Structure and Interface Design Enable Stable Li-Rich Cathode

Cui, Chunyu; Fan, Xiulin; Zhou, Xiuquan; Chen, Ji; Wang, Qinchao; Ma, Lu; Yang, Chongyin; Hu, Enyuan; Yang, Xiao-Qing; Wang, Chunsheng

doi:10.1021/jacs.0c02302

Title: Structure and Interface Design Enable Stable Li-Rich Cathode

Journal Article · Wed Apr 22 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c02302· OSTI ID:1616447

Cui, Chunyu ^[1];

^[2];

^[1];

^[1]; Wang, Qinchao ^[3]; Ma, Lu ^[4];

^[1];

^[3];

^[1]

Univ. of Maryland, College Park, MD (United States)
Zhejiang Univ., Hangzhou (China)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Li-rich layered-oxide cathodes have the highest theoretical energy density among all the intercalated cathodes, which have attracted intense interests for high energy Li-ion batteries. However, O3-structured layered-oxide cathodes suffer from a low initial Coulombic efficiency (CE), severe voltage fade, and poor cycling stability because of the continuous oxygen release, structural rearrangements due to irreversible transition-metal migration, and serious side reactions between the delithiated cathode and electrolyte. In this work, we report that these challenges are migrated by using a stable O2-structured Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ (O2-LR-NCM) and all-fluorinated electrolyte. The O2-LR-NCM can restrict the transition metals migrating into the Li layer and the in situ formed fluorinated cathode electrolyte interphase (CEI) on the surface of the O2-LR-NCM from the decomposition of all-fluorinated electrolyte during initial cycles effectively restrains the structure transition, suppresses the O2 release, and thereby safeguards the transition metal redox couples, enabling a highly reversible and stable oxygen redox reaction. O2-LR-NCM in all fluorinated electrolytes achieves a high initial CE of 99.82 % and cycling CE of and cycling CE of >99.9%, high reversible capacity of 278 mAh/g, and high capacity retention of 83.3% after 100 cycles. The synergic design of electrolyte and cathode structure represents a promising direction to stabilize high-energy cathodes.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); national Science Foundation (NSF)

Grant/Contract Number:: SC0012704; EE0008200

OSTI ID:: 1616447

Report Number(s):: BNL-215884-2020-JAAM

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 19; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 121 works

Citation information provided by
Web of Science

References (49)

