Electrochemical Aging Protocol Governed Capacity Losses and Structure Degradations in Layered LiNi0.8Co0.1Mn0.1O2 Oxides

Abstract The comparatively poor endurance of Ni‐rich cathode materials restricts their application in high‐energy lithium‐ion batteries. A thorough understanding of the degradation characteristics of such materials under complex electrochemical aging protocols is required to further improve their reliability. In this work, the irreversible capacity losses of LiNi 0.8 Mn 0.1 Co 0.1 O 2 under different electrochemical aging protocols are quantitatively evaluated via a well‐designed experiment. In addition, it is discovered that the origin of irreversible capacity losses is highly related to electrochemical cycling parameters and can be divided into two types. Type I is heterogeneous degradation caused by low C‐rate or high upper cut‐off voltage cycling and features abundant capacity loss during H2‐H3 phase transition. Such capacity loss is attributed to the irreversible surface phase transition that limits the accessible state of charge during the H2‐H3 phase transition stage via the pinning effect. Type II is fast charging/discharging induced homogeneous capacity loss that occurs consistently throughout the whole phase transition time. This degradation pathway shows a distinctive surface crystal structure, which is dominated by a bending layered structure rather than a typical rock‐salt phase structure. This work offers detailed insight into the failure mechanism of Ni‐rich cathodes and provides guidance on designing long‐cycle life, high‐reliability electrode materials.