In Situ Conversion of Artificial Proton‐Rich Shell to Inorganic Maskant Toward Stable Single‐Crystal Ni‐Rich Cathode

Xue, Haoyu; Liang, Yongzhi; Huang, Yuxiang; Ji, Yuchen; Xu, Zhongxing; Chen, Xinhan; Wang, Honghao; Liu, Jiajie; Amine, Khalil; Liu, Tongchao; Tan, Xinghua; Pan, Feng

doi:10.1002/adma.202415860

In Situ Conversion of Artificial Proton‐Rich Shell to Inorganic Maskant Toward Stable Single‐Crystal Ni‐Rich Cathode

Journal Article · Thu Dec 26 00:00:00 EST 2024 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202415860· OSTI ID:2572895

Xue, Haoyu ^[1]; Liang, Yongzhi ^[1]; Huang, Yuxiang ^[2]; Ji, Yuchen ^[1]; Xu, Zhongxing ^[1]; Chen, Xinhan ^[3]; Wang, Honghao ^[4]; Liu, Jiajie ^[1]; Amine, Khalil ^[5]; Liu, Tongchao ^[5]; Tan, Xinghua ^[6]; ^[1]

Peking University, Shenzhen (China)
Univ. of Hong Kong (China)
Sun Yat‐sen University, Shenzhen (China)
The Chinese University of Hong Kong, Shenzhen (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Peking University, Shenzhen (China); Chinese Academy of Sciences (CAS), Shenyang (China)

Single-crystal high-nickel oxide with an integral structure can prevent intergranular cracks and the associated detrimental reactions. Yet, its low surface-to-volume ratio makes surficial degradation a more critical factor in electrochemical performance. Herein, artificial proton-rich (ammonium bicarbonate) shell is successfully introduced on the nickel-rich LiNi_0.92Co_0.06Mn_0.02O₂ single crystals for in situ electrochemically conversing into inorganic maskant to enhance stability of cathode. The process is that the surficial enriched proton, once released from the ammonium bicarbonate shell (proton reservoir) during 1st charge, is immediately captured by LiPF₆, in situ electrochemically conversing to LiF and Li₃PO₄ sub-nano particle dense maskant (sub-nano F-&P-maskant). The in situ formed compact nano F-&P-maskant significantly resists the cathode against electrolyte attack and improves the surface stability of particles during long-term cycling. Consequently, this surface modification enables 95% capacity retention after 100 cycles at a high voltage of 4.5 V in the half cell and 83% capacity retention after 800 cycles in the full cell. In conclusion, this work demonstrates a strategy for reconstructing the protective layer using the rational design of surficial enriched proton shells for advanced lithium batteries.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Basic and Applied Basic Research Foundation of Guangdong Province; Guangdong Key Laboratory of Design and calculation of New Energy Materials; International joint Research Center for Electric Vehicle Power Battery and Materials; Liaoning Provincial Science Fund for Distinguished Young Scholar; Shenzhen Key Laboratory of New Energy Resources Genome Preparation and Testing; USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2572895

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 7 Vol. 37; ISSN 1521-4095; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

