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Lithium-Ion, Lithium Metal and Alternative Rechargeable Battery Technologies: The Odyssey for High Energy Density

  • Mercedes-Benz AG
  • Fraunhofer FFB
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Abstract and Figures

Since their market introduction in 1991, lithium ion batteries (LIBs) have developed evolutionary in terms of their specific energies (Wh/kg) and energy densities (Wh/L). Currently, they do not only dominate the small format battery market for portable electronic devices, but have also been successfully implemented as the technology of choice for electromobility as well as for stationary energy storage. Besides LIBs, a variety of different technologically promising battery concepts exists that, depending on the respective technology, might also be suitable for various application purposes. These systems of the “next generation,” the so-called post-lithium ion batteries (PLIBs), such as metal/sulfur, metal/air or metal/oxygen, or “post-lithium technologies” (systems without Li), which are based on alternative single (Na⁺, K⁺) or multivalent ions (Mg²⁺, Ca²⁺), are currently being studied intensively. From today’s point of view, it seems quite clear that there will not only be a single technology for all applications (technology monopoly), but different battery systems, which can be especially suitable or combined for a particular application (technology diversity). In this review, we place the lithium ion technology in a historical context and give insights into the battery technology diversity that evolved during the past decades and which will, in turn, influence future research and development.
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Lithium ion, lithium metal, and alternative rechargeable battery
technologies: the odyssey for high energy density
Tobias Placke
&Richard Kloepsch
&Simon Dühnen
&Martin Winter
Received: 20 March 2017 /Accepted: 17 April 2017 /Published online: 17 May 2017
#Springer-Verlag Berlin Heidelberg 2017
Abstract Since their market introduction in 1991, lithium ion
batteries (LIBs) have developed evolutionary in terms of their
specific energies (Wh/kg) and energy densities (Wh/L).
Currently, they do not only dominate the small format battery
market for portable electronic devices, but have also been
successfully implemented as the technology of choice for
electromobility as well as for stationary energy storage.
Besides LIBs, a variety of different technologically promising
battery concepts exists that, depending on the respective tech-
nology, might also be suitable for various application pur-
poses. These systems of the Bnext generation,^the so-called
post-lithium ion batteries (PLIBs), such as metal/sulfur, metal/
air or metal/oxygen, or Bpost-lithium technologies^(systems
without Li), which are based on alternative single (Na
multivalent ions (Mg
), are currently being studied
intensively. From todays point of view, it seems quite clear
that there will not only be a single technology for all applica-
tions (technology monopoly), but different battery systems,
which can be especially suitable or combined for a particular
application (technology diversity). In this review, we place the
lithium ion technology in a historical context and give insights
into the battery technology diversity that evolved during the
past decades and which will, in turn, influence future research
and development.
Keywords Lithium ion batteries .Lithium metal batteries .
Post-lit hium ion batteries .Energydensity .History of batteries
One of todays most challenging issues of mankind is the
preservation of a consistent energy supply that is able to meet
the worlds increasing energy demands. The development of
novel technologies is of utmost importance to ensure sustain-
able long-term energy generation, conversion and storage.
The present Benergy economy^is considered to be at serious
risk as it is still and to a large extent depending on fossil fuels.
This risk concern gives rise to the development of renewable
energies such as wind or solar power. This trend is not only
due to the increasing shortages of non-renewable (fossil) re-
sources, but also related to the growing concerns about the
environmental impact of fossil fuel combustion products in-
cluding global warming and (air) pollution. Beijing has be-
come famous as just one representative for a vast number of
metropolitan cities where the people strongly suffer from the
high air pollution by smoke and fog, better known as smog. It
has been known for quite some time that air pollutants such as
ozone or fine dust particles are harmful to health. According to
the most recent estimates of the international energy agency
(IEA), more than six million people worldwide die from the
consequences of combustion exhaust gases per year [1].
