battery system.
It helps analyze the behavior of ions, charge distribution, and
electrochemical reactions at the electrode-electrolyte interfaces.
Multi-scale modeling integrates different modeling techniques,
such as atomistic simulations (e.g., DFT, MD) and continuum
models (e.g., FEM), to capture phenomena occurring at multi-
ple lengths and time scales. It enables studying complex interac-
tions between atomic, mesoscale, and macroscopic behavior in
battery materials, offering a more comprehensive understand-
ing of their performance and optimizing their properties. Be-
sides, computer-aided design (CAD) software (e.g., SolidWorks)
enables the creation and optimization of battery structures, in-
cluding electrodes and cell configurations.[248] It allows for pre-
cise control over the internal geometry and arrangement of com-
ponents, optimizing factors of packing density, surface area, and
electrolyte distribution.
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During the manufacturing stage, advanced computer tech-
nology, coupled with additive manufacturing software (e.g., slic-
ing for additive layer control and multi-axis autonomy for struc-
tural variability), can facilitate the precise fabrication of elec-
trodes and solid electrolytes. Computer-controlled printing pro-
cesses enable the deposition of active materials in complex ge-
ometries, enhancing electrode performance and enabling the cre-
ation of custom electrode designs tailored to specific applica-
tions. More importantly, computer-guided assembly techniques,
such as robotic automation, can streamline the manufacturing
process of battery devices and battery performance. Automated
systems can accurately position and connect components, en-
suring consistency and reducing human error. As relevant, Sec-
tion 5.4 described the role of data analytics during the mate-
rial processing and assembly/disassembly procedures. For exam-
ple, process optimization tools can help better manufacturing
parameters, e.g., viscosity, shear rates, electrode mass loading,
electrode thickness, and porosity. These tools include Reinforce-
ment Learning (RL), Bayesian Optimization, Particle Swarm Op-
timization (PSO), and NeuroEvolution of Augmenting Topolo-
gies (NEAT), which are highly dependent upon advanced com-
putational capabilities.[249,250 ]
During the lifecycle analysis stage, advanced computer tech-
nology (e.g., ANSYS Granta Edupack) can aid in conducting
lifecycle assessments to evaluate the environmental impact of
battery designs and manufacturing processes.[251,252 ] It enables
the identification of opportunities for optimization, resource
efficiency, and reduced waste generation. More importantly,
computer-based sorting and separation techniques can be em-
ployed to recover valuable materials from spent batteries dur-
ing recycling. Computer vision (e.g., convolutional neural net-
works (CNN), Object Detection algorithms (e.g., YOLO, SSD),
Image Classification models (e.g., ResNet, Inception)), robotic
systems (e.g., robotic arms, Gantry systems, Delta robotics, auto-
mated conveyor systems), and data analytics (e.g., machine learn-
ing, deep learning, artificial intelligence) as mentioned above,
can assist in the identification, classification, and sorting of
battery components and materials for efficient recovery and
recycling.[253,254 ] For example, image analysis and computer vi-
sion tools, including OpenCV (Open Source Computer Vision
Library), TensorFlow, PyTorch, MATLAB, Caffe, and scikit-image
as a Python library for image processing and analysis, can assist
with battery recycling in pyrometallurgical, hydrometallurgical,
and biological recycling methods.
Overall, advanced computer technology plays a crucial role in
advancing the transformation and upgrading of traditional 3D-
printed batteries. It enables the exploration of novel materials and
structures, enhances manufacturing precision and efficiency,
and supports environmentally sustainable practices throughout
the battery lifecycle. By leveraging computational tools and au-
tomation, the battery industry can achieve more remarkable per-
formance, customization, and sustainability in battery design,
production, and recycling processes.
5.9. Challenges and Opportunities in 3D Printable Batteries
While 3D printing offers several advantages in battery manufac-
turing, it also has some drawbacks to be addressed. Here are a
few challenges and potential technological developments to over-
come them:
Energy Density Limitations: 3D printing techniques, such as
direct ink writing or powder-based processes, may have lim-
itations in achieving high-energy-density batteries. Traditional
winding processes used in battery manufacturing allow for
tightly packed electrode structures, which can optimize energy
density. To overcome this limitation, advancements in 3D print-
ing technologies are required to enable precise control over the
microstructure and porosity of printed electrodes. This could in-
volve the development of new printing methods or optimized ma-
terial formulations specifically designed for higher energy den-
sity, as we discussed in Section 5.2.
Post-processing Limitations: Coated electrodes, commonly
used in conventional battery manufacturing, offer ease of han-
dling and integration into battery cell designs. In contrast, 3D-
printed electrodes may have complexities in terms of post-
processing, assembly, and integration. Technological advance-
ments should focus on developing efficient and automated post-
processing methods, such as electrode surface treatment, stack-
ing, and interconnection techniques, on ensuring the conve-
nience and seamless integration of 3D-printed electrodes into
battery cells, as we described in Sections 5.2 and 5.3.
Material Selection and Performance Limitations: The choice
of suitable materials for 3D printing in battery manufacturing
is crucial. While various printable materials are available, find-
ing materials that exhibit high electrochemical performance, sta-
bility, and compatibility with 3D printing processes can be chal-
lenging. The development of new printable materials specifically
designed for high-performance batteries is an ongoing area of
research. This includes exploring novel electrode materials, elec-
trolytes, and additives that can be successfully utilized in 3D
printing processes while maintaining excellent battery perfor-
mance. This content can be found in Sections 5.1 and 5.7.
Production Scalability and Processing Resolution Limitations:
3D printing, particularly for large-scale battery production, may
face challenges in terms of scalability and production effi-
ciency in the short term. Traditional manufacturing methods
can achieve higher production rates and economies of scale.
To address this, technological advancements are needed to en-
hance the speed and throughput of AM without compromis-
ing the processing quality and printing accuracy of the printed
battery components. Specific approaches may help mitigate the
scalability-resolution trade-off, including but not limited to multi-
scale printing, hybrid manufacturing, advanced process control,
iterative optimization, and new material innovation. This could
involve innovations in printer design, multi-head printing sys-
tems, or novel fabrication strategies to increase productivity while
not sacrificing manufacturing precision, as we have relevant con-
tent in Sections 5.1–5.3 and 5.6,5.7.
Integration of Multi-Material Component Limitations: Battery
cells often comprise multiple components, such as electrodes,
current collectors, separators, and electrolytes. Ensuring seam-
less integration of these components in 3D-printed batteries can
be a complex task. Future developments should focus on advanc-
ing multi-material 3D printing techniques that enable the simul-
taneous printing of multiple materials with different properties.
This would facilitate the direct printing of fully integrated bat-
tery cells, eliminating the need for additional assembly steps. We
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have summarized the state of the art in Sections 2–4. Overall,
technological advancements in 3D printing processes, printable
materials, post-processing techniques, and integration methods
are essential to overcome the drawbacks associated with battery
manufacturing using 3D printing. Ongoing research and devel-
opment efforts should be focused on addressing these challenges
to unlock the full potential of 3D printing in the battery industry.
