ABSTRACT Vanadium oxides, owing to their multivalent nature and open framework structure, represent highly promising cathode candidates for aqueous zinc‐ion batteries (AZIBs). However, their application is constrained by degradation resulting from V‐dissolution at the cathode. In this study, Al 1.87 V 8 O 20 ·4H 2 O (AlVO) was synthesized at a current density of 0.5 A g −1 , the capacity retention rate was 91% after 500 cycles. Theoretical calculations indicate that, compared to Ga 3+ , pre‐intercalated Al 3+ increases the solubility energy of AlVO, endowing it with greater intrinsic structural strength. During dynamic cycling, Al 3+ helps maintain the structural integrity of the material, effectively reducing the increase in system entropy, and regulates Gibbs free energy at the thermodynamic level. Additionally, Al 3+ significantly reduces the energy barrier for Zn 2+ migration, resulting in a higher proportion of Zn 2+ in the AlVO system during Zn 2+ /H + co‐intercalation compared to Ga 2.67 V 8 O 20 ·4H 2 O (GaVO). According to Le Chatelier's principle, reducing the H + incorporation ratio in AlVO can effectively inhibit the kinetic process of vanadium dissolution. This study elucidates the dissolution process of vanadium‐based cathode materials from the perspectives of thermodynamic principles and kinetic mechanisms, providing a viable approach for designing stable vanadium‐based cathodes.
Xiong et al. (Wed,) studied this question.