Nuclear magnetic resonance spin-lattice relaxation of lithium ions in aqueous solution by NMR and molecular dynamics.

Abstract

We study the aqueous solvation dynamics of lithium ions using nuclear magnetic resonance spectroscopy, molecular dynamics, and viscosity measurements. Several relaxation mechanisms are examined to explain the strong increases of spin-lattice relaxation toward high concentrations. The use of both 6Li and 7Li isotopes is helpful to identify the quadrupolar contribution to the relaxation rate. In particular, it is found that the quadrupolar interaction constitutes the strongest contribution above a concentration of ∼10 molal. The next-strongest contribution arises from interactions that scale with the square of the gyromagnetic ratio (mostly the dipolar interaction), and the experimental relaxation rates appear to be fully accounted for when these mechanisms are combined over the concentration range up to the saturation concentration. The study of solvation dynamics, particularly at high concentrations, could be of relevance for electrolyte dynamics in aqueous Li-ion rechargeable batteries.