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Vol. 18 (2026)

Unlocking Electrochemical-Driven Surface Oxygen Vacancies-Regulated Cathode–Electrolyte Interphase for Stabilizing Li-Ion Cells

https://doi.org/10.1007/s40820-026-02170-3
Chenxi Yan
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Xing Liu
School of Materials and New Energy, South China Normal University, Shanwei 516600, People’s Republic of China
Xuanlong He
School of Materials and New Energy, South China Normal University, Shanwei 516600, People’s Republic of China
Junjie Han
School of Materials and New Energy, South China Normal University, Shanwei 516600, People’s Republic of China
Longjun He
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Na Tian
School of Materials and New Energy, South China Normal University, Shanwei 516600, People’s Republic of China
Yanyi Wang
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Qiang Li
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Ning Zhao
College of Materials and Environmental Engineering, Shenzhen Polytechnic University, Shenzhen 518055, People’s Republic of China
Lipeng Zhang
School of Materials and New Energy, South China Normal University, Shanwei 516600, People’s Republic of China
Peixin Zhang
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China
Dingtao Ma
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, People’s Republic of China

Corresponding Author: Dingtao Ma

mdt2500@szu.edu.cn

Nano-Micro Letters, Vol. 18 (2026), Article Number: 361

Abstract

A stable cathode–electrolyte interphase (CEI) significantly enhances the durability of lithium-ion batteries; however, the intricate chemistry underlying its formation makes predesign exceedingly challenging. This work demonstrates that surface oxygen vacancy (OV) concentration dually regulates CEI thickness and composition. We develop an in situ strategy where Li2C4O4 incorporation into LiCoO2 (LCO) spontaneously decomposes during cycling, generating surface OVs. Combined experimental and theoretical calculations reveal these OVs enhance interfacial electron/Li⁺ migration rates while stabilizing the CEI. Notably, through 18O isotope labeling with time-of-flight secondary ion mass spectrometry, we innovatively provide direct experimental evidence that surface lattice oxygen serves as the predominant oxygen source for CEI oxygen-containing decomposition products, establishing the mechanism for OV-mediated CEI modulation. Based on this theory, the linear correlation and causal relationship among Li2C2O4 content, surface OV concentration, and LiF/LixPOyFz ratio in CEI are revealed. This strategy endows the OV-rich LCO cathode with 71.1% capacity retention after 600 cycles at 1 C within 3–4.4 V (23.9% for bare LCO) and achieves universal validation at 4.5 V and in LiNi0.8Co0.1Mn0.1O2 (NCM811). This study elucidates the critical function of surface OVs in prolonging cycle life and establishes a new design principle for tailored cathode interfaces and CEI chemistry.


Highlights:
1 In situ electrochemically induced surface oxygen vacancies (OVs) by Li2C4O4 decomposition enable dual regulation of cathode electrolyte interphase (CEI) thickness and composition, a novel strategy for tailored CEI engineering in Li ion batteries.
2 For the first time,18O isotope labeling combined with TOF SIMS directly verifies that lattice oxygen of LiCoO2 (LCO) serves as the predominant oxygen source for LixPOyFz in CEI, clarifying the long debated LiPF6 decomposition mechanism at the cathode inte rface.
3 The OV mediated strategy endows LCO with 71.1% capacity retention after 600 cycles at 1 C (3–4.4 V) (vs. 23.9% for bare LCO) and achieves universal applicability in 4.5 V high voltage systems and NCM811 cathodes, establishing a new design principle for stable high performance cathodes.

Keywords

Cathode material Oxygen vacancies Cathode–electrolyte interphase LiCoO2 Li2C4O4
Yan, Chenxi, Xing Liu, Xuanlong He, Junjie Han, Longjun He, Na Tian, Yanyi Wang, Qiang Li, Ning Zhao, Lipeng Zhang, Peixin Zhang, and Dingtao Ma. 2026. “Unlocking Electrochemical-Driven Surface Oxygen Vacancies-Regulated Cathode–Electrolyte Interphase for Stabilizing Li-Ion Cells”. Nano-Micro Letters 18 (May):361. https://doi.org/10.1007/s40820-026-02170-3.
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