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Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes

Abstract

Rechargeable batteries paired with sodium metal anodes are considered to be one of the most promising high-energy and low-cost energy-storage systems. However, the use of highly reactive sodium metal and the formation of sodium dendrites during battery operation have caused safety concerns, especially when highly flammable liquid electrolytes are used. Here we design and develop solvent-free solid polymer electrolytes (SPEs) based on a perfluoropolyether-terminated polyethylene oxide (PEO)-based block copolymer for safe and stable all-solid-state sodium metal batteries. Compared with traditional PEO SPEs, our results suggest that block copolymer design allows for the formation of self-assembled nanostructures leading to high storage modulus at elevated temperatures with the PEO domains providing transport channels even at high salt concentration (ethylene oxide/sodium = 8/2). Moreover, it is demonstrated that the incorporation of perfluoropolyether segments enhances the Na+ transference number of the electrolyte to 0.46 at 80 °C and enables a stable solid electrolyte interface. The new SPE exhibits highly stable symmetric cell-cycling performance at high current density (0.5 mA cm−2 and 1.0 mAh cm−2, up to 1,000 h). Finally, the assembled all-solid-state sodium metal batteries demonstrate outstanding capacity retention, long-term charge/discharge stability (Coulombic efficiency, 99.91%; >900 cycles with Na3V2(PO4)3 cathode) and good capability with high loading NaFePO4 cathode (>1 mAh cm−2).

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Fig. 1: Chemical structures and physical properties of the polymer electrolytes.
Fig. 2: Morphology and electrochemical properties of the polymer electrolytes.
Fig. 3: Molecular-level interactions between polymer electrolytes and NaFSI.
Fig. 4: Na/Na plating/stripping performance.
Fig. 5: Morphologies of sodium metal deposition.
Fig. 6: All-solid-state Na/NVP cell performance.

Data availability

All the data supporting the findings of this work are in the paper and Supplementary Information. Additional data are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

The authors acknowledge the support of the Australia–India Strategic Research Fund (AISRF 48515) and the Australian Research Council for funding through the Industry Transformation Training Centre Scheme (IC180100049). The research reported here was partially supported by the National Science Foundation (NSF) through the Materials Research Science and Engineering Center at UC Santa Barbara, DMR-1720256 (IRG-2). A.K.W. and C.Z. acknowledge support from the Australian Research Council (CE140100036) and National Health and Medical Research Council for an Early Career Fellowship (APP1157440 to C.Z.). The authors acknowledge the use of the facilities and the assistance of Y. Hora at the Monash X-ray platform. The Australian National Fabrication Facility, Queensland Node, is also acknowledged for access to some items of equipment.

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Contributions

X.W., C.Z. and M.F. conceived the idea. C.Z. designed and characterized the PFPE block polymers. C.F., Y.W. and X.T. prepared the block copolymers. X.W. led the electrolyte design, electrolyte characterization and battery experiments. T.C.M. synthesized the NFP active materials and prepared the cathodes. J.S. conducted XPS and interpreted results with C.Z. and X.W. M.S., Q.Y., F.C., D.J.S. and P.K. performed simulations and interpreted results. X.W. and C.Z. prepared the draft manuscript. P.C.H., C.J.H., A.K.W. and M.F. contributed to data interpretation and manuscript editing.

Corresponding authors

Correspondence to Xiaoen Wang, Cheng Zhang, Andrew K. Whittaker or Maria Forsyth.

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Nature Materials thanks Shinichi Komaba and Ying Shirley Meng for their contribution to the peer review of this work.

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Supplementary materials, preparation and characterization, and Supplementary Figs. 1–30 and Tables 1–4.

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Wang, X., Zhang, C., Sawczyk, M. et al. Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes. Nat. Mater. 21, 1057–1065 (2022). https://doi.org/10.1038/s41563-022-01296-0

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