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Thiophosphates show promise as solid electrolytes for all-solid-state batteries (ASSBs), particularly Li3PS4-based materials, due to their cost-effectiveness and stability. To enhance conductivity for high-power applications, we developed affordable Li3PS4-LiCl (LPSCls) solid electrolytes with an ionic conductivity of ∼1.1 mS/cm (Li3PS4:LiCl = 2:1, 200 °C). Our study examines the long- and short-range structural order and ion dynamics of LPSCls, using neutron diffraction, magic-angle-spinning nuclear magnetic resonance (MAS NMR), and electrochemical impedance spectroscopy (EIS). 31P NMR reveals a unique disordered anion structure comprising a blend of Cl-modified β, γ, and amorphous PS43– units. Additionally, NMR relaxometry highlights enhanced Li+ mobility enabled by this diverse anion sublattice, allowing Li+ ions to migrate efficiently among different anions with similar affinity. Our findings unveil novel anion species within LPSCls, offering insights for optimizing ionic conductivity in solid electrolytes for ASSBs.
Wang et al. (Thu,) studied this question.