Pieremanuele Canepa

Pieremanuele Canepa
National University of Singapore | NUS · Department of Materials Science and Engineering

PhD

About

112
Publications
30,824
Reads
How we measure 'reads'
A 'read' is counted each time someone views a publication summary (such as the title, abstract, and list of authors), clicks on a figure, or views or downloads the full-text. Learn more
5,696
Citations
Additional affiliations
July 2015 - present
Lawrence Berkeley National Laboratory
Position
  • Research Associate
July 2013 - July 2015
Massachusetts Institute of Technology
Position
  • PostDoc Position
December 2012 - July 2013
Wake Forest University
Position
  • PostDoc Position
Education
August 2013
Massachusetts Institute of Technology
Field of study
  • Material Science
December 2011 - August 2013
Wake Forest University
Field of study
  • Materials Science
January 2009 - February 2012
University of Kent
Field of study
  • Physical Chemistry and Materials Science

Publications

Publications (112)
Article
Ge‐based hybrid perovskite materials have demonstrated great potential for Second Harmonic Generation (SHG) due to the geometry and lone‐pair induced non‐centrosymmetric structures. Here, we report a new family of hybrid three‐dimensional (3D) Ge‐based bromide perovskites A GeBr 3 , A = CH 3 NH 3 (MA), CH(NH 2 ) 2 (FA), Cs and FAGe 0.5 Sn 0.5 Br 3...
Article
Full-text available
Lithium and sodium (Na) mixed polyanion solid electrolytes for all-solid-state batteries display some of the highest ionic conductivities reported to date. However, the effect of polyanion mixing on the ion-transport properties is still not fully understood. Here, we focus on Na1+xZr2SixP3−xO12 (0 ≤ x ≤ 3) NASICON electrolyte to elucidate the role...
Article
Ge‐based hybrid perovskite materials have demonstrated great potential for Second Harmonic Generation (SHG) due to the geometry and lone‐pair induced non‐centrosymmetric structures. Here, we report a new family of hybrid three‐dimensional (3D) Ge‐based bromide perovskites A GeBr 3 , A = CH 3 NH 3 (MA), CH(NH 2 ) 2 (FA), Cs and FAGe 0.5 Sn 0.5 Br 3...
Article
The development of inexpensive batteries based on magnesium (Mg) chemistry will contribute remarkably toward developing high-energy-density storage systems that can be used worldwide. Significant challenges remain in developing practical Mg batteries, the chief of which is designing materials that can provide facile transport of Mg. In this review,...
Article
Full-text available
Facile ionic mobility within host frameworks is crucial to the design of high-energy-density batteries with high-power-densities, where the migration barrier (Em) is the governing factor. Here, we assess the accuracy and computational performance of generalized gradient approximation (GGA), the strongly constrained and appropriately normed (SCAN),...
Preprint
The development of energy storage technologies that are alternative to the state-of-the-art lithium-ion batteries but exhibit similar energy densities, lower cost and better safety, is an important step in ensuring a sustainable energy future. Electrochemical systems based on Calcium (Ca)-intercalation form such an alternative energy storage techno...
Preprint
A crucial ingredient in lithium (Li) and sodium (Na)-ion batteries (LIBs and NIBs) is the electrolytes. The use of Li-metal (Na-metal) as anode in liquid electrolyte LIBs (NIBs) is constrained by several issues including thermal runway and flammability, electrolyte leakage, and limited chemical stability. Considerable effort has been devoted toward...
Article
Full-text available
In the pursuit of urgently needed, energy dense solid-state batteries for electric vehicle and portable electronics applications, halide solid electrolytes offer a promising path forward with exceptional compatibility against high-voltage oxide electrodes, tunable ionic conductivities, and facile processing. For this family of compounds, synthesis...
Article
Full-text available
Sodium thiophosphates are promising materials for large-scale energy storage applications benefiting from high ionic conductivities and the geopolitical abundance of the elements. A representative of this class is Na4P2S6, which currently shows two known polymorphs-α and β. This work describes a third polymorph of Na4P2S6, γ, that forms above 580 °...
Preprint
The solid-electrolyte interphase (SEI) is crucial to the electrochemical performance of all-solid-state batteries (ASSBs). Theoretical characterization of SEI properties will help understand the origin of interfacial stability (and instability) between solid electrolytes and electrodes. Among solid electrolytes for Lithium(Li)-ion ASSBs, the lithiu...
