Surface Design with Cation and Anion Dual Gradient Stabilizes High‐Voltage LiCoO2

LiCoO2 (LCO) is the most successful cathode material for commercial lithium‐ion batteries. Cycling LCO to high potentials up to 4.5 V or even 4.6 V can significantly elevate the capacity but cause structural degradation due to the serious surface side reaction between the highly oxidized Co4+ and O−...

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Bibliographic Details
Published in:Advanced energy materials 2022-05, Vol.12 (20), p.n/a
Main Authors: Huang, Weiyuan, Zhao, Qi, Zhang, Mingjian, Xu, Shenyang, Xue, Haoyu, Zhu, Chen, Fang, Jianjun, Zhao, Wenguang, Ren, Guoxi, Qin, Runzhi, Zhao, Qinghe, Chen, Haibiao, Pan, Feng
Format: Article
Language:English
Subjects:
Anions
Cathodes
Cations
Cycles
Diffusion layers
dual gradient
Electrode materials
high voltage
LiCoO 2 cathodes
Lithium compounds
Lithium-ion batteries
Nonaqueous electrolytes
stable surface structure
Surface structure
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Summary:LiCoO2 (LCO) is the most successful cathode material for commercial lithium‐ion batteries. Cycling LCO to high potentials up to 4.5 V or even 4.6 V can significantly elevate the capacity but cause structural degradation due to the serious surface side reaction between the highly oxidized Co4+ and O− species with organic electrolytes. To tackle this concern, a new strategy, constructing cation and anion dual gradients at the surface of LCO (DG‐LCO), is proposed. Specifically, the electrochemically inactive cation and anion are selected to substitute Co3+ and O2− at the surface in a gradated manner, thus minimizing the highly oxidized Co4+ and O− species at high potentials and suppressing the induced surface side reactions. Unexpectedly, this dual gradient design leads to a spinel‐like surface structure coherently with bulk layered structure, which facilitates Li+ diffusion kinetics. Thus, DG‐LCO achieves high capacity and excellent cycling stability at 4.6 V (≈216 mA h g−1 at 0.1 C, a capacity retention of 88.6% after 100 cycles in 1.8 A h pouch full cell at 1 C), as well as improved rate capability (≈140 mA h g−1 at 5 C). These studies provide useful guidelines for future design of cathode materials with long lifespan and high rate capability. A new strategy; cation and anion dual gradient, is proposed and successfully constructed at the surface of LiCoO2 to minimize the highly oxidized Co4+ and O− species when charged to high potentials, which not only suppresses the relevant surface side reactions, but also affected the Li+ diffusion kinetics through the induced spinel‐like surface structure, making LiCoO2 exhibit excellent cycling stability and rate capability at the high cutoff voltage of 4.6 V, further validated in the 4.55 V pouch full cell (equivalent to 4.6 V vs Li/Li+).
ISSN:1614-6832
1614-6840
DOI:10.1002/aenm.202200813