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The solvation structure and transport properties of Li+ in ionic liquid (IL) electrolytes based on n-methyl-n-butylpyrrolidinium cyano(trifluoromethanesulfonyl)imide [PYR14][CTFSI] and [Li][CTFSI] (0 ≤ xLi ≤ 0.7) were studied by Raman and Nuclear Magnetic Resonance (NMR) diffusometry, and molecular dynamics (MD) simulations. At xLi < 0.3, Li+ coordination is dominated by the cyano group. As xLi is increased, free cyano-sites become limited, resulting in increased coordination via the sulfonyl group. The 1:1 mixture of the symmetric anions bis(trifluoromethanesulfonyl)imide ([TFSI]) and dicyanamide ([DCA]) results in similar physical properties as the IL with [CTFSI]. However, anion asymmetry is shown to increase Li-salt solubility and promote Li+ transference. The lifetimes of Li+-cyano coordination for [CTFSI] are calculated to be shorter than those for [DCA], indicating that the competition from the sulfonyl group weakens its solvation with Li+. This resulted in higher Li+ transference for the electrolyte with [CTFSI]. In relation to the utility of these electrolytes in energy storage, the Li–LiFePO4 half cells assembled with IL electrolyte (xLi = 0.3, 0.5, and 0.7) demonstrated a nominal capacity of 140 mAh/g at 0.1C rate and 90 °C where the cell with xLi = 0.7 IL electrolyte demonstrated 61% capacity retention after 100 cycles and superior rate capability owing to increased electrochemical stability. 

Abstract Aqueous electrolytes typically suffer from poor electrochemical stability; however, eutectic aqueous solutions—25 wt.% LiCl and 62 wt.% H₃PO₄—cooled to −78 °C exhibit a significantly widened stability window. Integrated experimental and simulation results reveal that, upon cooling, Li⁺ions become less hydrated and pair up with Cl⁻, ice‐like water clusters form, and H⋅⋅⋅Cl⁻bonding strengthens. Surprisingly, this low‐temperature solvation structure does not strengthen water molecules’ O−H bond, bucking the conventional wisdom that increasing water's stability requires stiffening the O−H covalent bond. We propose a more general mechanism for water's low temperature inertness in the electrolyte: less favorable solvation of OH⁻and H⁺, the byproducts of hydrogen and oxygen evolution reactions. To showcase this stability, we demonstrate an aqueous Li‐ion battery using LiMn₂O₄cathode and CuSe anode with a high energy density of 109 Wh/kg. These results highlight the potential of aqueous batteries for polar and extraterrestrial missions.