The heteroatom-doped graphene has attracted a lot of research due to its excellent physical, chemical and electrochemical properties considered to be the most promising electrocatalytic material for oxygen reduction reaction (ORR). Multi-doping can exert the synergistic effect between different doped heteroatoms and effectively improve the catalytic activity of doped graphene catalysts. N, P, S tri-doped graphene catalysts were prepared by simple and convenient hydrothermal and high-temperature treatment. The experimental results show that different phosphorus sources have a significant impact on the structure and performance of the prepared catalyst materials. The NSP-Gr-1 catalyst shows the high onset potential (1.035 V), half-wave potential (0.79 V) and limiting current density (−5.33 mA cm−2) for ORR. The power density of the zinc-air battery assembled with the NSP-Gr-1 catalyst achieves 163.1 mW cm−2 at 186.7 mA cm−2, which is much higher than the maximum power density of 140.0 mW cm−2 at 190 mA cm−2 for commercial Pt/C. The discharge stability under different current densities is outstanding.
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