Effective Bidirectional Mott–Schottky Catalysts Derived from Spent LiFePO4 Cathodes for Robust Lithium−Sulfur Batteries

It is deemed as a tough yet profound project to comprehensively cope with a range of detrimental problems of lithium–sulfur batteries (LSBs), mainly pertaining to the shuttle effect of lithium polysulfides (LiPSs) and sluggish sulfur conversion. Herein, a Co2P‐Fe2P@N‐doped carbon (Co2P‐Fe2P@NC) Mott–Schottky catalyst is introduced to enable bidirectionally stimulated sulfur conversion. This catalyst is prepared by simple carbothermal reduction of spent LiFePO4 cathode and LiCoO2. The experimental and theoretical calculation results indicate that thanks to unique surface/interface properties derived from the Mott–Schottky effect, full anchoring of LiPSs, mediated Li2S nucleation/dissolution, and bidirectionally expedited “solid⇌liquid⇌solid” kinetics can be harvested. Consequently, the S/Co2P‐Fe2P@NC manifests high reversible capacity (1569.9 mAh g−1), superb rate response (808.9 mAh g−1 at 3C), and stable cycling (a low decay rate of 0.06% within 600 cycles at 3C). Moreover, desirable capacity (5.35 mAh cm−2) and cycle stability are still available under high sulfur loadings (4–5 mg cm−2) and lean electrolyte (8 µL mg−1) conditions. Furthermore, the as‐proposed universal synthetic route can be extended to the preparation of other catalysts such as Mn2P‐Fe2P@NC from spent LiFePO4 and MnO2. This work unlocks the potential of carbothermal reduction phosphating to synthesize bidirectional catalysts for robust LSBs. Cathode materials of Li‐ion batteries (e.g. LiFePO4) were once used to drive speeding cars, now they can also be recycled to prepare Mott‐Schottky bidirectional catalysts (Co2P‐Fe2P@NC and Mn2P‐Fe2P@NC) for lithium‐sulfur batteries. These catalysts can render batteries mitigated shuttle effect, high specific capacity and long‐term cycling.