Coupling isolated Ni single atoms with sub-10 nm Pd nanocrystals embedded in porous carbon frameworks to boost oxygen electrocatalysis for Zn-air batteries

• Published in: Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2022-03, Vol.1 (11), p.686-695
• Main Authors: Wang, Shangzhi, Lin, Zinan, Li, Mengmeng, Yu, Zehan, Zhang, Minjun, Gong, Mingxing, Tang, Yawen, Qiu, Xiaoyu
• Format: Article
• Language: English
• Subjects: Batteries; Benchmarks; Carbon; Carbon sources; Catalysts; Cathodes; Crystals; Electron transfer; Flux density; Incompatibility; Metal air batteries; Metals; Nanocrystals; Noble metals; Oxygen; Palladium; Pyrolysis; Rechargeable batteries; Synergistic effect; Thermal stability; Zinc; Zinc-oxygen batteries
• ISSN: 2050-7488; 2050-7496
• DOI: 10.1039/d1ta06897k

Developing effective bifunctional catalysts for the oxygen reduction and evolution reaction (ORR/OER) is essential for accelerating the cathode efficiency of Zn-air batteries. Herein, atomically dispersed Ni single atoms are supported by sub-10 nm Pd nanocrystals embedded in N-doped carbon frameworks (Ni SAs-Pd@NC), in an effort to achieve superior bifunctional activity in both the ORR and OER. The key synthetic point depends on the protection mechanism of 1-naphthylamine, which could provide a carbon source for Ni SAs and restrict the Pd size under sub-10 nm during 600 °C pyrolysis, simultaneously. The synergistic effect of sub-10 nm Pd with superior ORR activity and Ni-N 4 SAs with favourable OER activity leads to bifunctional catalytic performance, meanwhile the rod-like carbon frameworks with ultrathin, porous and N-doped features contribute to accelerated electron transfer and structural robustness. As a proof-of-concept application, Ni SAs-Pd@NC demonstrates ultrahigh ORR activity with a positive half-wave potential of 0.84 V and a low OER overpotential of 380 mV at 10 mA cm −2 , in an alkaline medium. For a rechargeable Zn-air battery, the Ni SAs-Pd@NC cathode delivers a low charge-discharge voltage gap of 0.87 V, a high energy density of 884.6 W h kg Zn −1 , a high power density of 134.2 mW cm −2 and remarkable long-term cyclability for operation over 700 cycles, outperforming commercial Pt/C + RuO 2 benchmarks. This work successfully integrates single atom sites with small-sized noble metals to break out their incompatibility in synthesis and to improve their thermostability, which offers a versatile approach to develop single atom-based bifunctional catalysts for energy devices. Atomically dispersed Ni sites are coupled with sub-5 nm Pd nanocrystals embedded in carbon frameworks to form a bifunctional catalyst, which could serve as a highly efficient catalyst for the ORR, OER, and Zn-air batteries.