Anion Adsorption at the Inner‐Helmholtz Plane Directs Cathode Electrolyte Interphase Formation

Constructing a stable cathode-electrolyte-interphase (CEI) on cathode surface constitutes the foundation of realizing high-voltage Li-ion batteries, yet its formation, a highly heterogeneous process involving irreversible reactions between electrolyte components and cathode materials, remains poorly understood. Herein, combining multiple in situ/operando interfacial characterization techniques, we establish the correlation between interfacial structure and interphasial chemistry, and reveal the key role played by adsorptive behavior of various electrolyte components in the inner-Helmholtz plane during CEI formation. Quartz crystal microbalance equipped with dissipation modification detects that difluorooxalatoborate (DFOB<sup>-</sup>) anion preferentially adsorbed on LiCoO<sub>2</sub> tends to expel carbonate solvents from the adsorption layer, thus suppressing their electrochemical decomposition at high voltages and leading to a more compact CEI derived from anions with limited contribution from organic ingredients. Consequently, the CoO<sub>2</sub> lattice structure protected by the dense CEI remains intact despite near-complete delithiation, thereby ensuring excellent cycling stability for 4.7 V operation of LiCoO<sub>2</sub> cathode. The atomistic-level insight into the key factors that govern CEI formation provides directive knowledge that accelerates electrolyte design for high-voltage batteries.

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Publication Details

Journal
Angewandte Chemie International Edition
Published
2025-03-06
DOI
https://doi.org/10.1002/anie.202425535
Citations
23
Primary Topic
Membrane-based Ion Separation Techniques
Type
article
Field-Weighted Citation Impact
15.50

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article

Anion Adsorption at the Inner‐Helmholtz Plane Directs Cathode Electrolyte Interphase Formation

Tao Shen, Zu‐Wei Yin, Shida Xue, Kunchen Xie et al.
23 citations
Angewandte Chemie International Edition
Membrane-based Ion Separation Techniques
15.50
article

Anion Adsorption at the Inner‐Helmholtz Plane Directs Cathode Electrolyte Interphase Formation

Tao Shen, Zu‐Wei Yin, Shida Xue, Kunchen Xie, Jimin Qiu, Feng Ming Pan, Zihang Dong, Xudong Zhao, Guorui Zheng, Yuxiang Huang, Jianjun Fang, Haoyu Xue, Luyi Yang, Kai Yang, Peng‐Hu Du, Peng Liu, Kang Xu, Shiqi Liu, Hai Lin, Shiming Chen, Yuchen Ji, Aimin Cao
article en
23 citations

Abstract

Constructing a stable cathode-electrolyte-interphase (CEI) on cathode surface constitutes the foundation of realizing high-voltage Li-ion batteries, yet its formation, a highly heterogeneous process involving irreversible reactions between electrolyte components and cathode materials, remains poorly understood. Herein, combining multiple in situ/operando interfacial characterization techniques, we establish the correlation between interfacial structure and interphasial chemistry, and reveal the key role played by adsorptive behavior of various electrolyte components in the inner-Helmholtz plane during CEI formation. Quartz crystal microbalance equipped with dissipation modification detects that difluorooxalatoborate (DFOB<sup>-</sup>) anion preferentially adsorbed on LiCoO<sub>2</sub> tends to expel carbonate solvents from the adsorption layer, thus suppressing their electrochemical decomposition at high voltages and leading to a more compact CEI derived from anions with limited contribution from organic ingredients. Consequently, the CoO<sub>2</sub> lattice structure protected by the dense CEI remains intact despite near-complete delithiation, thereby ensuring excellent cycling stability for 4.7 V operation of LiCoO<sub>2</sub> cathode. The atomistic-level insight into the key factors that govern CEI formation provides directive knowledge that accelerates electrolyte design for high-voltage batteries.

Angewandte Chemie International EditionVol. 64(20)
Xiamen University (CN), Peking University (CN), University of Surrey (GB), Lishui University (CN), University Town of Shenzhen (CN), Beijing University of Technology (CN), Biolin Scientific (United Kingdom) (GB), Tsinghua–Berkeley Shenzhen Institute (CN), Ai Corporation (United Kingdom) (GB), Peking University Shenzhen Hospital (CN), Division of Materials Science and Engineering (AU), Tsinghua University (CN)
National Natural Science Foundation of China, Guangdong Science and Technology Department, Science, Technology and Innovation Commission of Shenzhen Municipality
Openalex Percentile: Top 1%
Membrane-based Ion Separation Techniques
15.50
DOIOpen Access PDFOpenAlex
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