Expandable Li Percolation Network: The Effects of Site Distortion in Cation-Disordered Rock-Salt Cathode Material

Sun, Yujian; Jiao, Sichen; Wang, Junyang; Zhang, Yuanpeng; Liu, Jue; Wang, Xuelong; Kang, Le; Yu, Xiqian; Li, Hong; Chen, Liquan; Huang, Xuejie

doi:10.1021/jacs.3c02041

Expandable Li Percolation Network: The Effects of Site Distortion in Cation-Disordered Rock-Salt Cathode Material

Journal Article · Wed May 17 00:00:00 EDT 2023 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.3c02041· OSTI ID:2251629

Sun, Yujian ^[1]; Jiao, Sichen ^[1]; ^[1]; ^[2]; ^[2]; Wang, Xuelong ^[3]; Kang, Le ^[4]; ^[1]; ^[1]; Chen, Liquan ^[3]; ^[3]

Chinese Academy of Sciences (CAS), Beijing (China); University of Chinese Academy of Sciences, Beijing (China)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Chinese Academy of Sciences (CAS), Beijing (China)
Chinese Academy of Sciences (CAS), Beijing (China); Spallation Neutron Source Science Center, Dongguan (China)

Cation-disordered rock-salt (DRX) materials receive intensive attention as a new class of cathode candidates for high-capacity lithium-ion batteries (LIBs). Unlike traditional layered cathode materials, DRX materials have a three-dimensional (3D) percolation network for Li⁺ transportation. The disordered structure poses a grand challenge to a thorough understanding of the percolation network due to its multiscale complexity. In this work, we introduce the large supercell modeling for DRX material Li_1.16Ti_0.37Ni_0.37Nb_0.10O₂ (LTNNO) via the reverse Monte Carlo (RMC) method combined with neutron total scattering. Here, through a quantitative statistical analysis of the material’s local atomic environment, we experimentally verified the existence of short-range ordering (SRO) and uncovered an element-dependent behavior of transition metal (TM) site distortion. A displacement from the original octahedral site for Ti⁴⁺ cations is pervasive throughout the DRX lattice. Density functional theory (DFT) calculations revealed that site distortions quantified by the centroid offsets could alter the migration barrier for Li⁺ diffusion through the tetrahedral channels, which can expand the previously proposed theoretical percolating network of Li. The estimated accessible Li content is highly consistent with the observed charging capacity. The newly developed characterization method here uncovers the expandable nature of the Li percolation network in DRX materials, which may provide valuable guidelines for the design of superior DRX materials.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2251629

