Correlating Rate-Dependent Transition Metal Dissolution between Structure Degradation in Li-Rich Layered Oxides

Cao, Bo; Li, Tianyi; Zhao, Wenguang; Yin, Liang; Cao, Hongbin; Chen, Dong; Li, Luxi; Pan, Feng; Zhang, Mingjian

doi:10.1002/smll.202301834

Correlating Rate-Dependent Transition Metal Dissolution between Structure Degradation in Li-Rich Layered Oxides

Journal Article · Tue Jun 20 00:00:00 EDT 2023 · Small

DOI:https://doi.org/10.1002/smll.202301834· OSTI ID:2565585

Cao, Bo ^[1]; Li, Tianyi ^[2]; Zhao, Wenguang ^[1]; Yin, Liang ^[2]; Cao, Hongbin ^[1]; Chen, Dong ^[1]; Li, Luxi ^[2]; Pan, Feng ^[1]; ^[3]

Peking University, Beijing (China)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
The Chinese University of Hong Kong (Hong Kong)

Understanding the mechanism of the rate-dependent electrochemical performance degradation in cathodes is crucial to developing fast charging/discharging cathodes for Li-ion batteries. Here, in this work, taking Li-rich layered oxide Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ as the model cathode, the mechanisms of performance degradation at low and high rates are comparatively investigated from two aspects, the transition metal (TM) dissolution and the structure change. Quantitative analyses combining spatial-resolved synchrotron X-ray fluorescence (XRF) imaging, synchrotron X–ray diffraction (XRD) and transmission electron microscopy (TEM) techniques reveal that low-rate cycling leads to gradient TM dissolution and severe bulk structure degradation within the individual secondary particles, and especially the latter causes lots of microcracks within secondary particles, and becomes the main reason for the fast capacity and voltage decay. In contrast, high-rate cycling leads to more TM dissolution than low-rate cycling, which concentrates at the particle surface and directly induces the more severe surface structure degradation to the electrochemically inactive rock-salt phase, eventually causing a faster capacity and voltage decay than low-rate cycling. These findings highlight the protection of the surface structure for developing fast charging/discharging cathodes for Li-ion batteries.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Shenzhen Science and Technology Research Grant; National Key Research and Development Program of China

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2565585

Journal Information:: Small, Journal Name: Small Journal Issue: 42 Vol. 19; ISSN 1613-6810

