In Situ Formed Heterostructure Interface and Well-Tuned Electronic Structure Ensuring Long Cycle Stability for 4.9 V High-Voltage Li-Rich Layered Oxide Cathodes

Gang Zhou; Datong Zhang; Youquan Zhang; Wenran Wang; Tomoki Uchiyama; Chunxiao Zhang; Yoshiharu Uchimoto; Weifeng Wei

doi:10.1021/acsami.3c02173

In Situ Formed Heterostructure Interface and Well-Tuned Electronic Structure Ensuring Long Cycle Stability for 4.9 V High-Voltage Li-Rich Layered Oxide Cathodes

ACS Appl Mater Interfaces. 2023 Apr 19;15(15):19055-19065. doi: 10.1021/acsami.3c02173. Epub 2023 Apr 10.

Authors

Gang Zhou^{1

2}, Datong Zhang³, Youquan Zhang², Wenran Wang², Tomoki Uchiyama³, Chunxiao Zhang², Yoshiharu Uchimoto³, Weifeng Wei²

Affiliations

¹ School of Environment and Civil Engineering, Dongguan University of Technology, Dongguan, Guangdong 523000, P. R. China.
² State Key Laboratory of Powder Metallurgy, Central South University, Changsha, Hunan 410083, P. R. China.
³ Graduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu Cho, Sakyo, Kyoto 606-8501, Japan.

PMID: 37036492
DOI: 10.1021/acsami.3c02173

Abstract

High-voltage lithium-rich manganese-based layered oxides (LMLOs) are considered as the most competitive cathode materials for next-generation high-energy-density lithium-ion batteries (LIBs). However, LMLOs still suffer from irreversible lattice oxygen release, uncontrollable interface side reactions, and surface structural degradation. Herein, we propose an integration strategy combining La/Al codoping and Li_xCoPO₄ nanocoating to improve the electrochemical performance of LMLOs comprehensively. La/Al codoping regulates the electronic structure to enhance the redox activity of anions and cations and inhibit structural degradation. The Li_xCoPO₄ nanocoating formed by in situ reaction with the surface residual lithium can not only promote Li-ion migration but also reduce interfacial side reactions. The induced Layered@Rocksalt@Li_xCoPO₄ heterostructure suppresses lattice volume variation and structural degradation during cycling. Under the synergistic effect of the heterostructure interface and well-tuned electronic structure, the capacity retention rate of comodified LMLO materials reaches 80.06% after 500 cycles (2.0-4.65 V) and 75.1% after 340 cycles at 1C under a high cut-off voltage of 4.9 V.

Keywords: electrochemical performance; electronic structure; heterostructure interface; high voltage; lithium-rich manganese-based oxides.