Rational Design of Spinel Cobalt Vanadate Oxide Co 2 VO 4 for Superior Electrocatalysis.

Electrochemical energy devices, such as fuel cells and metal-air batteries, convert chemical energy directly into electricity without adverse environmental impact. Attractive alternatives to expensive noble metals used in these renewable energy technologies are earth-abundant transition metal oxides. However, they are often limited by catalytic and conductive capabilities. Here reported is a spinel oxide, Co ₂ VO ₄ , by marrying metallic vanadium atomic chains with electroactive cobalt cations for superior oxygen reduction reaction (ORR)-a key process for fuel cells, metal-air batteries, etc. The experimental and simulated electron energy-loss spectroscopy analyses reveal that Co ²⁺ cations at the octahedral sites take the low spin state with one e _g electron ( t 2 g 6 e g 1 ) , favoring advantageous ORR energetics. Measurement of actual electrical conductivity confirms that Co ₂ VO ₄ has several orders of magnitude increase when compared with benchmark cobalt oxides. As a result, a zinc-air battery with new spinel cobalt vanadate oxide as the ORR catalyst shows excellent performance, together with a record-high discharge peak power density of 380 mW cm ^-2 . Crucially, this is superior to state-of-the-art Pt/C-based device and is greatest among zinc-air batteries assembled with metal, metal oxide, and carbon catalysts. The findings present a new design strategy for highly active and conductive oxide materials for a wide range of electrocatalytic applications, including ORR, oxygen evolution, and hydrogen evolution reactions.
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