In summary, 3D printing technologies have emerged as a
game-changing approach to enhance devices in the EES sector,
enabling the fabrication of wearables, miniaturized micro-robots,
medical devices, and micro-electronic storage devices with intri-
cate designs. Moreover, the use of ceramics and composite ma-
terials in 3D printing has revolutionized the manufacturing pro-
cess, offering unprecedented complexity and simplification. As
this technology continues to advance, the possibilities of creating
new materials, achieving ultrafine spatial resolution, data predic-
tion, and stimuli-responsive 3D printed materials are becoming
more feasible. Consequently, 3D printing is poised to become one
of the most promising manufacturing methods for the next gen-
eration of EES systems.
Acknowledgements
The authors appreciate the funding from NSF Graduate Research Fel-
lowships Program (GRFP # 1000343766), Qatar National Research Fund
(Grant # NPRP14S-0317-210064), the NSF Faculty Early Career Develop-
ment Program (CAREER) award (# 2145895), ACS PRF (award #62371-
ND10), Arizona Biomedical Research Center (award # RFGA2022-010-07),
and BSF (award #2020102).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
3D printing, batteries, electrodes, hierarchies, multimaterials, solid elec-
trolytes
Received: March 31, 2023
Revised: July 8, 2023
Published online: July 27, 2023
[1] K. H. Choi, D. B. Ahn, S. Y. Lee, ACS Energy Lett. 2018,3, 220.
[2] Z.Lyu,G.J.H.Lim,J.J.Koh,Y.Li,Y.Ma,J.Ding,J.Wang,Z.Hu,J.
Wang, W. Chen, Y. Chen, Joule 2021,5, 89.
[3] M. P. Browne, E. Redondo, M. Pumera, Chem. Rev. 2020,120, 2783.
[4] Y. Zhu, J. Qin, G. Shi, C. Sun, M. Ingram, S. Qian, J. Lu, S. Zhang, Y.
L. Zhong, Carbon Energy 2022,4, 1242.
[5] M. Idrees, S. Batool, M. A. U. Din, M. S. Javed, S. Ahmed, Z. Chen,
Nano Energy 2023,109, 108247.
[6] P. Chang, H. Mei, S. Zhou, K. G. Dassios, L. Cheng, J. Mater. Chem.
A2019,7, 4230.
[7] J. C. Ruiz-Morales, A. Tarancó, J. Canales-Vá zquez, J. Mé ndez-
Ramos, L. Herná ndez-Afonso, P. Acosta-Mora, J. R. Marí Rueda,
R. Ferná ndez-Gonzá lez, Energy Environ. Sci. 2017,10, 846.
[8] T. Chu, S. Park, K. Fu, K. Correspondence, Carbon Energy 2021,3,
424.
[9] M.Pei,H.Shi,F.Yao,S.Liang,Z.Xu,X.Pei,S.Wang,Y.Hu,J. Mater.
Chem. A 2021,9, 25237.
[10] Y. Pang, Y. Cao, Y. Chu, M. Liu, K. Snyder, D. MacKenzie, C. Cao, Adv.
Funct. Mater. 2020,30, 1906244.
[11] V. Egorov, U. Gulzar, Y. Zhang, S. Breen, C. O’Dwyer, Adv. Mater.
2020,32, 2000556.
[12] M. Zhang, H. Mei, P. Chang, L. Cheng, J. Mater. Chem. A 2020,8,
10670.
[ 1 3 ] Y. H a n , Y. Y o u , C . H o u , Y. X i o n g , Y. L i n , Q . X u e , G . K a u r , B . D . G a t e s ,
Z. Chen, W. Zhang, Z. Yang, Nanotechnology 2019,31, 012001.
[14] S. J. Dillon, K. Sun, Curr. Opin. Solid State Mater. Sci. 2012,16,
153.
[15] P. Zheng, J. Sun, H. Liu, R. Wang, C. Liu, Y. Zhao, J. Li, Y. Zheng, X.
Rui, Batteries Supercaps 2023,6, 202200481.
[16] Y. Zhu, J. Qin, G. Shi, C. Sun, M. Ingram, S. Qian, J. Lu, S. Zhang, Y.
Lin Zhong, Carbon Energy 2022,4, 1242.
[17] X. Gao, M. Zheng, X. Yang, R. Sun, J. Zhang, X. Sun, Mater. Today
2022,59, 161.
[18] Y.Lu,C.Z.Zhao,H.Yuan,J.K.Hu,J.Q.Huang,Q.Zhang,Matter
2022,5, 876.
[19] K. Fu, Y. Yao, J. Dai, L. Hu, Adv. Mater. 2017,29, 1603486.
[20] X. Tian, B. Xu, Small Methods 2021,5, 2100877.
[21] T. Zhang, F. Ran, Adv. Funct. Mater. 2021,31, 2010041.
[22] X.Li,H.Jiang,Y.Liu,X.Guo,G.He,Z.Chu,G.Yu,M.Science,E.
Program, EcoMat 2022,4, e12162.
[23] X.Tian,J.Jin,S.Yuan,C.K.Chua,S.B.Tor,K.Zhou,Adv. Energy
Mater. 2017,7, 1700127.
[24] O.C.Esan,X.Shi,Z.Pan,X.Huo,L.An,T.S.Zhao,Adv. Energy
Mater. 2020,10, 2000758.
[25] S. Abada, G. Marlair, A. Lecocq, M. Petit, V. Sauvant-Moynot, F.
Huet, J. Power Sources 2016,306, 178.
[26] H. Lu, J. Wang, J. Yang, J. Zou, Q.-K. Wang, J.-N. Shen, Y.-J. He, Z.-F.
Ma, Chin. Phys. B 2020,29, 068201.
[27] Z. Wang, H. Jiang, Y. Zhang, Y. An, C. Wei, L. Tan, S. Xiong, Y. Qian,
J. Feng, Adv. Funct. Mater. 2023,33, 2210184.
[28] J. T. Frith, M. J. Lacey, U. Ulissi, Nat. Commun. 2023,14, 420.
[29] S. Zhou, I. Usman, Y. Wang, A. Pan, Energy Storage Mater. 2021,38,
141.
[30] C. M. Costa, R. Gonçalves, S. Lanceros-Méndez, Energy Storage
Mater. 2020,28, 216.
[31] C. Y. Lee, A. C. Taylor, A. Nattestad, S. Beirne, G. G. Wallace, Joule
2019,3, 1835.
[32] J. C. Ruiz-Morales, A. Tarancón, J. Canales-Vázquez, J. Méndez-
Ramos, L. Hernández-Afonso, P. Acosta-Mora, J. R. Marín Rueda,
R. Fernández-González, Energy Environ. Sci. 2017,10, 846.
[33] J. Huang, Q. Qin, J. Wang, Processes 2020,8, 1138.
[34] S. Zakeri, M. Vippola, E. Levänen, Addit. Manuf. 2020,35, 101177.
