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We reported a new perspective on the correlation between the electronic structure of an ionic liquid (IL)-based electrolyte probed by X-ray photoelectron spectroscopy and the transport properties analyzed by impedance spectroscopy. We highlighted the core level chemical shifts of 1-hexyl-3-methylimidazolium (bis(trifluoromethanesulfonyl)imide) (C1C6ImTFSI), 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide (C1C6ImFSI), and 1-hexyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide (C1C1C6ImTFSI) laden with LiTFSI salt and vinyl
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