2018 Volume 126 Issue 10 Pages 852-859
This article provides the first critical review on the discovery and development of BaNdInO4. Exploring a new structure family of ionic conductors is an important task to develop ceramic ionic conductors. Since some A2BO4 compositions exhibit high oxide-ion conductivities, we investigated ABCO4 compositions to explore new oxide-ion conductors with A/B/C cation-ordered structures. Here A, B and C are cations [ionic radii: r(A) ≥ r(B) ≥ r(C)]. In 2014, we discovered a new material BaNdInO4 which belongs to a new structure family of perovskite-related structures. This BaNdInO4-type structure (monoclinic, P21/c) consists of alternative stacking of the A rare earth oxide unit and perovskite unit with a− b− c− tilt system. We also discovered new materials BaRInO4 (R = Sm, Y, Ho, Er, Yb) having the BaNdInO4-type structure, and report their lattice parameters and anisotropic chemical expansion. Electrical conductivity of BaNdInO4 was higher than those of BaRInO4 (R = Sm, Y, Er). Oxide-ion conduction was dominant for BaNdInO4 in the P(O2) region from 3.8 × 10−22 to 5.5 × 10−9 atm at 858°C. Oxide-ion conductivities of Ba1.1Nd0.9InO3.95, BaSr0.1Nd0.9InO3.95 and BaCa0.2Nd0.8InO3.9 were higher than that of BaNdInO4. Structure analyses of Ba1.1Nd0.9InO3.95 and BaSr0.1Nd0.9InO3.95 indicated that the excess Ba and doped Sr cations were partially substituted for Nd cation and that there existed oxygen vacancies, leading to the increase of the carrier concentration and higher oxide-ion conductivity. Following the discovery of BaNdInO4, BaRScO4 (R = Nd, Eu, Y, Yb) and SrYbInO4 were reported as new ABCO4 materials. BaYScO4 and BaYbScO4 have the BaNdInO4-type structure. BaNdScO4 and BaEuScO4 crystallize into the space group Cmcm, which has a higher symmetry than P21/c for BaNdInO4. SrYbInO4 is the first example of pure oxide-ion conductors with CaFe2O4-type structure. Further investigations of ABCO4 compositions and BaNdInO4 related materials will lead to development of materials science and solid state ionics.