The role of B-site cations on proton conductivity in double perovskite oxides La2MgTiO6 and La2MgZrO6

Acceptor-doped La2MgTiO6 (LMTO) and La2MgZrO6 (LMZO) have been investigated to contribute to clarify the role of the B-site cations in A2B′B″O6 double perovskite oxides on formation and mobility of protons. Thermogravimetry and a.c. conductivity measurements in the temperature range 1000-300 °C, as well as DFT-calculations of LMTO, have been the basis for evaluating hydration thermodynamics and transport parameters of the materials. Both compounds show exothermic hydration of oxygen vacancies, but low concentrations of protons. The proton transport is limited by relatively high activation energies of mobility; 0.84 eV and 0.78 eV for LMTO and LMZO, respectively. This is suggested to reflect association to effectively negative charged defects formed by site exchange among the B-site cations. Consequently, the maximum proton conductivity of LMTO and LMZO is in the order of 10−5 S/cm.

► Hydration of acceptor-doped La2MgTiO6 and La2MgZrO6 are exothermic processes.
► MgTi″-defects stabilize protons in La2MgTiO6, thereby acting as trapping sites.
► La2MgTiO6 and La2MgZrO6 show low solubility towards acceptor-doping.