[35] L. J. Hornbeck, in LEOS Summer Topical Meeting, IEEE, Piscataway,
NJ 1996, pp. 7–8.
[36] X. Peng, X. Kuang, D. J. Roach, Y. Wang, C. M. Hamel, C. Lu, H. J.
Qi, Addit. Manuf. 2021,40, 101911.
[37] H. X. Nguyen, H. Suen, B. Poudel, P. Kwon, H. Chung, CIRP Ann.
2020,69, 177.
[38] R. Chaudhary, P. Fabbri, E. Leoni, F. Mazzanti, R. Akbari, C. Antonini,
Prog. Addit. Manuf. 2022,8, 331.
[39] Y. Zhang, L. Wu, M. Zou, L. Zhang, Y. Song, Adv. Mater. 2022,34,
2107249.
[40] J. R. Tumbleston, D. Shirvanyants, N. Ermoshkin, R. Janusziewicz,
A. R. Johnson, D. Kelly, K. Chen, R. Pinschmidt, J. P. Rolland, A.
Ermoshkin, E. T. Samulski, J. M. DeSimone, Science 2015,347,
1349.
[41] B. Huang, Y. Zhou, L. Wei, R. Hu, X. Zhang, P. Coates, F. Sefat, W.
Zhang, C. Lu, Ind. Eng. Chem. Res. 2022,61, 13052.
[42] T. R. Yeazel-Klein, A. G. Davis, M. L. Becker, Adv. Mater. Technol.
2023,8, 2201904.
Small 2023,19, 2302718 © 2023 The Authors. Small published by Wiley-VCH GmbH
2302718 (40 of 44)
www.advancedsciencenews.com www.small-journal.com
[43] G. Lipkowitz, T. Samuelsen, K. Hsiao, B. Lee, M. T. Dulay, I. Coates,
H. Lin, W. Pan, G. Toth, L. Tate, E. S. G. Shaqfeh, J. M. DeSimone,
Sci. Adv. 2022,8, 3917.
[44] B. J. Lee, K. Hsiao, G. Lipkowitz, T. Samuelsen, L. Tate, J. M.
DeSimone, Addit. Manuf. 2022,55, 102800.
[45] Z. Huang, G. Shao, L. Li, Prog. Mater. Sci. 2023,131, 101020.
[46] B. E. Kelly, I. Bhattacharya, H. Heidari, M. Shusteff, C. M.
Spadaccini, H. K. Taylor, Science 2019,363, 1075.
[47] Q. Geng, D. Wang, P. Chen, S. C. Chen, Nat. Commun. 2019,10,
2179.
[48] J. W. Choi, H. C. Kim, R. Wicker, J. Mater. Process. Technol. 2011,211,
318.
[49] J. T. Toombs, M. Luitz, C. C. Cook, S. Jenne, C. C. Li, B. E. Rapp, F.
Kotz-Helmer, H. K. Taylor, Science 2022,376, 308.
[50] B. M. Schmitt, C. F. Zirbes, C. Bonin, D. Lohmann, D. C. Lencina, A.
da Costa Sabino Netto, Mater. Res. 2018,20, 883.
[51] M. Ratiu, M. A. Prichici, D. M. Anton, D. C. Negrau, IOP Conf. Ser.
Mater. Sci. Eng. 2021,1169, 012008.
[52] W. Xu, S. Jambhulkar, Y. Zhu, D. Ravichandran, M. Kakarla, B.
Vernon, D. G. Lott, J. L. Cornella, O. Shefi, G. Miquelard-Garnier,
Y. Yang, K. Song, Composites, Part B 2021,223, 109102.
[53] M. A. S. R. Saadi, A. Maguire, N. T. Pottackal, M. S. H. Thakur, M.
M. Ikram, A. J. Hart, P. M. Ajayan, M. M. Rahman, Adv. Mater. 2022,
34, 2108855.
[54] S. Tagliaferri, A. Panagiotopoulos, C. Mattevi, Mater. Adv. 2021,2,
540.
[55] L. del-Mazo-Barbara, M. P. Ginebra, J. Eur. Ceram. Soc. 2021,41, 18.
[56] A. Mazzoli, Med. Biol. Eng. Comput. 2013,51, 245.
[57] C. Yan, Y. Shi, L. Hao, Int. Polym. Process. 2011,26, 416.
[58] D. Drummer, S. Greiner, M. Zhao, K. Wudy, Addit. Manuf. 2019,27,
379.
[59] D. Drummer, D. Rietzel, F. Kühnlein, Phys. Procedia 2010,5, 533.
[60] N. K. Roy, D. Behera, O. G. Dibua, C. S. Foong, M. A. Cullinan, Mi-
crosyst. Nanoeng. 2019,5, 64.
[61] J. P. Kruth, P. Mercelis, J. van Vaerenbergh, L. Froyen, M. Rombouts,
Rapid Prototyping J. 2005,11, 26.
[62] B. Nagarajan, Z. Hu, X. Song, W. Zhai, J. Wei, Engineering 2019,5,
702.
[63] G. Z. Cheng, R. S. J. Estepar, E. Folch, J. Onieva, S. Gangadharan, A.
Majid, Chest 2016,149, 1136.
[64] H. N. Chia, B. M. Wu, J. Biol. Eng. 2015,9,4.
[65] J.Wang,Y.Liu,Z.Fan,W.Wang,B.Wang,Z.Guo,Adv. Compos.
Hybrid Mater. 2019,2,1.
[66] I. Gibson, D. Rosen, B. Stucker, M. Khorasani, in Additive Manufac-
turing Technologies (Eds:I.Gibson,D.Rosen,B.Strucker,M.Kho-
rasani), Springer, Cham, Switerzerland 2021, pp. 237–252.
[67] P.Shakor,S.H.Chu,A.Puzatova,E.Dini,Prog. Addit. Manuf. 2022,
7, 643.
[68] M. Ziaee, N. B. Crane, Addit. Manuf. 2019,28, 781.
[69] V. Popov, A. Fleisher, G. Muller-Kamskii, A. Shishkin, A. Katz-
Demyanetz, N. Travitzky, S. Goel, Sci. Rep. 2021,11, 2438.
[70] H. Sun, J. Zhu, D. Baumann, L. Peng, Y. Xu, I. Shakir, Y. Huang, X.
Duan, Nat. Rev. Mater. 2018,4, 45.
[71] C. Liu, Y. Qiu, Y. Liu, K. Xu, N. Zhao, C. Lao, J. Shen, Z. Chen, J. Adv.
Ceram. 2022,11, 295.
[72] E. Cohen, S. Menkin, M. Lifshits, Y. Kamir, A. Gladkich, G. Kosa, D.
Golodnitsky, Electrochim. Acta 2018,265, 690.
[73] G. Qi, H. Yao, Y. Zeng, J. Chen, J. Alloys Compd. 2023,935, 167941.
