High-Entropy Prussian Blue Analogue Derived Heterostructure Nanoparticles as Bifunctional Oxygen Conversion Electrocatalysts for the Rechargeable Zinc-Air Battery

Wuttichai Tanmathusorachai; Sofiannisa Aulia; Mia Rinawati; Ling-Yu Chang; Chia-Yu Chang; Wei-Hsiang Huang; Ming-Hsien Lin; Wei-Nien Su; Brian Yuliarto; Min-Hsin Yeh

doi:10.1021/acsami.4c13387

High-Entropy Prussian Blue Analogue Derived Heterostructure Nanoparticles as Bifunctional Oxygen Conversion Electrocatalysts for the Rechargeable Zinc-Air Battery

ACS Appl Mater Interfaces. 2024 Nov 13;16(45):62022-62032. doi: 10.1021/acsami.4c13387. Epub 2024 Nov 4.

Authors

Wuttichai Tanmathusorachai¹, Sofiannisa Aulia¹, Mia Rinawati¹, Ling-Yu Chang², Chia-Yu Chang³, Wei-Hsiang Huang⁴, Ming-Hsien Lin^{5

6}, Wei-Nien Su^{3

6}, Brian Yuliarto⁷, Min-Hsin Yeh^{1

6}

Affiliations

¹ Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan.
² Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei 10608, Taiwan.
³ Graduate Institute of Applied Science and Technology, National Taiwan University of Science and Technology, Taipei 10607, Taiwan.
⁴ National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan.
⁵ Department of Chemical and Materials Engineering, Chung Cheng Institute of Technology, National Defense University, Dasi, Taoyuan 335, Taiwan.
⁶ Sustainable Electrochemical Energy Development Center, National Taiwan University of Science and Technology, Taipei 10607, Taiwan.
⁷ Advanced Functional Materials Laboratory, Department of Engineering Physics, Institute of Technology Bandung (ITB), Bandung 40132, Indonesia.

Abstract

In response to energy challenges, rechargeable zinc-air batteries (RZABs) serve as an ideal platform for energy storage with a high energy density and safety. Nevertheless, addressing the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in RZAB requires highly active and robust electrocatalysts. High-entropy Prussian blue analogues (HEPBAs), formed by mixing diverse metals within a single lattice, exhibit enhanced stability due to their increased mixing entropy, which lowers the Gibbs free energy. HEPBAs innately enable sacrificial templating, an effective way to synthesize complex structures. Impressively, in this study, we successfully transform HEPBAs into exquisite multiphase (multimetallic alloy, metal carbide, and metal oxide) heterostructure nanoparticles through a controlled synthesis process. The elusive multiphase heterostructure nanoparticles manifested two active sites for selective ORR and OER. By integrating CNT into HEPBA-derived nanoparticles (HEPBA/CNT-800), the HEPBA/CNT-800 demonstrates superior activity toward both ORR (E_1/2 = 0.77 V) in a 0.1 M KOH solution and the OER (η = 330 mV at 50 mA cm^-2) in a 1 M KOH solution. The RZAB with a HEPBA/CNT-based air electrode demonstrated an open-circuit voltage of 1.39 V and provided a significant energy density of 71 mW cm^-2. Moreover, the charge and discharge cycles lasting up to 40 h at a current density of 5 mA cm^-2 demonstrate its excellent stability. This work provides an alternative avenue for the rational design of HEPBA's derivative for a sustainable rechargeable metal-air battery platform.

Keywords: Prussian blue analogues; bifunctional electrocatalyst; heterostructure nanoparticles; high entropy; rechargeable zinc−air battery.