Unraveling and Suppression of Multi-Directional Planar Slipping and Microcracking in Single-Crystal Co-Free, Ni-Rich Cathodes

Yuming Shu; Wengao Zhao; Hongyi Chen; Jing Lin; Di Chen; Jiangnan Huang; Fucheng Ren; Hanghang Lei; Qiuming Yan; Huinan Yu; Ke Du; Guorong Hu; Yanbing Cao; Zhongdong Peng; Xueyi Guo; Torsten Brezesinski; Xiaobo Ji; Xinming Fan; Yong Yang

doi:10.1002/anie.202512232

Unraveling and Suppression of Multi-Directional Planar Slipping and Microcracking in Single-Crystal Co-Free, Ni-Rich Cathodes

Yuming Shu
, Wengao Zhao
, Hongyi Chen
, Jing Lin
, Di Chen
, Jiangnan Huang
, Fucheng Ren
, Hanghang Lei
, Qiuming Yan
, Huinan Yu
, Ke Du
, Guorong Hu
, Yanbing Cao
, Zhongdong Peng
, Xueyi Guo
, Torsten Brezesinski
, Xiaobo Ji
, Xinming Fan
, Yong Yang

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Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

High-capacity Co-free Ni-rich layered oxides are promising cathode materials for lithium-based batteries, but they suffer from chemo–electro–mechanical instabilities. While single-crystal morphologies reduce these issues, slipping, and microcracking persist during extended cycling, and the degradation mechanisms remain inadequately understood. Herein, we report on multi-directional planar slipping and microcracking along the (003) and (100) planes in a single-crystal LiNi_0.75Mn_0.25O₂ (LNM) cathode. According to the Darken–Gurry theory and formation energy in LNM, magnesium (Mg²⁺) has been selected as the best pillaring element to strengthen the structural integrity and improve cycling stability. Notably, Li_0.99Mg_0.01Ni_0.75Mn_0.25O₂ (LMNM) achieves a capacity retention of 91% after 1000 cycles at 4.3 V operation against graphite by alleviating instability issues. We systematically unravel the pillaring effect, for the first time, from the quantum scale to the lattice level and from the microscale to the macroscopic level of the cathode particles, providing an in-depth understanding of chemo–electro–mechanical degradation.

Original language	English
Article number	e202512232
Journal	Angewandte Chemie - International Edition
Volume	64
Issue number	39
DOIs	https://doi.org/10.1002/anie.202512232
State	Published - Sep 22 2025

Funding

This work was supported by the National Key Research and Development Program of China (2024YFC3907300, 2021YFB3502000), the National Natural Science Foundation of China (52261135632, 22261160570, 21935009, 52325405, U21A20284, 52204328, 51874358, and 51772333), the Outstanding Youth Fund of Hunan Province (2024JJ4054), and the Natural Science Foundation of Hunan Province (2022JJ40595). Dr. Wengao Zhao is grateful for the support from the BELLA lab at KIT. This work was supported by the National Key Research and Development Program of China (2024YFC3907300, 2021YFB3502000), the National Natural Science Foundation of China (52261135632, 22261160570, 21935009, 52325405, U21A20284, 52204328, 51874358, and 51772333), the Outstanding Youth Fund of Hunan Province (2024JJ4054), and the Natural Science Foundation of Hunan Province (2022JJ40595). Dr. Wengao Zhao is grateful for the support from the BELLA lab at KIT.

Keywords

Chemo–electro–mechanical degradation
Microcracking
Multi-directional planar slipping
Pillaring effect
Single-crystal cathode

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10.1002/anie.202512232

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Shu, Y., Zhao, W., Chen, H., Lin, J., Chen, D., Huang, J., Ren, F., Lei, H., Yan, Q., Yu, H., Du, K., Hu, G., Cao, Y., Peng, Z., Guo, X., Brezesinski, T., Ji, X., Fan, X., & Yang, Y. (2025). Unraveling and Suppression of Multi-Directional Planar Slipping and Microcracking in Single-Crystal Co-Free, Ni-Rich Cathodes. Angewandte Chemie - International Edition, 64(39), Article e202512232. https://doi.org/10.1002/anie.202512232

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title = "Unraveling and Suppression of Multi-Directional Planar Slipping and Microcracking in Single-Crystal Co-Free, Ni-Rich Cathodes",

abstract = "High-capacity Co-free Ni-rich layered oxides are promising cathode materials for lithium-based batteries, but they suffer from chemo{\textendash}electro{\textendash}mechanical instabilities. While single-crystal morphologies reduce these issues, slipping, and microcracking persist during extended cycling, and the degradation mechanisms remain inadequately understood. Herein, we report on multi-directional planar slipping and microcracking along the (003) and (100) planes in a single-crystal LiNi0.75Mn0.25O2 (LNM) cathode. According to the Darken{\textendash}Gurry theory and formation energy in LNM, magnesium (Mg2+) has been selected as the best pillaring element to strengthen the structural integrity and improve cycling stability. Notably, Li0.99Mg0.01Ni0.75Mn0.25O2 (LMNM) achieves a capacity retention of 91\% after 1000 cycles at 4.3 V operation against graphite by alleviating instability issues. We systematically unravel the pillaring effect, for the first time, from the quantum scale to the lattice level and from the microscale to the macroscopic level of the cathode particles, providing an in-depth understanding of chemo{\textendash}electro{\textendash}mechanical degradation.",

