An inorganic-rich but LiF-free interphase for fast charging and long cycle life lithium metal batteries.

Rahman, Muhammad Mominur; Tan, Sha; Yang, Yang; Zhong, Hui; Ghose, Sanjit; Waluyo, Iradwikanari; Hunt, Adrian; Ma, Lu et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

Li metal batteries using Li metal as negative electrode and LiNi<sub>1-x-y</sub>Mn<sub>x</sub>Co<sub>y</sub>O<sub>2</sub> as positive electrode represent the next generation high-energy batteries. A major challenge facing these batteries is finding electrolytes capable of forming good interphases. Conventionally, electrolyte is fluorinated to generate anion-derived LiF-rich interphases. However, their low ionic conductivities forbid fast-charging. Here, we use CsNO<sub>3</sub> as a dual-functional additive to form stable interphases on both electrodes. Such strategy allows the use of 1,2-dimethoxyethane as the single solvent, promising superior ion transport and fast charging. LiNi<sub>1-x-y</sub>Mn<sub>x</sub>Co<sub>y</sub>O<sub>2</sub> is protected by the nitrate-derived species. On the Li metal side, large Cs<sup>+</sup> has weak interactions with the solvent, leading to presence of anions in the solvation sheath and an anion-derived interphase. The interphase is surprisingly dominated by cesium bis(fluorosulfonyl)imide, a component not reported before. Its presence suggests that Cs<sup>+</sup> is doing more than just electrostatic shielding as commonly believed. The interphase is free of LiF but still promises high performance as cells with high LiNi<sub>0.8</sub>Mn<sub>0.1</sub>Co<sub>0.1</sub>O<sub>2</sub> loading (21 mg/cm<sup>2</sup>) and low N/P ratio (~2) can be cycled at 2C (~8 mA/cm<sup>2</sup>) with above 80% capacity retention after 200 cycles. These results suggest the role of LiF and Cs-containing additives need to be revisited.