Proceedings of MATSUS Spring 2025 Conference (MATSUSSpring25)
DOI: https://doi.org/10.29363/nanoge.matsusspring.2025.367
Publication date: 16th December 2024
Rechargeable alkaline zinc–air batteries (ZAB) hold great promise as a viable, sustainable, and safe alternative energy storage system to the lithium-ion battery. However, the practical realization of ZABs is limited by their intrinsically low energy trip efficiency, stemming from a large charge and discharge potential gap. This overpotential is attributed to the four-electron oxygen evolution (OER) and reduction (ORR) reactions and their sluggish kinetics.
In this talk, I will show our new concept based on two-electron generation and consumption of hydrogen peroxide at the air electrode. The O2/peroxide chemistry, facilitated by a newly developed low-cost Ni-based bifunctional electrocatalyst, enables fast peroxide generation/consumption, and high energy efficiency, durability, and capacity. The proposed strategy profoundly relies on the availability of bifunctionally active ORR and POR electrocatalysts. Therefore, we developed an efficient, highly stable, inexpensive ORR and POR bifunctional catalyst based on NiNxCy single sites and Ni-based nanoparticles (Ni(OH)2 at the surface under operational conditions in an alkaline environment) engulfed in crystalline carbon. The new electrocatalyst exhibits state-of-the-art activity, selectivity (96 ± 2%) in the 0.15–0.79 V vs. RHE range, and long-term stability (>100 h) for both hydrogen peroxide synthesis (ORR) and oxidation (POR) in alkaline medium. The integration of the bifunctional catalyst in the ZPB results in an ultra-low initial charge potential of 1.28 V at a current density of 2 mA cm–2 (fixed capacity: 20 mAh cm–2) and 1.48 V at a high current density of 50 mA cm–2, corresponding to 97.3% and 74.8% energy efficiency, respectively. The new ZAB operates for at least 1000 h at a capacity of 50 mAh cm–2, demonstrating high durability. In situ measurements combined with theoretical calculations reveal that the bifunctional catalyst stabilizes an adsorbed hydroperoxyl intermediate, which constitutes a crucial step for both peroxide generation and oxidation reactions, allowing the battery’s unique performance. The new design offers substantial progress toward practical ZAB and green, cheap, and efficient electrochemical production of hydrogen peroxide, providing a step toward replacing the existing industrial energy-intensive and toxic process.
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