[74] H.Ning,J.H.Pikul,R.Zhang,X.Li,S.Xu,J.Wang,J.A.Rogers,W.
P. King, P. V. Braun, Proc. Natl. Acad. Sci. USA 2015,112, 6573.
[75] B. Wu, B. Guo, Y. Chen, Y. Mu, H. Qu, M. Lin, J. Bai, T. Zhao, L. Zeng,
Energy Storage Mater. 2023,54, 75.
[76] H. Ragones, S. Menkin, Y. Kamir, A. Gladkikh, T. Mukra, G. Kosa, D.
Golodnitsky, Sustainable Energy Fuels 2018,2, 1542.
[77] C. Reyes, R. Somogyi, S. Niu, M. A. Cruz, F. Yang, M. J. Catenacci, C.
P. Rhodes, B. J. Wiley, ACS Appl. Energy Mater. 2018,1, 5268.
[78] A. Maurel, M. Courty, B. Fleutot, H. Tortajada, K. Prashantha, M.
Armand, S. Grugeon, S. Panier, L. Dupont, Chem. Mater. 2018,30,
7484.
[79] C. W. Foster, G. Q. Zou, Y. Jiang, M. P. Down, C. M. Liauw, A. Garcia-
Miranda Ferrari, X. Ji, G. C. Smith, P. J. Kelly, C. E. Banks, Batteries
Supercaps 2019,2, 448.
[80] C. W. Foster, M. P. Down, Y. Zhang, X. Ji, S. J. Rowley-Neale, G. C.
Smith, P. J. Kelly, C. E. Banks, Sci. Rep. 2017,7, 42233.
[81] K. Fu, Y. Wang, C. Yan, Y. Yao, Y. Chen, J. Dai, S. Lacey, Y. Wang, J.
Wan, T. Li, Z. Wang, Y. Xu, L. Hu, Adv. Mater. 2016,28, 2587.
[82] C. Sun, S. Liu, X. Shi, C. Lai, J. Liang, Y. Chen, Chem. Eng. J. 2020,
381, 122641.
[83] T.-S. Wei, B. Yeop Ahn, J. Grotto, J. A. Lewis, Adv. Mater. 2018,30,
1703027.
[84] C. Liu, F. Xu, Y. Liu, J. Ma, P. Liu, D. Wang, C. Lao, Z. Chen, Elec-
trochim. Acta 2019,314, 81.
[85] W.He, C. Chen, J. Jiang, Z. Chen, H. Liao, H. Dou, X. Zhang, Batteries
Supercaps 2022,5, 202100258.
[86] J. Sha, Y. Li, R. Villegas Salvatierra, T. Wang, P. Dong, Y. Ji, S. K. Lee,
C. Zhang, J. Zhang, R. H. Smith, P. M. Ajayan, J. Lou, N. Zhao, J. M.
Tour , ACS Nano 2017,11, 6860.
[87] Y. T. Chen, F. Y. Hung, T. S. Lui, J. Z. Hong, Mater. Trans. 2017,58,
525.
[88] S. Guo, J. Li, L. Zhang, Y. Li, Mater. Lett. 2023,330, 133300.
[89] S. Lawes, Q. Sun, A. Lushington, B. Xiao, Y. Liu, X. Sun, Nano Energy
2017,36, 313.
[90] A. Kushwaha, M. K. Jangid, B. B. Bhatt, A. Mukhopadhyay, D. Gupta,
ACS Appl. Energy Mater. 2021,4, 7911.
[91] T.Chen,Y.Wang,Y.Yang,F.Huang,M.Zhu,B.T.W.Ang,J.M.Xue,
Adv. Funct. Mater. 2021,31, 2101607.
[92] A. Azhari, E. Marzbanrad, D. Yilman, E. Toyserkani, M. A. Pope, Car-
bon 2017,119, 257.
[93] J. Sha, R. V. Salvatierra, P. Dong, Y. Li, S. K. Lee, T. Wang, C. Zhang,
J. Zhang, Y. Ji, P. M. Ajayan, J. Lou, N. Zhao, J. M. Tour, ACS Appl.
Mater. Interfaces 2017,9, 7376.
[94] A. Maurel, S. Grugeon, B. Fleutot, M. Courty, K. Prashantha, H.
Tortajada, M. Armand, S. Panier, L. Dupont, Sci. Rep. 2019,9,
18031.
[95] X. Gao, X. Yang, S. Wang, Q. Sun, C. Zhao, X. Li, J. Liang, M. Zheng,
Y. Zhao, J. Wang, M. Li, R. Li, T. K. Sham, X. Sun, J. Mater. Chem. A
2019,8, 278.
[96] P. Bao, Y. Lu, P. Tao, B. Liu, J. Li, X. Cui, Ionics 2021,27, 2857.
[97] J. Hu, Y. Jiang, S. Cui, Y. Duan, T. Liu, H. Guo, L. Lin, Y. Lin, J. Zheng,
K. Amine, F. Pan, Adv. Energy Mater. 2016,6, 1600856.
[98] K. A. Acord, A. D. Dupuy, U. Scipioni Bertoli, B. Zheng, W. C. West,
Q. N. Chen, A. A. Shapiro, J. M. Schoenung, J. Mater. Process. Tech-
nol. 2021,288, 116827.
[99] Z. Shu, E. Beckert, R. Eberhardt, A. Tünnermann, J. Mater. Chem. C
2017,5, 11590.
[100] Y. Gu, A. Wu, H. Sohn, C. Nicoletti, Z. Iqbal, J. F. Federici, J. Manuf.
Process. 2015,20, 198.
[101] F. Xu, T. Wang, W. Li, Z. Jiang, Chem. Phys. Lett. 2003,375, 247.
[102] R. Rodriguez, L. J. Deiner, B. H. Tsao, J. P. Fellner, ACS Appl. Energy
Mater. 2021,4, 9507.
[103] L. J. Deiner, T. Jenkins, A. Powell, T. Howell, M. Rottmayer, Adv. Eng.
Mater. 2019,21, 1801281.
[104] C. Ke Sun, T.-S. Wei, B. Yeop Ahn, J. Yoon Seo, S. J. Dillon, J. A. Lewis,
Adv. Mater. 2013,25, 4539.
[105] S. Zekoll, C. Marriner-Edwards, A. K. O. Hekselman, J.
Kasemchainan, C. Kuss, D. E. J. Armstrong, D. Cai, R. J. Wallace, F.
H. Richter, J. H. J. Thijssen, P. G. Bruce, Energy Environ. Sci. 2018,
11, 185.
Small 2023,19, 2302718 © 2023 The Authors. Small published by Wiley-VCH GmbH
2302718 (41 of 44)
www.advancedsciencenews.com www.small-journal.com
[106] D. W. McOwen, S. Xu, Y. Gong, Y. Wen, G. L. Godbey, J. E. Gritton,
T. R. Hamann, J. Dai, G. T. Hitz, L. Hu, E. D. Wachsman, Adv. Mater.
2018,30, 1707132.
