Dramatic reduction in the densification temperature of garnet-type solid electrolytes

Cubic garnet Li₇La₃Zr₂O₁₂ (LLZO) and similar compositions of fast ion-conducting solid-state electrolytes have shown great potential for the development of high-energy-density solid-state Li-ion batteries. Although these materials have shown unprecedented ionic conductivities and chemical stability, these materials require high processing temperatures for synthesis. For many of the common compositions of LLZO, temperatures above 1000 °C are required to form the cubic garnet phase and to achieve high conductivities. Therefore, lowering the processing temperatures of these materials is of great interest for the purposes of scalability and fabrication. It has been reported that a Bi co-dopant not only stabilizes the cubic garnet phase but also lowers the densification temperature. In this study, Li₆La₃ZrBiO₁₂ (LLZBO) was prepared by a rapid-induction hot-pressing technique and characterized using a variety of techniques, including X-ray diffraction, scanning electron microscopy, and Raman spectroscopy. We demonstrate the ability to synthesize phase-pure LLZBO with higher relative densities (~?94%) than can be achieved by pressure-less sintering methods, at pressing temperatures of only 850 °C. The ionic conductivity was measured to be 0.1 mS cm^?1, which is comparable to the best reported conductivities of high-density LLZO. This demonstrates the ability to fabricate dense, phase-pure, and high-conductivity LLZBO at temperatures significantly lower than other garnet compositions, which will prove useful for scalability and reducing reactivity with cathodes during densification.