Superdry poly(vinylidene fluoride-co-hexafluoropropylene) coating on a lithium anode as a protective layer and separator for a high-performance lithium-oxygen battery

In this study, a dense polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) coating is fabricated on a lithium (Li) anode sheet, which acts as a synergistic protective layer and electrolyte separator for Li-oxygen (Li-O₂) batteries. This thin coating is dried through slow solvent evaporation and vacuum drying methods. The solvent-free, dense PVDF-HFP coating has a thickness of 45 µm and can absorb 62% of electrolyte. The battery containing the PVDF-HFP coating demonstrates a maximum peak power density of 3 mW cm⁻², significantly higher than that of the battery with the PVDF coating (0.8 mW cm⁻²) but lower than that without coating (equipped with a commercial glass fiber separator, 7.3 mW cm⁻²). However, the PVDF-HFP coating enables the Li-O₂ battery to reach a capacity of 4400 mA h g⁻¹, much higher than that without the coating (glass fiber separator, 850 mA h g⁻¹). The symmetric Li-Li cells further confirm steady and low overpotentials using the anode coating at a high current density of 1.0 mA cm⁻², indicating stable Li plating/stripping process. The PVDF-HFP-coated battery has a longer cycling lifetime (1700 h) than those with the PVDF coating (120 h) and a glass fiber separator (670 h). The Raman spectra show that there are lithium compounds (mainly lithium hydroxide) and residual PVDF-HFP on the aged anode surface. The dense PVDF-HFP coating on the Li anode plays dual roles: it creates a strong protective layer for stabilizing the solid-electrolyte interface (in the solid phase), and acts as a separator for modulating the Li metal deposition and stripping behaviors in liquid electrolyte.