Copper dual-doping strategy of porous carbon nanofibers and nickel fluoride nanorods as bi-functional oxygen electrocatalysis for effective zinc-air batteries.

Designing and developing efficient, low-cost bi-functional oxygen electrocatalysts is essential for effective zinc-air batteries. In this study, we propose a copper dual-doping strategy, which involves doping both porous carbon nanofibers (PCNFs) and nickel fluoride nanoparticles with copper alone, successfully preparing copper-doped nickel fluoride (NiF) nanorods and copper nanoparticles co-modified PCNFs (Cu@NiF/Cu-PCNFs) as an efficient bi-functional oxygen electrocatalyst. When copper is doped into the PCNFs in the form of metallic nanoparticles, the doped elemental copper can improve the electronic conductivity of composite materials to accelerate electron conduction. Meanwhile, the copper doping for NiF can significantly promote the transformation of nickel fluoride nanoparticles into nanorod structures, thus increasing the electrochemical active surface area and enhancing mass diffusion. The Cu-doped NiF nanorods also possess an optimized electronic structure, including a more negative d-band center, smaller bandgap width and lower reaction energy barrier. Under the synergistic effect of these advantages, the obtained Cu@NiF/Cu-PCNFs exhibit outstanding bi-functional catalytic performances, with a low overpotential of 0.68 V and a peak power density of 222 mW cm in zinc-air batteries (ZABs) and stable cycling for 800 h. This work proposes a one-step way based on the dual-doping strategy, providing important guidance for designing and developing efficient catalysts with well-designed architectures for high-performance ZABs.