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 21 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li _1.3 Ta _0.3 Mn _0.4 O ₂ Cathode Kan, Wang Hay; Wei, Chenxi; Chen, Dongchang Advanced Functional Materials, Vol. 29, Issue 17 https://doi.org/10.1002/adfm.201808294	journal	February 2019
Disordered Lithium-Rich Oxyfluoride as a Stable Host for Enhanced Li ⁺ Intercalation Storage Chen, Ruiyong; Ren, Shuhua; Knapp, Michael Advanced Energy Materials, Vol. 5, Issue 9 https://doi.org/10.1002/aenm.201401814	journal	February 2015
Another Strategy, Detouring Potential Decay by Fast Completion of Cation Mixing Liu, Shuai; Feng, Xin; Wang, Xuelong Advanced Energy Materials, Vol. 8, Issue 15 https://doi.org/10.1002/aenm.201703092	journal	February 2018
Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes Chen, Dongchang; Kan, Wang Hay; Chen, Guoying Advanced Energy Materials, Vol. 9, Issue 31 https://doi.org/10.1002/aenm.201901255	journal	July 2019
Effect of Fluorination on Lithium Transport and Short‐Range Order in Disordered‐Rocksalt‐Type Lithium‐Ion Battery Cathodes Ouyang, Bin; Artrith, Nongnuch; Lun, Zhengyan Advanced Energy Materials, Vol. 10, Issue 10 https://doi.org/10.1002/aenm.201903240	journal	March 2020
Thermodynamically Driven Synthetic Optimization for Cation‐Disordered Rock Salt Cathodes Cai, Zijian; Zhang, Ya‐Qian; Lun, Zhengyan Advanced Energy Materials, Vol. 12, Issue 21 https://doi.org/10.1002/aenm.202103923	journal	April 2022
Stabilizing the Oxygen Lattice and Reversible Oxygen Redox Chemistry through Structural Dimensionality in Lithium-Rich Cathode Oxides Zhao, Enyue; Li, Qinghao; Meng, Fanqi Angewandte Chemie International Edition, Vol. 58, Issue 13 https://doi.org/10.1002/anie.201900444	journal	February 2019
Role of Redox‐Inactive Transition‐Metals in the Behavior of Cation‐Disordered Rocksalt Cathodes Chen, Dongchang; Wu, Jinpeng; Papp, Joseph K. Small, Vol. 16, Issue 22 https://doi.org/10.1002/smll.202000656	journal	May 2020
Understanding the Effect of Local Short-Range Ordering on Lithium Diffusion in Li1.3Nb0.3Mn0.4O2 Single-Crystal Cathode Kan, Wang Hay; Deng, Biao; Xu, Yahong Chem, Vol. 4, Issue 9 https://doi.org/10.1016/j.chempr.2018.05.008	journal	September 2018
Design Principles for High-Capacity Mn-Based Cation-Disordered Rocksalt Cathodes Lun, Zhengyan; Ouyang, Bin; Cai, Zijian Chem, Vol. 6, Issue 1 https://doi.org/10.1016/j.chempr.2019.10.001	journal	January 2020
A disordered rock-salt Li-excess cathode material with high capacity and substantial oxygen redox activity: Li 1.25 Nb 0.25 Mn 0.5 O 2 Wang, Rui; Li, Xin; Liu, Lei Electrochemistry Communications, Vol. 60 https://doi.org/10.1016/j.elecom.2015.08.003	journal	November 2015
Structural and mechanistic revelations on high capacity cation-disordered Li-rich oxides for rechargeable Li-ion batteries Zhao, Enyue; He, Lunhua; Wang, Baotian Energy Storage Materials, Vol. 16 https://doi.org/10.1016/j.ensm.2018.06.016	journal	January 2019
Study of atomic ordering across the layer in lithium-rich layered positive electrode material towards preparation process optimization Kitamura, Naoto; Kubo, Yusuke; Ishida, Naoya Journal of Power Sources, Vol. 437 https://doi.org/10.1016/j.jpowsour.2019.226905	journal	October 2019
Activation and stabilization mechanisms of anionic redox for Li storage applications: Joint experimental and theoretical study on Li2TiO3–LiMnO2 binary system Kobayashi, Yuki; Sawamura, Miho; Kondo, Sayaka Materials Today, Vol. 37 https://doi.org/10.1016/j.mattod.2020.03.002	journal	July 2020
A new model on cation distribution in cation-disordered Li1+xTM1−xO2 cathodes Huang, Yang; Liu, Long; Zhu, Yuanyuan Solid State Ionics, Vol. 351 https://doi.org/10.1016/j.ssi.2020.115341	journal	August 2020
The Impact of Surface Structure Transformations on the Performance of Li-Excess Cation-Disordered Rocksalt Cathodes Kwon, Deok-Hwang; Lee, Jinhyuk; Artrith, Nongnuch Cell Reports Physical Science, Vol. 1, Issue 9 https://doi.org/10.1016/j.xcrp.2020.100187	journal	September 2020
Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode Clément, Raphaële J.; Kitchaev, Daniil; Lee, Jinhyuk Chemistry of Materials, Vol. 30, Issue 19 https://doi.org/10.1021/acs.chemmater.8b03794	journal	September 2018
Computational Investigation and Experimental Realization of Disordered High-Capacity Li-Ion Cathodes Based on Ni Redox Ji, Huiwen; Kitchaev, Daniil A.; Lun, Zhengyan Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.8b05096	journal	March 2019
