Elastic Lattice Enabling Reversible Tetrahedral Li Storage Sites in a High-Capacity Manganese Oxide Cathode

Huang, Weiyuan; Yang, Luyi; Chen, Zhefeng; Liu, Tongchao; Ren, Guoxi; Shan, Peizhao; Zhang, Bin‐Wei; Chen, Shiming; Li, Shunning; Li, Jianyuan; Lin, Cong; Zhao, Wenguang; Qiu, Jimin; Fang, Jianjun; Zhang, Mingjian; Dong, Cheng; Li, Fan; Yang, Yong; Sun, Cheng‐Jun; Ren, Yang; Huang, Qingzhen; Hou, Guangjin; Dou, Shi‐Xue; Lu, Jun; Amine, Khalil; Pan, Feng

doi:10.1002/adma.202202745

Title: Elastic Lattice Enabling Reversible Tetrahedral Li Storage Sites in a High-Capacity Manganese Oxide Cathode

Journal Article · 02 June 2022 · Advanced Materials

DOI: https://doi.org/10.1002/adma.202202745 · OSTI ID:1906340

Huang, Weiyuan ^[1]; Yang, Luyi ^[1]; Chen, Zhefeng ^[1]; Liu, Tongchao ^[2]; Ren, Guoxi ^[3]; Shan, Peizhao ^[4]; Zhang, Bin‐Wei ^[5]; Chen, Shiming ^[1]; Li, Shunning ^[1]; Li, Jianyuan ^[1]; Lin, Cong ^[1]; Zhao, Wenguang ^[1]; Qiu, Jimin ^[1]; Fang, Jianjun ^[1]; Zhang, Mingjian ^[1]; Dong, Cheng ^[1]; Li, Fan ^[6]; Yang, Yong ^[4]; Sun, Cheng‐Jun ^[2]; Ren, Yang ^[7] more »

Peking Univ. (China)
Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Division
Chinese Academy of Sciences (CAS), Shanghai (China)
Xiamen University (China)
Univ. of Wollongong, NSW (Australia)
Chinese Academy of Sciences (China); University of Chinese Academy of Sciences, Beijing (China)
Argonne National Lab. (ANL), Argonne, IL (United States). X‐Ray Science Division
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Chinese Academy of Sciences (China)
Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Division; Stanford Univ., CA (United States)

The key to breaking through the capacity limitation imposed by intercalation chemistry lies in the ability to harness more active sites that can reversibly accommodate more ions (e.g., Li⁺) and electrons within a finite space. However, excessive Li-ion insertion into the Li layer of layered cathodes results in fast performance decay due to the huge lattice change and irreversible phase transformation. Here, in this study, an ultrahigh reversible capacity is demonstrated by a layered oxide cathode purely based on manganese. Through a wealth of characterizations, it is clarified that the presence of low-content Li₂MnO₃ domains not only reduces the amount of irreversible O loss; but also regulates Mn migration in LiMnO₂ domains, enabling elastic lattice with high reversibility for tetrahedral sites Li-ion storage in Li layers. This work utilizes bulk cation disorder to create stable Li-ion-storage tetrahedral sites and an elastic lattice for layered materials, with a reversible capacity of 600 mA h g^–1, demonstrated in th range 0.6–4.9 V versus Li/Li⁺ at 10 mA g^–1. Admittedly, discharging to 0.6 V might be too low for practical use, but this exploration is still of great importance as it conceptually demonstrates the limit of Li-ions insertion into layered oxide materials.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Australian Research Council (ARC); National Key Research and Development Program of China; National Natural Science Foundation of China (NSFC); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1906340

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 30 Vol. 34; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (61)

