ABSTRACT
The density, microstructure, and ionic conductivity of solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 (LATP) ceramics prepared by cold sintering using liquid and solid sintering additives are studied. The effects of both liquid (water and water solutions of acetic acid and lithium hydroxide) and solid (lithium acetate) additives on densification are investigated. The properties of cold-sintered LATP are compared to those of conventionally sintered LATP. The materials cold-sintered at temperatures 140-280 °C and pressures 510-600 MPa show relative density in the range of 90-98% of LATP's theoretical value, comparable or higher than the density of conventionally sintered ceramics. With the relative density of 94%, a total ionic conductivity of 1.26 × 10-5 S/cm (room temperature) is achieved by cold sintering at the temperature of 200 °C and uniaxial pressure of 510 MPa using water as additive. The lower ionic conductivities of the cold-sintered ceramics compared to those prepared by conventional sintering are attributed to the formation of amorphous secondary phases in the intergranular regions depending on the type of additives used and on the processing conditions selected.
ABSTRACT
All solid-state batteries offer the possibility of increased safety at potentially higher energy densities compared to conventional lithium-ion batteries. In an all-ceramic oxide battery, the composite cathode consists of at least one ion-conducting solid electrolyte and an active material, which are typically densified by sintering. In this study, the reaction of the solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 (LATP) and the active material LiNi0.6Co0.2Mn0.2O2 (NCM622) is investigated by cosintering at temperatures between 550 and 650 °C. The characterization of the composites and the reaction layer is performed by optical dilatometry, X-ray diffractometry, field emission scanning electron microscopy with energy dispersive X-ray spectroscopy, time-of-flight secondary ion mass spectrometry, as well as scanning transmission electron microscopy (STEM). Even at low sintering temperatures, elemental diffusion occurs between the two phases, which leads to the formation of secondary phases and decomposition reactions of the active material and the solid electrolyte. As a result, the densification of the composite is prevented and ion-conducting paths between individual particles cannot be formed. Based on the experimental results, a mechanism of the reactions in cosintered LATP and NCM622 oxide composite cathodes is suggested.