Degradation Mechanisms in Li 2 VO 2 F Li-Rich Disordered Rock-Salt Cathodes Källquist, Ida; Naylor, Andrew J.; Baur, Christian Chemistry of Materials, Vol. 31, Issue 16 https://doi.org/10.1021/acs.chemmater.9b00829	journal	June 2019
Mn ⁴⁺ -Substituted Li-Rich Li _1.2 Mn _0.4 ³⁺ Mn _x ⁴⁺ Ti _{0.4– x} O ₂ Materials with High Energy Density Zheng, Shiyao; Zhou, Ke; Zheng, Feng ACS Applied Materials & Interfaces, Vol. 12, Issue 36 https://doi.org/10.1021/acsami.0c11544	journal	August 2020
Elucidating and Mitigating the Degradation of Cationic–Anionic Redox Processes in Li _1.2 Mn _0.4 Ti _0.4 O ₂ Cation-Disordered Cathode Materials Zhou, Ke; Zheng, Shiyao; Liu, Haodong ACS Applied Materials & Interfaces, Vol. 11, Issue 49 https://doi.org/10.1021/acsami.9b16011	journal	November 2019
Reversible Three-Electron Redox Reaction of Mo ³⁺ /Mo ⁶⁺ for Rechargeable Lithium Batteries Hoshino, Satoshi; Glushenkov, Alexey M.; Ichikawa, Shinnosuke ACS Energy Letters, Vol. 2, Issue 4 https://doi.org/10.1021/acsenergylett.7b00037	journal	March 2017
Distortions in Octahedrally Coordinated d ⁰ Transition Metal Oxides: A Continuous Symmetry Measures Approach Ok, Kang Min; Halasyamani, P. Shiv; Casanova, David Chemistry of Materials, Vol. 18, Issue 14 https://doi.org/10.1021/cm0604817	journal	July 2006
Probing the Local Site Disorder and Distortion in Pyrochlore High-Entropy Oxides Jiang, Bo; Bridges, Craig A.; Unocic, Raymond R. Journal of the American Chemical Society, Vol. 143, Issue 11 https://doi.org/10.1021/jacs.0c10739	journal	December 2020
Unraveling the Nature and Role of Layered Cation Ordering in Cation-Disordered Rock-Salt Cathodes Wang, You; Huang, Shengchi; Raji-Adefila, Basirat Journal of the American Chemical Society, Vol. 144, Issue 43 https://doi.org/10.1021/jacs.2c07473	journal	October 2022
Structural Modeling of Porous Carbons: Constrained Reverse Monte Carlo Method Pikunic, Jorge; Clinard, Christian; Cohaut, Nathalie Langmuir, Vol. 19, Issue 20 https://doi.org/10.1021/la034595y	journal	September 2003
Molecular Modeling of Porous Carbons Using the Hybrid Reverse Monte Carlo Method Jain, Surendra K.; Pellenq, Roland J. -M.; Pikunic, Jorge P. Langmuir, Vol. 22, Issue 24 https://doi.org/10.1021/la053402z	journal	November 2006
Modeling Structural Morphology of Microporous Carbons by Reverse Monte Carlo Thomson, Kendall T.; Gubbins, Keith E. Langmuir, Vol. 16, Issue 13 https://doi.org/10.1021/la991581c	journal	June 2000
Structural modelling of glasses using reverse Monte Carlo simulation Keen, D. A.; McGreevy, R. L. Nature, Vol. 344, Issue 6265 https://doi.org/10.1038/344423a0	journal	March 1990
Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries Yabuuchi, Naoaki; Nakayama, Masanobu; Takeuchi, Mitsue Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13814	journal	December 2016
A new active Li–Mn–O compound for high energy density Li-ion batteries Freire, M.; Kosova, N. V.; Jordy, C. Nature Materials, Vol. 15, Issue 2 https://doi.org/10.1038/nmat4479	journal	November 2015
Mitigating oxygen loss to improve the cycling performance of high capacity cation-disordered cathode materials Lee, Jinhyuk; Papp, Joseph K.; Clément, Raphaële J. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01115-0	journal	October 2017
Hidden structural and chemical order controls lithium transport in cation-disordered oxides for rechargeable batteries Ji, Huiwen; Urban, Alexander; Kitchaev, Daniil A. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08490-w	journal	February 2019
Non-topotactic reactions enable high rate capability in Li-rich cathode materials Huang, Jianping; Zhong, Peichen; Ha, Yang Nature Energy, Vol. 6, Issue 7 https://doi.org/10.1038/s41560-021-00817-6	journal	May 2021
Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries Lun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang Nature Materials, Vol. 20, Issue 2 https://doi.org/10.1038/s41563-020-00816-0	journal	October 2020
Reversible Mn2+/Mn4+ double redox in lithium-excess cathode materials Lee, Jinhyuk; Kitchaev, Daniil A.; Kwon, Deok-Hwang Nature, Vol. 556, Issue 7700 https://doi.org/10.1038/s41586-018-0015-4	journal	April 2018
Li ⁺ intercalation in isostructural Li ₂ VO ₃ and Li ₂ VO ₂ F with O ²⁻ and mixed O ²⁻ /F ⁻ anions Chen, Ruiyong; Ren, Shuhua; Yavuz, Murat Physical Chemistry Chemical Physics, Vol. 17, Issue 26 https://doi.org/10.1039/C5CP02505B	journal	January 2015