One major strategy to tackle these immense problems lies
in the integration of clean and efficient energy storage from
renewables into different energy sectors such as transportation
and stationary storage. Electrochemical energy storage in the
form of rechargeable batteries is the most efficient and feasible
solution for various types of storage applications, for small-
scale as well as large-scale utilization. The lithium ion tech-
nology revolutionized energy storage since its market
*Tobias Placke
*Martin Winter;
MEET Battery Research Center, Institute of Physical Chemistry,
University of Münster, Corrensstr. 46, 48149 Münster, Germany
Helmholtz Institute Münster, IEK-12, Forschungszentrum Jülich
GmbH, Corrensstr. 46, 48149 Münster, Germany
J Solid State Electrochem (2017) 21:19391964
DOI 10.1007/s10008-017-3610-7
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
... Since the aforementioned LIB types have already reached a high level of maturity, substantial further improvements regarding specific energy or energy density are not expected (Duffner et al. 2021b;Placke et al. 2017). This is contrary to the ambition of using lightweight and small traction batteries that enable long ranges over a long lifetime at moderate costs. ...
... Therefore, new battery technologies that enable a higher specific energy and energy density, as well as cause fewer safety issues, are required. Two promising technologies are LSBs and ASSBs (Duffner et al. 2021b;Placke et al. 2017). Figure 1 depicts the main differences between LIBs, LSBs, and ASSBs. ...
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Purpose Traction batteries are a key component for the performance and cost of electric vehicles. While they enable emission- free driving, their supply chains are associated with environmental and socio-economic impacts. Hence, the advancement of batteries increasingly focuses on sustainability next to technical performance. However, due to different system definitions, comparing the results of sustainability assessments is difficult. Therefore, a sustainability assessment of different batteries on a common basis considering the three sustainability dimensions is needed. Methods This paper investigates the sustainability of current and prospective traction battery technologies for electric vehicles. It provides a common base for the comparison of the predominant lithium-ion batteries with new technologies such as lithium-sulfur and all-solid-state batteries regarding the environmental and socio-economic impacts in their supply chain. A life cycle sustainability assessment of ten battery types is carried out using a cradle-to-gate perspective and consistent system boundaries. Four environmental impact categories (climate change, human toxicity, mineral resource depletion, photochemical oxidant formation), one economic performance indicator (total battery cost), and three social risk categories (child labor, corruption, forced labor) are analyzed. Results The assessment results indicate that the new battery technologies are not only favorable in terms of technical performance but also have the potential to reduce environmental impacts, costs, and social risks. This holds particularly for the lithium-sulfur battery with solid electrolyte. The environmental benefits are even amplified with a higher share of renewable energy for component and battery production. Nevertheless, hotspots related to the high energy demand of production and the supply chain of the active materials remain. Conclusions This article emphasizes the need to evaluate different battery technologies on a common basis to ensure comparability of the results and to derive reliable recommendations. The results indicate that the lithium-sulfur battery with solid electrolyte is preferable since this battery has the best indicator scores for all impact categories investigated. However, all-solid-state batteries are still under development so that no conclusive recommendation can be made, but further development of these battery technologies appears promising.
... Over the past few decades, electric vehicles have boomed with lithium-ion batteries that have high energy contents of 260 Wh kg −1 or 700 Wh L −1 at the cell level and higher efficiencies (>99%) [240]. The cathode seems critical in achieving these energy densities with high reversible specific capacities and discharge potentials vs. Li/Li + . ...
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Among the current battery technologies, lithium-ion batteries (LIBs) are essential in shaping future energy landscapes in stationary storage and e-mobility. Among all components, choosing active cathode material (CAM) limits a cell’s available energy density (Wh kg−1), and the CAM selection becomes critical. Layered Lithium transition metal oxides, primarily, LiNixMnyCozO2 (NMC) (x + y + z = 1), represent a prominent class of cathode materials for LIBs due to their high energy density and capacity. The battery performance metrics of NMC cathodes vary according to the different ratios of transition metals in the CAM. The non-electrode factors and their effect on the cathode performance of a lithium-ion battery are as significant in a commercial sense. These factors can affect the capacity, cycle lifetime, thermal safety, and rate performance of the NMC battery. Additionally, polycrystalline NMC comprises secondary clusters of primary crystalline particles prone to pulverization along the grain boundaries, which leads to microcrack formation and unwanted side reactions with the electrolyte. Single-crystal NMC (SC-NMC) morphology tackles the cycling stability issue for improved performance but falls short in enhancing capacity and rate capability. The compatibility of different combinations of electrolytes and additives for SC-NMC is discussed, considering the commercial aspects of NMC in electric vehicles. The review has targeted the recent development of non-aqueous electrolyte systems with various additives and aqueous and non-aqueous binders for NMC-based LIBs to stress their importance in the battery chemistry of NMC.
