Field assisted sintering of fine-grained Li7−3xLa3Zr2AlxO12 solid electrolyte and the influence of the microstructure on the electrochemical performance

The synthesis and processing of fine-grained Li7−3xLa3Zr2AlxO12 (x = 0.15, 0.17, 0.20) solid electrolyte (LLZO) is performed for the first time using a combination of nebulized spray pyrolysis (NSP) and field assisted sintering technique (FAST). Using FAST, the grain growth is suppressed and highly dense ceramics with 93% of the theoretical density are obtained. A tetragonal lattice distortion is observed after the sintering process. Although this structural modification has been reported to have lower Li-ion mobility compared to the cubic modification, the total conductivity of the sample at room temperature is found to be 0.33 mS cm−1, i.e. comparable to phase-pure cubic LLZO. The activation energy of 0.38 eV is also comparable to the literature values. Galvanostatic cycling of a symmetrical cell Li|LLZO|Li shows a good cycling stability over 100 h. The interfacial resistance in contact with Li-metal is determined using alternating current impedance spectroscopy to be 76 Ω cm2 and 69 Ω cm2 before and after cycling at different current densities, respectively.