Valence Engineering of Polyvalent Cobalt Encapsulated in a Carbon Nanofiber as an Efficient Trifunctional Electrocatalyst for the Zn–Air Battery and Overall Water Splitting

The rapid development of electrochemical power systems has prompted high demand for nonprecious trifunctional electrocatalysts with superior performance, prolonged stability, and low cost for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Here, a valence engineering strategy is devised to construct a morphology with polyvalent cobalt encapsulated in nitrogen-doped carbon nanofibers (Co/N–CNFs). The diverse cobalt valence states of the Co/N–CNF catalysts contribute to their excellent catalytic effect and high durability in multiple electrochemical processes. The optimal Co/N–CNF catalyst fabricated exhibits a high half-wave potential of ORR (0.86 V) and low overpotentials of OER (380 mV) and HER (241 mV) at 10 mA cm–2. The Co/N–CNF-based Zn–air battery possesses a high charge–discharge efficiency as well as a good cycle stability (50 h at 10 mA cm–2 and 120 h at 20 mA cm–2), much superior to the Pt/C-based batteries. Furthermore, the Co/N–CNF catalyst could perform efficient overall water splitting.