Grotthuss Topochemistry Realizes Ah‐Level Fast‐Chargeable Zinc‐Vanadium Pouch Battery

Abstract Aqueous zinc ion batteries (AZIBs) anodes have made significant progress in high area capacity, high zinc utilization. Different from the Zn 2+ plating/stripping process in the anodes, the cathodes usually involve the insertion/extraction of Zn 2+ . The kinetics of this process is much slower than anodes because of the low transfer rate of Zn 2+ in high‐loading electrodes. Therefore, simply increasing the thickness of the cathodes cannot achieve area capacity matching with the anodes. Utilizing Grotthuss topochemistry for fast H + transfer is expected to solve this problem. The radius of H + is much smaller than Zn 2+ , extremely mobile in aqueous electrolyte, which is favorable to enter the interior of high‐loading electrodes to participate in the reaction, thus improving the area capacity under high loading. In this work, a cluster‐structured material (HCVO) with numerous oxygen vacancies and line defects is designed, which satisfies the theoretical conditions of Grotthuss topochemistry. Based on fast H + transport, the HCVO cathode exhibits ultra high rate performance (196.7 mAh g −1 at 60 A g −1 ) and long cycle life (15800 cycles). Under high loading, the HCVO coin cell has an area capacity of 19.88 mAh cm −2, and the pouch cell is 7.37 mAh cm −2 . Notably, Ah‐level pouch cell (1209 mAh) can work 120 cycles (833 h) with a cumulative capacity of 129 Ah. HCVO pouch cell also supports fast charge, which charges requires only 249 s (381.2 mAh at 4.8 A) and works 420 cycles, showing better rate performance than the Ah level commercial lead‐acid cell. Renewable energy storage is achieved by charging the HCVO pouch cell through a solar panel, combined with fast charge characteristic, which has certain potential for commercial application.