Anhydrous Superprotonic Conductivity in the Zirconium Acid Triphosphate ZrH5(PO4)3

The development of solid‐state proton conductors with high proton conductivity at low temperatures is crucial for the implementation of hydrogen‐based technologies for portable and automotive applications. Here, we report on the discovery of a new crystalline metal acid triphosphate, ZrH5(PO4)3 (ZP3), which exhibits record‐high proton conductivity of 0.5–3.1×10−2 S cm−1 in the range 25–110 °C in anhydrous conditions. This is the highest anhydrous proton conductivity ever reported in a crystalline solid proton conductor in the range 25–110 °C. Superprotonic conductivity in ZP3 is enabled by extended defective frustrated hydrogen bond chains, where the protons are dynamically disordered over two oxygen centers. The high proton conductivity and stability in anhydrous conditions make ZP3 an excellent candidate for innovative applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer. We report the discovery of a new crystalline acid Zr triphosphate which exhibits record‐high proton conductivity of 0.5–3.1×10−2 S cm−1 in anhydrous conditions (relative humiditiy, RH, ≪1 %). This value of anhydrous proton conductivity is unprecedented and could unlock applications in fuel cells without the need for complex water management systems, and in other energy technologies requiring fast proton transfer.