[107] Q. Chen, R. Xu, Z. He, K. Zhao, L. Pan, J. Electrochem. Soc. 2017,
164, A1852.
[108] Y. He, S. Chen, L. Nie, Z. Sun, X. Wu, W. Liu, Nano Lett. 2020,20,
7136.
[109] K. Lee, Y. Shang, V. A. Bobrin, R. Kuchel, D. Kundu, N. Corrigan, C.
Boyer, Adv. Mater. 2022,34, 2204816.
[110] D. Melodia, A. Bhadra, K. Lee, R. Kuchel, D. Kundu, N. Corrigan, C.
Boyer, Small 2023,12, 2206639.
[111] A. Maurel, M. Armand, S. Grugeon, B. Fleutot, C. Davoisne, H.
Tortajada, M. Courty, S. Panier, L. Dupont, J. Electrochem. Soc. 2020,
167, 070536.
[112] A. Vinegrad, H. Ragones, N. Jayakody, G. Ardel, M. Goor, Y.
Kamir, M. M. Dorfman, A. Gladkikh, L. Burstein, Y. Horowitz,
S. Greenbaum, D. Golodnitsky, J. Electrochem. Soc. 2021,168,
110549.
[113] H. Rupp, R. Bhandary, A. Kulkarni, W. Binder, Adv. Mater. Technol.
2022,7, 2200088.
[114] J. Bae, S. Oh, B. Lee, C. H. Lee, J. Chung, J. Kim, S. Jo, S. Seo, J. Lim,
S. Chung, Energy Storage Mater. 2023,57, 277.
[115] P. E. Delannoy, B. Riou, B. Lestriez, D. Guyomard, T. Brousse, J. L.
Bideau, J. Power Sources 2015,274, 1085.
[116] Y. Gambe, H. Kobayashi, K. Iwase, S. Stauss, I. Honma, Dalton Trans.
2021,50, 16504.
[117] A. J. Blake, R. R. Kohlmeyer, J. O. Hardin, E. A. Carmona, B.
Maruyama, J. D. Berrigan, H. Huang, M. F. Durstock, Adv. Energy
Mater. 2017,7, 1602920.
[118] M. Cheng, Y. Jiang, W. Yao, Y. Yuan, R. Deivanayagam, T. Foroozan, Z.
Huang, B. Song, R. Rojaee, T. Shokuhfar, Y. Pan, J. Lu, R. Shahbazian-
Yassar, Adv. Mater. 2018,30, 1800615.
[119] Z. Katcharava, A. Marinow, R. Bhandary, W. H. Binder, Nanomateri-
als 2022,12, 1859.
[120] H. Ragones, A. Vinegrad, G. Ardel, M. Goor, Y. Kamir, M. M.
Dorfman, A. Gladkikh, D. Golodnitsky, J. Electrochem. Soc. 2020,
167, 070503.
[121] L. J. Deiner, T. Jenkins, T. Howell, M. Rottmayer, Adv. Eng. Mater.
2019,21, 1900952.
[122] R. Wei, S. Chen, T. Gao, W. Liu, Nano Sel. 2021,2, 2256.
[123] H. Rupp, R. Bhandary, A. Kulkarni, W. Binder, Adv. Mater. Technol.
2022,7, 2200088.
[124] P. E. Delannoy, B. Riou, B. Lestriez, D. Guyomard, T. Brousse, J. L.
Bideau, J. Power Sources 2015,274, 1085.
[125] Z. Fang, J. Wang, H. Wu, Q. Li, S. Fan, J. Wang, J. Power Sources 2020,
454, 227932.
[126] W. Xu, S. Jambhulkar, Y. Zhu, D. Ravichandran, M. Kakarla, B.
Vernon, D. G. Lott, J. L. Cornella, O. Shefi, G. Miquelard-Garnier,
Y. Yang, K. Song, Composites, Part B 2021,223, 109102.
[127] J. Li, Q. Jiang, N. Yuan, J. Tang, Materials 2018,11, 2280.
[128] T.Liu, R. Yan, H. Huang, L. Pan, X. Cao, A. deMello, M. Niederberger,
Adv. Funct. Mater. 2020,30, 2004410.
[129] Y. Yang, S. Jeong, L. Hu, H. Wu, S. W. Lee, Y. Cui, Proc. Natl. Acad.
Sci. USA 2011,108, 13013.
[130] F. S. Gittleson, D. Hwang, W. H. Ryu, S. M. Hashmi, J. Hwang, T.
Goh, A. D. Taylor, ACS Nano 2015,9, 10005.
[131] S. Oukassi, L. Baggetto, C. Dubarry, L. le Van-Jodin, S. Poncet, R.
Salot, ACS Appl. Mater. Interfaces 2019,11, 683.
[132] S. Jambhulkar, D. Ravichandran, B. Sundaravadivelan, K. Song, I. A.
Fulton, J. Mater. Chem. C 2023,11, 4333.
[133] J.-W. Choi, Y. Hwang, H. Yim, in Fabrication of transparent all-solid-
state thin film lithium ion battery,2022.
[134] H. Lee, H. Yim, K. B. Kim, J. W. Choi, J. Nanosci. Nanotechnol. 2015,
15, 8627.
[135] X. Zhang, T. Liu, S. Zhang, X. Huang, B. Xu, Y. Lin, B. Xu, L. Li, C. W.
Nan, Y. Shen, J. Am. Chem. Soc. 2017,139, 13779.
[136] Y. J. Shen, M. J. Reddy, P. P. Chu, Solid State Ionics 2004,175, 747.
[137] T. Zheng, Z. Jia, N. Lin, T. Langer, S. Lux, I. Lund, A. C. Gentschev,
J. Qiao, G. Liu, Polymers 2017,9, 657.
[138] L. Ma, D. Lu, P. Yang, X. Xi, R. Liu, D. Wu, Electrochim. Acta 2019,
319, 201.
[139] J. Wan, J. Xie, X. Kong, Z. Liu, K. Liu, F. Shi, A. Pei, H. Chen, W. Chen,
J. Chen, X. Zhang, L. Zong, J. Wang, L. Q. Chen, J. Qin, Y. Cui, Nat.
Nanotechnol. 2019,14, 705.
[140] Z. Ren, Y. Liu, K. Sun, X. Zhou, N. Zhang, Electrochim. Acta 2009,
54, 1888.
[141] B. Sun, J. Mindemark, K. Edström, D. Brandell, Solid State Ionics
2014,262, 738.
[142] J. Wu, K. Jiang, G. Li, Z. Zhao, Q. Li, F. Geng, Adv. Funct. Mater. 2019,
29, 1901576.
[143] L. Shen, Q. Dong, G. Zhu, Z. Dai, Y. Zhang, W. Wang, X. Dong, Adv.
Mater. Interfaces 2018,5, 1800362.
[144] T. Liu, M. Zhang, Y. L. Wang, Q. Y. Wang, C. Lv, K. X. Liu, S. Suresh,
Y. H. Yin, Y. Y. Hu, Y. S. Li, X. Bin Liu, S. W. Zhong, B. Y. Xia, Z. P. Wu,
Adv. Energy Mater. 2018,8, 1802349.
