We demonstrate that Li + hopping conduction, which cannot be explained by conventional models i.e., Onsager's theory and Stokes' law, emerges in highly concentrated liquid electrolytes composed of LiBF 4 and sulfolane (SL). Self-diffusion coefficients of Li + (D Li ), BF 4 − (D BF 4 ), and SL (D SL ) were measured with pulsed-field gradient NMR. In the concentrated electrolytes with molar ratios of SL/LiBF 4 ≤ 3, the ratios D SL /D Li and D BF 4 /D Li become lower than 1, suggesting faster diffusion of Li + than SL and BF 4 − , and thus the evolution of Li + hopping conduction. X-ray crystallographic analysis of the LiBF 4 /SL (1:1) solvate revealed that the two oxygen atoms of the sulfone group are involved in the bridging coordination of two different Li + ions. In addition, the BF 4 − anion also participates in the bridging coordination of Li + . The Raman spectra of the highly concentrated LiBF 4 −SL solution suggested that Li + ions are bridged by SL and BF 4 − even in the liquid state. Moreover, detailed investigation along with molecular dynamics simulations suggests that Li + exchanges ligands (SL and BF 4 − ) dynamically in the highly concentrated electrolytes, and Li + hops from one coordination site to another. The spatial proximity of coordination sites, along with the possible domain structure, is assumed to enable Li + hopping conduction. Finally, we demonstrate that Li + hopping suppresses concentration polarization in Li batteries, leading to increased limiting current density and improved rate capability compared to the conventional concentration electrolyte. Identification and rationalization of Li + ion hopping in concentrated SL electrolytes is expected to trigger a new paradigm of understanding for such unconventional electrolyte systems.

Following our recent study demonstrating predominant Li-ion hopping conduction in sulfolane (SL)-based highly concentrated electrolytes with LiBF4, LiClO4, and lithium bis­(fluorosulfonyl)­amide, herein a systematic study on transport properties and Li-ion coordination of SL-based electrolytes with lithium bis­(trifluoromethanesulfonyl)­amide was performed. In the highly concentrated region, Li ions clearly diffuse faster than SL and TFSA anions. The two oxygen atoms of the SL sulfonyl group tend to coordinate to two different neighboring Li ions and TFSA anions form ionic clusters with Li ions, verifying the previous observation of the unusual Li-ion conduction and its relevance to the SL- and anion-bridged, chainlike Li-ion coordination structure for the SL-based concentrated systems with other Li salts. Moreover, addition of hydrofluoroether (HFE) to the SL-based concentrated electrolytes greatly enhances diffusion coefficients but fragments the chainlike Li-ion coordination to smaller clusters, leading to a reduced contribution of Li-ion hopping to the overall Li-ion conduction. The SL-based concentrated electrolyte and its mixtures with HFE showed lower lithium polysulfide solubility and higher rate capability for lithium–sulfur (Li–S) cells compared with previously reported tetraglyme-based electrolytes. The SL-based electrolytes were found to manifest a significant improvement in Li-ion mass transfer as a sparingly solvating electrolyte, enabling the solid-state sulfur redox reactions in high-performance Li–S batteries.

Li+ ion hopping conduction through ligand (solvent and anion) exchange emerges in solvent-deficient liquid electrolytes of [Li salt]/[dinitrile] > 1.

Polar solvents dissolve Li and Na salts at high concentrations and are used as electrolyte solutions for batteries. The solvents interact strongly with the alkali metal cations to form complexes...