Coexistence of (O2)n− and Trapped Molecular O2 as the Oxidized Species in P2-Type Sodium 3d Layered Oxide and Stable Interface Enabled by Highly Fluorinated Electrolyte

The interface stability of cathode/electrolyte for Na-ion layered oxides is tightly related to the oxidized species formed during the electrochemical process. Herein, we for the first time decipher the coexistence of (O2)n− and trapped molecular O2 in the (de)sodiation process of P2-Na0.66[Li0.22Mn0.78]O2 by using advanced electron paramagnetic resonance (EPR) spectroscopy. An unstable interface of cathode/electrolyte can thus be envisaged with conventional carbonate electrolyte due to the high reactivity of the oxidized O species. We therefore introduce a highly fluorinated electrolyte to tentatively construct a stable and protective interface between P2-Na0.66[Li0.22Mn0.78]O2 and the electrolyte. As expected, an even and robust NaF-rich cathode–electrolyte interphase (CEI) film is formed in the highly fluorinated electrolyte, in sharp contrast to the nonuniform and friable organic-rich CEI formed in the conventional lowly fluorinated electrolyte. The in situ formed fluorinated CEI film can significantly mitigate the local structural degeneration of P2-Na0.66[Li0.22Mn0.78]O2 by refraining the irreversible Li/Mn dissolutions and O2 release, endowing a highly reversible oxygen redox reaction. Resultantly, P2-Na0.66[Li0.22Mn0.78]O2 in highly fluorinated electrolyte achieves a high Coulombic efficiency (CE) of >99% and an impressive cycling stability in the voltage range of 2.0–4.5 V (vs Na+/Na) under room temperature (147.6 mAh g–1, 100 cycles) and at 45 °C (142.5 mAh g–1, 100 cycles). This study highlights the profound impact of oxidized oxygen species on the interfacial stability of cathode/electrolyte and carves a new path for building stable interface and enabling highly stable oxygen redox reaction.