[145] K. Zhu, Y. Luo, F. Zhao, J. Hou, X. Wang, H. Ma, H. Wu, Y. Zhang,
K. Jiang, S. Fan, J. Wang, K. Liu, ACS Sustainable Chem. Eng. 2018,
6, 3426.
[146] S. Jambhulkar, W. Xu, R. Franklin, D. Ravichandran, Y. Zhu, K. Song,
J. Mater. Chem. C 2020,8, 9495.
[147] T. Jiang, F. Bu, X. Feng, I. Shakir, G. Hao, Y. Xu, ACS Nano 2017,11,
5140.
[148] R. Mo, D. Rooney, K. Sun, H. Y. Yang, Nat. Commun. 2017,8, 13949.
[149] W. Xi, Y. Zhang, J. Zhang, R. Wang, Y. Gong, B. He, H. Wang, J. Jin,
J. Mater. Chem. C 2023,11, 2414.
[150] K. Zhu, H. Zhang, K. Ye, W. Zhao, J. Yan, K. Cheng, G. Wang, B. Yang,
D. Cao, ChemElectroChem 2017,4, 3018.
[151] X. Zheng, H. Lee, T. H. Weisgraber, M. Shusteff, J. DeOtte, E.
B. Duoss, J. D. Kuntz, M. M. Biener, Q. Ge, J. A. Jackson, S. O.
Kucheyev, N. X. Fang, C. M. Spadaccini, Science 2014,344, 1373.
[152] R. Kumar, S. K. Sarangi, in Int. Conf. on Advances in Materials Pro-
cessing & Manufacturing Applications, Springer Science and Business
Media, Deutschland GmbH, Frankfurt, Germany 2021, pp. 531–538.
[153] W. Wu, P. Geng, G. Li, D. Zhao, H. Zhang, J. Zhao, Materials 2015,
8, 5834.
[154] J. A. Lewis, Adv. Funct. Mater. 2006,16, 2193.
[155] G. M. Gratson, F. García-Santamaría, V. Lousse, M. Xu, S. Fan, J. A.
Lewis, P. v. Braun, Adv. Mater. 2006,18, 461.
[156] C. M. S. Vicente, M. Sardinha, L. Reis, A. Ribeiro, M. Leite, Prog.
Addit. Manuf. 2023,8,1.
[157] A. Sharif, N. Farid, P. McGlynn, M. Wang, R. K. Vijayaraghavan, A.
Jilani, G. Leen, P. J. McNally, G. M. O’Connor, J. Phys. D: Appl. Phys.
2023,56, 075102.
[158] B. Gao, H. Zhao, L. Peng, Z. Sun, Micromachines 2022,14, 57.
[159] P. Goldberg-Oppenheimer, D. Eder, U. Steiner, Adv. Funct. Mater.
2011,21, 1895.
[160] I. Liashenko, J. Rosell-Llompart, A. Cabot, Nat. Commun. 2020,11,
753.
[161] A. Maurel, A. C. Martinez, S. Grugeon, S. Panier, L. Dupont, P.
Cortes, C. G. Sherrard, I. Small, S. T. Sreenivasan, E. MacDonald,
IEEE Access 2021,9, 140654.
[162] J. U. Park, M. Hardy, S. J. Kang, K. Barton, K. Adair, D. K.
Mukhopadhyay, C. Y. Lee, M. S. Strano, A. G. Alleyne, J. G.
Georgiadis, P. M. Ferreira, J. A. Rogers, Nat. Mater. 2007,6, 782.
[163] S. Zekoll, C. Marriner-Edwards, A. K. O. Hekselman, J.
Kasemchainan, C. Kuss, D. E. J. Armstrong, D. Cai, R. J. Wallace, F.
H. Richter, J. H. J. Thijssen, P. G. Bruce, Energy Environ. Sci. 2018,
11, 185.
Small 2023,19, 2302718 © 2023 The Authors. Small published by Wiley-VCH GmbH
2302718 (42 of 44)
www.advancedsciencenews.com www.small-journal.com
[164] K. Sachsenheimer, C. Richter, D. Helmer, F. Kotz, B. E. Rapp, Micro-
machines 2019,10, 588.
[165] A. Yadav, B. De, S. K. Singh, P. Sinha, K. K. Kar, ACS Appl. Mater.
Interfaces 2019,11, 7974.
[166] L. Zeng, H. Xi, X. Liu, C. Zhang, Nanomaterials 2021,11, 3454.
[167] D. Ji, H. Zheng, H. Zhang, W. Liu, J. Ding, Chem. Eng. J. 2022,433,
133815.
[168] M. Rafiee, F. Granier, D. Therriault, Adv. Mater. Technol. 2021,6,
2100356.
[169] D. Ravichandran, W. Xu, M. Kakarla, S. Jambhulkar, Y. Zhu, K. Song,
Addit. Manuf. 2021,47, 102322.
[170] M. A. Skylar-Scott, J. Mueller, C. W. Visser, J. A. Lewis, Nature 2019,
575, 330.
[171] A. Maurel, Thermoplastic Composite Filaments Formulation and 3D-
Printing of a Lithium-Ion Battery via Fused Deposition Modeling,Uni-
versitédePicardieJulesVerne,Amiens,France2020.
[172] V. L. Deringer, J. Phys.: Condens. Matter. 2020,2, 041003.
[173] H. Ko, Y. Lu, Z. Yang, N. Y. Ndiaye, P. Witherell, J. Manuf. Syst. 2023,
67, 213.
[174] M. Mani, B. Lane, A. Donmez, S. Feng, S. Moylan, R. Fesperman,
NIST Interagency/Internal Report (NISTIR), National Institute of
Standards and Technology, Gaithersburg, MD, https://doi.org/10.
6028/NIST.IR.8036 (accessed: March 2015).
[175] T. G. Spears, S. A. Gold, Integr. Mater. Manuf. Innovation 2016,5, 16.
[176] B. Lane, H. Yeung, J. Res. Natl. Inst. Stand. Technol. 2021,125,
125027.
[177] E. Brinksmeier, S. Reese, A. Klink, L. Langenhorst, T. Lübben, M.
Meinke, D. Meyer, O. Riemer, J. Sölter, Nanomanuf. Metrol. 2018,1,
193.
[178] V. Sandfort, K. Yan, P. J. Pickhardt, R. M. Summers, Nature 2019,9,
16884.
[179] A. Sancarlos, M. Cameron, A. Abel, E. Cueto, J. L. Duval, F. Chinesta,
Arch. Comput. Methods Eng. 2021,28, 979.
[180] Z. Wei, Q. He, Y. Zhao, J. Power Sources 2022,549, 232125.
[181] A. Adadi, M. Berrada, IEEE Access 2018,6, 52138.
