Influence of 3d Transition Metal Doping on Lithium Stabilized Na-β″-Alumina Solid Electrolytes.

Na-β″-alumina is the commercially most successful solid electrolyte due to its application in ZEBRA and NAS® batteries. In this work, Li-stabilized Na-β″-alumina electrolytes were doped with 3d transition metal oxides, namely TiO2, Mn3O4, and NiO, in order to improve their ionic conductivity and fracture strength. Due to XRD and EDX measurements, it was concluded that Mn- and Ni-ions are incorporated into the crystal lattice of Na-β″-alumina. In contrast, TiO2 doping results in the formation of secondary phases that enable liquid-assisted sintering at temperatures as low as 1500 °C. All dopants increased the characteristic fracture strength of the electrolytes; 1.5 wt% of NiO doping proved to be most efficient and led to a maximal characteristic fracture strength of 296 MPa. Regarding the ionic conductivity, TiO2 doping showed the uppermost value of up to 0.30 S cm−1 at 300 °C. In contrast to the other dopants, TiO2 doping lowered the sintering temperature needed to obtain a dense, stable, and highly conductive Na-β″-alumina electrolyte suitable for applications in Na based batteries.