A new class of high capacity cation-disordered oxides for rechargeable lithium batteries: Li–Ni–Ti–Mo oxides Lee, Jinhyuk; Seo, Dong-Hwa; Balasubramanian, Mahalingam Energy & Environmental Science, Vol. 8, Issue 11 https://doi.org/10.1039/C5EE02329G	journal	January 2015
Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox House, Robert A.; Jin, Liyu; Maitra, Urmimala Energy & Environmental Science, Vol. 11, Issue 4 https://doi.org/10.1039/C7EE03195E	journal	January 2018
Nanostructured Li ₂ MnO ₃ : a disordered rock salt type structure for high energy density Li ion batteries Freire, M.; Lebedev, O. I.; Maignan, A. J. Mater. Chem. A, Vol. 5, Issue 41 https://doi.org/10.1039/C7TA07476J	journal	January 2017
The atomic structure of a MgCo₂O₄ nanoparticle for a positive electrode of a Mg rechargeable battery Kitamura, Naoto; Tanabe, Yuhei; Ishida, Naoya Chemical Communications, Vol. 55, Issue 17 https://doi.org/10.1039/C8CC09713E	journal	January 2019
Investigation of the exceptional charge performance of the 0.93Li 4−x Mn 2 O 5 –0.07Li 2 O composite cathode for Li-ion batteries Freire, M.; Diaz-Lopez, M.; Bordet, P. Journal of Materials Chemistry A, Vol. 6, Issue 12 https://doi.org/10.1039/C8TA00234G	journal	January 2018
Metastable and nanosize cation-disordered rocksalt-type oxides: revisit of stoichiometric LiMnO ₂ and NaMnO ₂ Sato, Takahito; Sato, Kei; Zhao, Wenwen Journal of Materials Chemistry A, Vol. 6, Issue 28 https://doi.org/10.1039/C8TA03667E	journal	January 2018
Improving the oxygen redox stability of NaCl-type cation disordered Li 2 MnO 3 in a composite structure of Li 2 MnO 3 and spinel-type LiMn 2 O 4 Kataoka, R.; Taguchi, N.; Kojima, T. Journal of Materials Chemistry A, Vol. 7, Issue 10 https://doi.org/10.1039/C8TA11807H	journal	January 2019
Short-range ordering in a battery electrode, the ‘cation-disordered’ rocksalt Li 1.25 Nb 0.25 Mn 0.5 O 2 Jones, Michael A.; Reeves, Philip J.; Seymour, Ieuan D. Chemical Communications, Vol. 55, Issue 61 https://doi.org/10.1039/C9CC04250D	journal	January 2019
Improved cycling stability in high-capacity Li-rich vanadium containing disordered rock salt oxyfluoride cathodes Baur, Christian; Källquist, Ida; Chable, Johann Journal of Materials Chemistry A, Vol. 7, Issue 37 https://doi.org/10.1039/C9TA06291B	journal	January 2019
Effect of transition metal cations on the local structure and lithium transport in disordered rock-salt oxides Semykina, D. O.; Morkhova, Ye. A.; Kabanov, A. A. Physical Chemistry Chemical Physics, Vol. 24, Issue 10 https://doi.org/10.1039/D1CP04993C	journal	January 2022
Li trapping in nanolayers of cation ‘disordered’ rock salt cathodes Diaz-Lopez, Maria; Chater, Philip A.; Proux, Olivier Journal of Materials Chemistry A, Vol. 10, Issue 34 https://doi.org/10.1039/D2TA04262B	journal	January 2022
High-capacity electrode materials for rechargeable lithium batteries: Li ₃ NbO ₄ -based system with cation-disordered rocksalt structure Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu Proceedings of the National Academy of Sciences, Vol. 112, Issue 25 https://doi.org/10.1073/pnas.1504901112	journal	June 2015
Reverse Monte Carlo Simulation: A New Technique for the Determination of Disordered Structures McGreevy, R. L.; Pusztai, L. Molecular Simulation, Vol. 1, Issue 6 https://doi.org/10.1080/08927028808080958	journal	December 1988
Reverse Monte Carlo modelling McGreevy, R. L. Journal of Physics: Condensed Matter, Vol. 13, Issue 46 https://doi.org/10.1088/0953-8984/13/46/201	journal	November 2001
Reverse Monte Carlo modelling of crystalline disorder Keen, D. A.; Tucker, M. G.; Dove, M. T. Journal of Physics: Condensed Matter, Vol. 17, Issue 5 https://doi.org/10.1088/0953-8984/17/5/002	journal	January 2005
Electronic-Structure Origin of Cation Disorder in Transition-Metal Oxides Urban, Alexander; Abdellahi, Aziz; Dacek, Stephen Physical Review Letters, Vol. 119, Issue 17 https://doi.org/10.1103/PhysRevLett.119.176402	journal	October 2017
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries Lee, J.; Urban, A.; Li, X. Science, Vol. 343, Issue 6170 https://doi.org/10.1126/science.1246432	journal	January 2014
Metastable and Nanosized Li_1.2Nb_0.2V_0.6O₂ for High-Energy Li-ion Batteries Qi, Ruijie; CampÉOn, Benoît D. L.; Konuma, Itsuki Electrochemistry, Vol. 90, Issue 3 https://doi.org/10.5796/electrochemistry.22-00005	journal	March 2022

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