journal article·2025-04-17Open access

Binder-Free Fe-N-C-O Bifunctional Electrocatalyst in Nickel Foam for Aqueous Zinc–Air Batteries

Jorge González-Morales, Jadra Mosa, Mario Aparicio

Batteries· Volume 11· Issue 4

Abstract

The development of efficient, sustainable, and cost-effective catalysts is crucial for energy storage technologies, such as zinc–air batteries (ZABs). These batteries require bifunctional catalysts capable of efficiently and selectively catalyzing oxygen redox reactions. However, the high cost and low selectivity of conventional catalysts hinder the large-scale integration of ZABs into the electric grid. This study presents binder-free Fe-based bifunctional electrocatalysts synthesized via a sol–gel method, followed by thermal treatment under ammonia flow. Supported on nickel foam, the catalyst exhibits enhanced activity for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), essential for ZAB operation. This work addresses two critical challenges in the development of ZABs: first, the replacement of costly cobalt or platinum-group-metal (PGM)-based catalysts with an efficient alternative; second, the achievement of prolonged battery performance under real conditions without passivation. Structural analysis confirms the integration of iron nitrides, oxides, and carbon, resulting in high conductivity and catalytic stability without relying on precious or cobalt-based metals. Electrochemical tests reveal that the catalyst calcined at 800 °C delivers superior performance, achieving a four-electron ORR mechanism and prolonged operational life compared to its 900 °C counterpart. Both catalysts outperform conventional Pt/C-RuO2 systems in stability and selective bifunctionality, offering a more sustainable and cost-effective alternative. The innovative combination of nitrogen, carbon, and iron compounds overcomes limitations associated with traditional materials, paving the way for scalable, high-performance applications in renewable energy storage. This work underscores the potential of transition metal-based catalysts in advancing the commercial viability of ZABs.
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Research context

OpenAlex topics: Advanced battery technologies research · Electrocatalysts for Energy Conversion · Supercapacitor Materials and Fabrication

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Instituto de Cerámica y Vidrio, Consejo Superior de Investigaciones Científicas (CSIC), Kelsen 5, 28049 Madrid, Spain

Funding

Proyectos de generación de conocimiento, Ministerio de Ciencia, Innovación y Universidades · Programas de Actividades de I+D entre grupos de investigación de la Comunidad de Madrid en Tecnologías 2024 · predoctoral contract

References (50)

