Challenges of Scaling-up the Wet-Chemical Synthesis of β-Li3PS4

Abstract

All-solid-state batteries are considered the next generation in battery technology due to increased energy and power density as well as freedom of design, e.g. by constructing batteries in bipolar stacks. Solid-state electrolytes offer advantages over conventional liquid electrolytes, such as greater thermal safety, because of high melting points, and higher mechanical strength. This is believed to suppress growth of lithium dendrites and, therefore, opens up the possibility of using a lithium metal anode. One promising material group is sulfides, because they are ductile and have a good intrinsic ionic conductivity. Some sulfide solid electrolytes can be synthesized wet-chemically. This offers advantages like tailoring the particle size, working at ambient temperatures, short synthesis durations, stabilizing meta-stable phases by using new synthesis routes and the possibility of transferring the routine to a continuous process. The particle size and morphology are important factors regarding the suitability to produce all-solid-state batteries wherefore small (< 10 µm) and homogeneous particles are preferred. The present research mainly focusses on finding and improving new materials and their usage in battery production, but there is little progress on mass-production of sulfide solid electrolytes. To scale-up a synthesis, multiple aspects have to be considered since they often influence both product and process. Therefore, an analysis and optimization of the synthesis process is necessary to support the development and to increase the economic attractiveness of new materials.In this presentation, the reaction enthalpy and the influences of concentration and solvent variation of synthesizing the sulfide solid electrolyte β-Li3PS4 are examined and discussed. β-Li3PS4 is synthesized by mixing lithium sulfide and phosphorus pentasulfide in a solvent, e.g. THF, at ambient conditions. After removing the solvent, heat treatment is used to obtain the crystalline product. We found that the mixing step contains a highly exothermic reaction and determined the reaction enthalpies using a reaction calorimeter. To handle the heat development, two options were investigated: First, the solvent amount was increased and second, the synthesis was performed using alternative solvents with different thermal properties. The examined solvents are THF, ethyl acetate and ethyl propionate. The reaction enthalpies of the synthesis in different solvents are compared. A strong influence on the particle size and morphology caused by the amount and choice of solvent could be detected by SEM. While the particle size increases with increasing amount of solvent, the shape of the particles alters under solvent variation. With low solvent amount the smallest particle sizes (< 10 µm) are synthesized. Finally, suggestions regarding the scale-up will be given based on the findings of these examinations.