An Air‐Stable High‐Nickel Cathode with Reinforced Electrochemical Performance Enabled by Convertible Amorphous Li ₂ CO ₃ Modification Sheng, Hang; Meng, Xin‐Hai; Xiao, Dong‐Dong Advanced Materials, Vol. 34, Issue 12 https://doi.org/10.1002/adma.202108947	journal	February 2022
Densification of Cathode/Electrolyte Interphase to Enhance Reversibility of LiCoO₂ at 4.65 V Ren, Hengyu; Hu, Jiaxuan; Ji, Haocheng Advanced Materials, Vol. 36, Issue 40 https://doi.org/10.1002/adma.202408875	journal	August 2024
Physical Vapor Deposition in Solid‐State Battery Development: From Materials to Devices Lobe, Sandra; Bauer, Alexander; Uhlenbruck, Sven Advanced Science, Vol. 8, Issue 11 https://doi.org/10.1002/advs.202002044	journal	March 2021
Electrolyte Engineering Toward High Performance High Nickel (Ni ≥ 80%) Lithium‐Ion Batteries Dong, Tiantian; Zhang, Shenghang; Ren, Zhongqin Advanced Science, Vol. 11, Issue 7 https://doi.org/10.1002/advs.202305753	journal	December 2023
Highly Stable Operation of Lithium Metal Batteries Enabled by the Formation of a Transient High-Concentration Electrolyte Layer Zheng, Jianming; Yan, Pengfei; Mei, Donghai Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201502151	journal	February 2016
From Surface ZrO ₂ Coating to Bulk Zr Doping by High Temperature Annealing of Nickel-Rich Lithiated Oxides and Their Enhanced Electrochemical Performance in Lithium Ion Batteries Schipper, Florian; Bouzaglo, Hana; Dixit, Mudit Advanced Energy Materials, Vol. 8, Issue 4 https://doi.org/10.1002/aenm.201701682	journal	September 2017
A Growing Appreciation for the Role of LiF in the Solid Electrolyte Interphase Tan, Jian; Matz, John; Dong, Pei Advanced Energy Materials, Vol. 11, Issue 16 https://doi.org/10.1002/aenm.202100046	journal	March 2021
Safe and Stable Lithium Metal Batteries Enabled by an Amide-Based Electrolyte Wu, Wanbao; Bo, Yiyang; Li, Deping Nano-Micro Letters, Vol. 14, Issue 1 https://doi.org/10.1007/s40820-021-00780-7	journal	January 2022
An Effective Way to Stabilize Ni-Rich Layered Cathodes Lu, Jingyu; Xu, Chao Chem, Vol. 6, Issue 12 https://doi.org/10.1016/j.chempr.2020.11.007	journal	December 2020
Synthesis and electrochemical analysis of vapor-deposited carbon-coated LiFePO4 Belharouak, I.; Johnson, C.; Amine, K. Electrochemistry Communications, Vol. 7, Issue 10 https://doi.org/10.1016/j.elecom.2005.06.019	journal	October 2005
The mechanism of HF formation in LiPF6 based organic carbonate electrolytes Lux, S. F.; Lucas, I. T.; Pollak, E. Electrochemistry Communications, Vol. 14, Issue 1 https://doi.org/10.1016/j.elecom.2011.10.026	journal	January 2012
Construction of core-shell Li3PO4@LiNi0·5Co0·2Mn0·3O2 cathode with improved cycling stability for lithium ion batteries Chen, Hao; Xiao, Li; Chen, Han Electrochimica Acta, Vol. 344 https://doi.org/10.1016/j.electacta.2020.136142	journal	June 2020
Revealing proton-coupled exchange mechanism in aqueous ion-exchange synthesis of nickel-rich layered cathodes for lithium-ion batteries Luo, Yu-Hong; Pan, Qing-Lin; Wei, Han-Xin eScience, Vol. 4, Issue 4 https://doi.org/10.1016/j.esci.2024.100229	journal	August 2024
Enhanced cyclic stability of NCM-622 cathode by Ti3+ doped TiO2 coating Xi, Xiaoshuang; Fan, Yunying; Liu, Yichun Journal of Alloys and Compounds, Vol. 872 https://doi.org/10.1016/j.jallcom.2021.159664	journal	August 2021
Resolving atomic-scale phase transformation and oxygen loss mechanism in ultrahigh-nickel layered cathodes for cobalt-free lithium-ion batteries Wang, Chunyang; Han, Lili; Zhang, Rui Matter, Vol. 4, Issue 6 https://doi.org/10.1016/j.matt.2021.03.012	journal	June 2021
Regulating cation mixing for enhanced structural stability of layered oxide cathodes by ion-exchange strategy Luo, Yu-hong; Pan, Qing-lin; Wei, Han-xin Materials Today, Vol. 69 https://doi.org/10.1016/j.mattod.2023.08.006	journal	October 2023
Significantly improving cycling performance of cathodes in lithium ion batteries: The effect of Al2O3 and LiAlO2 coatings on LiNi0.6Co0.2Mn0.2O2 Liu, Wen; Li, Xifei; Xiong, Dongbin Nano Energy, Vol. 44 https://doi.org/10.1016/j.nanoen.2017.11.010	journal	February 2018
