Porous Cyclodextrin Polymer Enables Dendrite‐Free and Ultra‐Long Life Solid‐State Zn‐I2 Batteries

Abstract Zn‐I 2 batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD‐Si) by nucleophilic reaction of β ‐cyclodextrin with SiCl 4 , and CD‐Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD‐Si) to solve above‐mentioned problems. Through the anchoring of the CD‐Si, a conductive network with dual transmission channels was successfully constructed. Due to the non‐covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10 −3 S cm −1 at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite‐free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm −2 and 1200 h at 20 mA cm −2 ). The solid‐state Zn‐I 2 battery shows an ultra‐long life of over 35,000 cycles at 2 A g −1 . Molecular dynamics simulations are performed to elucidate the working mechanism of CD‐Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn‐I 2 batteries.