A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries

Yangfang Wan; Cheng Li; Yingzhi Li; Raquel De Benito Munoz; Jacob Williams; Josh Stratford; Zhiqiang Li; Chun Zeng; Ning Qin; Hongzhi Wang; Yulin Cao; Dominic Gardner; Wilgner Lima da Silva; Sahil Tippireddy; Qingmeng Gan; Fangchang Zhang; Wen Luo; Joshua Makepeace; Ke-Jin Zhou; Kaili Zhang; Fucai Zhang; Phoebe K. Allan; Zhouguang Lu

doi:10.1002/anie.202422789

A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries

Yangfang Wan
, Cheng Li
, Yingzhi Li
, Raquel De Benito Munoz
, Jacob Williams
, Josh Stratford
, Zhiqiang Li
, Chun Zeng
, Ning Qin
, Hongzhi Wang
, Yulin Cao
, Dominic Gardner
, Wilgner Lima da Silva
, Sahil Tippireddy
, Qingmeng Gan
, Fangchang Zhang
, Wen Luo
, Joshua Makepeace
, Ke-Jin Zhou
, Kaili Zhang

Fucai Zhang^*, Phoebe K. Allan^*, Zhouguang Lu^*

^*Corresponding author for this work

Chemistry

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

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Abstract

Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy‐density lithium‐ion batteries. However, achieving long‐term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt‐free layered oxide, Li_0.693[Li_0.153Ni_0.190Mn_0.657]O₂ (LLNMO). After 50 cycles at 50 mA/g (~0.2 C), the cathode retains 97.4 % of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable O6‐type structure (R‐3m symmetry) with unique local geometry. The face‐sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration‐induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de‐/lithiation (

Original language	English
Article number	e202422789
Number of pages	13
Journal	Angewandte Chemie International Edition
Early online date	4 Feb 2025
DOIs	https://doi.org/10.1002/anie.202422789
Publication status	E-pub ahead of print - 4 Feb 2025

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This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Keywords

Metastable
Anion redox
oxygen activity
layered cathode
lithium-ion batteries
Layered Cathode
Anion Redox
Lithium-ion Batteries
Oxygen Activity

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WangY2025AMetastable_AAM
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Accepted author manuscript, 3.49 MBLicence: Other (please specify with Rights Statement)

Linking formation mechanisms, nanostructure and function in metal oxide nanosheets using multimodal characterisation.
Allan, P. (Principal Investigator)
Engineering & Physical Science Research Council
1/04/23 → 16/10/26
Project: Research Councils

Cite this

Wan, Y., Li, C., Li, Y., De Benito Munoz, R., Williams, J., Stratford, J., Li, Z., Zeng, C., Qin, N., Wang, H., Cao, Y., Gardner, D., Lima da Silva, W., Tippireddy, S., Gan, Q., Zhang, F., Luo, W., Makepeace, J., Zhou, K.-J., ... Lu, Z. (2025). A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries. Angewandte Chemie International Edition, Article e202422789. Advance online publication. https://doi.org/10.1002/anie.202422789

@article{9ea37cb1cfb3497ea902f1659612fc32,

title = "A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries",

abstract = "Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy‐density lithium‐ion batteries. However, achieving long‐term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt‐free layered oxide, Li0.693[Li0.153Ni0.190Mn0.657]O2 (LLNMO). After 50 cycles at 50 mA/g (\textasciitilde{}0.2 C), the cathode retains 97.4 \% of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable O6‐type structure (R‐3m symmetry) with unique local geometry. The face‐sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration‐induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de‐/lithiation (",

keywords = "Metastable, Anion redox, oxygen activity, layered cathode, lithium-ion batteries, Layered Cathode, Anion Redox, Lithium-ion Batteries, Oxygen Activity",

author = "Yangfang Wan and Cheng Li and Yingzhi Li and \{De Benito Munoz\}, Raquel and Jacob Williams and Josh Stratford and Zhiqiang Li and Chun Zeng and Ning Qin and Hongzhi Wang and Yulin Cao and Dominic Gardner and \{Lima da Silva\}, Wilgner and Sahil Tippireddy and Qingmeng Gan and Fangchang Zhang and Wen Luo and Joshua Makepeace and Ke-Jin Zhou and Kaili Zhang and Fucai Zhang and Allan, \{Phoebe K.\} and Zhouguang Lu",

