Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes

Wang, Faxing; Zuo, Peng; Xue, Zhichen; Liu, Yijin; Wang, Chongmin; Chen, Guoying

doi:10.1021/acsenergylett.3c02697

Title: Fluorination Effect on Lithium- and Manganese-Rich Layered Oxide Cathodes

Journal Article · 27 February 2024 · ACS Energy Letters

DOI: https://doi.org/10.1021/acsenergylett.3c02697 · OSTI ID:2315063

Wang, Faxing ^[1];

^[2]; Xue, Zhichen ^[3]; Liu, Yijin ^[3];

^[2];

^[1]

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Lithium- and manganese-rich (LMR) layered oxides are promising high-energy cathodes for next-generation lithium-ion batteries, yet their commercialization has been hindered by a number of performance issues. While fluorination has been explored as a mitigating approach, results from polycrystalline- particle-based studies are inconsistent and the mechanism for improvement in some reports remains unclear. In the present study, we develop an in situ fluorination method that leads to fluorinated LMR with no apparent impurities. Using well-defined single-crystal Li_1.2Ni_0.2Mn_0.6O₂ (LNMO) as a platform, we show that a high fluorination level leads to decreased oxygen activities, reduced side reactions at high voltages, and a broadly improved cathode performance. Detailed characterization reveals a particle-level Mn³⁺ concentration gradient from the surface to the bulk of fluorinated-LNMO crystals, ascribed to the formation of a Nirich Li_zNi_xMn_2–xO_4–yF_y (x > 0.5) spinel phase on the surface and a “spinel-layered” coherent structure in the bulk where domains of a LiNi_0.5Mn_1.5O₄ high-voltage spinel phase are integrated into the native layered framework. This work provides fundamental understanding of the fluorination effect on LMR and key insights for future development of high-energy Mn-based cathodes with an intergrown/composite crystal structure.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830; AC02-76SF00515

OSTI ID:: 2315063

Alternate ID(s):: OSTI ID: 2322412; OSTI ID: 2322511

Report Number(s):: PNNL-SA-195217

Journal Information:: ACS Energy Letters, Vol. 9, Issue 3; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (51)