Preprint
Full-text available
In the pursuit of urgently-needed, energy dense solid-state batteries for electric vehicle and portable electronics applications, halide solid electrolytes offer a promising path forward with exceptional compatibility against high-voltage oxide electrodes, tunable ionic conductivities, and facile processing. For this family of compounds, synthesis...
Article
To date, battery research largely follows an "Edisonian"approach based on experimental trial-and-error in contrast to a systematic strategy of design-of-experiments. Battery interfaces are arguably the most important yet the least understood components of energy storage devices. To transform the way we perform battery research, theory and computati...
Preprint
Full-text available
Understanding the reactivity of ubiquitous molecules on complex oxides has broad impacts in energy applications and catalysis. The garnet-type Li$_7$La$_3$Zr$_2$O$_{12}$ is a promising solid-state electrolyte for lithium(Li)-ion batteries, and it readily reacts with H$_2$O and CO$_2$ when exposed to ambient air. Such reactions form a contamination...
Article
Understanding the reactivity of ubiquitous molecules on complex oxides has broad impacts in energy applications and catalysis. The garnet-type Li 7 La 3 Zr 2 O 12 is a promising solid-state electrolyte for lithium(Li)-ion batteries, and it...
Preprint
Full-text available
Sodium thiophophates are promising materials for large-scale energy storage applications benefiting from high ionic conductivities and the-political abundance of the elements. A representative of this class is Na4P2S6, which currently shows two known polymorphs–α and β. This work describes a third polymorph of Na4P2S6, γ, that forms above 580◦C, ex...
Article
We elucidate the complex thermodynamics of sodium (Na) intercalation into the sodium super-ionic conductor (NaSICON)-type electrode, NaxV2(PO4)3, for promising Na-ion batteries with high-power density. This is the first report of a computational temperature-composition phase diagram of the NaSICON-type electrode NaxV2(PO4)3. Based on our computatio...
Preprint
Full-text available
Lithium and sodium (Na) mixed polyanion solid electrolytes for all-solid-state batteries display some of the highest ionic conductivities reported to date. However, the effect of polyanion mixing on ion transport properties is still debated. Here, we focus on Na 1+x Zr 2 Si x P 3-x O 12 (0 ≤ x ≤ 3) NASICON electrolyte to elucidate the role of polya...
Preprint
Full-text available
The Na-superionic-conductor (NASICON) Na3V2(PO4)3 is an important positive electrode material for Na-ion batteries. Here, we investigate the mechanisms of phase transition in NaxV2(PO4)3 (1 ≤ x ≤ 4) upon a non-equilibrium battery cycling. Unlike the widely believed two-phase reaction in Na3V2(PO4)3 – Na1V2(PO4)3 system, we determine a new intermedi...
Preprint
The Na-superionic-conductor (NASICON) Na3V2(PO4)3 is an important positive electrode material for Na-ion batteries. Here, we investigate the mechanisms of phase transition in NaxV2(PO4)3 (1 ≤ x ≤ 4) upon a non-equilibrium battery cycling. Unlike the widely believed two-phase reaction in Na3V2(PO4)3 – Na1V2(PO4)3 system, we determine a new intermedi...
Preprint
We elucidate the thermodynamics of sodium (Na) intercalation into the sodium super-ionic conductor (NaSICON)-type electrode, Na$_x$V$_2$(PO$_4$)$_3$, for promising Na-ion batteries with high-power density. This is the first report of a computational temperature-composition phase diagram of the NaSICON-type electrode Na$_x$V$_2$(PO$_4$)$_3$. We iden...
Preprint
Solid-state batteries (SSBs) can offer a paradigm shift in battery safety and energy density. Yet, the promise hinges on the ability to integrate high-performance electrodes with state-of-the-art solid electrolytes. For example, lithium (Li) metal, the most energy-dense anode candidate, suffers from severe interfacial chemomechanical issues that le...
Article
Full-text available
Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na⁺ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperat...
Preprint
Full-text available
The identification of alternatives to the Lithium-ion battery architecture remains a crucial priority in the diversification of energy storage technologies. Accompanied by the low reduction potential of $\mathrm{Ca^{2+}/Ca}$, -2.87 V vs. SHE, metal-anode-based rechargeable Calcium (Ca) batteries appear competitive in terms of energy densities. Howe...
