In‐Situ Self‐Respiratory Solid‐to‐Hydrogel Electrolyte Interface Evoked Well‐Distributed Deposition on Zinc Anode for Highly Reversible Zinc‐Ion Batteries

Abstract The aqueous zinc‐ion batteries (AZIB) have emerged as a promising technology in the realm of electrochemical energy storage. Despite its potential advantages in terms of safety, cost‐effectiveness, and inherent safety, AZIB faces significant challenges. Issues attributed to unsupported thermodynamics and non‐uniform potential distribution and deposition, present formidable obstacles that necessitate resolution. To tackle these challenges, a novel strategy adapting hybrid organic–inorganic in situ derived solid‐to‐hydrogel electrolyte interface (StHEI) has been developed from coordination reactions and self‐respiratory process, establishing uniform diffusion channels by ion bridges and accelerating ion transport. Self‐respiratory pattern of StHEI realized through in situ inorganic component conversion further prolongs the protecting duration, which effectively mitigates corrosion and passivation but enhance the mechanical properties of the StHEI measured through Young's modulus. This novel StHEI promotes well‐distributed potential lines within the Helmholtz regions. Zn 2+ are finally induced to deposit and nucleate in a compact, fine, and uniform manner. Asymmetrical batteries assembled with the modified Zn electrode and bare Zn exhibit exceptional stability over 3000 h (1 mA cm −2 –0.5 mAh cm −2 ). The asymmetrical Cu//Zn cell achieved an outstanding average Coulombic efficiency (CE) of 99.6 % over 1200 cycles.