High-temperature oxygen non-stoichiometry, conductivity and structure in strontium-rich nickelates La2−xSrxNiO4−δ (x = 1 and 1.4)

Oxygen non-stoichiometry, electrical conductivity and thermal expansion of La2−xSrxNiO4−δ phases with high levels of strontium-substitution (1 ≤ x ≤ 1.4) have been investigated in air and oxygen atmosphere in the temperature range 20–1050 °C. These phases retain the K2NiF4-type structure of La2NiO4 (tetragonal, space group I4/mmm). The oxygen vacancy fraction was determined independently from thermogravimetric and neutron diffraction experiments, and is found to increase considerably on heating. The electrical resistivity, thermal expansion and cell parameters with temperature show peculiar variations with temperature, and differ notably from La2NiO4±δ in this respect. These variations are tentatively correlated with the evolution of nickel oxidation state, which crosses from a Ni3+/Ni4+ to a Ni2+/Ni3+ equilibrium on heating.