Thermal and Electrochemical Interface Compatibility of a Hydroborate Solid Electrolyte with 3 V-Class Cathodes for...

Thermal stability of solid electrolytes and their compatibility with battery electrodes are key factors to ensure stable cycling and high operational safety of all-solid-state batteries. Here, we study the compatibility of a hydroborate solid electrolyte Na₄(B₁₂H₁₂)(B₁₀H₁₀) with 3 V-class cathode active materials: NaCrO₂, NaMnO₂, and NaFeO₂. Among these layered sodium transition metal oxide cathodes, NaCrO₂ shows the highest thermal compatibility in contact with the hydroborate solid electrolyte up to 525 °C in the discharged state. Furthermore, the electrolyte remains intact upon the internal thermal decomposition of the charged, that is, desodiated, cathode (Na_0.5CrO₂) above 250 °C, demonstrating the potential for highly safe hydroborate-based all-solid-state batteries with a wide operating temperature range. The experimentally determined onset temperatures of thermal decomposition of Na₄(B₁₂H₁₂)(B₁₀H₁₀) in contact with 3 V-class cathodes surpass those of sulfide and selenide solid electrolytes, exceeding previous thermodynamic calculations. Our results also highlight the need to identify relevant decomposition pathways of hydroborates to enable more valid theoretical predictions.