Effect of electrolyte composition on rock salt surface degradation in NMC cathodes during high-voltage potentiostatic holds Tornheim, Adam; Sharifi-Asl, Soroosh; Garcia, Juan C. Nano Energy, Vol. 55 https://doi.org/10.1016/j.nanoen.2018.10.065	journal	January 2019
Improving the reversibility of the H2-H3 phase transitions for layered Ni-rich oxide cathode towards retarded structural transition and enhanced cycle stability Wu, Feng; Liu, Na; Chen, Lai Nano Energy, Vol. 59 https://doi.org/10.1016/j.nanoen.2019.02.027	journal	May 2019
Realizing superior cycling stability of Ni-Rich layered cathode by combination of grain boundary engineering and surface coating Cheng, Xiaopeng; Zheng, Jianming; Lu, Junxia Nano Energy, Vol. 62 https://doi.org/10.1016/j.nanoen.2019.05.021	journal	August 2019
Crack-free single-crystalline Ni-rich layered NCM cathode enable superior cycling performance of lithium-ion batteries Fan, Xinming; Hu, Guorong; Zhang, Bao Nano Energy, Vol. 70 https://doi.org/10.1016/j.nanoen.2020.104450	journal	April 2020
Dual Stabilization and Sacrificial Effect of Na ₂ CO ₃ for Increasing Capacities of Na-Ion Cells Based on P2-Na _x MO ₂ Electrodes Sathiya, Mariyappan; Thomas, Joy; Batuk, Dmitry Chemistry of Materials, Vol. 29, Issue 14 https://doi.org/10.1021/acs.chemmater.7b01542	journal	July 2017
Operando Monitoring of F ^– Formation in Lithium Ion Batteries Bolli, Christoph; Guéguen, Aurélie; Mendez, Manuel A. Chemistry of Materials, Vol. 31, Issue 4 https://doi.org/10.1021/acs.chemmater.8b03810	journal	January 2019
A Mg-Doped High-Nickel Layered Oxide Cathode Enabling Safer, High-Energy-Density Li-Ion Batteries Xie, Qiang; Li, Wangda; Manthiram, Arumugam Chemistry of Materials, Vol. 31, Issue 3 https://doi.org/10.1021/acs.chemmater.8b03900	journal	January 2019
Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries Giordano, Livia; Karayaylali, Pinar; Yu, Yang The Journal of Physical Chemistry Letters, Vol. 8, Issue 16 https://doi.org/10.1021/acs.jpclett.7b01655	journal	August 2017
Chemomechanically Stable Ultrahigh-Ni Single-Crystalline Cathodes with Improved Oxygen Retention and Delayed Phase Degradations Wang, Chunyang; Zhang, Rui; Siu, Carrie Nano Letters, Vol. 21, Issue 22 https://doi.org/10.1021/acs.nanolett.1c03852	journal	November 2021
Beyond Doping and Coating: Prospective Strategies for Stable High-Capacity Layered Ni-Rich Cathodes Sun, H. Hohyun; Ryu, Hoon-Hee; Kim, Un-Hyuck ACS Energy Letters, Vol. 5, Issue 4 https://doi.org/10.1021/acsenergylett.0c00191	journal	March 2020
Electrolyte-Additive-Driven Interfacial Engineering for High-Capacity Electrodes in Lithium-Ion Batteries: Promise and Challenges Kim, Koeun; Ma, Hyunsoo; Park, Sewon ACS Energy Letters, Vol. 5, Issue 5 https://doi.org/10.1021/acsenergylett.0c00468	journal	April 2020
Structural Stability of Single-Crystalline Ni-Rich Layered Cathode upon Delithiation Han, Gi-Mun; Kim, Ye-Sung; Ryu, Hoon-Hee ACS Energy Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsenergylett.2c01521	journal	August 2022
Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives Myung, Seung-Taek; Maglia, Filippo; Park, Kang-Joon ACS Energy Letters, Vol. 2, Issue 1 https://doi.org/10.1021/acsenergylett.6b00594	journal	December 2016
Phase Compatible NiFe₂O₄ Coating Tunes Oxygen Redox in Li-Rich Layered Oxide Peng, Jiming; Li, Yu; Chen, Zhiqiang ACS Nano, Vol. 15, Issue 7 https://doi.org/10.1021/acsnano.1c02023	journal	June 2021
Effects of MgO Coating on the Structural and Electrochemical Characteristics of LiCoO ₂ as Cathode Materials for Lithium Ion Battery Shim, Jae-Hyun; Lee, Sanghun; Park, Sung Soo Chemistry of Materials, Vol. 26, Issue 8 https://doi.org/10.1021/cm403846a	journal	April 2014
Proton-Induced Disproportionation of Jahn–Teller-Active Transition-Metal Ions in Oxides Due to Electronically Driven Lattice Instability Yaghoobnejad Asl, Hooman; Manthiram, Arumugam Journal of the American Chemical Society, Vol. 142, Issue 50 https://doi.org/10.1021/jacs.0c10044	journal	December 2020