... In the present scenario, portable energy storage devices like batteries seem to be an innate choice to provide a ubiquitous energy solution. However, from the wearable electronics point of view, the adoption of battery is quite difficult, since it has a rigid and bulky structure that makes it unfit at skin interfaces [160], contains toxic electrochemicals that may restrict their bio-integrated application [161], shows irreversible chemical reaction, has low specific power, inferior charge discharge rate capability, and limited lifetime [162][163][164][165]. Therefore, a ubiquitous, environmentally acceptable, and sustainable energy solution is very desirable. ...
“Smart textiles”, also known as functional fabrics or e-textiles, are changing the way of thinking about fabrics. The term “functional textiles” refers to textiles with integrated functions that control or adjust according to the application. Nowadays, electronics and photonics have greatly influenced the evolution of technical textiles. Smart textiles are functional fabrics integrated with a sensor array or functional nanomaterial/polymer or an optical fibre. Various fibres (conductive and high-performance), chemicals/additives (finishing and coating chemicals, smart polymers, nanomaterials, etc.) and technologies (spinning, weaving, knitting, nonwoven, braiding, finishing, coating, lamination, etc.) are combined to create smart fabrics, depending on their use. This chapter covers all the main areas of applications of smart and functional textiles, including textiles with various functionalities (antimicrobial, UV-resistant, fireretardant, oil/water-repellent, stain-repellent, wrinkle-resistant, anti-order, antistatic, superabsorbent, etc.), coated/laminated high-performance textiles, conductive textiles, textile-based sensors, energy-harvesting textiles, medical textiles, protective textiles, textiles for military and defence, automotive textiles, and so on. This chapter also discusses the potential of emerging 3D printing technologies for making smart and functional textiles. Finally, the current challenges as well as future perspectives of functional and smart textiles have also been summarized.
... Lithium ion batteries (LIBs) are state-of-the-art electrochemical energy storage technology, currently dominating the market for portable electronic devices and electromobility. 1 Besides the improvement of battery performance, the sustainability of LIBs production is drawing great attention, with respect to not only the raw materials but also the processing. 2−4 To that regard, aqueous processing is of great interest to reduce the environmental impact of LIBs production, e.g., reduce CO 2 emissions and carbon footprint, compared to conventional manufacturing, employing organic solvents such as hazardous N-methyl-2-pyrrolidione (NMP). ...
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To fabricate ceramic composite cathodes LiCoO 2 − Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 (LCO-LLZTO) on an industrial scale, a water-based tape-casting process was developed, which is scalable and environmentally friendly. Additionally, the cosintering behavior of the two materials, often leading to poor electrochemical performance , was optimized via a Li 2 O-rich atmosphere. The resulting dense, free-standing, and phase-pure LCO-LLZTO mixed cathodes were assembled into full cells using a dual-layer solid polymer-ceramic separator and an In−Li anode. These cells show very high utilization rates for LCO of approximately 90% at a high areal capacity of over 3 mAh cm −2 , demonstrating the potential of water-based tape-casting for a scalable and sustainable manufacturing of oxide-ceramic based solid-state Li batteries.
The direct correlation between the surface area of the current collector (CC) and the ‘dead Li’ is evaluated in this study.
