Remodeling Proton Insertion Chemistry via Interfacial Organic Layer for Fast‐Charging and Robust Zn‐VO ₂ Batteries

ABSTRACT Aqueous Zn‐vanadium (Zn‐V) batteries with high theoretical capacity are limited by sluggish Zn ²⁺ diffusion kinetics, limited electronic conductivity, and structural instability, which impede the battery lifespan and rate capability. Herein, we fabricate a core–shell organic/inorganic heterostructure of modified VO ₂ (denoted as P‐VO ₂ ) uniformly wrapped by poly(p‐phenylenediamine, p‐PDA) featuring interfacial V─N bonds for enhanced structural integrity and suppressed V dissolution. Theoretical calculations and in/ex situ characterizations proved the regulated proton insertion chemistry via ─C═N/─NH‐ chemistry in poly(p‐PDA) for facilitated V ⁵⁺ /V ⁴⁺ /V ³⁺ reaction kinetics and reversibility. As a result, the Zn//P‐VO ₂ battery showed a superb capacity of 383 mAh g ⁻¹ at 0.2 A g ⁻¹ , superior rate performance (330 mAh g ⁻¹ at 5 A g ⁻¹ ), and extraordinary lifespan over 16 000 cycles. Moreover, a 143.6 Wh kg ⁻¹ pouch cell shows ultrastability at −15°C after 200 cycles, underscoring its considerable potential. This work provides a new perspective on the study of organic‐modified vanadium oxides for advanced Zn batteries.