How individual vs shared coordination governs the degree of correlation in rotational vs residence times in a high-viscosity lithium electrolyte

Commercially used carbonate-based electrolytes in lithium-ion batteries are susceptible to many challenges, including flammability, volatility, and lower thermal stability. Solvated ionic liquids of LiTFSI salt (lithium bis(trifluoromethylsulfonyl)-amide) and glyme-based solvents are potential alternative candidates for commonly used electrolytes. We perform classical molecular dynamics (MD) simulations study the effect of concentration and temperature on the translational and rotational dynamics. The radial distribution function shows stronger coordination of Li$^+$ ions with tetraglyme(G4), as shown in earlier studies, and forms a stable [Li(G4)]$^+$ cation complex. The self-diffusion coefficients are lower than the values experimentally observed but show better improvement over other classical force fields. An increase in the salt concentrations leads to a higher viscosity of the system and reduces the overall ionic mobility of Li$^{+}$ ions. Diluting the system with a larger number of glyme molecules leads to shorter rotational relaxation times for both TFSI and tetraglyme. Ion-residence times show that Li$^+$ ions form stable and long-lasting complexes with G4 molecules than TFSI anions. The residence time of [Li(G4)]$^+$ complex increases at higher salt concentrations due to the availability of fewer G4 molecules to coordinate with a Li$^+$ ion. G4 is also seen to form polydentate complexes with Li$^+$ without a shared coordination, allowing rotation without breaking coordination, unlike TFSI, which requires coordination disruption for rotation. This distinction explains the poor correlation between rotation and residence time for G4 and the strong correlation for TFSI.

💡 Research Summary

The manuscript presents a comprehensive molecular dynamics (MD) investigation of lithium bis(trifluoromethylsulfonyl)‑amide (LiTFSI) dissolved in tetraglyme (G4), a promising solvated‑ionic‑liquid electrolyte for lithium‑ion batteries. The authors explore four stoichiometric ratios (1:4, 1:2, 1:1, and 2:1 LiTFSI : G4) at two temperatures (300 K and 500 K) using a re‑parameterized OPLS‑AA force field. Partial atomic charges for both LiTFSI and G4 are derived from high‑level wB97x‑D4/def2‑tzvpp calculations via the CHELPG scheme, and a fixed +0.87 charge is assigned to Li⁺ based on its bound state. Simulations are performed for 100 ns in the NVT ensemble, providing statistically robust trajectories for structural, translational, and rotational analyses.

Key structural findings are obtained from radial distribution functions (RDFs). The first solvation shell of Li⁺ appears at 1.9 Å for O atoms of G4 and at 2.0 Å for O atoms of TFSI. In the equimolar mixture, the average coordination numbers are ≈3.6 for Li⁺‑O(G4) (essentially a four‑fold coordination) and ≈0.7 for Li⁺‑O(TFSI). As the proportion of G4 increases, the Li⁺‑O(G4) coordination approaches four, while Li⁺‑O(TFSI) coordination diminishes, indicating that at high salt concentration (2 : 1) virtually all Li⁺ ions are bound in a