Nucleation‐Controlled Synthesis and a Unified Descriptor for Rational Interlayer Design of Vanadium‐Oxide Cathodes toward High‐Performance Zinc‐Ion Batteries

Abstract

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) are promising for large‐scale energy storage, yet their development is constrained by the cathode that suffers from energy‐intensive synthesis and poorly understood interlayer‐ion chemistry. NH 4 V 4 O 10 (NVO) exemplifies these challenges, as hydrothermal preparation hampers scalability and the stabilizing role of intercalated cations remains ambiguous. Here, by revisiting vanadium‐oxide synthesis history and nucleation mechanisms, we establish a nucleation‐kinetics–driven, pH‐controlled supersaturation strategy that enables mild and scalable NVO synthesis. Moreover, this method provides a reliable platform for systematic interlayer chemistry studies. A comparative investigation of cations‐intercalated NVO establishes a unified descriptor, weighted ionic potential, δ = Z/r × EN( (valence/radius) × electronegativity), which quantifies the effective polarizing power and metal–oxygen interaction of interlayer cations. Experimental correlation and theory analysis identify the most effective stabilizing species. To further enhance capacity without sacrificing stability, redox‐active molecules are co‐intercalated into Al 3+ ‐stabilized NVO. The resulting cathode exhibits accelerated Zn 2+ transport, modified redox chemistry, and additional charge storage, delivering high specific capacities of ∼420 mAh g −1 at 0.1 A g −1 , 248 mAh g −1 at 5 A g −1 , and ∼83% retention over 8000 cycles. Overall, this work integrates scalable synthesis and descriptor‐guided interlayer design to advance high‐performance vanadium‐oxide cathodes toward practical AZIBs.