A High-Capacity O2-Type Li-Rich Cathode Material with a Single-Layer Li ₂ MnO ₃ Superstructure Zuo, Yuxuan; Li, Biao; Jiang, Ning Advanced Materials, Vol. 30, Issue 16 https://doi.org/10.1002/adma.201707255	journal	March 2018
Suppressing Surface Lattice Oxygen Release of Li-Rich Cathode Materials via Heterostructured Spinel Li ₄ Mn ₅ O ₁₂ Coating Zhang, Xu-Dong; Shi, Ji-Lei; Liang, Jia-Yan Advanced Materials, Vol. 30, Issue 29 https://doi.org/10.1002/adma.201801751	journal	May 2018
Understanding Rechargeable Battery Function Using In Operando Neutron Powder Diffraction Liang, Gemeng; Didier, Christophe; Guo, Zaiping Advanced Materials https://doi.org/10.1002/adma.201904528	journal	September 2019
A High‐Performance Li–Mn–O Li‐rich Cathode Material with Rhombohedral Symmetry via Intralayer Li/Mn Disordering Song, Jin; Li, Biao; Chen, Yuyang Advanced Materials, Vol. 32, Issue 16 https://doi.org/10.1002/adma.202000190	journal	March 2020
Stabilizing Anionic Redox Chemistry in a Mn‐Based Layered Oxide Cathode Constructed by Li‐Deficient Pristine State Cao, Xin; Li, Haifeng; Qiao, Yu Advanced Materials, Vol. 33, Issue 2 https://doi.org/10.1002/adma.202004280	journal	December 2020
Revealing Roles of Co and Ni in Mn‐Rich Layered Cathodes Huang, Weiyuan; Lin, Cong; Zhang, Mingjian Advanced Energy Materials, Vol. 11, Issue 41 https://doi.org/10.1002/aenm.202102646	journal	October 2021
Structure and electrochemistry of Li1±yNiO2 and a new Li2NiO2 phase with the Ni (OH)2 structure Dahn, J. Solid State Ionics, Vol. 44, Issue 1-2 https://doi.org/10.1016/0167-2738(90)90049-W	journal	December 1990
Structure of 1T-Li2NiO2 from powder neutron diffraction Davidson, I.; Greedan, J.; Vonsacken, U. Solid State Ionics, Vol. 46, Issue 3-4 https://doi.org/10.1016/0167-2738(91)90222-W	journal	July 1991
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
The role of Li2MO2 structures (M=metal ion) in the electrochemistry of (x)LiMn0.5Ni0.5O2·(1−x)Li2TiO3 electrodes for lithium-ion batteries Johnson, Christopher S.; Kim, Jeom-Soo; Jeremy Kropf, A. Electrochemistry Communications, Vol. 4, Issue 6 https://doi.org/10.1016/S1388-2481(02)00346-6	journal	June 2002
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
Delocalized Li@Mn6 superstructure units enable layer stability of high-performance Mn-rich cathode materials Huang, Weiyuan; Lin, Cong; Qiu, Jimin Chem, Vol. 8, Issue 8 https://doi.org/10.1016/j.chempr.2022.04.012	journal	August 2022
Surface Ni-rich engineering towards highly stable Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials Zheng, Hongfei; Hu, Zhenyu; Liu, Pengfei Energy Storage Materials, Vol. 25 https://doi.org/10.1016/j.ensm.2019.10.029	journal	March 2020
Cycling mechanism of Li2MnO3: Li–CO2 batteries and commonality on oxygen redox in cathode materials Zhuo, Zengqing; Dai, Kehua; Qiao, Ruimin Joule, Vol. 5, Issue 4 https://doi.org/10.1016/j.joule.2021.02.004	journal	April 2021
Roles of surface structure and chemistry on electrochemical processes in lithium-rich layered oxide cathodes Wei, Weifeng; Chen, Libao; Pan, Anqiang Nano Energy, Vol. 30 https://doi.org/10.1016/j.nanoen.2016.10.066	journal	December 2016
Ni/Li Disordering in Layered Transition Metal Oxide: Electrochemical Impact, Origin, and Control Zheng, Jiaxin; Ye, Yaokun; Liu, Tongchao Accounts of Chemical Research, Vol. 52, Issue 8 https://doi.org/10.1021/acs.accounts.9b00033	journal	June 2019
Probing Reversible Multielectron Transfer and Structure Evolution of Li _1.2 Cr _0.4 Mn _0.4 O ₂ Cathode Material for Li-Ion Batteries in a Voltage Range of 1.0–4.8 V Lyu, Yingchun; Zhao, Nijie; Hu, Enyuan Chemistry of Materials, Vol. 27, Issue 15 https://doi.org/10.1021/acs.chemmater.5b01362	journal	July 2015
Correlations between Transition-Metal Chemistry, Local Structure, and Global Structure in Li ₂ Ru _0.5 Mn _0.5 O ₃ Investigated in a Wide Voltage Window Lyu, Yingchun; Hu, Enyuan; Xiao, Dongdong Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b02299	journal	November 2017