[182] H. Ko, P. Witherell, Y. Lu, S. Kim, D. W. Rosen, Addit. Manuf. 2021,
37, 101620.
[183] P. Xu, D. H. S. Tan, B. Jiao, H. Gao, X. Yu, Z. Chen, Adv. Funct. Mater.
2023,33, 2213168.
[184] K. K. Jena, A. Alfantazi, A. T. Mayyas, EnergyFuels 2021,35,
18257.
[185] Y. Huang, Z. Qin, C. Shan, Y. Xie, X. Meng, D. Qian, G. He, D. Mao,
L. Wan, J. Energy Chem. 2023,80, 492.
[186] H. Wang, S. Burke, R. Yuan, J. F. Whitacre, J. Energy Storage 2023,
60, 106616.
[187] G. Ji, J. Wang, Z. Liang, K. Jia, J. Ma, Z. Zhuang, G. Zhou, H. M.
Cheng, Nature 2023,14, 584.
[188] Y. Yang, X. Meng, H. Cao, X. Lin, C. Liu, Y. Sun, Y. Zhang, Z. Sun,
Green Chem. 2018,20, 3121.
[189] J. Zhang, J. Hu, Y. Liu, Q. Jing, C. Yang, Y. Chen, C. Wang, ACS Sus-
tainable Chem. Eng. 2019,7, 5626.
[190] L. X. Yuan, Z. H. Wang, W. X. Zhang, X. L. Hu, J. T. Chen, Y.H. Huang,
J. B. Goodenough, Energy Environ. Sci. 2011,4, 269.
[191] W. Lv, X. Zheng, L. Li, H. Cao, Y. Zhang, R. Chen, H. Ou, F. Kang, Z.
Sun, Front. Chem. Sci. Eng. 2021,15, 1243.
[192] Y. Li, W. Lv, H. Huang, W. Yan, X. Li, P. Ning, H. Cao, Z. Sun, Green
Chem. 2021,23, 6139.
[193] Z. Lianqi, G. Jian, Z. Enlou, CN105742743A, 2016.
[194] S. Natarajan, K. Subramanyan, R. B. Dhanalakshmi, A. M. Stephan,
V. Arav i n d a n, Batteries Supercaps 2020,3, 581.
[195] F. Larouche, F. Tedjar, K. Amouzegar, G. Houlachi, P. Bouchard, G.
P. Demopoulos, K. Zaghib, Materials 2020,13, 801.
[196] J. Dunn, A. Kendall, M. Slattery, Resour., Conserv. Recycl. 2022,185,
106488.
[197] M. Chen, X. Ma, B. Chen, R. Arsenault, P. Karlson, N. Simon, Y.
Wan g, Joule 2019,3, 2622.
[198] S. Vangala, B. Casagranda, Clim. Energy 2023,39, 19.
[199] L. Albertsen, J. L. Richter, P. Peck, C. Dalhammar, A. Plepys, Resour.,
Conserv. Recycl. 2021,172, 105658.
[200] N. O. Bonsu, J. Cleaner Prod. 2020,256, 120659.
[201] W. A. Shaikh, M. A. Kalwar, M. A. Khan, A. Nawaz Wassan, M.
Hussain Wadho, M. Faisal Shahzad, Jordan J. Mech. Ind. Eng. 2023,
17, 19956665.
[202] Y. Deng, Y. Mu, X. Wang, S. Jin, K. He, H. Jia, S. Li, J. Zhang, Energy
Rep. 2023,9, 337.
[203] V. M. Leal, J. S. Ribeiro, E. L. D. Coelho, M. B. J. G. Freitas, J. Energy
Chem. 2023,79, 118.
[204] V. E. O. Santos, V. G. Celante, M. F. F. Lelis, M. B. J. G. Freitas, J.
Power Sources 2012,218, 435.
[205] S. yin Tan, D. J. Payne, J. P. Hallett, G. H. Kelsall, Curr. Opin. Elec-
trochem. 2019,16, 83.
[206] X. Yu, W. Li, V. Gupta, H. Gao, D. Tran, S. Sarwar, Z. Chen, Global
Challenges 2022,6, 2200099.
[207] C. M. Costa, J. C. Barbosa, R. Gonçalves, H. Castro, F. J. D. Campo,
S. Lanceros-Méndez, Energy Storage Mater. 2021,37, 433.
[208] L. Lander, T. Cleaver, M. A. Rajaeifar, V. Nguyen-Tien, R. J. R. Elliott,
O. Heidrich, E. Kendrick, J. S. Edge, G. Offer, iScience 2021,24,
102787.
[209] F. Momeni, J. Ni, Engineering 2020,6, 1035.
[210] D. Ravichandran, M. Kakarla, W. Xu, S. Jambhulkar, Y. Zhu, M.
Bawareth, N. Fonseca, D. Patil, K. Song, Composites, Part B 2022,
247, 110352.
[211] D. Ravichandran, R. J. Ahmed, R. Banerjee, M. Ilami, H. Marvi, G.
Miquelard-Garnier, Y. Golan, K. Song, J. Mater. Chem. C 2022,10,
13762.
[212] H. Wei, Q. Zhang, Y. Yao, L. Liu, Y. Liu, J. Leng, ACS Appl. Mater.
Interfaces 2017,9, 876.
[213] J. C. Breger, C. Yoon, R. Xiao, H. R. Kwag, M. O. Wang, J. P. Fisher, T.
D.Nguyen,D.H.Gracias,ACS Appl. Mater. Interfaces 2015,7, 3398.
[214] L. K. Rivera-Tarazona, T. Shukla, K. Abhay Singh, A. K. Gaharwar, Z.
T. Ca m p b e ll, T. H. W are, Adv. Funct. Mater. 2022,32, 2106843.
[215] C. Cui, L. An, Z. Zhang, M. Ji, K. Chen, Y. Yang, Q. Su, F. Wang, Y.
Cheng, Y. Zhang, Adv. Funct. Mater. 2022,32, 2203720.
[216] Y. Wang, C. Chen, H. Xie, T. Gao, Y. Yao, G. Pastel, X. Han, Y. Li, J.
Zhao, K. Fu, L. Hu, Adv. Funct. Mater. 2017,27, 1703140.
[217] S. Weng, X. Kuang, Q. Zhang, C. M. Hamel, D. J. Roach, N. Hu, H.
Jerry Qi, ACS Appl. Mater. Interfaces 2021,13, 12797.
[218] P. Rewatkar, P. K. Enaganti, M. Rishi, S. Mukhopadhyay, S. Goel, Int.
J. Hydrogen Energy 2021,46, 35408.
[219] H. He, L. Zeng, D. Luo, J. He, X. Li, Z. Guo, C. Zhang, Adv. Mater.
2023,35, 2211498.
[220] L. Zeng, H. He, H. Chen, D. Luo, J. He, C. Zhang, Adv. Energy Mater.
2022,12, 2103708.
[221] K. Sirengo, A. Babu, B. Brennan, S. C. Pillai, J. Energy Chem. 2023,
81, 321.
