Designing Breathing Air‐electrode and Enhancing the Oxygen Electrocatalysis by Thermoelectric Effect for Efficient Zn‐air Batteries

The sluggish kinetics and mutual interference of oxygen evolution and reduction reactions (OER and ORR) in the air electrode resulted in large charge/discharge overpotential and low energy efficiency of Zn-air batteries. In this work, we designed a breathing air-electrode configuration in Zn-air batteries using P-type Ca3Co4O9 and N-type CaMnO3 as charge and discharge thermoelectrocatalysts, respectively. The Seebeck voltages generated from thermoelectric effect of Ca3Co4O9 and CaMnO3 synergistically compensated the OER and ORR overpotentials. The carrier migration and accumulation on the cold surface of Ca3Co4O9 and CaMnO3 optimized the electronic structure of metallic sites and thus enhanced their intrinsic catalytic activity. The OER and ORR overpotentials were enhanced by 101 and 90 mV, respectively, at temperature gradient of 200 °C. The breathing Zn-air battery displayed a remarkable energy efficiency of 68.1%. This work provides an efficient avenue towards utilizing waste heat for improving the energy efficiency of Zn-air batteries.