Equilibrium Particle Shape and Surface Chemistry of Disordered Li-Excess, Mn-Rich Li-ion Cathodes through First-Principles Modeling

A novel methodology for calculating the surface energy of a disordered material was developed and is described here. The method was used to calculate the range of surface energies for {100}, {110}, {111}, and {112} type facets of the disordered rock salt (DRX) cathode material Li2MnO2F, as a function of surface cation and anion decoration. Boltzmann averaging was used to determine average surface energies for each facet which were then used to calculate the equilibrium particle shape. It was found that Li2MnO2F displays predominantly {100} type lithium/fluorine-rich facets favoring a cubic particle shape. The density of states along with electronic structure-based bonding analyses are calculated to rationalize differences observed in surface energy. Importantly, it is found that surface lithium and fluorine lower the surface energy of the majority facets, suggesting that surfaces of Li2MnO2F are likely enriched in lithium and fluorine and display less oxygen and manganese, which has implications for capacity and rate retention.

[1]  Guoying Chen,et al.  Role of Fluorine in Chemomechanics of Cation-Disordered Rocksalt Cathodes , 2021, Chemistry of Materials.

[2]  Guoying Chen,et al.  Fluorination‐Enhanced Surface Stability of Cation‐Disordered Rocksalt Cathodes for Li‐Ion Batteries , 2021, Advanced Functional Materials.

[3]  Guoying Chen,et al.  An Overview of Cation-Disordered Lithium-Excess Rocksalt Cathodes , 2021 .

[4]  Guoying Chen,et al.  Understanding cation-disordered rocksalt oxyfluoride cathodes , 2021 .

[5]  B. McCloskey,et al.  Tailoring the Redox Reactions for High‐Capacity Cycling of Cation‐Disordered Rocksalt Cathodes , 2021, Advanced Functional Materials.

[6]  Y. Meng,et al.  Electrochemical Utilization of Iron IV in the Li 1.3 Fe 0.4 Nb 0.3 O 2 Disordered Rocksalt Cathode , 2021 .

[7]  Michael L. Waskom,et al.  Seaborn: Statistical Data Visualization , 2021, J. Open Source Softw..

[8]  G. Ceder,et al.  The Impact of Surface Structure Transformations on the Performance of Li-Excess Cation-Disordered Rocksalt Cathodes , 2020, Cell Reports Physical Science.

[9]  B. McCloskey,et al.  Anion Reactivity in Cation‐Disordered Rocksalt Cathode Materials: The Influence of Fluorine Substitution , 2020, Advanced Energy Materials.

[10]  Guoying Chen,et al.  A Fluorination Method for Improving Cation‐Disordered Rocksalt Cathode Performance , 2020, Advanced Energy Materials.

[11]  Chongmin Wang,et al.  Redox Behaviors in a Li-Excess Cation-Disordered Mn–Nb–O–F Rocksalt Cathode , 2020 .

[12]  Zhengyan Lun,et al.  Cation-disordered rocksalt transition metal oxides and oxyfluorides for high energy lithium-ion cathodes , 2020, Energy & Environmental Science.

[13]  G. Ceder,et al.  Effect of Fluorination on Lithium Transport and Short‐Range Order in Disordered‐Rocksalt‐Type Lithium‐Ion Battery Cathodes , 2020, Advanced Energy Materials.

[14]  J. Michael,et al.  Role of defects on the surface properties of HfC , 2019, Applied Surface Science.

[15]  Tongchao Liu,et al.  Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery , 2019, Nature Communications.

[16]  Guoying Chen,et al.  Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes , 2019, Advanced Energy Materials.

[17]  G. Ceder,et al.  Improved Cycling Performance of Li‐Excess Cation‐Disordered Cathode Materials upon Fluorine Substitution , 2018, Advanced Energy Materials.

[18]  G. Ceder,et al.  Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode , 2018, Chemistry of Materials.

[19]  Adam J. Jackson,et al.  sumo: Command-line tools for plotting and analysis of periodic *ab initio* calculations , 2018, J. Open Source Softw..

[20]  P. Bruce,et al.  Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox , 2018 .

[21]  G. Ceder,et al.  Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials , 2018, Nature.

[22]  W. Richards,et al.  Fluorination of Lithium‐Excess Transition Metal Oxide Cathode Materials , 2018 .

[23]  G. Ceder,et al.  Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials , 2017, Nature Communications.

