journal article·2020-05-26

High-Voltage Cycling Induced Thermal Vulnerability in LiCoO2 Cathode: Cation Loss and Oxygen Release Driven by Oxygen Vacancy Migration

Congli Sun, Xiaobin Liao, Fanjie Xia, Yan Zhao, Lei Zhang, Sai Mu, Shanshan Shi, Yanxi Li, Haoyang Peng, Gustaaf Van Tendeloo, Kangning Zhao, Jinsong Wu

ACS Nano· Volume 14· Issue 5
Publisher page

Abstract

The release of the lattice oxygen due to the thermal degradation of layered lithium transition metal oxides is one of the major safety concerns in Li-ion batteries. The oxygen release is generally attributed to the phase transitions from the layered structure to spinel and rocksalt structures that contain less lattice oxygen. Here, a different degradation pathway in LiCoO2 is found, through oxygen vacancy facilitated cation migration and reduction. This process leaves undercoordinated oxygen that gives rise to oxygen release while the structure integrity of the defect-free region is mostly preserved. This oxygen release mechanism can be called surface degradation due to the kinetic control of the cation migration but has a slow surface to bulk propagation with continuous loss of the surface cation ions. It is also strongly correlated with the high-voltage cycling defects that end up with a significant local oxygen release at low temperatures. This work unveils the thermal vulnerability of high-voltage Li-ion batteries and the critical role of the surface fraction as a general mitigating approach.
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Research context

OpenAlex topics: Advancements in Battery Materials · Advanced Battery Materials and Technologies · Semiconductor materials and devices

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China

NRC (Nanostructure Research Centre), Wuhan University of Technology, Wuhan 430070, China

Materials Department, University of California, Santa Barbara, California 93106-5050, United States

College of Sciences & Institute for Sustainable Energy, Shanghai University, Shanghai 200444, China

Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States

EMAT (Electron Microscopy for Materials Science), University of Antwerp, 2020 Antwerp, Belgium

Funding

Wuhan University of Technology · National Natural Science Foundation of China · State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology · State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology

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