Effects of Vinyl Ethylene Carbonate Additive on Elevated-Temperature Performance of Cathode Material in Lithium Ion Batteries Li, Jie; Yao, Wanhao; Meng, Ying S. The Journal of Physical Chemistry C, Vol. 112, Issue 32 https://doi.org/10.1021/jp800336n	journal	July 2008
New class of nonaqueous electrolytes for long-life and safe lithium-ion batteries Chen, Zonghai; Ren, Yang; Jansen, Andrew N. Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2518	journal	February 2013
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
In situ inorganic conductive network formation in high-voltage single-crystal Ni-rich cathodes Fan, Xinming; Ou, Xing; Zhao, Wengao Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25611-6	journal	September 2021
Rational design of mechanically robust Ni-rich cathode materials via concentration gradient strategy Liu, Tongchao; Yu, Lei; Lu, Jun Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-26290-z	journal	October 2021
Enabling high energy lithium metal batteries via single-crystal Ni-rich cathode material co-doping strategy Ou, Xing; Liu, Tongchao; Zhong, Wentao Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30020-4	journal	April 2022
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
Stalling oxygen evolution in high-voltage cathodes by lanthurization Cai, Mingzhi; Dong, Yanhao; Xie, Miao Nature Energy, Vol. 8, Issue 2 https://doi.org/10.1038/s41560-022-01179-3	journal	January 2023
Effect of standard light illumination on electrolyte’s stability of lithium-ion batteries based on ethylene and di-methyl carbonates Bouteau, Gaspard; Van-Nhien, Albert Nguyen; Sliwa, Michel Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-018-36836-9	journal	January 2019
Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy Zhang, Yirui; Katayama, Yu; Tatara, Ryoichi Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/C9EE02543J	journal	January 2020
Role of surface coating on cathode materials for lithium-ion batteries Chen, Zonghai; Qin, Yan; Amine, Khalil Journal of Materials Chemistry, Vol. 20, Issue 36, p. 7606-7612 https://doi.org/10.1039/c0jm00154f	journal	January 2010
High-voltage electrosynthesis of organic-inorganic hybrid with ultrahigh fluorine content toward fast Li-ion transport Lu, Gongxun; Qiao, Qiangqiang; Zhang, Mengtian Science Advances, Vol. 10, Issue 32 https://doi.org/10.1126/sciadv.ado7348	journal	August 2024
Reducing Carbon in LiFePO[sub 4]/C Composite Electrodes to Maximize Specific Energy, Volumetric Energy, and Tap Density Chen, Zhaohui; Dahn, J. R. Journal of The Electrochemical Society, Vol. 149, Issue 9 https://doi.org/10.1149/1.1498255	journal	January 2002
Some Physical Properties of Ethylene Carbonate-Free Electrolytes Xiong, D. J.; Bauer, M.; Ellis, L. D. Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.0511802jes	journal	January 2018
Study of the Failure Mechanisms of LiNi _0.8 Mn _0.1 Co _0.1 O ₂ Cathode Material for Lithium Ion Batteries Li, Jing; Downie, Laura E.; Ma, Lin Journal of The Electrochemical Society, Vol. 162, Issue 7 https://doi.org/10.1149/2.1011507jes	journal	January 2015
Surface Characterization and Anodic Polarization of Nitrogen-Ion-Implanted Nickel-Free Co–Cr–Mo Alloy Hiromoto, Sachiko; Kano, Kazuto; Suzuki, Yoshiaki MATERIALS TRANSACTIONS, Vol. 46, Issue 7 https://doi.org/10.2320/matertrans.46.1627	journal	January 2005

Similar Records

Importance of High Valence Element Nb in Ni-Rich Layered Cathodes for High-Voltage Lithium-Metal Batteries

Journal Article · Mon Sep 30 20:00:00 EDT 2024 · ACS Energy Letters · OSTI ID:2569441

A facile cathode design combining Ni-rich layered oxides with Li-rich layered oxides for lithium-ion batteries

Journal Article · Thu Sep 01 00:00:00 EDT 2016 · Journal of Power Sources · OSTI ID:1340858

Related Subjects

25 ENERGY STORAGE
LiF and Li3PO4 sub-nano particle
dense maskant
electrochemical conversion
nickel-rich single crystal
proton

In Situ Conversion of Artificial Proton‐Rich Shell to Inorganic Maskant Toward Stable Single‐Crystal Ni‐Rich Cathode

Citation Formats

References (49)

Similar Records

Related Subjects