Structural evolution during solution-based synthesis of Li₇P₃S₁₁ solid electrolyte by synchrotron X-ray total scattering

Solution-based synthesis has emerged as a promising approach for scalable and efficient synthesis of solid electrolytes (SEs). However, the ionic conductivity of solution-synthesized SEs is much lower than that of SEs synthesized by solid state approaches. The structural evolution during the synthesis of SEs is crucial to explaining the decreased ionic conductivities but has not been well understood. Here, we use synchrotron X-ray total scattering combined with pair distribution function (PDF) analysis to understand the structural evolution during annealing of the solution-processed precursor for the synthesis of Li7P3S11 SEs. Combining Bragg diffraction and diffuse scattering, X-ray total scattering enables detection of structural information including phase transition and crystallinity. The results show that the formation of Li7P3S11 glass-ceramic starts at 230 & DEG;C. Increasing the annealing temperature helps to improve the crystallinity, but the degree of crystallization is still lower than 70.3% even after annealing at 290 & DEG;C when thermal decomposition of Li7P3S11 to Li4P2S6 has occurred. PDF analysis also revealed the existence of acetonitrile used in the solution-based synthesis in the SEs after annealing at high temperatures. The results rationalize the synthesis-property relationship, explain why annealing at 290 & DEG;C provides the highest ionic conductivity at the studied temperatures due to an optimal balance for achieving a high crystallinity while suppressing severe decomposition of Li7P3S11, and provide novel insights to develop approaches for synthesizing superior Li7P3S11 SEs on a large scale.