Surface F-doping for stable structure and high electrochemical performance of Li-rich Mn-based cathode materials Wang, Bo; Cui, Jing; Li, Zhaojin Journal of Alloys and Compounds, Vol. 929 https://doi.org/10.1016/j.jallcom.2022.167304	journal	December 2022
Advances in Stabilizing ‘Layered-Layered’ xLi₂MnO₃·(1-x)LiMO₂(M=Mn, Ni, Co) Electrodes with a Spinel Component Long, Brandon R.; Croy, Jason R.; Park, Joong Sun Journal of The Electrochemical Society, Vol. 161, Issue 14, p. A2160-A2167 https://doi.org/10.1149/2.0681414jes	journal	January 2014
Addressing voltage decay in Li-rich cathodes by broadening the gap between metallic and anionic bands Zhang, Jicheng; Zhang, Qinghua; Wong, Deniz Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23365-9	journal	May 2021
Suppressing Mn Reduction of Li-Rich Mn-Based Cathodes by F-Doping for Advanced Lithium-Ion Batteries Wang, Yong; Gu, Hai-Tao; Song, Jin-Hua The Journal of Physical Chemistry C, Vol. 122, Issue 49 https://doi.org/10.1021/acs.jpcc.8b08669	journal	November 2018
Enhanced Electrochemical Performance of Li-Rich Cathode Materials by Organic Fluorine Doping and Spinel Li _{1+ x} Ni _y Mn _{2– y} O ₄ Coating Chen, Shengzhou; Xie, Yuxiang; Chen, Wen ACS Sustainable Chemistry & Engineering, Vol. 8, Issue 1 https://doi.org/10.1021/acssuschemeng.9b04665	journal	November 2019
Enhance performances of Co-free Li-rich cathode by eutesctic melting salt treatment Zhao, He; Li, Wenting; Li, Jinxing Nano Energy, Vol. 92 https://doi.org/10.1016/j.nanoen.2021.106760	journal	February 2022
Direct Visualization of the Reversible O ²⁻ /O ⁻ Redox Process in Li-Rich Cathode Materials Li, Xiang; Qiao, Yu; Guo, Shaohua Advanced Materials, Vol. 30, Issue 14 https://doi.org/10.1002/adma.201705197	journal	February 2018
Single-crystal Li-rich layered cathodes with suppressed voltage decay by double-layer interface engineering Zeng, Weihao; Liu, Fang; Yang, Jinlong Energy Storage Materials, Vol. 54 https://doi.org/10.1016/j.ensm.2022.11.016	journal	January 2023
Accurate Control of Initial Coulombic Efficiency for Lithium‐rich Manganese‐based Layered Oxides by Surface Multicomponent Integration Luo, Dong; Ding, Xiaokai; Fan, Jianming Angewandte Chemie International Edition, Vol. 59, Issue 51 https://doi.org/10.1002/anie.202010531	journal	October 2020
Gradient “Single‐Crystal” Li‐Rich Cathode Materials for High‐Stable Lithium‐Ion Batteries Wu, Tianhao; Zhang, Xu; Wang, Yinzhong Advanced Functional Materials, Vol. 33, Issue 4 https://doi.org/10.1002/adfm.202210154	journal	November 2022
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
Suppressing the voltage-fading of layered lithium-rich cathode materials via an aqueous binder for Li-ion batteries Zhang, Tao; Li, Jun-tao; Liu, Jie Chemical Communications, Vol. 52, Issue 25 https://doi.org/10.1039/C5CC10534J	journal	January 2016
Cathode Electrolyte Interphase Formation and Electrolyte Oxidation Mechanism for Ni-Rich Cathode Materials Takahashi, Ikuma; Kiuchi, Hisao; Ohma, Atsushi The Journal of Physical Chemistry C, Vol. 124, Issue 17 https://doi.org/10.1021/acs.jpcc.0c02198	journal	April 2020
Paving Pathways Toward Long‐Life Graphite/LiNi _0.5 Mn _1.5 O ₄ Full Cells: Electrochemical and Interphasial Points of View Cui, Zehao; Zou, Feng; Celio, Hugo Advanced Functional Materials, Vol. 32, Issue 36 https://doi.org/10.1002/adfm.202203779	journal	June 2022
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
Reaction Mechanisms of Layered Lithium‐Rich Cathode Materials for High‐Energy Lithium‐Ion Batteries Zhao, Shuoqing; Yan, Kang; Zhang, Jinqiang Angewandte Chemie International Edition, Vol. 60, Issue 5 https://doi.org/10.1002/anie.202000262	journal	September 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
