Water-Mediated Surface Engineering Enhances High-Voltage Stability of Fast-Charge LiCoO2 Cathodes.

Abstract

Maintaining the surface structure stability of LiCoO₂ (LCO) during rapid charge-discharge processes (>5C) and under high-voltage conditions (>4.2 V) is challenging due to interfacial side reactions, cobalt dissolution, and oxygen redox activity at deeply delithiated states, all of which contribute to performance degradation. Herein, different from traditional surface coating methods, we report a water-mediated strategy that modifies the surface architecture of LCO, creating a passivating layer to inhibit surface degradation and enhance cycling stability under fast charging conditions. The surface etching of LCO by H₂O is accompanied by a concurrent Li⁺/H⁺ cation exchange, which passivates surface oxygen with H⁺ ions, thereby enhancing both the hydrophobicity and structural stability. Consequently, the modified LCO exhibits superior capacity retention, which is 2.5 times that of the pristine LCO, after 100 cycles at a current density of 1000 mA g^-1 (∼6C at 4.5 V). Even at an elevated temperature of 45 °C, it maintains impressive cycling stability at a current density of 500 mA g^-1 (∼3C), as demonstrated in practical full-cell configurations. Investigation with multiple samples confirmed that the water-mediated strategy demonstrated broad applicability. We emphasize that the water-mediated modification of the surface architecture on cathode materials offers significant insights into enhancing the stability of high-energy-density lithium-ion batteries (LIBs).