keywords = "Chemo{\textendash}electro{\textendash}mechanical degradation, Microcracking, Multi-directional planar slipping, Pillaring effect, Single-crystal cathode",

author = "Yuming Shu and Wengao Zhao and Hongyi Chen and Jing Lin and Di Chen and Jiangnan Huang and Fucheng Ren and Hanghang Lei and Qiuming Yan and Huinan Yu and Ke Du and Guorong Hu and Yanbing Cao and Zhongdong Peng and Xueyi Guo and Torsten Brezesinski and Xiaobo Ji and Xinming Fan and Yong Yang",

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year = "2025",

month = sep,

day = "22",

doi = "10.1002/anie.202512232",

language = "English",

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Shu, Y, Zhao, W, Chen, H, Lin, J, Chen, D, Huang, J, Ren, F, Lei, H, Yan, Q, Yu, H, Du, K, Hu, G, Cao, Y, Peng, Z, Guo, X, Brezesinski, T, Ji, X, Fan, X & Yang, Y 2025, 'Unraveling and Suppression of Multi-Directional Planar Slipping and Microcracking in Single-Crystal Co-Free, Ni-Rich Cathodes', Angewandte Chemie - International Edition, vol. 64, no. 39, e202512232. https://doi.org/10.1002/anie.202512232

TY - JOUR

T1 - Unraveling and Suppression of Multi-Directional Planar Slipping and Microcracking in Single-Crystal Co-Free, Ni-Rich Cathodes

AU - Shu, Yuming

AU - Zhao, Wengao

AU - Chen, Hongyi

AU - Lin, Jing

AU - Chen, Di

AU - Huang, Jiangnan

AU - Ren, Fucheng

AU - Lei, Hanghang

AU - Yan, Qiuming

AU - Yu, Huinan

AU - Du, Ke

AU - Hu, Guorong

AU - Cao, Yanbing

AU - Peng, Zhongdong

AU - Guo, Xueyi

AU - Brezesinski, Torsten

AU - Ji, Xiaobo

AU - Fan, Xinming

AU - Yang, Yong

PY - 2025/9/22

Y1 - 2025/9/22

N2 - High-capacity Co-free Ni-rich layered oxides are promising cathode materials for lithium-based batteries, but they suffer from chemo–electro–mechanical instabilities. While single-crystal morphologies reduce these issues, slipping, and microcracking persist during extended cycling, and the degradation mechanisms remain inadequately understood. Herein, we report on multi-directional planar slipping and microcracking along the (003) and (100) planes in a single-crystal LiNi0.75Mn0.25O2 (LNM) cathode. According to the Darken–Gurry theory and formation energy in LNM, magnesium (Mg2+) has been selected as the best pillaring element to strengthen the structural integrity and improve cycling stability. Notably, Li0.99Mg0.01Ni0.75Mn0.25O2 (LMNM) achieves a capacity retention of 91% after 1000 cycles at 4.3 V operation against graphite by alleviating instability issues. We systematically unravel the pillaring effect, for the first time, from the quantum scale to the lattice level and from the microscale to the macroscopic level of the cathode particles, providing an in-depth understanding of chemo–electro–mechanical degradation.

AB - High-capacity Co-free Ni-rich layered oxides are promising cathode materials for lithium-based batteries, but they suffer from chemo–electro–mechanical instabilities. While single-crystal morphologies reduce these issues, slipping, and microcracking persist during extended cycling, and the degradation mechanisms remain inadequately understood. Herein, we report on multi-directional planar slipping and microcracking along the (003) and (100) planes in a single-crystal LiNi0.75Mn0.25O2 (LNM) cathode. According to the Darken–Gurry theory and formation energy in LNM, magnesium (Mg2+) has been selected as the best pillaring element to strengthen the structural integrity and improve cycling stability. Notably, Li0.99Mg0.01Ni0.75Mn0.25O2 (LMNM) achieves a capacity retention of 91% after 1000 cycles at 4.3 V operation against graphite by alleviating instability issues. We systematically unravel the pillaring effect, for the first time, from the quantum scale to the lattice level and from the microscale to the macroscopic level of the cathode particles, providing an in-depth understanding of chemo–electro–mechanical degradation.

KW - Chemo–electro–mechanical degradation

KW - Microcracking

KW - Multi-directional planar slipping

KW - Pillaring effect

KW - Single-crystal cathode

UR - https://www.scopus.com/pages/publications/105013543483

U2 - 10.1002/anie.202512232

DO - 10.1002/anie.202512232

M3 - Article

C2 - 40824001

AN - SCOPUS:105013543483

SN - 1433-7851

VL - 64

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 39

M1 - e202512232

ER -

Unraveling and Suppression of Multi-Directional Planar Slipping and Microcracking in Single-Crystal Co-Free, Ni-Rich Cathodes

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Keywords

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