Kinetically Dormant Ni-Rich Layered Cathode During High-Voltage Operation

Cai, Jiyu; Zhou, Xinwei; Li, Luxi; Yang, Zhenzhen; Huang, Xingkang; Li, Jiantao; Wang, Guanyi; Zhu, Qijia; Li, Tianyi; Sun, Cheng‐Jun; Zhuo, Zengqing; Suzana, Ana; Bai, Jianming; Gudavalli, Ganesh; Karami, Niloofar; Chernova, Natasha A.; Upreti, Shailesh; Prevel, Brad; Yang, Wanli; Liu, Yuzi; Xu, Wenqian; Chen, Yanbin; Song, Shunlin; Zhang, Xuequan; Wang, Li; He, Xiangming; Wang, Feng; Xu, Gui‐Liang; Chen, Zonghai

doi:10.1002/adma.202419253

Kinetically Dormant Ni-Rich Layered Cathode During High-Voltage Operation

Journal Article · Mon Mar 03 00:00:00 EST 2025 · Advanced Materials

DOI:https://doi.org/10.1002/adma.202419253· OSTI ID:2530426

Cai, Jiyu ^[1]; Zhou, Xinwei ^[2]; Li, Luxi ^[3]; Yang, Zhenzhen ^[1]; Huang, Xingkang ^[1]; Li, Jiantao ^[1]; Wang, Guanyi ^[2]; Zhu, Qijia ^[1]; Li, Tianyi ^[3]; Sun, Cheng‐Jun ^[3]; Zhuo, Zengqing ^[4]; Suzana, Ana ^[5]; Bai, Jianming ^[5]; Gudavalli, Ganesh ^[6]; Karami, Niloofar ^[6]; Chernova, Natasha A. ^[6]; Upreti, Shailesh ^[6]; Prevel, Brad ^[7]; Yang, Wanli ^[4]; Liu, Yuzi ^[2] more »

Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Binghamton University, Vestal, NY (United States). Charge CCCV (C4V) Center of Excellence
Primet Precision Materials, Ithaca, NY (United States)
Beijing Easpring Material Technology Co., Ltd., Beijing (China)
Tsinghua University, Beijing (China)

The degradation of Ni-rich cathodes during long-term operation at high voltage has garnered significant attention from both academia and industry. Despite many post-mortem qualitative structural analyses, precise quantification of their individual and coupling contributions to the overall capacity degradation remains challenging. Here, by leveraging multiscale synchrotron X-ray probes, electron microscopy, and post-galvanostatic intermittent titration technique, the thermodynamically irreversible and kinetically reversible capacity loss is successfully deconvoluted in a polycrystalline LiNi_0.83Mn_0.1Co_0.07O₂ cathode during long-term charge/discharge cycling in full cell configuration. Contradicting the dramatic capacity loss, the layered structure remains highly alive even after 1000 cycles at 4.6 V while undergoing a three-order of magnitude reduction in the mass transfer kinetics, leading to almost fully recoverable capacity under kinetic-free conditions. Such kinetic dormant behavior after cycling is not simply ascribed to poor chemical diffusion by reconstructed cathode surface but highly synchronizes with the lattice strain evolution stemming from the structural heterogeneity between deeply delithiated layered and degraded rock-salt phases at high voltage. These findings deepen the degradation mechanism of high-voltage cathodes to achieve long-cycling and fast-charging performance.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: New York State Empire State Development Regional Economic Development Council (NYS-ESD-REDC); US Department of Energy; USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 ); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; SC0012704

OSTI ID:: 2530426

Alternate ID(s):: OSTI ID: 2530428
OSTI ID: 2563041
OSTI ID: 2572108

Report Number(s):: BNL--228078-2025-JAAM

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Journal Issue: 14 Vol. 37; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
degradation
high voltage
kinetics
lattice strain
nickel-rich layered cathodes
quantification
thermodynamics

Kinetically Dormant Ni-Rich Layered Cathode During High-Voltage Operation

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