Enhancement of microstructure and electrochemical properties of LLZTO solid state electrolyte by co-doping with Ga and Y

Recently, there has been strong interest in inorganic solid-state electrolytes for all-solid-state batteries, among which the garnet electrolyte LLZO has attracted much attention due to its excellent properties, such as high ionic conductivity and broad electrochemical stability. The aim of our study was to improve the performance of Ta-doped LLZO (LLZTO) by co-doping Ga and Y at the Li and La sites using conventional solid-phase synthesis methods. We thoroughly investigated how Ga and Y affect the microstructure and electrochemical properties of LLZTO. The results show that the relative density of Ga- and Y-doped LLZTO increases significantly up to 94% under the same sintering conditions. This doping resulted in a significant increase in ionic conductivity from 2.0 × 10−4 S·cm−1 to 1.05 × 10−3 S·cm−1 and a decrease in electronic conductivity from 2.16 × 10−7 S·cm−1 to 9.18 × 10−8 S·cm−1. Subsequently, the symmetric cells were assembled and tested, and it was found that the interfaces of the doped solid-state electrolytes were much more stable and that the cycling time was longer. Thus, our study successfully coordinated the co-doping of Ga, Y, and Ta, providing valuable insights for the subsequent production of LLZO materials with higher densities and better performance. This study is a promising step toward the realization of safer all-solid-state batteries with higher energy densities. •Innovative further doping of two elements on top of LLZTO solid electrolyte, harmonizing the doping of three elements.•An order of magnitude increases in ionic conductivity of LLZTO solid state electrolytes after doping.•The doped LLZTO solid state electrolyte has better suitability with lithium metal anode.