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Decoupling the Failure Mechanism of Li‐Rich Layered Oxide Cathode During High‐Temperature Storage in Pouch‐Type Full‐Cell: A Practical Concern on Anionic Redox Reaction

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Advanced Energy Materials
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Baodan Zhang at Chongqing University
Baodan Zhang
Kang Zhang
Kang Zhang
Kang Zhang
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Xiaohong Wu
Xiaohong Wu
Xiaohong Wu
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Zheng Qizheng at Xiamen University
Zheng Qizheng
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Abstract and Figures

In addressing the global climate crisis, the energy storage performance of Li‐ion batteries (LIBs) under extreme conditions, particularly for high‐energy‐density Li‐rich layered oxide (LRLO) cathode, is of the essence. Despite numerous researches into the mechanisms and optimization of LRLO cathodes under ideal moderate environment, there is a dearth of case studies on their practical/harsh working environments (e.g., pouch‐type full‐cell, high‐temperature storage), which is a critical aspect for the safety and commercial application. In this study, using pouch‐type full‐cells as prototype investigation target, the study finds the cell assembled with LRLO cathode present severer voltage decay than typical NCM layered cathode after high‐temperature storage. Further decoupling elucidates the primary failure mechanism is the over‐activation of lattice oxidized oxygen (aggravate by high‐temperature storage) and subsequent escape of oxidized oxygen species (Oⁿ⁻), which disrupts transition metal (TM) coordination and exacerbates electrolyte decomposition, leading to severe TM dissolution, interfacial film reconstruction, and harmful shuttle effects. These chain behaviors upon high‐temperature storage significantly influence the stability of both electrodes, causing substantial voltage decay and lithium loss, which accelerates full‐cell failure. Although the anionic redox reaction can bring additional energy, but the escape of metastable Oⁿ⁻ species would introduce new concerns in practical cell working conditions.
a) The discharge and corresponding dQ/dV curves of LRLO pouch‐type full‐cells at 1 and 300 cycles (pouch‐type full‐cell photograph is inserted). b) The capacity retention and energy retention of LRLO pouch‐type full‐cell during cycling at room temperature. c) Ideal discharge curves of cathode influenced by typical factors. d) The discharge capacity curves and corresponding dQ/dV plots of NCM532 and LRLO pouch‐type full‐cells before and after high‐temperature storage.
a) The discharge and corresponding dQ/dV curves of LRLO pouch‐type full‐cells at 1 and 300 cycles (pouch‐type full‐cell photograph is inserted). b) The capacity retention and energy retention of LRLO pouch‐type full‐cell during cycling at room temperature. c) Ideal discharge curves of cathode influenced by typical factors. d) The discharge capacity curves and corresponding dQ/dV plots of NCM532 and LRLO pouch‐type full‐cells before and after high‐temperature storage.
… 
a) TMS data of the LRLO cathode electrodes before and after high‐temperature storage. b) O K‐edge results of the charged LRLO cathode electrodes before and after high‐temperature storage. c) Mn L‐edge results of the charged LRLO cathode electrodes before and after high‐temperature storage (the fitting results of Mn³⁺ and Mn⁴⁺ to L2 peak are summarized in the illustration). d) The evolution of nucleophilic oxidized oxygen species during charging and storage at room/high‐temperature conditions, monitored via in situ surface‐enhanced Raman spectroscopy. e) Cartoon diagram of nucleophilic oxidized lattice oxygen evolution process.
a) TMS data of the LRLO cathode electrodes before and after high‐temperature storage. b) O K‐edge results of the charged LRLO cathode electrodes before and after high‐temperature storage. c) Mn L‐edge results of the charged LRLO cathode electrodes before and after high‐temperature storage (the fitting results of Mn³⁺ and Mn⁴⁺ to L2 peak are summarized in the illustration). d) The evolution of nucleophilic oxidized oxygen species during charging and storage at room/high‐temperature conditions, monitored via in situ surface‐enhanced Raman spectroscopy. e) Cartoon diagram of nucleophilic oxidized lattice oxygen evolution process.