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Molten Salt Synthesis and High Rate Performance of the “Desert-Rose” form of LiCoO2 Chen, Hailong; Grey, Clare P. Advanced Materials, Vol. 20, Issue 11 https://doi.org/10.1002/adma.200702655	journal	June 2008
Binder-Free LiCoO ₂ /Carbon Nanotube Cathodes for High-Performance Lithium Ion Batteries Luo, Shu; Wang, Ke; Wang, Jiaping Advanced Materials, Vol. 24, Issue 17 https://doi.org/10.1002/adma.201104720	journal	March 2012
Few Atomic Layered Lithium Cathode Materials to Achieve Ultrahigh Rate Capability in Lithium‐Ion Batteries Tai, Zhixin; Subramaniyam, Chandrasekar M.; Chou, Shu‐Lei Advanced Materials, Vol. 29, Issue 34 https://doi.org/10.1002/adma.201700605	journal	July 2017
Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries de Biasi, Lea; Schwarz, Björn; Brezesinski, Torsten Advanced Materials, Vol. 31, Issue 26 https://doi.org/10.1002/adma.201900985	journal	April 2019
Mesoporous Single‐Crystal Lithium Titanate Enabling Fast‐Charging Li‐Ion Batteries Jin, Xu; Han, Yehu; Zhang, Zhengfeng Advanced Materials, Vol. 34, Issue 18 https://doi.org/10.1002/adma.202109356	journal	March 2022
A Novel Bifunctional Self‐Stabilized Strategy Enabling 4.6 V LiCoO 2 with Excellent Long‐Term Cyclability and High‐Rate Capability Wang, Longlong; Ma, Jun; Wang, Chen Advanced Science, Vol. 6, Issue 12 https://doi.org/10.1002/advs.201900355	journal	April 2019
Extremely Durable High-Rate Capability of a LiNi0.4Mn0.4Co0.2O2 Cathode Enabled with Single-Walled Carbon Nanotubes Ban, Chunmei; li, Zheng; Wu, Zhuangchun Advanced Energy Materials, Vol. 1, Issue 1 https://doi.org/10.1002/aenm.201000001	journal	December 2010
In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes Zhao, Jianqing; Zhang, Wei; Huq, Ashfia Advanced Energy Materials, Vol. 7, Issue 3 https://doi.org/10.1002/aenm.201601266	journal	October 2016
Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches Sharifi‐Asl, Soroosh; Lu, Jun; Amine, Khalil Advanced Energy Materials, Vol. 9, Issue 22 https://doi.org/10.1002/aenm.201900551	journal	April 2019
Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries Liu, Wen; Oh, Pilgun; Liu, Xien Angewandte Chemie International Edition, Vol. 54, Issue 15 https://doi.org/10.1002/anie.201409262	journal	March 2015
Advances in the Cathode Materials for Lithium Rechargeable Batteries Lee, Wontae; Muhammad, Shoaib; Sergey, Chernov Angewandte Chemie International Edition, Vol. 59, Issue 7 https://doi.org/10.1002/anie.201902359	journal	February 2020
On the Manganese Dissolution Process from LiMn₂O₄ Cathode Materials Tesfamhret, Yonas; Liu, Haidong; Chai, Zhigang ChemElectroChem, Vol. 8, Issue 8 https://doi.org/10.1002/celc.202001496	journal	April 2021
Identifying rate limitation and a guide to design of fast‐charging Li‐ion battery Zhang, Sheng S. InfoMat, Vol. 2, Issue 5 https://doi.org/10.1002/inf2.12058	journal	December 2019
Fast Charging Lithium Batteries: Recent Progress and Future Prospects Zhu, Gao‐Long; Zhao, Chen‐Zi; Huang, Jia‐Qi Small, Vol. 15, Issue 15 https://doi.org/10.1002/smll.201805389	journal	March 2019
Investigation of various layered lithium ion battery cathode materials by plasma- and X-ray-based element analytical techniques Evertz, Marco; Kasnatscheew, Johannes; Winter, Martin Analytical and Bioanalytical Chemistry, Vol. 411, Issue 1 https://doi.org/10.1007/s00216-018-1441-8	journal	October 2018
Preparation of a new crystal form of manganese dioxide: λ-MnO₂ Hunter, James C. Journal of Solid State Chemistry, Vol. 39, Issue 2, p. 142-147 https://doi.org/10.1016/0022-4596(81)90323-6	journal	September 1981
Cobalt dissolution in LiCoO₂-based non-aqueous rechargeable batteries Amatucci, G. G.; Tarascon, J. M.; Klein, L. C. Solid State Ionics, Vol. 83, Issue 1-2, p. 167-173 https://doi.org/10.1016/0167-2738(95)00231-6	journal	January 1996
Mechanisms of manganese spinels dissolution and capacity fade at high temperature Aoshima, Takayuki; Okahara, Kenji; Kiyohara, Chikara Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00551-1	journal	July 2001
Asymmetric Temperature Modulation for Extreme Fast Charging of Lithium-Ion Batteries Yang, Xiao-Guang; Liu, Teng; Gao, Yue Joule, Vol. 3, Issue 12 https://doi.org/10.1016/j.joule.2019.09.021	journal	December 2019
A new approach to improve the high-voltage cyclic performance of Li-rich layered cathode material by electrochemical pre-treatment Ito, Atsushi; Li, Decheng; Ohsawa, Yasuhiko Journal of Power Sources, Vol. 183, Issue 1, p. 344-346 https://doi.org/10.1016/j.jpowsour.2008.04.086	journal	August 2008
Cyclic deterioration and its improvement for Li-rich layered cathode material Li[Ni_0.17Li_0.2Co_0.07Mn_0.56]O₂ Ito, Atsushi; Li, Decheng; Sato, Yuichi Journal of Power Sources, Vol. 195, Issue 2, p. 567-573 https://doi.org/10.1016/j.jpowsour.2009.07.052	journal	January 2010
Visualizing elemental deposition patterns on carbonaceous anodes from lithium ion batteries: A laser ablation-inductively coupled plasma-mass spectrometry study on factors influencing the deposition of lithium, nickel, manganese and cobalt after dissolution and migration from the Li 1 [Ni 1/3 Mn 1/3 Co 1/3 ]O 2 and LiMn 1.5 Ni 0.5 O 4 cathode Schwieters, Timo; Evertz, Marco; Fengler, Alexander Journal of Power Sources, Vol. 380 https://doi.org/10.1016/j.jpowsour.2018.01.088	journal	March 2018