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day = "4",

doi = "10.1002/anie.202422789",

language = "English",

journal = "Angewandte Chemie International Edition",

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Wan, Y, Li, C, Li, Y, De Benito Munoz, R, Williams, J, Stratford, J, Li, Z, Zeng, C, Qin, N, Wang, H, Cao, Y, Gardner, D, Lima da Silva, W, Tippireddy, S, Gan, Q, Zhang, F, Luo, W, Makepeace, J, Zhou, K-J, Zhang, K, Zhang, F, Allan, PK & Lu, Z 2025, 'A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries', Angewandte Chemie International Edition. https://doi.org/10.1002/anie.202422789

TY - JOUR

T1 - A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries

AU - Wan, Yangfang

AU - Li, Cheng

AU - Li, Yingzhi

AU - De Benito Munoz, Raquel

AU - Williams, Jacob

AU - Stratford, Josh

AU - Li, Zhiqiang

AU - Zeng, Chun

AU - Qin, Ning

AU - Wang, Hongzhi

AU - Cao, Yulin

AU - Gardner, Dominic

AU - Lima da Silva, Wilgner

AU - Tippireddy, Sahil

AU - Gan, Qingmeng

AU - Zhang, Fangchang

AU - Luo, Wen

AU - Makepeace, Joshua

AU - Zhou, Ke-Jin

AU - Zhang, Kaili

AU - Zhang, Fucai

AU - Allan, Phoebe K.

AU - Lu, Zhouguang

PY - 2025/2/4

Y1 - 2025/2/4

N2 - Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy‐density lithium‐ion batteries. However, achieving long‐term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt‐free layered oxide, Li0.693[Li0.153Ni0.190Mn0.657]O2 (LLNMO). After 50 cycles at 50 mA/g (~0.2 C), the cathode retains 97.4 % of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable O6‐type structure (R‐3m symmetry) with unique local geometry. The face‐sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration‐induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de‐/lithiation (

AB - Simultaneously harnessing cation and anion redox activities in the cathode is crucial for the development of high energy‐density lithium‐ion batteries. However, achieving long‐term stability for both mechanisms remains a significant challenge due to pronounced anisotropic volume changes at low lithium content, unfavorable cation migration, and oxygen loss. Here, we demonstrate exceptionally stable cation and anion redox behavior in a metastable, cobalt‐free layered oxide, Li0.693[Li0.153Ni0.190Mn0.657]O2 (LLNMO). After 50 cycles at 50 mA/g (~0.2 C), the cathode retains 97.4 % of its initial capacity (222.4 mAh/g) with negligible voltage decay. This remarkable stability is attributed to its metastable O6‐type structure (R‐3m symmetry) with unique local geometry. The face‐sharing connectivity between lithium layers and alternating transition metal (TM) layers effectively suppresses TM migration‐induced voltage decay during anion redox. Additionally, the structure balances interlayer cation/cation and anion/anion repulsions, resulting in minimal expansion and contraction during de‐/lithiation (

KW - Metastable

KW - Anion redox

KW - oxygen activity

KW - layered cathode

KW - lithium-ion batteries

KW - Layered Cathode

KW - Anion Redox

KW - Lithium-ion Batteries

KW - Oxygen Activity

U2 - 10.1002/anie.202422789

DO - 10.1002/anie.202422789

M3 - Article

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

M1 - e202422789

ER -

A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries

Abstract

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Keywords

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Projects

Linking formation mechanisms, nanostructure and function in metal oxide nanosheets using multimodal characterisation.

Cite this