TY - JOUR
T1 - A Metastable Oxygen Redox Cathode for Lithium-Ion Batteries
AU - Wang, Yanfang
AU - Li, Cheng
AU - Li, Yingzhi
AU - de Benito, Raquel
AU - Williams, Jacob
AU - Stratford, Joshua M.
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 W.
AU - Zhou, Ke-Jin
AU - Zhang, Kaili
AU - Zhang, Fucai
AU - Allan, Phoebe K.
AU - Lu, Zhouguang
PY - 2025/4/11
Y1 - 2025/4/11
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 (<2.3 % along the c-axis) and excellent structural reversibility. These findings highlight that layered oxides with a metastable framework are promising cathode candidates for next-generation ultra-high-energy lithium-ion batteries. © 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.
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 (<2.3 % along the c-axis) and excellent structural reversibility. These findings highlight that layered oxides with a metastable framework are promising cathode candidates for next-generation ultra-high-energy lithium-ion batteries. © 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.
KW - Anion Redox
KW - Layered Cathode
KW - Lithium-ion Batteries
KW - Metastable
KW - Oxygen Activity
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U2 - 10.1002/anie.202422789
DO - 10.1002/anie.202422789
M3 - RGC 21 - Publication in refereed journal
SN - 1433-7851
VL - 64
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 16
M1 - e202422789
ER -