Article
Sodium (Na) batteries are promising devices for smart grids and electric vehicles due to cost effectiveness arising from the overall abundance of and its even geographical distribution. The energy density of Na-ion batteries is limited by the positive electrode chemistry [1,2]. The Natrium Superionic CONductor (NaSICON) is known for its wide range...
Article
The accurate determination of compositional fluctuations is pivotal in understanding their role in the reduction of efficiency in high indium content InxGa1–xN light emitting diodes (LEDs), the origin of which is still poorly understood. Here we have combined electron energy loss spectroscopy (EELS) imaging at subnanometer resolution with multiscal...
Preprint
Full-text available
The accurate determination of the compositional fluctuations is pivotal in understanding their role in the reduction of efficiency in high indium content $In_{x}Ga_{1-x}N$ light-emitting diodes, the origin of which is still poorly understood. Here we have combined electron energy loss spectroscopy (EELS) imaging at sub-nanometer resolution with mul...
Article
Solid electrolytes for all-solid-state batteries are generating remarkable research interest as a means to improve, their safety, stability and performance. Solid electrolytes are often polycrystalline and the effect that grain boundaries have on the material properties is often not fully characterised. Here, we present a comprehensive molecular dy...
Preprint
Solid electrolytes are crucial for next generation solid state batteries and Na<sub>3</sub>PS<sub>4</sub> is one of the most promising Na<sup>+</sup> conductors for such applications. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na<sub>3</sub>PS<sub>4</sub> under the effect of temperature i...
Article
Na-ion batteries are promising devices for smart grids and electric vehicles due to cost effectiveness arising from the overall abundance of sodium (Na) and its even geographical distribution. Among other factors, the energy density of Na-ion batteries is limited by the positive electrode chemistry. NaSICON-based positive electrode materials are kn...
Article
A major bottleneck for the development of Mg batteries is the identification of liquid electrolytes that are simultaneously compatible with the Mg-metal anode and high-voltage cathodes [1,2]. A viable strategy to widen the stability windows of current nonaqueous electrolytes is to introduce protective coating materials at the electrodes, where thes...
Article
An avenue to create safer batteries is to replace the liquid electrolyte with a non-flammable solid electrolyte. 1–3 A good candidate is the Natrium superionic conductor (NaSiCON) Na 1+x Zr 2 Si x P 3-x O 12 (0 x 3) which displays high bulk ionic conductivity and good relative stability towards other NaSiCON-based electrodes. ² Despite the sizeable...
Preprint
Rechargeable solid-state batteries continue to gain prominence due to their increased safety. However, a number of outstanding challenges have prevented their adoption in mainstream technology. In this study, we reveal the origins of electronic conductivity (s<sub>e</sub>) in solid electrolytes (SEs), which is deemed responsible for solid-state bat...
Preprint
div> Na-ion batteries are promising devices for smart grids and electric vehicles due to cost effectiveness arising from the overall abundance of sodium (Na) and its even geographical distribution. Among other factors, the energy density of Na-ion batteries is limited by the positive electrode chemistry. NaSICON-based positive electrode materials...
Preprint
div> Fast-ion conductors are critical to the development of solid-state batteries. The effects of mechanochemical synthesis that lead to increased ionic conductivity in an archetypical sodium-ion conductor Na<sub>3</sub>PS<sub>4</sub> are not fully understood. We present here a comprehensive analysis based on diffraction (Bragg, pair distribution...
Article
The replacement of the presently used liquid electrolytes by a non-flammable solid electrolyte is an important avenue to create safer batteries. The Natrium Superionic CONductor (NaSiCON) Na1+xZr2SixP3–xO12 (0 ≤ x ≤ 3) that displays high bulk ionic conductivity and good stability towards other NaSiCON-based electrodes is a good solid electrolyte in...
Article
Full-text available
As for other multivalent systems, the interface between the calcium (Ca) metal anode and the electrolyte is of paramount importance for reversible plating/stripping. Here, we combined experimental and theoretical approaches to unveil the potential solid electrolyte interphase (SEI) components enabling facile Ca plating. Borates compounds, in the fo...
Preprint
p>The replacement of the presently used liquid electrolytes by a non-flammable solid electrolyte is an important avenue to create safer batteries. The Natrium Superionic CONductor (NaSiCON) Na<sub>1+x</sub>Zr<sub>2</sub>Si<sub>x</sub>P<sub>3-x</sub>O<sub>12</sub> (0 < x < 3) that displays high bulk ionic conductivity and good stability towards othe...
