Dataset for publication "Probing Li-Ion Conduction in Glassy Li₂S–P₂S₅ Electrolytes Using NMR"

This collection contains the raw SSNMR experimental data that were used in the article "Probing Li-Ion Conduction in Glassy Li₂S–P₂S₅ Electrolytes Using NMR". Abstract: Understanding Lithium-ion conduction mechanisms is key to develop new solid-state electrolytes. However, Li-ion dynamics in glassy electrolytes are intricate and remain unclear due to the challenges in understanding the local structures of glasses. In this work, we probe the Li-ion conduction mechanism in Li2S-P2S5 binary glassy system using the combination of variable-temperature 7Li and 31P NMR relaxometry. The temperature-dependent 31P NMR spin-lattice relaxation measurements show that dynamics of thiophosphate dimers are sluggish in 67Li2S-33P2S5 and 70Li2S-30P2S5 glasses while in 75Li2S-25P2S5 glass, the anionic dynamics are enhanced significantly due to the increased amounts of isolated PS43- units. The energy barrier for 31P rotation is decreased by a factor of ~2, indicating drastic enhancement in 31P dynamics. We find that the cation and anion motion is highly cooperative in the glassy electrolyte system. The long-range Li-ion diffusion barrier decreases from 0.30 eV in 67Li2S-33P2S5 glass to 0.14 eV in 75Li2S-25P2S5 glass. It is clear that the rapid PS43- rotation can speed up Li-ion migration. Moreover, a large amount of PS43- ions break the rigid networks formed by thiophosphate dimers. This may loosen the glass matrix, expanding Li-ion percolation channels in the 75Li2S-25P2S5 glass.