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Low-solvation electrolytes for high-voltage sodium-ion batteries

Abstract

Sodium-ion batteries (NIBs) have attracted worldwide attention for next-generation energy storage systems. However, the severe instability of the solid–electrolyte interphase (SEI) formed during repeated cycling hinders the development of NIBs. In particular, the SEI dissolution in NIBs with a high-voltage cathode is more severe than in the case of Li-ion batteries (LIBs) and leads to continuous side reactions, electrolyte depletion and irreversible capacity loss, making NIBs less stable than LIBs. Here we report a rational electrolyte design to suppress the SEI dissolution and enhance NIB performance. Our electrolyte lowers the solvation ability for SEI components and facilitates the formation of insoluble SEI components, which minimizes the SEI dissolution. In addition to the stable SEI on a hard carbon (HC) anode, we also show a stable interphase formation on a NaNi0.68Mn0.22Co0.1O2 (NaNMC) cathode. Our HC||NaNMC full cell with this electrolyte demonstrates >90% capacity retention after 300 cycles when charged to 4.2 V. This study enables high-voltage NIBs with long cycling performance and provides a guiding principle in electrolyte design for sodium-ion batteries.

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Fig. 1: Electrolyte design principles to suppress the SEI dissolution for highly stable high-voltage sodium-ion batteries.
Fig. 2: Electrochemical performance of HC||NaNMC full cells.
Fig. 3: XPS characterization to identity SEI dissolution.
Fig. 4: SEI dissolution analysis by capacity loss of Cu||Na cells in three electrolytes.
Fig. 5: CEI components and structures of the cycled NaNMC cathodes.

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Acknowledgements

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technologies Office, Advanced Battery Materials Research (BMR) programme of the US Department of Energy (DOE) under contract number DE-AC05-76RL01830. The cathode material development was supported by the US DOE Office of Electricity (contract number 70247 A). The TEM and XPS were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL). TEM sample preparation was performed in the Radiological Microscopy Suite (RMS), located in the Radiochemical Processing Laboratory (RPL) at PNNL. PNNL is operated by Battelle for the DOE under contract DE-AC05-76RL01830.

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Authors

Contributions

J.-G.Z. proposed the research. Y.J. designed experiments, performed the electrochemical measurements, characterized materials and analysed the data. Y.X., B.E.M. and C.W. performed the FIB scanning electron microscope and TEM. P.G. performed the simulation. M.H.E. performed the XPS measurements. B.X. and X.L. synthesized the NaNMC cathode materials. L.Z. performed the viscosity measurement. P.M.L.L., T.D.V. and R.Y. prepared electrodes. X.C. and J.H. helped the gas generation test. J.L. contributed to the discussion and provided suggestions. Y.J., X.L. and J.-G.Z. wrote the manuscript with input from all other co-authors.

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Correspondence to Ji-Guang Zhang.

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Nature Energy thanks Philipp Adelhelm, Reza Younesi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–20, Notes 1–12 and Tables 1 and 2.

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Jin, Y., Le, P.M.L., Gao, P. et al. Low-solvation electrolytes for high-voltage sodium-ion batteries. Nat Energy 7, 718–725 (2022). https://doi.org/10.1038/s41560-022-01055-0

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