Towards greener and more sustainable batteries for electrical energy storage Larcher, D.; Tarascon, J-M. Nature Chemistry, Vol. 7, Issue 1 https://doi.org/10.1038/nchem.2085	journal	November 2014
Promise and reality of post-lithium-ion batteries with high energy densities Choi, Jang Wook; Aurbach, Doron Nature Reviews Materials, Vol. 1, Issue 4 https://doi.org/10.1038/natrevmats.2016.13	journal	March 2016
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Lithium metal rechargeable cells using Li2MnO3 as the positive electrode Kalyani, P.; Chitra, S.; Mohan, T. Journal of Power Sources, Vol. 80, Issue 1-2 https://doi.org/10.1016/S0378-7753(99)00066-X	journal	July 1999
Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries Lu, Zhonghua; MacNeil, D. D.; Dahn, J. R. Electrochemical and Solid-State Letters, Vol. 4, Issue 11 https://doi.org/10.1149/1.1407994	journal	January 2001
Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li- and Mn-Rich Cathode Materials for Li-Ion Batteries Nayak, Prasant Kumar; Erickson, Evan M.; Schipper, Florian Advanced Energy Materials, Vol. 8, Issue 8 https://doi.org/10.1002/aenm.201702397	journal	December 2017
Li‐ and Mn‐Rich Cathode Materials: Challenges to Commercialization Zheng, Jianming; Myeong, Seungjun; Cho, Woongrae Advanced Energy Materials, Vol. 7, Issue 6 https://doi.org/10.1002/aenm.201601284	journal	December 2016
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen Luo, Kun; Roberts, Matthew R.; Hao, Rong Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2471	journal	March 2016
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
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
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
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
Surface-to-Bulk Redox Coupling through Thermally Driven Li Redistribution in Li- and Mn-Rich Layered Cathode Materials Li, Shaofeng; Lee, Sang-Jun; Wang, Xuelong Journal of the American Chemical Society, Vol. 141, Issue 30 https://doi.org/10.1021/jacs.9b05349	journal	July 2019
Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study Mohanty, Debasish; Sefat, Athena S.; Li, Jianlin Physical Chemistry Chemical Physics, Vol. 15, Issue 44 https://doi.org/10.1039/c3cp53658k	journal	January 2013
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
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries Boulineau, Adrien; Simonin, Loïc; Colin, Jean-François Nano Letters, Vol. 13, Issue 8 https://doi.org/10.1021/nl4019275	journal	July 2013
The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li₂MnO₃ ∙ 0.5 LiNi_0.44Co_0.25Mn_0.31O₂ Electrodes in Lithium Cells Kang, S.-H.; Johnson, C. S.; Vaughey, J. T. Journal of The Electrochemical Society, Vol. 153, Issue 6, p. A1186-A1192 https://doi.org/10.1149/1.2194764	journal	January 2006
Surface Modification of Li-Excess Mn-based Cathode Materials Yu, Denis Y. W.; Yanagida, Katsunori; Nakamura, Hiroshi Journal of The Electrochemical Society, Vol. 157, Issue 11 https://doi.org/10.1149/1.3479382	journal	January 2010
Enhancing the Kinetics of Li-Rich Cathode Materials through the Pinning Effects of Gradient Surface Na ⁺ Doping Qing, Ren-Peng; Shi, Ji-Lei; Xiao, Dong-Dong Advanced Energy Materials, Vol. 6, Issue 6 https://doi.org/10.1002/aenm.201501914	journal	December 2015
High Capacity, Surface-Modified Layered Li [Li _(1−x) ∕ ₃Mn _(2−x) ∕ ₃Ni_x ∕ ₃Co_{x ∕ 3} ] O₂ Cathodes with Low Irreversible Capacity Loss Wu, Y.; Manthiram, A. Electrochemical and Solid-State Letters, Vol. 9, Issue 5, p. A221-A224 https://doi.org/10.1149/1.2180528	journal	March 2006
Eliminating the irreversible capacity loss of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode by blending with other lithium insertion hosts Gao, J.; Manthiram, A. Journal of Power Sources, Vol. 191, Issue 2 https://doi.org/10.1016/j.jpowsour.2009.02.005	journal	June 2009
Understanding the Effect of Lithium Bis(oxalato) Borate (LiBOB) on the Structural and Electrochemical Aging of Li and Mn Rich High Capacity Li _1.2 Ni _0.16 Mn _0.56 Co _0.08 O ₂ Cathodes Nayak, Prasant Kumar; Grinblat, Judith; Levi, Mikhael Journal of The Electrochemical Society, Vol. 162, Issue 4 https://doi.org/10.1149/2.0251504jes	journal	January 2015
Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution Zheng, Jianming; Gu, Meng; Genc, Arda Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl500486y	journal	April 2014
Lithium Deficiencies Engineering in Li-Rich Layered Oxide Li _1.098 Mn _0.533 Ni _0.113 Co _0.138 O ₂ for High-Stability Cathode Liu, Pengfei; Zhang, Hong; He, Wei Journal of the American Chemical Society, Vol. 141, Issue 27 https://doi.org/10.1021/jacs.9b04974	journal	June 2019
Al Doping for Mitigating the Capacity Fading and Voltage Decay of Layered Li and Mn-Rich Cathodes for Li-Ion Batteries Nayak, Prasant Kumar; Grinblat, Judith; Levi, Mikhael Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201502398	journal	February 2016
The effects of Mo doping on 0.3Li[Li0.33Mn0.67]O2·0.7Li[Ni0.5Co0.2Mn0.3]O2 cathode material Park, Jin-Hwan; Lim, Jinsub; Yoon, Jaegu Dalton Transactions, Vol. 41, Issue 10 https://doi.org/10.1039/c2dt11833e	journal	January 2012
The effects of TiO2 coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium-ion battery Zheng, J. M.; Li, J.; Zhang, Z. R. Solid State Ionics, Vol. 179, Issue 27-32 https://doi.org/10.1016/j.ssi.2008.01.091	journal	September 2008
Improving high-capacity Li1.2Ni0.15Mn0.55Co0.1O2-based lithium-ion cells by modifiying the positive electrode with alumina Bettge, Martin; Li, Yan; Sankaran, Bharat Journal of Power Sources, Vol. 233 https://doi.org/10.1016/j.jpowsour.2013.01.082	journal	July 2013
Cobalt-Free O2-Type Lithium-Rich Layered Oxides de Boisse, Benoit Mortemard; Jang, Jeonguk; Okubo, Masashi Journal of The Electrochemical Society, Vol. 165, Issue 16 https://doi.org/10.1149/2.1331814jes	journal	January 2018
New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries Yabuuchi, Naoaki; Hara, Ryo; Kajiyama, Masataka Advanced Energy Materials, Vol. 4, Issue 13 https://doi.org/10.1002/aenm.201301453	journal	May 2014
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
A new variety of LiCoO2 with an unusual oxygen packing obtained by exchange reaction Delmas, Claude; Braconnier, Jean-Jacques; Hagenmuller, Paul Materials Research Bulletin, Vol. 17, Issue 1 https://doi.org/10.1016/0025-5408(82)90192-1	journal	January 1982
Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries Fan, Xiulin; Chen, Long; Borodin, Oleg Nature Nanotechnology, Vol. 13, Issue 8 https://doi.org/10.1038/s41565-018-0183-2	journal	July 2018
Designing In-Situ-Formed Interphases Enables Highly Reversible Cobalt-Free LiNiO2 Cathode for Li-ion and Li-metal Batteries Deng, Tao; Fan, Xiulin; Cao, Longsheng Joule, Vol. 3, Issue 10 https://doi.org/10.1016/j.joule.2019.08.004	journal	October 2019
Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery Fan, Xiulin; Ji, Xiao; Han, Fudong Science Advances, Vol. 4, Issue 12 https://doi.org/10.1126/sciadv.aau9245	journal	December 2018
Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction Mohanty, Debasish; Kalnaus, Sergiy; Meisner, Roberta A. Journal of Power Sources, Vol. 229 https://doi.org/10.1016/j.jpowsour.2012.11.144	journal	May 2013
Uniform Li1.2Ni0.13Co0.13Mn0.54O2 hollow microspheres with improved electrochemical performance by a facile solvothermal method for lithium ion batteries Li, Honglei; Wei, Xin; Yang, Puheng Electrochimica Acta, Vol. 261 https://doi.org/10.1016/j.electacta.2017.10.119	journal	January 2018
Lithium Extraction Mechanism in Li-Rich Li ₂ MnO ₃ Involving Oxygen Hole Formation and Dimerization Chen, Hungru; Islam, M. Saiful Chemistry of Materials, Vol. 28, Issue 18 https://doi.org/10.1021/acs.chemmater.6b02870	journal	September 2016
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries Saubanère, M.; McCalla, E.; Tarascon, J. -M. Energy & Environmental Science, Vol. 9, Issue 3 https://doi.org/10.1039/C5EE03048J	journal	January 2016
Strongly frustrated triangular spin lattice emerging from triplet dimer formation in honeycomb Li2IrO3 Nishimoto, Satoshi; Katukuri, Vamshi M.; Yushankhai, Viktor Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10273	journal	January 2016
Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni_0.2Li_0.2Mn_0.6]O₂ Armstrong, A. Robert; Holzapfel, Michael; Novák, Petr Journal of the American Chemical Society, Vol. 128, Issue 26 https://doi.org/10.1021/ja062027+	journal	June 2006
Oxygen-Release-Related Thermal Stability and Decomposition Pathways of Li _x Ni _0.5 Mn _1.5 O ₄ Cathode Materials Hu, Enyuan; Bak, Seong-Min; Liu, Jue Chemistry of Materials, Vol. 26, Issue 2 https://doi.org/10.1021/cm403400y	journal	December 2013
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
Stable lithium electrodeposition in liquid and nanoporous solid electrolytes Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A. Nature Materials, Vol. 13, Issue 10 https://doi.org/10.1038/nmat4041	journal	August 2014
Achieving High Energy Density through Increasing the Output Voltage: A Highly Reversible 5.3 V Battery Chen, Long; Fan, Xiulin; Hu, Enyuan Chem, Vol. 5, Issue 4 https://doi.org/10.1016/j.chempr.2019.02.003	journal	April 2019
Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi1/3Mn1/3Co1/3O2 in half cells with Li metal counter electrode Qian, Yunxian; Niehoff, Philip; Börner, Markus Journal of Power Sources, Vol. 329 https://doi.org/10.1016/j.jpowsour.2016.08.023	journal	October 2016
Surface chemistry of metal oxide coated lithium manganese nickel oxide thin film cathodes studied by XPS Baggetto, Loïc; Dudney, Nancy J.; Veith, Gabriel M. Electrochimica Acta, Vol. 90 https://doi.org/10.1016/j.electacta.2012.11.120	journal	February 2013
Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries Li, Wangda; Dolocan, Andrei; Oh, Pilgun Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14589	journal	April 2017
Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes Jurng, Sunhyung; Brown, Zachary L.; Kim, Jiyeon Energy & Environmental Science, Vol. 11, Issue 9 https://doi.org/10.1039/C8EE00364E	journal	January 2018

