Co2P-Assisted Atomic Co-N4 Active Sites with a Tailored Electronic Structure Enabling Efficient ORR/OER for Rechargeable Zn-Air Batteries.

Oxygen reduction and evolution reactions (ORR and OER, respectively) are vital steps for metal-air batteries, which are plagued by their sluggish kinetics. It is still a challenge to develop highly effective and low-cost non-noble-metal-based electrocatalysts. Herein, a simple and reliable method was reported to synthesize a Co2P-assisted Co single-atom (Co-N4 centers) electrocatalyst (Co2P/Co-NC) via evaporative drying and pyrolysis processes. The Co2P nanoparticles and Co-N4 centers are uniformly distributed on the nitrogen-doped carbon matrix. Notably, Co2P/Co-NC showed excellent activities in both ORR (initial potential, 1.01 V; half-wave potential, 0.88 V) and OER (overpotential, 369 mV at 10 mA cm-2). The above results were comparable to those of commercial catalysts (such as Pt/C and RuO2). Based on the experimental and theoretical analyses, the impressive activity can be ascribed to the tailored electronic structure of Co-N4 centers by the adjacent Co2P, enabling the electron transfer from the Co atom to the neighboring C atoms, leading to a downshift of the d-band center, and improved reaction kinetics were achieved. The assembled Zn-air batteries using Co2P/Co-NC as the air cathode showed a peak power density of 187 mW cm-2 and long-life cycling stability for 140 h at 5 mA cm-2. This work may pave a promising avenue to design hybrid bifunctional electrocatalysts for highly efficient ORR/OER.

Embedding Co2P nanoparticles in Cu doping carbon fibers for Zn-air batteries and supercapacitors.

Developing highly efficient and non-precious materials for Zn-air batteries (ZABs) and supercapacitors (SCs) are still crucial and challenging. Herein, electronic reconfiguration and introducing conductive carbon-based materials are simultaneously conducted to enhance the ZABs and SCs performance of Co2P. We develop a simple and efficient electrospinning technology followed by carbonization process to synthesize embedding Co2P nanoparticles in Cu doping carbon nanofibers (Cu-Co2P/CNFs). As a result, the 7% Cu-Co2P/CNFs presents high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity (half-wave potential of 0.792 V for ORR, an overpotential of 360 mV for OER). The ZABs exhibit a power density of 230 mW cm-2and excellent discharge-charge stability of 80 h. In addition, the 7% Cu-Co2P/CNFs show the specific capacitance of 558 F g-1at 1 A g-1. Moreover, the 7% Cu-Co2P/CNFs//CNFs asymmetric supercapacitor was assembled applying 7% Cu-Co2P/CNFs electrode and pure CNFs, which exhibits a high energy density (25.9 Wh kg-1), exceptional power density (217.5 kW kg-1) and excellent cycle stability (96.6% retention after 10 000 cycles). This work may provide an effective way to prepared Co2P based materials for ZABs and SCs applications.