Anisotropic thermal expansion and ionic conductivity of a crystal-oriented, Mg²⁺-conducting NASICON-type solid electrolyte

Multivalent ion-conducting ceramics are required for the manufacture of high-safety, high-capacity rechargeable batteries. However, the low ionic conductivity of solid electrolytes and discrepancies in the thermal expansion between the battery components limit their widespread application. Furthermore, anisotropic thermal expansion in crystals during battery manufacturing and the charge-discharge cycles causes the formation of microcracks, which degrade the battery performance. The physical properties of ceramic materials with anisotropic crystal structures can be modified by varying the crystallographic orientation of their grains. In this study, a co-precipitation approach was used to synthesize an Mg²⁺-conducting (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ solid electrolyte, and the grain orientation in the bulk sample was controlled using strong magnetic fields during the slip casting process. The results showed that inducing an orientation along the c-axis enhanced the apparent ionic conductivity of the bulk sample. It was also observed that (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ crystal has a negative volumetric thermal expansion despite a positive linear thermal expansion along its c-axis. By adjusting the c-axis orientation of the grains, (Mg_0.1Hf_0.9)_4/3.8Nb(PO₄)₃ electrolytes with negative or positive linear thermal expansion coefficient have been produced. The findings of this study suggest that solid-electrolytes with negative, positive, or zero linear thermal expansion can be produced to create more compatible and higher-performance solid-state devices.