Persistent and partially mobile oxygen vacancies in Li-rich layered oxides Csernica, Peter M.; Kalirai, Samanbir S.; Gent, William E. Nature Energy, Vol. 6, Issue 6 https://doi.org/10.1038/s41560-021-00832-7	journal	June 2021
Synthesis of F-doped LiFePO4/C cathode materials for high performance lithium-ion batteries using co-precipitation method with hydrofluoric acid source Gao, Chao; Zhou, Jian; Liu, Guizhen Journal of Alloys and Compounds, Vol. 727 https://doi.org/10.1016/j.jallcom.2017.08.149	journal	December 2017
Composite ‘Layered-Layered-Spinel’ Cathode Structures for Lithium-Ion Batteries Kim, Donghan; Sandi, Giselle; Croy, Jason R. Journal of The Electrochemical Society, Vol. 160, Issue 1, p. A31-A38 https://doi.org/10.1149/2.049301jes	journal	November 2012
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
Synthesis of “Li[sub 1.1](Ni[sub 0.425]Mn[sub 0.425]Co[sub 0.15])[sub 0.9]O[sub 1.8]F[sub 0.2]” Materials by Different Routes: Is There Fluorine Substitution for Oxygen? Croguennec, L.; Bains, J.; Ménétrier, M. Journal of The Electrochemical Society, Vol. 156, Issue 5 https://doi.org/10.1149/1.3080659	journal	January 2009
Effects of Fluorine and Chromium Doping on the Performance of Lithium-Rich Li _{1+ x} MO ₂ (M = Ni, Mn, Co) Positive Electrodes Pang, Wei Kong; Lin, Hsiu-Fen; Peterson, Vanessa K. Chemistry of Materials, Vol. 29, Issue 24 https://doi.org/10.1021/acs.chemmater.7b02930	journal	November 2017
Layered Li(Li_0.2Ni_0.15+0.5zCo_0.10Mn_0.55−0.5z)O_2−zF_z cathode materials for Li-ion secondary batteries Kang, S.-H.; Amine, K. Journal of Power Sources, Vol. 146, Issue 1-2, p. 654-657 https://doi.org/10.1016/j.jpowsour.2005.03.152	journal	August 2005
A cation/anion co-doped Li1.12Na0.08Ni0.2Mn0.6O1.95F0.05 cathode for lithium ion batteries Liu, Dongming; Fan, Xiaojian; Li, Zeheng Nano Energy, Vol. 58 https://doi.org/10.1016/j.nanoen.2019.01.080	journal	April 2019
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release Hu, Enyuan; Yu, Xiqian; Lin, Ruoqian Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0207-z	journal	July 2018
Improving the oxygen redox reversibility of Li-rich battery cathode materials via Coulombic repulsive interactions strategy Li, Qingyuan; Ning, De; Wong, Deniz Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-28793-9	journal	March 2022
Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance Kuppan, Saravanan; Shukla, Alpesh Khushalchand; Membreno, Daniel Advanced Energy Materials, Vol. 7, Issue 11 https://doi.org/10.1002/aenm.201602010	journal	January 2017
Additive engineering for robust interphases to stabilize high-Ni layered structures at ultra-high voltage of 4.8 V Tan, Sha; Shadike, Zulipiya; Li, Jizhou Nature Energy, Vol. 7, Issue 6 https://doi.org/10.1038/s41560-022-01020-x	journal	May 2022
Ni and Co Segregations on Selective Surface Facets and Rational Design of Layered Lithium Transition-Metal Oxide Cathodes Yan, Pengfei; Zheng, Jianming; Zheng, Jiaxin Advanced Energy Materials, Vol. 6, Issue 9 https://doi.org/10.1002/aenm.201502455	journal	February 2016
Gradient Li-rich oxide cathode particles immunized against oxygen release by a molten salt treatment Zhu, Zhi; Yu, Daiwei; Yang, Yang Nature Energy, Vol. 4, Issue 12 https://doi.org/10.1038/s41560-019-0508-x	journal	December 2019
Lithium–manganese–nickel-oxide electrodes with integrated layered–spinel structures for lithium batteries Park, S.; Kang, S.; Johnson, C. Electrochemistry Communications, Vol. 9, Issue 2, p. 262-268 https://doi.org/10.1016/j.elecom.2006.09.014	journal	February 2007
Origin of structural degradation in Li-rich layered oxide cathode Liu, Tongchao; Liu, Jiajie; Li, Luxi Nature, Vol. 606, Issue 7913 https://doi.org/10.1038/s41586-022-04689-y	journal	June 2022
