Vertical VOPO4·2H2O Nanosheets with Richly Exposed (200) Plane Enable Fast‐Kinetics High‐Mass‐Loading Cathodes for Zn‐Ion Batteries

Abstract Extending the layer spacing of the (001) planes to regulate the mobility of Zn 2+ is widely adopted to optimize the performance of VOPO 4 ·2H 2 O cathode for zinc‐ion batteries. However, the unique function originating from other planes is often neglected. Herein, an effective in situ conversion methodology is proposed for the synthesis of the (200) oriented growth of vertical VOPO 4 ·2H 2 O nanosheets with oxygen vacancies (V Od ‐VOPO 4 ). Theoretical simulation and ex situ characterizations collaboratively demonstrate that the richly exposed (200) plane with tetragonal channels can offer quick pathways for in‐layer and cross‐layer migration of Zn 2+ , exhibiting enhanced transfer kinetics with improved reversible capacity. Meanwhile, efficient electron migration in V Od ‐VOPO 4 is guaranteed by the introduction of oxygen vacancies. Thus, the as‐prepared V Od ‐VOPO 4 harvests exceptional discharge capacity, impressive rate capability, and remarkable long‐cycle stability at high mass loading. Notably, the V Od ‐VOPO 4 electrode (15 mg cm −2 ) provides a capacity of 213.5 mAh g −1 with an ultrahigh areal capacity of 3.02 mAh cm −2 at 0.1 A g −1 , showing great potential for applications. This study highlights the orientated growth strategy for facilitating ion storage and migration, offering novel perspectives on the development of high‐performance electrodes and beyond.