… 
a) The schematic illustrates the semiquantitative analysis of gaseous by‐products and liquid by‐products by comparing the same amount of gas extracted from gas bags through GC‐MS/BID and by collecting the electrolyte from different pouch cells through NMR, in LRLO and NCM532 pouch‐type full‐cells after 60 °C storage. b) The statistical results of CO, CH3OH, CO2, C2H5OH gas evolution after high‐temperature in NCM532 and LRLO pouch‐type full‐cells. c) ¹H NMR results of LRLO pouch‐type full‐cell before and after high‐temperature storage.
a) The schematic illustrates the semiquantitative analysis of gaseous by‐products and liquid by‐products by comparing the same amount of gas extracted from gas bags through GC‐MS/BID and by collecting the electrolyte from different pouch cells through NMR, in LRLO and NCM532 pouch‐type full‐cells after 60 °C storage. b) The statistical results of CO, CH3OH, CO2, C2H5OH gas evolution after high‐temperature in NCM532 and LRLO pouch‐type full‐cells. c) ¹H NMR results of LRLO pouch‐type full‐cell before and after high‐temperature storage.
… 
a) TOF‐SIMS characterization of the LRLO cathode electrodes before and after high‐temperature storage. Normalized depth profiles of the interface and bulk fragments illustrate the structure of the CEI. b) 3D renderings of selected secondary ion fragments of the LRLO cathode electrodes before and after high‐temperature storage. The sputtered volume is 100 µm (length) × 100 µm (width) × 150 nm (height). c,d) The TEM and IFFT images of LRLO cathode before and after high‐temperature storage. e) Scheme of CEI formation and revolution on the LRLO cathode electrodes before and after high‐temperature storage.
a) TOF‐SIMS characterization of the LRLO cathode electrodes before and after high‐temperature storage. Normalized depth profiles of the interface and bulk fragments illustrate the structure of the CEI. b) 3D renderings of selected secondary ion fragments of the LRLO cathode electrodes before and after high‐temperature storage. The sputtered volume is 100 µm (length) × 100 µm (width) × 150 nm (height). c,d) The TEM and IFFT images of LRLO cathode before and after high‐temperature storage. e) Scheme of CEI formation and revolution on the LRLO cathode electrodes before and after high‐temperature storage.
… 
a) TOF‐SIMS characterization of the anode electrodes before and after high‐temperature storage. Normalized depth profiles of the interface and bulk fragments illustrate the structure of the SEI. b) 3D renderings of selected secondary ion fragments of the anode electrodes before and after high‐temperature storage. The sputtered volume is 100 µm (length) × 100 µm (width) × 150 nm (height). c,d) The TEM images of Gr anode before and after high‐temperature storage in LRLO pouch‐type full‐cell. e) Scheme of SEI formation and revolution (inserted images) on the anode electrodes before and after high‐temperature storage.
+1
a) TOF‐SIMS characterization of the anode electrodes before and after high‐temperature storage. Normalized depth profiles of the interface and bulk fragments illustrate the structure of the SEI. b) 3D renderings of selected secondary ion fragments of the anode electrodes before and after high‐temperature storage. The sputtered volume is 100 µm (length) × 100 µm (width) × 150 nm (height). c,d) The TEM images of Gr anode before and after high‐temperature storage in LRLO pouch‐type full‐cell. e) Scheme of SEI formation and revolution (inserted images) on the anode electrodes before and after high‐temperature storage.