[222] W. Wang, C. Li, S. Liu, J. Zhang, D. Zhang, J. Du, Q. Zhang, Y. Yao,
W. Wang, C. Li, S. Liu, Y. Yao, J. Zhang, D. Zhang, J. Du, Q. Zhang,
Adv. Energy Mater. 2023,13, 2300250.
[223] Y. Ren, F. Meng, S. Zhang, B. Ping, H. Li, B. Yin, T. Ma, Carbon Energy
2022,4, 446.
[224] M. Zhang, L. Pan, Z. Jin, X. Wang, H. Mei, L. Cheng, L. Zhang, Adv.
Energy Mater. 2023,13, 2204058.
[225] H. Lu, J. Hu, Y. Zhang, K. Zhang, X. Yan, H. Li, J. Li, Y. Li, J. Zhao, B.
Xu, Adv. Mater. 2023,35, 2209886.
[226] G. Zhang, X. Zhang, H. Liu, J. Li, Y. Chen, H. Duan, Adv. Energy
Mater. 2021,11, 2003927.
[227] M. Zhang, T. Hu, X. Wang, P. Chang, Z. Jin, L. Pan, H. Mei, L. Cheng,
L. Zhang, J. Mater. Chem. A 2022,10, 7195.
Small 2023,19, 2302718 © 2023 The Authors. Small published by Wiley-VCH GmbH
2302718 (43 of 44)
www.advancedsciencenews.com www.small-journal.com
[228] X. Gao, K. Liu, C. Su, W. Zhang, Y. Dai, I. P. Parkin, C. J. Carmalt, G.
He, SmartMat 2023,3, e1197.
[229] G. Zhang, X. Zhang, H. Liu, J. Li, Y. Chen, H. Duan, Adv. Energy
Mater. 2021,11, 2003927.
[230] J. Ma, S. Zheng, L. Chi, Y. Liu, Y. Zhang, K. Wang, Z.-S. Wu, J. Ma, S.
Zheng, L. Chi, Y. Liu, Y. Zhang, Z.-S. Wu, K. Wang, Adv. Mater. 2022,
34, 2205569.
[231] Z. Li, Y. Gao, H. Huang, W. Wang, J. Zhang, Q. Yu, Composites, Part
B2023,258, 110712.
[232] J. Zheng, C. Hu, L. Nie, H. Chen, S. Zang, M. Ma, Q. Lai, Adv. Mater.
Technol. 2023,8, 2201591.
[233] M. Shi, T. Li, H. Shang, D. Zhang, H. Qi, T. Huang, Z. Xie, J. Qi, F.
Wei, Q. Meng, B. Xiao, Q. Yin, Y. Li, D. Zhao, X. Xue, Y. Sui, J. Energy
Storage 2023,68, 107765.
[234] Z. Li, J. Häcker, M. Fichtner, Z. Zhao-Karger, Adv. Energy Mater.
2023,13, 2300682.
[235] Z. Huang, X. Du, M. Ma, S. Wang, Y. Xie, Y. Meng, W. You, L. Xiong,
ChemSusChem 2023,16, 202202358.
[236] V. Verma, S. Kumar, W. Manalastas, R. Satish, M. Srinivasan, Adv.
Sustainable Syst. 2019,3, 1800111.
[237] X. Wang, R. Xiao, H. Li, L. Chen, J. Materiomics 2017,3, 178.
[238] M. Attarian Shandiz, R. Gauvin, Comput. Mater. Sci. 2016,117, 270.
[239] R. A. Eremin, P. N. Zolotarev, O. Y. Ivanshina, I. A. Bobrikov, J. Phys.
Chem. C 2017,121, 28293.
[240] O. Allam, B. W. Cho, K. C. Kim, S. S. Jang, RSC Adv. 2018,8, 39414.
[241] R. Jalem, K. Kanamori, I. Takeuchi, M. Nakayama, H. Yamasaki, T.
Saito, Sci. Rep. 2018,8, 5845.
[242] B. Liu, J. Yang, H. Yang, C. Ye, Y. Mao, J. Wang, S. Shi, J. Yang, W.
Zhang, J. Mater. Chem. A 2019,7, 19961.
[243] M. Dixit, N. Muralidharan, A. Bisht, C. J. Jafta, C. T. Nelson, R. Amin,
R. Essehli, M. Balasubramanian, I. Belharouak, ACS Energy Lett.
2023,5, 2356.
[244] R. Car, Quant. Struct.-Act. Relat. 2002,21, 97.
[245] T. Hansson, C. Oostenbrink, W. F. Van Gunsteren, Curr. Opin. Struct.
Biol. 2002,12, 190.
[246] T. P. Fries, T. Belytschko, Int. J. Numer. Methods Eng. 2010,84, 253.
[247] J. T. Katsikadelis, M. S. Nerantzaki, Eng. Anal. Boundary Elem. 1999,
23, 365.
[248] B. Regassa Hunde, A. Debebe Woldeyohannes, Results Eng. 2022,
14, 100478.
[249] K. J. Prabuchandran, S. Penubothula, C. Kamanchi, S. Bhatnagar,
Appl. Intell. 2021,51, 1565.
[250] S. Lang, T. Reggelin, J. Schmidt, M. Müller, A. Nahhas, Expert Syst.
Appl. 2021,172, 114666.
[251] J. M. Tarascon, Nat. Mater. 2022,21, 979.
[252] M. Zheng, H. Salim, T. Liu, R. A. Stewart, J. Lu, S. Zhang, Energy
Environ. Sci. 2021,14, 5801.
[253] S. Haghi, M. F. V. Hidalgo, M. F. Niri, R. Daub, J. Marco, Batteries
Supercaps 2023,6, 202300046.
[254] A. Pregowska, M. Osial, W. Urba´
nska, Recycling 2022,7,81.
Nathan Fonseca, currently a Ph.D. student at Arizona State University (ASU), is under the guidance
of Prof. Kenan Song. He completed his B.S. in engineering with a specialization in mechanical en-
gineering systems at ASU in 2018. Nathan’s research encompasses several areas, including addi-
tive manufacturing for improved performance in energy storage devices, sensing, textiles, and co-
design/manufacturing strategies. Presently,his primary focus lies in developing a novel approach to
3D printing interdigitated batteries using co-axial printing. This technique aims to enhance the ionic
kinetic energy within energy storage devices by enabling the deposition of the battery in a single pro-
cess.
Kenan Song is currently holding an associate professor position at the University of Georgia (UGA)
and is affiliated with Arizona State University.Dr. Song’s research interest includes the processing-
structure-property relationships, especially advanced manufacturing, characterization, simulation,
and application of polymer-based nanoparticle-filled composites for energy,sustainability, health,
and smart systems. Kenan Song has been the recipient of the NSF CAREER Award (2022), ACS PMSE
Young Investigator Award (2022), SAMPE North America Young Professionals Emerging Leadership
Award (YPELA) (2022), and DHS New Investigator Award (NIA).
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