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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 Na 3 V 2 (PO 4 ) 3 cathode) and good capability with high loading NaFePO 4 cathode (>1 mAh cm -2 )., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Non-uniform metal deposition and dendrite formation in high-density energy storage devices reduces the efficiency, safety and life of batteries with metal anodes. Superconcentrated ionic-liquid electrolytes (for example 1:1 ionic liquid:alkali ion) coupled with anode preconditioning at more negative potentials can completely mitigate these issues, and therefore revolutionize high-density energy storage devices. However, the mechanisms by which very high salt concentration and preconditioning potential enable uniform metal deposition and prevent dendrite formation at the metal anode during cycling are poorly understood, and therefore not optimized. Here, we use atomic force microscopy and molecular dynamics simulations to unravel the influence of these factors on the interface chemistry in a sodium electrolyte, demonstrating how a molten-salt-like structure at the electrode surface results in dendrite-free metal cycling at higher rates. Such a structure will support the formation of a more favourable solid electrolyte interphase, accepted as being a critical factor in stable battery cycling. This new understanding will enable engineering of efficient anode electrodes by tuning the interfacial nanostructure via salt concentration and high-voltage preconditioning.

The future of lithium metal batteries as a widespread, safe and reliable form of high-energy-density rechargeable battery depends on a significant advancement in the electrolyte material used in these devices. Molecular solvent-based electrolytes have been superceded by polymer electrolytes in some prototype devices, primarily in a drive to overcome leakage and flammability problems, but these often exhibit low ionic conductivity and prohibitively poor lithium-ion transport. To overcome this, it is necessary to encourage dissociation of the lithium ion from the anionic polymer backbone, ideally without the introduction of competing, mobile ionic species. Here we demonstrate the effect of zwitterionic compounds, where the cationic and anionic charges are immobilized on the same molecule, as extremely effective lithium ion 'dissociation enhancers'. The zwitterion produces electrolyte materials with conductivities up to seven times larger than the pure polyelectrolyte gels, a phenomenon that appears to be common to a number of different copolymer and solvent systems.