Pressure Dependence of Solid Electrolyte Ionic Conductivity: A Particle Dynamics Study

The search for safe, reliable, and compact high-capacity energy storage devices has led to increased interest in all-solid-state battery research. The use of solid electrolytes provides enhanced safety and durability due to their reduced flammability and increased mechanical strength compared to organic liquid electrolytes. Still, the use of solid electrolytes remains challenging. A significant issue is their generally low Li-ion conductivity, which depends on the lattice diffusion of Li ions through the solid phase, as well as on the limited contact area between the electrolyte particles. While the lattice diffusion can be addressed through the chemistry of the solid electrolyte material, the contact area is a mechanical and structural problem of packing and compression of the electrolyte particles depending on their size and shape. This work studies the effect of pressurization on the electrolyte conductivity exploring cases of low as well as high grain boundary (GB) conductivity, compared to the bulk conductivity. Scaling dependence, σ ∼ Pη, of the conductivity σ with pressure P is revealed. For an idealized electrolyte represented as spheres in hexagonal closely packed configuration, η = 2/3 and η = 1/3 have been theoretically calculated for the two cases of low and high GB conductivity, respectively. For randomly packed spheres, the equivalent exponent values were numerically estimated to be approximately 3/4 and 1/2, respectively, which are higher than the closed packed values due to the additional decrease of porosity with the increase in pressure. As demonstrated in the study, experimental measurement of η can indicate which type of bulk or GB conductivity is dominant in a particular electrolyte powder and could be used in addition to electrochemical impedance spectroscopy measurements.