[24]  E. Olivetti,et al.  Lithium-Ion Battery Supply Chain Considerations: Analysis of Potential Bottlenecks in Critical Metals , 2017 .

[25]  Daniel M. Kammen,et al.  Energy storage deployment and innovation for the clean energy transition , 2017, Nature Energy.

[26]  K. Persson,et al.  Surface Morphology and Surface Stability against Oxygen Loss of the Lithium-Excess Li2MnO3 Cathode Material as a Function of Lithium Concentration. , 2016, ACS applied materials & interfaces.

[27]  Kristin A. Persson,et al.  Surface energies of elemental crystals , 2016, Scientific Data.

[28]  L. Curtiss,et al.  Thermodynamic Stability of Low- and High-Index Spinel LiMn2O4 Surface Terminations. , 2016, ACS applied materials & interfaces.

[29]  K. Persson,et al.  Revealing the Intrinsic Li Mobility in the Li2MnO3 Lithium-Excess Material , 2016 .

[30]  Richard Dronskowski,et al.  LOBSTER: A tool to extract chemical bonding from plane‐wave based DFT , 2016, J. Comput. Chem..

[31]  Christopher R. Cherry,et al.  E-bikes in the Mainstream: Reviewing a Decade of Research , 2016 .

[32]  Kristin A. Persson,et al.  Structural and Chemical Evolution of the Layered Li‐Excess LixMnO3 as a Function of Li Content from First‐Principles Calculations , 2014 .

[33]  L. Gu,et al.  Surface Structure Evolution of LiMn2O4 Cathode Material upon Charge/Discharge , 2014 .

[34]  Gerbrand Ceder,et al.  Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries , 2014, Science.

[35]  B. Yildiz,et al.  Quantification of electronic band gap and surface states on FeS2(100) , 2013 .

[36]  Richard Dronskowski,et al.  Analytic projection from plane‐wave and PAW wavefunctions and application to chemical‐bonding analysis in solids , 2013, J. Comput. Chem..

[37]  Jun Lu,et al.  Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems , 2013, Nature Communications.

[38]  Chong Seung Yoon,et al.  Improvement of long-term cycling performance of Li[Ni0.8Co0.15Al0.05]O2 by AlF3 coating , 2013 .

[39]  Xunhui Xiong,et al.  A low temperature fluorine substitution on the electrochemical performance of layered LiNi0.8Co0.1Mn0.1O2−zFz cathode materials , 2013 .

[40]  Anubhav Jain,et al.  Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis , 2012 .

[41]  J. Choi,et al.  A truncated manganese spinel cathode for excellent power and lifetime in lithium-ion batteries. , 2012, Nano letters.

[42]  R. V. Duyne,et al.  Wulff construction for alloy nanoparticles. , 2011, Nano letters.

[43]  Volker L. Deringer,et al.  Crystal orbital Hamilton population (COHP) analysis as projected from plane-wave basis sets. , 2011, The journal of physical chemistry. A.

[44]  J. Robertson,et al.  Defect states at III-V semiconductor oxide interfaces , 2011 .

[45]  David P. Dobkin,et al.  The quickhull algorithm for convex hulls , 1996, TOMS.

[46]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[47]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[48]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[49]  Hafner,et al.  Ab initio molecular dynamics for liquid metals. , 1995, Physical review. B, Condensed matter.

[50]  Ceder,et al.  Model for configurational thermodynamics in ionic systems. , 1995, Physical review letters.

[51]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[52]  Hafner,et al.  Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. , 1994, Physical review. B, Condensed matter.

[53]  Richard Dronskowski,et al.  Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations , 1993 .

[54]  F. Ducastelle,et al.  Generalized cluster description of multicomponent systems , 1984 .

[55]  W. K. Hastings,et al.  Monte Carlo Sampling Methods Using Markov Chains and Their Applications , 1970 .

[56]  N. Metropolis,et al.  Equation of State Calculations by Fast Computing Machines , 1953, Resonance.

[57]  Fraser Jake,et al.  Study on future demand and supply security of nickel for electric vehicle batteries , 2021 .

[58]  Katharina Wagner,et al.  Solid State Physics Advances In Research And Applications , 2016 .

[59]  Christopher S. Johnson,et al.  Solid State NMR Studies of Li2MnO3 and Li-Rich Cathode Materials: Proton Insertion, Local Structure, and Voltage Fade , 2015 .