Switch of the Charge Storage Mechanism of Li _x Ni _0.80 Co _0.15 Al _0.05 O ₂ at Overdischarge Conditions Robert, Rosa; Novák, Petr Chemistry of Materials, Vol. 30, Issue 6 https://doi.org/10.1021/acs.chemmater.7b04784	journal	March 2018
O2-Type Li_0.78[Li_0.24Mn_0.76]O₂ Nanowires for High-Performance Lithium-Ion Battery Cathode Shang, Huaifang; Zuo, Yuxuan; Shen, Feiran Nano Letters, Vol. 20, Issue 8 https://doi.org/10.1021/acs.nanolett.0c01640	journal	July 2020
One-Pot Synthesis of Lithium-Rich Cathode Material with Hierarchical Morphology Luo, Kun; Roberts, Matthew R.; Hao, Rong Nano Letters, Vol. 16, Issue 12 https://doi.org/10.1021/acs.nanolett.6b03296	journal	November 2016
Novel Ordered Rocksalt-Type Lithium-Rich Li ₂ Ru _{1– x} Ni _x O _3−δ (0.3 ≤ x ≤ 0.5) Cathode Material with Tunable Anionic Redox Potential Zheng, Shiyao; Zheng, Feng; Liu, Haodong ACS Applied Energy Materials, Vol. 2, Issue 8 https://doi.org/10.1021/acsaem.9b01051	journal	June 2019
Distinct Oxygen Redox Activities in Li₂MO₃ (M = Mn, Ru, Ir) Zhuo, Zengqing; Dai, Kehua; Wu, Jinpeng ACS Energy Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acsenergylett.1c01101	journal	September 2021
⁶ Li MAS NMR Studies of the Local Structure and Electrochemical Properties of Cr-doped Lithium Manganese and Lithium Cobalt Oxide Cathode Materials for Lithium-Ion Batteries Pan, Chanjuan; Lee, Young Joo; Ammundsen, Brett Chemistry of Materials, Vol. 14, Issue 5 https://doi.org/10.1021/cm011623u	journal	May 2002
Synthesis, Electrochemical Properties, and Phase Stability of Li ₂ NiO ₂ with the Immm Structure Kang, Kisuk; Chen, Ching-Hsiang; Hwang, Bing Joe Chemistry of Materials, Vol. 16, Issue 13 https://doi.org/10.1021/cm049922h	journal	June 2004
A First-Principles Approach to Studying the Thermal Stability of Oxide Cathode Materials Wang, L.; Maxisch, T.; Ceder, G. Chemistry of Materials, Vol. 19, Issue 3 https://doi.org/10.1021/cm0620943	journal	February 2007
Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution Jarvis, Karalee A.; Deng, Zengqiang; Allard, Lawrence F. Chemistry of Materials, Vol. 23, Issue 16 https://doi.org/10.1021/cm200831c	journal	August 2011
Structural and Chemical Evolution of Li- and Mn-Rich Layered Cathode Material Zheng, Jianming; Xu, Pinghong; Gu, Meng Chemistry of Materials, Vol. 27, Issue 4 https://doi.org/10.1021/cm5045978	journal	February 2015
Electrochemical and Structural Study of the Layered, “Li-Excess” Lithium-Ion Battery Electrode Material Li[Li _1/9 Ni _1/3 Mn _5/9 ]O ₂ Jiang, Meng; Key, Baris; Meng, Ying S. Chemistry of Materials, Vol. 21, Issue 13 https://doi.org/10.1021/cm900279u	journal	July 2009
NMR Studies of Cathode Materials for Lithium-Ion Rechargeable Batteries Grey, Clare P.; Dupré, Nicolas Chemical Reviews, Vol. 104, Issue 10 https://doi.org/10.1021/cr020734p	journal	October 2004
Weakly Solvating Solution Enables Chemical Prelithiation of Graphite–SiO _x Anodes for High-Energy Li-Ion Batteries Choi, Jinkwan; Jeong, Hyangsoo; Jang, Juyoung Journal of the American Chemical Society, Vol. 143, Issue 24 https://doi.org/10.1021/jacs.1c03648	journal	June 2021
New Insight into the Atomic Structure of Electrochemically Delithiated O3-Li _{(1– x )} CoO ₂ (0 ≤ x ≤ 0.5) Nanoparticles Lu, Xia; Sun, Yang; Jian, Zelang Nano Letters, Vol. 12, Issue 12 https://doi.org/10.1021/nl303036e	journal	February 2012
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries Gu, Meng; Belharouak, Ilias; Zheng, Jianming ACS Nano, Vol. 7, Issue 1 https://doi.org/10.1021/nn305065u	journal	December 2012
Quantification of thickness and wrinkling of exfoliated two-dimensional zeolite nanosheets Kumar, Prashant; Agrawal, Kumar Varoon; Tsapatsis, Michael Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8128	journal	May 2015
Intrinsic ripples in graphene Fasolino, A.; Los, J. H.; Katsnelson, M. I. Nature Materials, Vol. 6, Issue 11 https://doi.org/10.1038/nmat2011	journal	September 2007
