Polarly modulated solvent strategy for high-voltage cathode materials

• Anchor-oxygen interface layer is rationally designed. • Interfacial quasicrystal bonding effects are ingeniously aroused. • Formation energy of oxygen vacancy is effectively elevated. • Capacity/voltage fading is significantly mitigated. Sacrificial additive as an electrolyte engineering could regulate the electrode/electrolyte interface for advanced energy storage devices. In particular, the evolution of cathode electrolyte interface (CEI) is closely related with the epitaxial coordination environment of cathode materials. Herein, polarly modulated solvent strategy is successfully achieved, in which the electrochemical oxidation potential of perfluorinated electrolyte with tris(trimethylsilyl)borate additive is manipulated by the polarity of solvent structure. By taking Li-rich Mn-based oxide (LRM) as a model cathode, the interfacial quasicrystal bonding effects are ingeniously aroused between the interfacial lattice oxygen of LRM cathode and anchor oxygen CEI layer. More greatly, the formation energy of oxygen vacancy is effectively elevated by constructing the epitaxially strong covalent B/Si-O bonding, thereby considerably mitigating the lattice oxygen escaping and inhibiting the irreversible phase transformation. Consequently, LRM cathode with robust anchor oxygen CEI renders improved cycling stability after 200 loops with 87.5% capacity retention at 1 C as compared to anchor oxygen-free LRM with only 61.9%. Given this, these findings inform new chemical and interface strategies to facilitate the application of high voltage cathodes.