Interface Engineering of Branched PdCoP x Nanostructures for High‐Performance Lithium–Oxygen Batteries

Abstract Developing advanced cathode materials plays a positive role in lowering the charge/discharge overpotentials and improving the cycling performance of lithium–oxygen batteries (LOBs). Here we report a direct synthesis strategy to prepare high‐dimensional branched PdCoP x series nanostructures, in which the Pd atoms are well dispersed within cobalt phosphide, leading to rich Pd─Co─P interfaces and evoking a prominent ligand effect between the elements. The Pd 1 Co 2 P x exhibits an excellent and stable activity for oxygen reduction reaction (ORR) in alkaline media, with a mass activity of 1.46 A mg Pd −1 , far exceeding that of commercial Pd/C (0.12 A mg Pd −1 ) and Pt/C (0.17 A mg Pt −1 ). Using Pd 1 Co 2 P x as the cathode, the resulting LOB shows an ultralow discharge/charge overpotential of 0.40 V and could run stably for over 240 cycles, which is a significant improvement compared with the counterparts using CoP x and Pd/C cathodes. Experimental and density functional theory (DFT) calculation results indicate that the dispersed Pd atoms could significantly enhance the ORR kinetics, and the Pd─Co─P interfaces could direct the two‐dimensional growth of Li 2 O 2 , thereby facilitating the formation of more easily decomposable film‐like Li 2 O 2 products. This feature successfully elevates both the charge and discharge performances, as well as the stability of the LOB.