Lithium-Lithium Correlations and the Emergence of Transport Properties in Solvate Ionic Liquid Electrolytes
Abstract
Solvate ionic liquids (SILs), equimolar mixtures of lithium salts and chelating glymes, are promising electrolytes for energy storage due to their high thermal stability and low vapor pressure. However, the low lithium transference numbers and modest ionic conductivities of SILs limit device performance. Here, long-timescale molecular dynamics simulations combined with transport characterization identify the Li+-Li+ structural decorrelation as the key descriptor governing ion transport in SILs composed of lithium bis(trifluoromethanesulfonyl)imide and glymes of various lengths. These SILs have extended ionic networks in which anions bridge multiple Li+ centers, generating long-lived structural correlations. SIL ion transport is initiated by speciation exchange, which disrupts the ionic network and leads to structural decorrelation on nanosecond timescales. Decreasing glyme chain length increases anion bridging, slows structural decorrelation, and decreases ionic conductivity, while increasing lithium transference. These results establish structural decorrelation as a key descriptor of transport in SILs. While the anion-mediated decorrelation is demonstrated for SILs, this framework is general and can be applied to any high concentration electrolyte in which transport emerges from the reorganization of correlated ionic networks.
Related
- Ion Transport Dynamics in Poly(ethylene oxide) and Poly(pentyl malonate) Electrolytes for Lithium Batteries
- Composition‐Dependent Solvation in Low‐Concentration Multi‐Salt DME Electrolytes: Correlations With Lithium Deposition and Interfacial Evolution
- Transport and mechanical properties of pseudo-zwitterionic polymer electrolytes from non-equilibrium molecular dynamics simulations
- Machine Learning Prediction of Transport Properties in Amorphous Polymer Electrolytes Using Chemically Informed Structural Descriptors
- Comparative Assessment of Exchange-Correlation Functionals for the Structural, Thermodynamic, and Transport Properties of Liquid Lithium
BibTeX
@misc{kuroda2026lithiumlithium,
title = {{Lithium-Lithium Correlations and the Emergence of Transport Properties in Solvate Ionic Liquid Electrolytes}},
author = {Daniel G. Kuroda and Orlando Carrillo-Bohórquez and Revati Kumar},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009552/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009552/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Lithium-Lithium Correlations and the Emergence of Transport Properties in Solvate Ionic Liquid Electrolytes
AU - Daniel G. Kuroda
AU - Orlando Carrillo-Bohórquez
AU - Revati Kumar
PY - 2026
DA - 2026/09/28
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009552/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009552/v1
AB - Solvate ionic liquids (SILs), equimolar mixtures of lithium salts and chelating glymes, are promising electrolytes for energy storage due to their high thermal stability and low vapor pressure. However, the low lithium transference numbers and modest ionic conductivities of SILs limit device performance. Here, long-timescale molecular dynamics simulations combined with transport characterization identify the Li+-Li+ structural decorrelation as the key descriptor governing ion transport in SILs composed of lithium bis(trifluoromethanesulfonyl)imide and glymes of various lengths. These SILs have extended ionic networks in which anions bridge multiple Li+ centers, generating long-lived structural correlations. SIL ion transport is initiated by speciation exchange, which disrupts the ionic network and leads to structural decorrelation on nanosecond timescales. Decreasing glyme chain length increases anion bridging, slows structural decorrelation, and decreases ionic conductivity, while increasing lithium transference. These results establish structural decorrelation as a key descriptor of transport in SILs. While the anion-mediated decorrelation is demonstrated for SILs, this framework is general and can be applied to any high concentration electrolyte in which transport emerges from the reorganization of correlated ionic networks.
ER -