Investigation on the Overlithiation Mechanism of LiCoO2 Cathode for Lithium Ion Batteries. Issue 5 (11th May 2021)

• Record Type: Journal Article
• Authors: Yu, Lele; Tian, Yexing; Xiao, Xiang; Hou, Chen; Xing, Yiran; Si, Yongheng; Lu, Han; Zhao, Yujuan
• Is Part Of: Journal of the Electrochemical Society. Volume 168:Issue 5(2021)
• Publication Date: 2021-05-11
• Subjects: LiCoO2 -- Overlithiation mechanism -- Composition -- Electrolyte decomposition; Electrochemistry -- Periodicals; 541.3705
• DOI: 10.1149/1945-7111/abfc9e
• Languages: English
• ISSNs: 0013-4651

Abstract

Abstract : Overlithiation of lithium ion batteries often causes a structural transformation of the electrode and capacity degradation and may even lead to severe safety problems. In this study, the electrode structure, surface morphology and compositions at the different overlithiation depths of LiCoO2 cathode material were investigated in detailed by examining the LCO/Li cells and anode-free cells, combined with post-mortem characterizations. When LiCoO2 is found in a slight overlithiation state, the cycle capacity fades slightly and minority of LiCoO2 reduces to CoO and Li2 O. After LiCoO2 undergoes a deep overlithiation reaction, a long flat voltage plateau appears at 1.2 V and the cycle performance is greatly deteriorated. SEM and EIS tests show that the single-crystal particles are fractured into small particles with thick-layer formation at the surface and the shape of the EIS curve changes strongly with increasing overlithiation depth. Additionally, as shown by XPS Ar-ion etching and TEM characterization, the LiCoO2 surface is converted into greater amounts of Li2 O, CoO and Co metal associated with the severe electrolyte decomposition, and LiF, Li2 CO3 and Lix POy Fz are the main electrolyte decomposition products. The detailed investigation of the overlithiation mechanism of LiCoO2 provides comprehensive and thorough guidance for understanding the overlithiation mechanism of cathode materials as well as important reference information for practical all-solid-state battery applications.