Fluorination of Lithium-Excess Transition Metal Oxide Cathode Materials Richards, William D.; Dacek, Stephen T.; Kitchaev, Daniil A. Advanced Energy Materials, Vol. 8, Issue 5 https://doi.org/10.1002/aenm.201701533	journal	October 2017
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
Cathode Electrolyte Interface Engineering by Gradient Fluorination for High‐Performance Lithium Rich Cathode Di, Lu; Yufang, Chen; Weiwei, Sun Advanced Energy Materials, Vol. 13, Issue 34 https://doi.org/10.1002/aenm.202301765	journal	July 2023
Fluoroacidity evaluation in molten salts Bieber, A. L.; Massot, L.; Gibilaro, M. Electrochimica Acta, Vol. 56, Issue 14 https://doi.org/10.1016/j.electacta.2011.03.099	journal	May 2011
Role of Substitution Elements in Enhancing the Structural Stability of Li-Rich Layered Cathodes Zhang, Baodan; Zhang, Yiming; Wang, Xiaotong Journal of the American Chemical Society https://doi.org/10.1021/jacs.3c01999	journal	April 2023
Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification Vanaphuti, Panawan; Bai, Jianming; Ma, Lu Energy Storage Materials, Vol. 31 https://doi.org/10.1016/j.ensm.2020.08.003	journal	October 2020
NMR evidence of LiF coating rather than fluorine substitution in Li(Ni0.425Mn0.425Co0.15)O2 Ménétrier, M.; Bains, J.; Croguennec, L. Journal of Solid State Chemistry, Vol. 181, Issue 12 https://doi.org/10.1016/j.jssc.2008.09.002	journal	December 2008
Surface modification by fluorine doping to increase discharge capacity of Li1.2Ni0.2Mn0.6O2 cathode materials Jiang, Yun-shan; Sun, Gang; Yu, Fu-da Ionics, Vol. 26, Issue 1 https://doi.org/10.1007/s11581-019-03202-2	journal	August 2019
Elucidating anionic oxygen activity in lithium-rich layered oxides Xu, Jing; Sun, Meiling; Qiao, Ruimin Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03403-9	journal	March 2018
Oxygen Redox Chemistry in Rechargeable Li-Ion and Na-Ion Batteries Rahman, Muhammad Mominur; Lin, Feng Matter, Vol. 4, Issue 2 https://doi.org/10.1016/j.matt.2020.12.004	journal	February 2021
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides Gent, William E.; Lim, Kipil; Liang, Yufeng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02041-x	journal	December 2017
Understanding the Role of NH ₄ F and Al ₂ O ₃ Surface Co-modification on Lithium-Excess Layered Oxide Li _1.2 Ni _0.2 Mn _0.6 O ₂ Liu, Haodong; Qian, Danna; Verde, Michael G. ACS Applied Materials & Interfaces, Vol. 7, Issue 34 https://doi.org/10.1021/acsami.5b04932	journal	August 2015
Li-rich cathodes for rechargeable Li-based batteries: reaction mechanisms and advanced characterization techniques Zuo, Wenhua; Luo, Mingzeng; Liu, Xiangsi Energy & Environmental Science, Vol. 13, Issue 12 https://doi.org/10.1039/D0EE01694B	journal	January 2020
Regulating the Potential of Anion Redox to Reduce the Voltage Hysteresis of Li-Rich Cathode Materials Zuo, Yuxuan; Shang, Huaifang; Hao, Jiazheng Journal of the American Chemical Society, Vol. 145, Issue 9 https://doi.org/10.1021/jacs.2c11640	journal	February 2023
Highly reversible oxygen redox in layered compounds enabled by surface polyanions Chen, Qing; Pei, Yi; Chen, Houwen Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-17126-3	journal	July 2020
Cationic–anionic redox couple gradient to immunize against irreversible processes of Li-rich layered oxides Pei, Yi; Li, Shuang; Chen, Qing Journal of Materials Chemistry A, Vol. 9, Issue 4 https://doi.org/10.1039/D0TA09609A	journal	January 2021
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
LiNi_0.5Mn_1.5O₄ Cathode Microstructure for All-Solid-State Batteries Lee, Hyeon Jeong; Liu, Xiaoxiao; Chart, Yvonne Nano Letters, Vol. 22, Issue 18 https://doi.org/10.1021/acs.nanolett.2c02426	journal	September 2022

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