Enhancing Zinc Electrode Stability Through Pre‐Desolvation and Accelerated Charge Transfer via a Polyimide Interface for Zinc‐Ion Batteries

Abstract Aqueous zinc‐based energy storage devices possess superior safety, cost‐effectiveness, and high energy density; however, dendritic growth and side reactions on the zinc electrode curtail their widespread applications. In this study, these issues are mitigated by introducing a polyimide (PI) nanofabric interfacial layer onto the zinc substrate. Simulations reveal that the PI nanofabric promotes a pre‐desolvation process, effectively desolvating hydrated zinc ions from Zn(H₂O)₆²⁺ to Zn(H₂O)₄²⁺ before approaching the zinc surface. The exposed zinc ion in Zn(H₂O)₄²⁺ provides an accelerated charge transfer process and reduces the activation energy for zinc deposition from 40 to 21 kJ mol⁻¹. The PI nanofabric also acts as a protective barrier, reducing side reactions at the electrode. As a result, the PI‐Zn symmetric cell exhibits remarkable cycling stability over 1200 h, maintaining a dendrite‐free morphology and minimal byproduct formation. Moreover, the cell exhibits high stability and low voltage hysteresis even under high current densities (20 mA cm⁻², 10 mAh cm⁻²) thanks to the 3D porous structure of PI nanofabric. When integrated into full cells, the PI‐Zn||AC hybrid zinc‐ion capacitor and PI‐Zn||MnVOH@SWCNT zinc‐ion battery achieve impressive lifespans of 15000 and 600 cycles with outstanding capacitance retention. This approach paves a novel avenue for high‐performance zinc metal electrodes.