High-temperature proton conductivity and defect structure of TiP2O7

Nominally undoped TiP2O7 and TiP2O7 with 2 mol-% substitution of Ti by Al were synthesized from TiO2 (Al2O3) and H3PO4(aq), sintered at 1050 °C, and characterized by XRD, TEM and SEM. The electrical conductivity was investigated at 300–1000 °C as a function of p(O2), p(H2O), and p(D2O). The material's phase transition around 700 °C is clearly visible in the conductivity curves. Al substitution hardly increased the conductivity. The conductivity was higher in H2O- than in D2O-containing and dry atmospheres, indicating the dominance of proton conduction. The conductivity was accordingly mainly independent of p(O2). A slight increase in the conductivity with decreasing p(O2) at the highest temperatures was indicative of a minor contribution of n-type electronic conduction. The p(H2O) and temperature dependencies of the conductivity have been modelled as a sum of proton and electron partial conductivities under a situation with protons charge compensated by oxygen interstitials as dominating defects.