Hydrogen‐Bond Locked Quasi‐Solid Electrolyte Enables Zn Metal Batteries Operating at −106 °C

Abstract Solid‐state Zn metal batteries hold great potential for sustainable and high‐safety reserves, yet their practicality has been severely constrained by poor low‐temperature performance. Herein, an innovative hydrogen‐bond locked quasi‐solid electrolyte (HLQE) is developed and realizes the operation of solid‐state Zn metal batteries at −106 °C. The HLQE reconstructs the Zn ²⁺ chemical environment and enhances ion transport kinetics, achieving a high Zn ²⁺ transference number (0.79) and remarkable ionic conductivity (3.42 × 10 ⁻⁴ S cm ⁻¹ ), thus inhibiting the Zn dendrite growth even at −70 °C. As a result, the assembled batteries demonstrate remarkable performance at −70 °C, with Zn||Cu cells exhibiting 82.3% Coulombic efficiency after 300 cycles, Zn||Zn cells operating stably for 465 h, and PANI||Zn full cells achieving 554 cycles. More significantly, HLQE possesses outstanding abuse tolerance, in which the polyaniline (PANI)||Zn pouch cells successfully powered micro‐displays at −106 °C after mechanical damage. This work breaks through the low‐temperature limit of solid‐state Zn metal batteries and enriches the design concepts of solid‐state electrolytes in extreme environments.