The Role of Li‐Rich Disordered Domain in Li‐Rich Cathodes
Abstract
ABSTRACT Li‐rich cathodes suffer from electrochemical degradation due to structural incompatibility between the Li‐rich and LiTMO 2 ‐like phases (transition metal [TM] = Mn, Ni). This study identifies and characterizes a previously overlooked transitional phase, the Li‐rich disordered (LRD) domain, which bridges these two primary phases and is the fundamental origin of heterogeneous redox‐driven strain and lattice displacements. Advanced structural analyses reveal that transition metals, particularly Ni, occupy Li sites within this LRD domain. We demonstrate that tailoring the synthesis to constrict the LRD domain effectively mitigates its structural evolution during (de)lithiation. This constricted domain acts as a buffer layer, isolating the anisotropic lattice strain between adjacent domains, thereby suppressing oxygen loss and enhancing structural integrity. In situ high‐temperature XRD further tracks the formation of this domain during synthesis. Consequently, the engineered cathode delivers a 15% (25 mA g −1 , 50 cycles) and 26% (250 mA g −1 , 300 cycles) increase in specific capacity than pristine within 2.0–4.8 V, alongside enhanced long‐term cycling stability. This work elucidates the critical role of the constricted LRD domain in stabilizing anionic redox, offering a fundamental insight for designing advanced Li‐rich cathodes.
Article Details
Authors (10)
Gui‐Jing Xu
State Key Laboratory of Space Power‐Sources MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage MOE Engineering Research Center for Electrochemical Energy Storage and Carbon Neutrality in Cold Regions School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin China
Jia‐Ji Tang
State Key Laboratory of Space Power‐Sources MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage MOE Engineering Research Center for Electrochemical Energy Storage and Carbon Neutrality in Cold Regions School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin China
Wang Ke
State Key Laboratory of Space Power‐Sources MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage MOE Engineering Research Center for Electrochemical Energy Storage and Carbon Neutrality in Cold Regions School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin China
Fu‐Da Yu
Engineering Research Center of Environment‐Friendly Functional Materials Ministry of Education College of Materials Science and Engineering Huaqiao University Xiamen China
Yun‐Shan Jiang
School of Energy and Environment City University of Hong Kong Hong Kong SAR China
Nian Zhang
Shanghai Synchrotron Radiation Facility
Zhong‐Miao Liao
School of Materials Science and Engineering Dongguan University of Technology Dongguan China
Liang Deng
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry
Lei Zhao
School of Life Sciences, Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, and Hubei Key Laboratory of Genetic Regulation and Integrative Biology, Central China Normal University
Zhen‐Bo Wang
State Key Laboratory of Space Power‐Sources MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage MOE Engineering Research Center for Electrochemical Energy Storage and Carbon Neutrality in Cold Regions School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin China