Solid state batteries (SSBs) are expected to be the next-generation of batteries due to their high energy density and safety. To emphasize the battery performance of SSBs, it is crucial to analyze and design the electrode structure. The powder compression process is one of the most important processes for determining the battery structure. Powder compression is a molding method used to transform powders into solid and high-density compacts. The powder properties and compression conditions influence the packing structure and density of compacts. In this study, we elucidated the effect of the size distribution of a sulfide solid electrolyte on the ionic conductivity of pellets. The particle size distributions of lithium phosphorus sulfur chloride (LPSCl), a solid electrolyte with high plastic deformability, were prepared to evaluate its effect on the relative density and electrochemical properties. The average particle size of LPSCl was reduced through the milling process, and the resulting compacts were evaluated by impedance measurement after mixing raw and milled LPSCl with different mass fractions. The ionic conductivity of the compacts was found to be improved with the broadening of the particle size distribution of the solid electrolyte. Furthermore, the effect of the particle size distribution of the solid electrolyte on the electrode structure was also investigated numerically. The numerical simulations were performed in consideration of the actual particle size distribution to evaluate the void fraction and tortuosity of the electrodes. A discrete element method (DEM) can simulate the powder behavior by calculating the motion of individual particles based on Newton’s second law. Edinburgh elasto-plastic adhesive (EEPA) model, which can consider particle plasticity and cohesiveness, was applied as the contact force model. Particle plasticity parameter λ p was calibrated based on force-displacement curves obtained by nanoindentation tests. The compression process was calculated assuming an infinite flat plate. Although the calculated relative densities agreed with the experimental trend, the values differed from the experimental values owing to the disregard of particle shape. In addition, tortuosity was evaluated by the shortest path algorithm using the powder bed obtained from the numerical analyses. An effective tortuosity was calculated by weighting the contributions of the conductive paths by its number of particles. The effective tortuosity also increased due to the higher number of particles generated during the LPSCl milling process. The combination of DEM analysis and the shortest path algorithm, taking into account grain boundary resistance, demonstrated that is was possible to correlate the electrode structure of the SSB with its electrochemical performance.
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