This anion group effect is explained using molecular dynamics simulations to identify preferred solvation structures, density functional theory calculations of their binding energies and Raman spectroscopy confirmation of solvation structure. Electrolytes containing LiTFSI salt, with or without LiPF 6, exhibit about 100-fold higher exchange current density under otherwise identical conditions. Here, we perform electrodynamic measurements on single electrode particles of ~6 nAh capacity, decouple bulk and interfacial transport from other pathways and show that Li intercalation into LiNi 0.33Mn 0.33Co 0.33O 2 (NMC333) is primarily impeded by interfacial kinetics when using a conventional LiPF 6 salt. To access the full performance potential of advanced batteries, electrodes and electrolytes must be designed to facilitate ion transport at all applicable length scales.
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