Polymer composite electrolytes (PCEs), i.e., materials combining the disciplines of polymer chemistry, inorganic chemistry, and electrochemistry, have received tremendous attention within academia and industry for lithium‐based battery applications. While PCEs often comprise 3D micro‐ or nanoparticles, this review thoroughly summarizes the prospects of 2D layered inorganic, organic, and hybrid nanomaterials as active (ion conductive) or passive (nonion conductive) fillers in PCEs. The synthetic inorganic nanofillers covered here include graphene oxide, boron nitride, transition metal chalcogenides, phosphorene, and MXenes. Furthermore, the use of naturally occurring 2D layered clay minerals, such as layered double hydroxides and silicates, in PCEs is also thoroughly detailed considering their impact on battery cell performance. Despite the dominance of 2D layered inorganic materials, their organic and hybrid counterparts, such as 2D covalent organic frameworks and 2D metal–organic frameworks are also identified as tuneable nanofillers for use in PCE. Hence, this review gives an overview of the plethora of options available for the selective development of both the 2D layered nanofillers and resulting PCEs, which can revolutionize the field of polymer‐based solid‐state electrolytes and their implementation in lithium and post‐lithium batteries. This review summarizes the plethora of options available for the selective development of 2D layered inorganic, organic, and hybrid nanomaterials as active (ionically conductive) or passive (ionically non‐conductive conductive) fillers in polymer composite electrolytes, which has potential applications in the field of solid‐state lithium and post‐lithium batteries.
Lithium ion battery technology is the most promising energy storage system thanks to many advantages such as high capacity, cycle life, rate performance and modularity. Many transportation applications including marine, aerospace and railway have been utilizing lithium ion batteries. Likewise, there is a dramatic transition from conventional vehicles having internal combustion engines to electric vehicles (EVs). In this review, current lithium ion technology and electric vehicles are introduced. Furthermore, expected future technological advancements are discussed from the active materials to scalability. It can be summarized that consumers have three main concerns towards electric vehicles: range, charging time and life time. Possible solutions to overcome the range anxiety, charging time, and lifetime are exhibited from mostly material and cell design perspectives. Although it is possible to enlarge the volume of this review, the key subjects are presented by introducing the most current advancements which can be adapted to current production infrastructures. Those achievements in the battery level will transform the global transportation sector.
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The rapidly expanding field of nonaqueous multi-valent intercalation batteries offers a promising way to overcome safety, cost, and energy density limitations of state-of-the-art Li-ion battery technology. We present a critical and rigorous analysis of the increasing volume of multivalent battery research, focusing on a wide range of intercalation cathode materials and the mechanisms of multivalent ion insertion and migration within those frameworks. The present analysis covers a wide variety of material chemistries, including chalcogenides, oxides, and polyanions, highlighting merits and challenges of each class of materials as multivalent cathodes. The review underscores the overlap of experiments and theory, ranging from charting the design metrics useful for developing the next generation of MV-cathodes to targeted in-depth studies rationalizing complex experimental results. On the basis of our critical review of the literature, we provide suggestions for future multivalent cathode studies, including a strong emphasis on the unambiguous characterization of the intercalation mechanisms.
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Increasing electrode thickness, thus increasing the volume ratio of active materials, is one effective method to enable the development of high energy density Li-ion batteries. In this study, an energy density versus power density optimization of LiNi0.8Co0.15Al0.05O2 (NCA)/graphite cell stack was conducted via mathematical modeling. The energy density was found to have a maximum point versus electrode thickness (critical thickness) at given discharging C rates. The physics-based factors that limit the energy/power density of thick electrodes were found to be increased cell polarization and underutilization of active materials. The latter is affected by Li-ion diffusion in active materials and Li-ion depletion in the electrolyte phase. Based on those findings, possible approaches were derived to surmount the limiting factors. The improvement of the energy–power relationship in an 18,650 cell was used to demonstrate how to optimize the thick electrode parameters in cell engineering. Graphical Abstract