… 
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RESEARCH ARTICLE
www.advenergymat.de
Decoupling the Failure Mechanism of Li-Rich Layered Oxide
Cathode During High-Temperature Storage in Pouch-Type
Full-Cell: A Practical Concern on Anionic Redox Reaction
Baodan Zhang, Kang Zhang, Xiaohong Wu, Qizheng Zheng, Haiyan Luo, Haitang Zhang,
Yilong Chen, Shiyuan Zhou, Yuanlong Zhu, Jianhua Yin, Yeguo Zou, Hong-Gang Liao,
Wen Jiao, Na Liu, Yaru Qin,* Bin-Wei Zhang,* Chongheng Shen,* Yu Qiao,*
and Shi-Gang Sun
In addressing the global climate crisis, the energy storage performance
of Li-ion batteries (LIBs) under extreme conditions, particularly for
high-energy-density Li-rich layered oxide (LRLO) cathode, is of the essence.
Despite numerous researches into the mechanisms and optimization of LRLO
cathodes under ideal moderate environment, there is a dearth of case studies
on their practical/harsh working environments (e.g., pouch-type full-cell, high-
temperature storage), which is a critical aspect for the safety and commercial
application. In this study, using pouch-type full-cells as prototype investigation
target, the study finds the cell assembled with LRLO cathode present severer
voltage decay than typical NCM layered cathode after high-temperature
storage. Further decoupling elucidates the primary failure mechanism is the
over-activation of lattice oxidized oxygen (aggravate by high-temperature stor-
age) and subsequent escape of oxidized oxygen species (On−), which disrupts
transition metal (TM) coordination and exacerbates electrolyte decomposition,
leading to severe TM dissolution, interfacial film reconstruction, and harmful
shuttle effects. These chain behaviors upon high-temperature storage sig-
nificantly influence the stability of both electrodes, causing substantial voltage
decay and lithium loss, which accelerates full-cell failure. Although the anionic
redox reaction can bring additional energy, but the escape of metastable On−
species would introduce new concerns in practical cell working conditions.
B. Zhang, B.-W. Zhang, S.-G. Sun
Center of Advanced Electrochemical Energy
Institute of Advanced Interdisciplinary Studies
School of Chemistry and Chemical Engineering
Chongqing University
Chongqing 401331, China
E-mail: binwei@cqu.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202404391
DOI: 10.1002/aenm.202404391
1. Introduction
The explosive growth of LIBs in the
electrochemical energy storage market
is a powerful strategy for alleviating the
energy crisis.[,]In the drive to accel-
erate green development, high-energy,
safe LIBs are the shared expectation of
both scientific research and industry.[–]
The advancement of LIBs heavily de-
pends on the development of cathode
materials,[,]which primarily determine
the battery voltage, capacity, and total
cost.[]LRLO are highly attractive for
numerous commercial products, from
portable consumer electronics to elec-
tric vehicles, due to their considerable
capacity, better safety, low production
cost, and additional advantages.[–]
Despite abundant literature indicating
that LRLO batteries can provide ultra-
high energy density (> Wh kg−)
primarily through the simultaneous
activation of both cation and anion redox
reactions,[–]their industrialization
B. Zhang, K. Zhang, X. Wu, Q. Zheng, H. Luo, H. Zhang, Y. Chen,
S.Zhou,Y.Zhu,J.Yin,Y.Zou,H.-G.Liao,Y.Qiao,S.-G.Sun
State Key Laboratory of Physical Chemistry of Solid Surfaces
Collaborative Innovation Center of Chemistry for Energy Materials
(iChEM)
Department of Chemistry
College of Chemistry and Chemical Engineering
Xiamen University
Xiamen 361005, China
E-mail: yuqiao@xmu.edu.cn
W.Jiao,N.Liu,C.Shen
Materials Innovation Department (MID)
Contemporary Amperex Technology Co. Limited (CATL)
Ningde 352100, China
E-mail: ShenCH@catl.com
Y. Q i n
School of Chemistry and Materials Science
Qinghai Minzu University
Xining 810007, China
E-mail: qhmuqyr@126.com
Adv. Energy Mater. 2025,15, 2404391 © 2024 Wiley-VCH GmbH
2404391 (1 of 13)
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