Article
Bismuth trihalides, BiX3 (X = F, Cl, Br, and I), have been thrust into prominence recently because of their close chemical relationship to the halide perovskites of lead, which exhibit remarkable performance as active layers in photovoltaic cells and other optoelectronic devices. In the present work, we have used calculations based on density funct...
Article
Mg batteries utilizing oxide cathodes can theoretically surpass the energy density of current Li-ion technologies. The absence of functional devices so far has been ascribed to impeded Mg²⁺ migration within oxides, which severely handi-caps intercalation reactions at the cathode. Broadly, knowledge of divalent cation migration in solid frameworks i...
Chapter
Computational materials science based on first-principles calculations is widely used to evaluate the thermodynamic, kinetic and electronic properties of materials, ranging from alloys, semiconductors and ceramics for a wide range of energy applications. The accuracy of density functional theory in estimating materials properties enables the screen...
Article
A major bottleneck for the development of Mg batteries is the identification of liquid electrolytes that are simultaneously compatible with the Mg-metal anode and high-voltage cathodes. One strategy to widen the stability windows of current non-aqueous electrolytes is to introduce protective coating materials at the electrodes, where coating materi...
Article
Full-text available
In the critical area of sustainable energy storage, solid-state batteries have attracted considerable attention due to their potential safety, energy-density and cycle-life benefits. This Review describes recent progress in the fundamental understanding of inorganic solid electrolytes, which lie at the heart of the solid-state battery concept, by a...
Preprint
A major bottleneck for the development of Mg batteries is the identification of liquid electrolytes that are simultaneously compatible with the Mg-metal anode and high-voltage cathodes. One strategy to widen the stability windows of current non-aqueous electrolytes is to introduce protective coating materials at the electrodes, where coating materi...
Preprint
div> We identify the existence of nonlinear optical (NLO) activity in a number of novel ABX3-type metal-free perovskites, where A is a highly tuneable organic cation, B is a NH4 cation and X a halide anion. Through systematic first-principles calculations, we identify important trends to chart the second-harmonic generation of this class of mater...
Article
Solid electrolytes provide a route to the development of all-solid-state batteries that can potentially surpass the safety and performance of conventional liquid electrolyte-based devices. Sulfide solid electrolytes have received particular attention as a result of their high ionic conductivities. One of the main reasons for such high ionic conduct...
Preprint
Solid electrolytes provide a route to the development of all-solid-state batteries that can potentially surpass the safety and performance of conventional liquid electrolyte-based devices. Sulfide solid electrolytes have received particular attention as a result of their high ionic conductivities. One of the main reasons for such high ionic conduct...
Article
Full-text available
Materials for energy-related applications, which are crucial for a sustainable energy economy, rely on combining materials that form complex heterogenous interfaces. Simultaneously, progress in computational materials science in describing complex interfaces is critical for improving the understanding and performance of energy materials. Hence, we...
Article
Full-text available
Mg batteries utilizing a Mg metal anode with a high-voltage intercalation cathode define a potential pathway toward energy storage with high energy density. However, the making of Mg batteries is plagued by the instability of existing electrolytes against the Mg-metal anode and high-voltage cathode materials. One viable solution to this problem is...
Article
Full-text available
We identify the existence of nonlinear optical (NLO) activity in a number of novel ABX 3 -type metal-free perovskites, where A is a highly tuneable organic cation, B is a NH 4 cation and X is a halide anion.
Article
Crystallography is a powerful descriptor of the atomic structure of solid-state matter and can be applied to analyse the phenomena present in functional materials. Especially for ion diffusion – one of the main processes found in electrochemical energy storage materials – crystallography can describe and evaluate the elementary steps for the hoppin...
Article
Full-text available
A thermodynamic analysis of the driving forces is presented for intercalation and conversion reactions in battery cathodes across a range of possible working ion, transition metal, and anion chemistries. Using this body of results, the importance of polymorph selection as well as chemical composition on the ability of a host cathode to support inte...
Article
Full-text available
Solid electrolytes for solid-state Li-ion batteries are stimulating considerable interest for next-generation energy storage applications. The Li7La3Zr2O12 garnet-type solid electrolyte has received appreciable attention as a result of its high ionic conductivity. However, several challenges for the successful application of solid-state devices bas...