content increases, anions increasingly penetrate the first solvation sphere, reaching ∼3 anions per [Li] + at the highest salt content. The mixtures show minimal temperature dependence, but structural changes are significant with varying composition. Our work confirms the transition from two-fold to one-fold G3 coordination at x([Li][NTf 2 ]) ≤ 1/3, as reported previously. However, in equimolar mixtures, one-fold G3-coordinated [Li] + cations are typically sat-urated by one additional anion, which is fewer than in high-salt mixtures.