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Stable lithium electrodeposition in liquid and nanoporous solid electrolytes

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Abstract

Rechargeable lithium, sodium and aluminium metal-based batteries are among the most versatile platforms for high-energy, cost-effective electrochemical energy storage. Non-uniform metal deposition and dendrite formation on the negative electrode during repeated cycles of charge and discharge are major hurdles to commercialization of energy-storage devices based on each of these chemistries. A long-held view is that unstable electrodeposition is a consequence of inherent characteristics of these metals and their inability to form uniform electrodeposits on surfaces with inevitable defects. We report on electrodeposition of lithium in simple liquid electrolytes and in nanoporous solids infused with liquid electrolytes. We find that simple liquid electrolytes reinforced with halogenated salt blends exhibit stable long-term cycling at room temperature, often with no signs of deposition instabilities over hundreds of cycles of charge and discharge and thousands of operating hours. We rationalize these observations with the help of surface energy data for the electrolyte/lithium interface and impedance analysis of the interface during different stages of cell operation. Our findings provide support for an important recent theoretical prediction that the surface mobility of lithium is significantly enhanced in the presence of lithium halide salts. Our results also show that a high electrolyte modulus is unnecessary for stable electrodeposition of lithium.

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Figure 1: d.c. ionic conductivity of 1 M ((1 − y) LiTFSI + y LiX)–PC electrolytes with various LiF mole percentages (y × 100%) as a function of temperature.
Figure 2: Voltage versus time for a symmetric lithium cell where each half-cycle lasts 3 h.
Figure 3: Short-circuit time Tsc from galvanostatic polarization measurements for symmetric lithium cells.
Figure 4: Voltage profile at a fixed current density and impedance spectra of the three stages s1, s2 and s3 at 25 °C and 70 °C.
Figure 5: The morphology and distribution of LiF clusters on lithium foil by SEM and EDX.
Figure 6: Charge–discharge characteristics of Li/Li4Ti5O12 (Li/LTO) with 30 mol% LiF+LiTFSI/EC:DEC and LiTFSI/EC:DEC electrolytes at room temperature.

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Acknowledgements

This material is based on work supported as part of the Energy Materials Center at Cornell, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DESC0001086. This work made use of the electrochemical characterization facilities of the KAUST-CU Center for Energy and Sustainability, which is supported by the King Abdullah University of Science and Technology (KAUST) through Award number KUS-C1-018-02. Y.L. thanks J. Jiang and C. Ober in the department of Material Science & Engineering at Cornell University for help with contact angle measurements. The thick LTO electrodes were produced at the US Department of Energy’s (DOE) Cell Fabrication Facility, Argonne National Laboratory. The Cell Fabrication Facility is fully supported by the DOE Vehicle Technologies Program (VTP) within the core funding of the Applied Battery Research (ABR) for Transportation Program.

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Y.L. and L.A.A. conceived the experiments reported in the manuscript. Y.L. performed all studies of the liquid electrolytes. These results are presented in Figs 1a,2a–c,3,4 and 6. Z.T. performed experiments in which liquid electrolytes are infused in nanoporous alumina. These results are reported in Figs 1b and 2d. Y.L. and Z.T. performed the SEM and EDX analyses (Figs 2e–g and 5). Z.T. carried out the XPS analysis in the Supplementary Information. Y.L. and L.A.A. wrote the paper.

Corresponding author

Correspondence to Lynden A. Archer.

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Lu, Y., Tu, Z. & Archer, L. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nature Mater 13, 961–969 (2014). https://doi.org/10.1038/nmat4041

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