Directly Regenerating of Spent LiCoO₂ with Gradient F‐Doped Subsurface towards Ultra‐Stable Storage Properties

As great potential recycling strategy, the direct regeneration of spent LiCoO₂ (LCO) is beneficial for lowering environmental pollutions and promoting global sustainability. However, owing to the using of binder and electrolyte, some fluorine impurities would be remained into spent materials. Considering the doping behaviors of F-elements, their suitable content introducing would facilitate the energy-storage abilities of regenerated LCO. Herein, through the tailored introduction of F-elements, spent LCO are successfully regenerated with physical-chemical evolutions. Benefitting from the existed oxygen vacancies, the diffusion energy-barrier of F-elements is reduced from 1.73 eV to 0.61 eV, facilitating the establishment of gradient F-doped subsurface, along with the formation of rigid CoO₅F. Meanwhile, excess F-elements (1 wt %, as a threshold) lead to the formation of LiF passivation layer on the surface. Thus, the as-optimized sample displays a considerable capacity of 154.4 mAh g^-1 even at 5.0 C, with retention rate (88.3 %) in 3.0-4.5 V. Supported by detailed electrochemical and kinetic analysis, the structural advantages are confirmed to boost the improved redox activity of Co-ions and the alleviating of irreversible oxygen-release. Give this, the work is anticipated to reveal the evolutions of regenerated LCO with the introduced F-elements, whilst providing the practical regeneration strategies toward excellent high-voltage properties.