The practical progress of lithium–sulfur
batteries is hindered
by the serious shuttle effect and the slow oxidation–reduction
kinetics of polysulfides. Herein, the ZnFe<sub>2</sub>O<sub>4</sub>–Ni<sub>5</sub>P<sub>4</sub> Mott–Schottky heterojunction
material is prepared to address these issues. Benefitting from a self-generated
built-in electric field, ZnFe<sub>2</sub>O<sub>4</sub>–Ni<sub>5</sub>P<sub>4</sub> as an efficient bidirectional catalysis regulates
the charge distribution at the interface and accelerates electron
transfer. Meanwhile, the synergy of the strong adsorption capacity
derived from metal oxides and the outstanding catalytic performance
that comes from metal phosphides strengthens the adsorption of polysulfides,
reduces the energy barrier during the reaction, accelerates the conversion
between sulfur species, and further accelerates the reaction kinetics.
Hence, the cell with ZnFe<sub>2</sub>O<sub>4</sub>–Ni<sub>5</sub>P<sub>4</sub>/S harvests a high discharge capacity of 1132.4 mAh
g<sup>–1</sup> at 0.5C and displays a high Coulombic efficiency
of 99.3% after 700 cycles. The ZnFe<sub>2</sub>O<sub>4</sub>–Ni<sub>5</sub>P<sub>4</sub>/S battery still maintains a capacity of 610.1
mAh g<sup>–1</sup> with 84.4% capacity retention after 150
cycles at 0.1C under a high sulfur loading of 3.2 mg cm<sup>–2</sup>. This work provides a favorable reference and advanced guidance
for developing Mott–Schottky heterojunctions in lithium–sulfur
batteries.