Similar Records

Electrolytes Polymerization‐Induced Cathode‐Electrolyte‐Interphase for High Voltage Lithium‐Ion Batteries

Journal Article · Sun Sep 12 00:00:00 EDT 2021 · Advanced Energy Materials · OSTI ID:1616447

Yang, Jixiang; Liu, Xiang; Wang, Yian; +11 more

Depth-Dependent Understanding of Cathode Electrolyte Interphase (CEI) on the Layered Li-Ion Cathodes Operated at Extreme High Temperature

Journal Article · Tue May 03 00:00:00 EDT 2022 · Chemistry of Materials · OSTI ID:1616447

Nagarajan, Sudhan; Weiland, Conan; Hwang, Sooyeon; +2 more

Bulk Oxygen Stabilization via Electrode‐Electrolyte Interphase Tailored Surface Activities of Li‐Rich Cathodes

Journal Article · Wed Nov 23 00:00:00 EST 2022 · Advanced Energy Materials · OSTI ID:1616447

Zhang, Xu; Zhao, Jingteng; Lee, Gi‐Hyeok; +6 more

Related Subjects

25 ENERGY STORAGE
Li-rich cathodes
O2-structure
fluorinated CEI
high initial Columbic efficiency
little voltage fade

Title: Structure and Interface Design Enable Stable Li-Rich Cathode

Citation Formats

References (49)

Similar Records

Related Subjects