Crystal‐Facet Manipulation and Interface Regulation via TMP‐Modulated Solid Polymer Electrolytes toward High‐Performance Zn Metal Batteries

Abstract Rechargeable Zn‐ion batteries (ZIBs), prospective candidates for broad‐scale energy storage, still encounter many challenges such as hydrogen evolution corrosion, Zn dendrite growth, and capacity fading. Therefore, one specific strategy for tuning the internal structure of solid polymer electrolytes (SPEs) via organic additives is proposed to address these urgent bottlenecks simultaneously. With trimethyl phosphate (TMP) addition, the coordination environment of Zn 2+ in SPEs is altered and exists as Zn 2+ (TMP) x (OTf − ) y coordinated molecules. Meanwhile, the strong interaction between TMP and Zn enables the preferential growth of Zn(002) planes during electrodeposition, which is proved based on first‐principles calculations, finite element simulations, and multiple in situ characterizations. Such excellent interfacial engineering in situ forms the solid electrolyte interface rich in Zn 3 (PO 4 ) 2 fast ion conductor and guarantees one ultra‐long cycle life for more than 6000 h in a Zn|Zn symmetric cell at 0.1 mA cm −2 . Moreover, the universality of TMP‐modified SPEs shows 1000 times stable cycling of VO 2 (B)|Zn full cells at 1 A g −1 under 0 °C with 95.24% capacity retention, which satisfies potential applications of wide‐ranging energy storage based on solid‐state ZIBs.