Die Lithium-Ionen-Batterie wird zukünftig zwei großtechnische Anwendungen dominieren: Hybrid- und Elektrofahrzeuge im Bereich zukünftiger Mobilitätsstrategien und Zwischenspeicher elektrischer Energie im Umfeld der Dezentralisierung der Energieerzeugung. Das vorliegende Fachbuch stellt das Speichersystem Lithium-Ionen-Batterien in all seinen Facetten vor. Nach einer Übersicht über die heute verfügbaren Speichersysteme werden die Komponenten einer Lithium-Ionen-Batterie - von den Anoden- und Kathodenmaterialien bis hin zu den notwendigen Dichtungen und Sensoren - ausführlich beschrieben; auch die Battery-Disconnect-Unit, das thermische Management und das Batterie-Management-System werden abgehandelt. Ein weiteres Kapitel behandelt die Fertigungsverfahren, die dazu notwendigen Anlagen und den Aufbau einer Fabrik zur Fertigung von Zelle und Batterie. Die beiden großen Anwendungsbereiche der Lithium-Ionen-Batterie-Technologie, also der Einsatz in Hybrid- und Elektrofahrzeugen und die Nutzung als Zwischenspeicher, werden ebenfalls dargestellt, bevor im letzten Kapitel Querschnittsthemen wie Recycling, Transport, elektrische und chemische Sicherheit oder Normung diskutiert werden. Ein umfangreiches Glossar schließt das Buch ab. Der Inhalt Einleitung.- Übersicht über die Speichersysteme / Batteriesysteme.- Lithium-Ionen Batterien.- Batterieproduktion.- Querschnittstehmen.- Batterieanwendungen.- Autorenverzeichnis.- Index. Die Zielgruppen Das Fachbuch wendet sich an alle Personen, die im Umfeld der Lithium-Ionen-Batterie tätig sind: Von Studierenden im Bereich der Energietechnik bis hin zum Geschäftsführer von Zulieferfirmen im Umfeld der Automobilindustrie. Der Herausgeber Dr. Reiner Korthauer, geboren 1955, hat nach dem Abitur Elektrotechnik an der Universität Hannover studiert, bevor er Mitarbeiter der Universität Paderborn wurde. Die Promotion erfolgte an der Johannes Kepler Universität Linz. Nach seiner Tätigkeit bei der Nixdorf Computer AG wurde er Mitarbeiter im ZVEI - Zentralverband Elektrotechnik‐ und Elektronikindustrie e.V. Dort ist er Geschäftsführer des Fachverbandes Transformatoren und Stromversorgungen und seit 2010 Herausgeber der Handbücher Elektromobilität.
Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium–air, lithium–sulfur and lithium–bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a ‘mediator-ion’ solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface.
Rechargeable Li-ion batteries with higher energy density are in urgent demand to address the global challenge of energy storage. In comparison with anode materials, the relatively low capacity of cathode oxides, which exhibit classical cationic redox activity, has become one of the major bottlenecks to reach higher energy density. Recently, anionic activity, such as oxygen redox reaction, has been discovered in the electrochemical processes, providing extra reversible capacity for certain transition-metal oxides. Consequently, a more complete understanding and precise controlling on anionic electrochemical activity in these high-capacity oxides have become a flourishing, yet challenging subject. This perspective highlights: (1) key features of the anionic electrochemical activities; (2) computational and experimental tools to characterize and quantify the anionic activity; (3) design principles that correlate the chemical and structural compositions with high reversible capacity to accelerate the discovery of novel cathode oxides for next generation Li-ion batteries.
The review summarizes the development of lithium ion batteries beginning with the research of the 1970–1980s which lead to modern intercalation type batteries. Following the history of lithium ion batteries, material developments are outlined with a look at cathode materials, electrolyte solutions and anode materials. Finally, with lithium sulfur and lithium oxygen batteries two post intercalation type lithium batteries are discussed. The focus of the material discussions lies on basic understanding, problems and opportunities related to the materials.
This year, the battery industry celebrates the 25th anniversary of the introduction of the lithium ion rechargeable battery by Sony Corporation. The discovery of the system dates back to earlier work by Asahi Kasei in Japan, which used a combination of lower temperature carbons for the negative electrode to prevent solvent degradation and lithium cobalt dioxide modified somewhat from Goodenough's earlier work. The development by Sony was carried out within a few years by bringing together technology in film coating from their magnetic tape division and electrochemical technology from their battery division. The past 25 years has shown rapid growth in the sales and in the benefits of lithium ion in comparison to all the earlier rechargeable battery systems. Recent work on new materials shows that there is a good likelihood that the lithium ion battery will continue to improve in cost, energy, safety and power capability and will be a formidable competitor for some years to come.