3D LiCoO2 nanosheets assembled nanorod arrays via confined dissolution-recrystallization for advanced aqueous lithium-ion batteries Xue, Liang; Zhang, Qinghua; Zhu, Xiaohui Nano Energy, Vol. 56 https://doi.org/10.1016/j.nanoen.2018.11.085	journal	February 2019
Kinetic Pathways Templated by Low-Temperature Intermediates during Solid-State Synthesis of Layered Oxides Bai, Jianming; Sun, Wenhao; Zhao, Jianqing Chemistry of Materials, Vol. 32, Issue 23 https://doi.org/10.1021/acs.chemmater.0c02568	journal	September 2020
First-Principles Modeling of Mn(II) Migration above and Dissolution from Li _x Mn ₂ O ₄ (001) Surfaces Leung, Kevin Chemistry of Materials, Vol. 29, Issue 6 https://doi.org/10.1021/acs.chemmater.6b04429	journal	November 2016
Blow-Spinning Enabled Precise Doping and Coating for Improving High-Voltage Lithium Cobalt Oxide Cathode Performance Tian, Te; Zhang, Tian-Wen; Yin, Yi-Chen Nano Letters, Vol. 20, Issue 1 https://doi.org/10.1021/acs.nanolett.9b04486	journal	December 2019
Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials Sharifi-Asl, Soroosh; Yurkiv, Vitaliy; Gutierrez, Arturo Nano Letters, Vol. 20, Issue 2 https://doi.org/10.1021/acs.nanolett.9b04620	journal	December 2019
Multiscale Deficiency Integration by Na-Rich Engineering for High-Stability Li-Rich Layered Oxide Cathodes Liu, Qun; Xie, Te; Xie, Qingshui ACS Applied Materials & Interfaces, Vol. 13, Issue 7 https://doi.org/10.1021/acsami.0c19040	journal	February 2021
Hierarchical Fusiform Microrods Constructed by Parallelly Arranged Nanoplatelets of LiCoO₂ Material with Ultrahigh Rate Performance Zhou, Shiyuan; Mei, Tao; Liu, Jiapeng ACS Applied Materials & Interfaces, Vol. 12, Issue 15 https://doi.org/10.1021/acsami.9b21526	journal	March 2020
Unusual Stability of Acetonitrile-Based Superconcentrated Electrolytes for Fast-Charging Lithium-Ion Batteries Yamada, Yuki; Furukawa, Keizo; Sodeyama, Keitaro Journal of the American Chemical Society, Vol. 136, Issue 13, p. 5039-5046 https://doi.org/10.1021/ja412807w	journal	March 2014
Electrolyte additive enabled fast charging and stable cycling lithium metal batteries Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai Nature Energy, Vol. 2, Issue 3 https://doi.org/10.1038/nenergy.2017.12	journal	March 2017
Quantifying the factors limiting rate performance in battery electrodes Tian, Ruiyuan; Park, Sang-Hoon; King, Paul J. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09792-9	journal	April 2019
Correlation between manganese dissolution and dynamic phase stability in spinel-based lithium-ion battery Liu, Tongchao; Dai, Alvin; Lu, Jun Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12626-3	journal	October 2019
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
Reaction inhomogeneity coupling with metal rearrangement triggers electrochemical degradation in lithium-rich layered cathode Wang, Liguang; Liu, Tongchao; Dai, Alvin Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-25686-1	journal	September 2021
Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries Yan, Pengfei; Zheng, Jianming; Liu, Jian Nature Energy, Vol. 3, Issue 7 https://doi.org/10.1038/s41560-018-0191-3	journal	June 2018
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
First-cycle voltage hysteresis in Li-rich 3d cathodes associated with molecular O2 trapped in the bulk House, Robert A.; Rees, Gregory J.; Pérez-Osorio, Miguel A. Nature Energy, Vol. 5, Issue 10 https://doi.org/10.1038/s41560-020-00697-2	journal	September 2020
Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries Xu, Chao; Märker, Katharina; Lee, Juhan Nature Materials, Vol. 20, Issue 1 https://doi.org/10.1038/s41563-020-0767-8	journal	August 2020
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
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
Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries Wu, Feixiang; Maier, Joachim; Yu, Yan Chemical Society Reviews, Vol. 49, Issue 5 https://doi.org/10.1039/C7CS00863E	journal	January 2020
A core–shell structured LiNi _0.5 Mn _1.5 O ₄ @LiCoO ₂ cathode material with superior rate capability and cycling performance Deng, Yunlong; Mou, Jirong; He, Lihua Dalton Transactions, Vol. 47, Issue 2 https://doi.org/10.1039/C7DT03963H	journal	January 2018
Reining in dissolved transition-metal ions Asl, Hooman Yaghoobnejad; Manthiram, Arumugam Science, Vol. 369, Issue 6500 https://doi.org/10.1126/science.abc5454	journal	July 2020
Optimized LiFePO[sub 4] for Lithium Battery Cathodes Yamada, A.; Chung, S. C.; Hinokuma, K. Journal of The Electrochemical Society, Vol. 148, Issue 3 https://doi.org/10.1149/1.1348257	journal	January 2001
Review—An Unpredictable Hazard in Lithium-ion Batteries from Transition Metal Ions: Dissolution from Cathodes, Deposition on Anodes and Elimination Strategies Li, Weishan Journal of The Electrochemical Society, Vol. 167, Issue 9 https://doi.org/10.1149/1945-7111/ab847f	journal	April 2020
Re-Deposition of Manganese Species on Spinel LiMn ₂ O ₄ Electrode after Mn Dissolution Kim, Daesoo; Park, Sangjin; Chae, Oh B. Journal of The Electrochemical Society, Vol. 159, Issue 3 https://doi.org/10.1149/2.003203jes	journal	January 2012
Manganese Dissolution from Lithium Doped Li-Mn-O Spinel Cathode Materials into Electrolyte Solution Komaba, Shinichi; Kumagai, Naoaki; Sasaki, Tomoya Electrochemistry, Vol. 69, Issue 10 https://doi.org/10.5796/electrochemistry.69.784	journal	January 2001

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