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
Structural evolution at the oxidative and reductive limits in the first electrochemical cycle of Li1.2Ni0.13Mn0.54Co0.13O2 Yin, Wei; Grimaud, Alexis; Rousse, Gwenaelle Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14927-4	journal	March 2020
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries Assat, Gaurav; Tarascon, Jean-Marie Nature Energy, Vol. 3, Issue 5 https://doi.org/10.1038/s41560-018-0097-0	journal	April 2018
Ultrahigh power and energy density in partially ordered lithium-ion cathode materials Ji, Huiwen; Wu, Jinpeng; Cai, Zijian Nature Energy, Vol. 5, Issue 3 https://doi.org/10.1038/s41560-020-0573-1	journal	March 2020
Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes Eum, Donggun; Kim, Byunghoon; Kim, Sung Joo Nature Materials, Vol. 19, Issue 4 https://doi.org/10.1038/s41563-019-0572-4	journal	January 2020
Injection of oxygen vacancies in the bulk lattice of layered cathodes Yan, Pengfei; Zheng, Jianming; Tang, Zhen-Kun Nature Nanotechnology, Vol. 14, Issue 6 https://doi.org/10.1038/s41565-019-0428-8	journal	April 2019
Structural origin of the high-voltage instability of lithium cobalt oxide Li, Jianyuan; Lin, Cong; Weng, Mouyi Nature Nanotechnology, Vol. 16, Issue 5 https://doi.org/10.1038/s41565-021-00855-x	journal	February 2021
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
Superstructure control of first-cycle voltage hysteresis in oxygen-redox cathodes House, Robert A.; Maitra, Urmimala; Pérez-Osorio, Miguel A. Nature, Vol. 577, Issue 7791 https://doi.org/10.1038/s41586-019-1854-3	journal	December 2019
Understanding structural stability of monoclinic LiMnO 2 and NaMnO 2 upon de-intercalation Tian, Meng; Gao, Yurui; Wang, Zhaoxiang Physical Chemistry Chemical Physics, Vol. 18, Issue 26 https://doi.org/10.1039/C6CP02019D	journal	January 2016
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
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
Harnessing the surface structure to enable high-performance cathode materials for lithium-ion batteries Yang, Luyi; Yang, Kai; Zheng, Jiaxin Chemical Society Reviews, Vol. 49, Issue 14 https://doi.org/10.1039/D0CS00137F	journal	January 2020
Rechargeable lithium batteries Owen, John R. Chemical Society Reviews, Vol. 26, Issue 4 https://doi.org/10.1039/cs9972600259	journal	January 1997
Photon-in/photon-out endstation for studies of energy materials at beamline 02B02 of Shanghai Synchrotron Radiation Facility Ren, Guoxi; Zhang, Nian; Feng, Xuefei Chinese Physics B, Vol. 29, Issue 1 https://doi.org/10.1088/1674-1056/ab5d04	journal	January 2020
Band theory and Mott insulators: Hubbard U instead of Stoner I Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K. Physical Review B, Vol. 44, Issue 3, p. 943-954 https://doi.org/10.1103/PhysRevB.44.943	journal	July 1991
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Structural stability of lithium manganese oxides Mishra, S. K.; Ceder, G. Physical Review B, Vol. 59, Issue 9 https://doi.org/10.1103/PhysRevB.59.6120	journal	March 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
TOPAS and TOPAS-Academic : an optimization program integrating computer algebra and crystallographic objects written in C++ Coelho, Alan A. Journal of Applied Crystallography, Vol. 51, Issue 1 https://doi.org/10.1107/S1600576718000183	journal	February 2018
High-Performance Li-Rich Layered Transition Metal Oxide Cathode Materials for Li-Ion Batteries Redel, Katarzyna; Kulka, Andrzej; Plewa, Anna Journal of The Electrochemical Society, Vol. 166, Issue 3 https://doi.org/10.1149/2.0511903jes	journal	January 2019

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25 ENERGY STORAGE
Li-ion batteries
elastic lattices
layered oxide cathodes
reversible tetrahedral sites
ultrahigh capacity

Title: Elastic Lattice Enabling Reversible Tetrahedral Li Storage Sites in a High-Capacity Manganese Oxide Cathode

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