Improved Stability of Single‐Crystal LiCoO₂ Cathodes at 4.8 V through Solvation Structure Regulation

Abstract Increasing the charging cut‐off voltage can significantly improve the capacity of LiCoO₂ cathode. However, when the cut‐off voltage exceeds 4.5 V (vs Li/Li⁺), LiCoO₂ undergoes irreversible phase transitions, leading to particle cracking and structural failure. Additionally, the decomposition of the electrolyte compromises the stability of the cathode/electrolyte interface, resulting in diminished battery capacity. Herein, the elements Al, Mg, and Zr are doped into single‐crystal LiCoO₂ to enhance the structural stability of LiCoO₂. Moreover, a 3 Å zeolite film is used to regulate the solvation structure to enhance the oxidation resistance of the electrolyte. This design enables a more stable cathode/electrolyte interface during high‐voltage cycling. At a cut‐off voltage of 4.8 V, the Li||LiCoO₂ battery exhibits an initial discharge capacity of 236.2 mAh g⁻¹ at 0.1 C and maintains 86.6% capacity retention after 100 cycles at 1 C. The pouch full cell, which utilizes a graphite anode and LiCoO₂ cathode, operating within a charge–discharge range of 2.8–4.65 V, achieves a specific energy of 276 Wh kg⁻¹ with 81% capacity retention after 200 cycles. This work introduces a desolvated electrolyte into the LiCoO₂ battery system, providing a professional approach to addressing the challenges of high‐voltage LiCoO₂.