Domain-Defined Coordination Modulation of Vanadium Oxide Cathodes for Wide-Temperature-Tolerant Aqueous Zinc-Ion Batteries.

Layered hydrated vanadium oxides are promising cathode materials for aqueous zinc-ion batteries but suffer from sluggish kinetics and severe V dissolution. To address this challenge, we propose a "spatial coordination domain differentiation" concept, dividing the local V coordination into two spatially functional regions. In this framework, the inner-coordination domain (ICD) is defined as first-shell [VO6] octahedra governing orbital hybridization and structural integrity, whereas the outer-coordination domain (OCD) comprises the interlayer gallery that accommodates guest ions and mediates long-range electrostatic interactions. By combining x-ray absorption, photoelectron spectroscopies, and theoretical calculations, we demonstrate that the precise pre-intercalation of In3+ into OCD enables targeted perturbation of ICD. Such dual-domain regulation homogenizes [VO6] octahedral distortion and promotes electron redistribution around V centers, leading to enhanced V 3d-O 2p orbital hybridization. As a result, V dissolution is effectively suppressed, while Zn2+/H+ cointercalation kinetics are markedly accelerated. Consequently, the optimized In0.55V10O24·4.35H2O cathode delivers specific capacities as high as 500 mAh g-1 at 60°C and 300 mAh g-1 at -60°C (0.1 A g-1), while maintaining capacity of 91.9% and 97.2% after 10,000 cycles at 25°C and -60°C, respectively. This work offers an orbital-level design principle for developing high-stability energy storage materials.