Proton conductivity and phase relationship in solid KOH between 248 and 406°C

Existing evidence indicates that between 248°C and the melting point at 406°C, KOH is a rotator phase. We have shown that, as might be expected, this results in enhanced proton conductivity, and a value of 2×10⁻³ ohms⁻¹ cm⁻¹ was found at 350°C, which is the highest reported for proton conducting solid electrolytes in this temperature range. Excess protons are provided by water molecules residing on the normal OH^- sites, and charge compensation is provided by CO²⁻₃ ions in the solid solution of KOH(≈ 1 m/o K₂CO₃, 1.3m/o H₂O). The activation energy for proton hopping between adjacent H₂O and OH⁻ species probably accounts for most of the observed activation energy of 53±3 kJ mol⁻¹. From TGA studies the isobars at 0.05 and 10 Torr were established for KOH-rich compositions in the KOH---H₂O system, and it was shown that the rotator phase of KOH is stable between these vapour pressures.