Achieving ultra-low voltage fading in Co-free Li-rich layered oxides via effortless surface defect engineering

Abstract

Cobalt (Co)-free lithium (Li)-rich layered oxides (LLOs) have emerged as promising cathode materials for the next generation of Li-ion batteries, attributed to their competitive market positioning and high energy density. Nevertheless, challenges arise from surface oxygen loss due to irreversible anionic redox reactions, leading to severe voltage and capacity decay that hinder the large-scale adoption of LLOs. Herein, we present an innovative, facile, and environmentally friendly hydrothermal approach to induce surface reconstruction of Li1.2Mn0.6Ni0.2O2 material. A multifaceted combination involving the spinel phase, oxygen vacancies, and reduced manganese is orchestrated to alleviate the irreversible oxygen redox and impressively enhance Li-ion diffusion. The modified sample, owing to this surface transition, demonstrates low-strain and low-distortion properties along with a substantial improvement in structural stability, supported by both experimental validations and theoretical studies. As a result, the engineered sample exhibits exceptional capacity retention of 97.12% after 150 cycles at 1C, with an ultra-low voltage decay (0.91 mV cycle−1). Additionally, noteworthy enhancements in initial coulombic efficiency and rate performance are also observed. This straightforward surface defect engineering method offers a pathway to developing “low-strain” LLOs with superior electrochemical performance, thereby laying a solid foundation for future commercial applications.