Abstract Fluorescence Correlation Spectroscopy, a commonly used technique for measuring diffusion of biomolecules and tracer dyes in different solvents, is employed to characterise the local transport properties in battery electrolytes. Diffusion of ions, a major limiting factor in battery capacity and charging rates, depends on the local interactions and structuredness of the electrolytic species. Structuredness in the electrolyte results from typical solvation behaviour of diffusing ions/molecules leading to long-range interactions. In this work, we have used FCS to measure tracer diffusion of Coumarin 343 in a mixture of Ethylene Carbonate (EC) and Dimethyl Carbonate (DMC), commonly used as electrolyte solvent in Li-ion batteries. The measured diffusion is found to depend on lithium-ion concentrations. It is found that the addition of LiPF6 to an EC-DMC equimolar mixture slows down tracer diffusion significantly. Indeed, the bulk viscosity of the electrolyte added with LiPF6 salt varies with salt concentration. However, the change in bulk viscosity (global behaviour) at high ion concentrations does not match the one inferred from applying Stoke-Einstein’s relation to the diffusion data (local behaviour). This indicates that the homogeneity of the electrolyte does not extend spatially to molecular scales around the diffusing tracer molecule. Measurements made on coin cells prepared with different concentrations of LiPF6 show battery performance limited at higher concentrations, characterized by specific capacity loss at faster charging cycles. This limitation is directly related to the local behaviour of the electrolyte as quantified by measurements of tracer diffusion, which slows down, which remarkably outweighs the advantage of high carrier densities.