Show source-provided references
1. Olabi, G., Sayed, E.T., Wilberforce, T., Jamal, A., Alami, A.H., Elsaid, K., Rahman, S.M.A., Shah, S.K., and Abdelkareem, M.A. (2021). Metal-Air Batteries—A Review. Energies, 14.10.3390/en14217373 ↗
2. A Critical Review of Li/Air Batteries10.1149/2.086202jes ↗
3. High performance secondary zinc-air/silver hybrid battery10.1016/j.est.2020.102103 ↗
4. Zinc—Air alkaline batteries—A review10.1016/0378-7753(81)80027-4 ↗
5. Long-battery-life flexible zinc–air battery with near-neutral polymer electrolyte and nanoporous integrated air electrode10.1039/C9TA09137H ↗
6. Advanced Architectures and Relatives of Air Electrodes in Zn–Air Batteries10.1002/advs.201700691 ↗
7. First-principle study of doping effects (Ti, Cu, and Zn) on electrochemical performance of Li2MnO3 cathode materials for lithium-ion batteries
8. Graphitic-shell encapsulated FeNi alloy/nitride nanocrystals on biomass-derived N-doped carbon as an efficient electrocatalyst for rechargeable Zn-air battery
9. Vaitsis, C., Mechili, M., Argirusis, N., Pandis, P.K., Sourkouni, G., and Argirusis, C. (2022). MOF nanomaterials for battery cathodes. Metal-Organic Framework-Based Nanomaterials for Energy Conversion and Storage, Elsevier Science.10.1016/B978-0-323-91179-5.00013-9 ↗
10. Recent advances in cobalt-based electrocatalysts for hydrogen and oxygen evolution reactions10.1016/j.jallcom.2019.153542 ↗
11. Electrodeposited Amorphous Tungsten-doped Cobalt Oxide as an Efficient Catalyst for the Oxygen Evolution Reaction
12. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries10.1038/srep07665 ↗
13. Significant improvement in Mn2O3 transition metal oxide electrical conductivity via high pressure10.1038/srep44078 ↗
14. A Review of Carbon-Composited Materials as Air-Electrode Bifunctional Electrocatalysts for Metal–Air Batteries10.1007/s41918-018-0002-3 ↗
15. 2D Nanoporous Fe−N/C Nanosheets as Highly Efficient Non-Platinum Electrocatalysts for Oxygen Reduction Reaction in Zn-Air Battery10.1002/smll.201601887 ↗
16. A facile iron-sulfur double-doping strategy to prepare high performance FeNx/S-NC electrocatalyst for oxygen reduction reaction in zinc-air battery
17. Facile hydrothermal synthesis of manganese-metal organic framework nanostructures in the presence of various organic ligands for SO2 and CO2 gas adsorption10.1007/s10934-015-0090-y ↗
18. González-Morales, J., Aparicio, M., Rosero-Navarro, N.C., Zanotto, F.M., Franco, A.A., and Mosa, J. (2024). Electrochemical and structural properties of binder-free iron-based bifunctional catalyst for aqueous Zinc-Oxygen batteries. Open Ceramics., 100667.10.1016/j.oceram.2024.100667 ↗
19. Kaur Muuli, R., Kumar, R., Mooste, M., Gudkova, V., Treshchalov, A., Piirsoo, H.-M., Kikas, A., Aruväli, J., Kisand, V., and Tamm, A. (2023). Iron, cobalt, and nickel phthalocyanine tri-doped electrospun carbon nanofibre-based catalyst for rechargeable zinc–air battery air electrode. Materials, 16.10.3390/ma16134626 ↗
20. Synthesis and characterization of phenolic resins based on pyrolysis bio-oil separated by fractional condensation and water extraction
21. Synthesis of titanium nitride powders by reactive ball milling of titanium and urea
22. The effects of urea modification and heat treatment on the process of NO2 removal by wood-based activated carbon
23. Multielectron electrode reaction kinetics with RDE and RRDE: An advanced electrochemical laboratory experiment10.1021/acs.jchemed.1c00202 ↗
24. Thermal decomposition (pyrolysis) of urea in an open reaction vessel
25. Urea-assisted combustion synthesis of porous Li1.2Ni0.13Co0.13Mn0.54O2 microspheres as high-performance lithium-ion battery cathodes10.1049/mnl.2015.0306 ↗
26. Ultra fine carbon nitride nanocrystals synthesized by laser ablation in liquid solution10.1007/s11051-006-9192-4 ↗
27. Synthesis and properties of novel poly(amide-imide)s derived from 2,4-diaminotriphenylamine and imide ring-preformed dicarboxylic acids10.1007/s10965-004-5481-8 ↗
28. Dong, H.T. (2021). Synthesis and Reactivity of Non-Heme Iron-Nitrosyl Complexes That Model the Active Sites of NO Reductases. [Ph.D. Thesis, University of Michigan].
29. Synthesis and characterization of iron oxide nanoparticles for phenyl hydrazine sensor applications10.1166/sl.2014.3224 ↗
30. Raman spectroscopy of iron oxides and (oxy)hydroxides at low laser power and possible applications in environmental magnetic studies10.1111/j.1365-246X.2009.04122.x ↗
31. Raman investigation of anodic undermining of coated steel during environmental exposure10.5006/1358 ↗
32. Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials
33. Characterization of ALCVD-Al2O3 and ZrO2 layer using X-ray photoelectron spectroscopy10.1016/S0022-3093(02)00970-5 ↗
34. XPS of nitrogen-containing functional groups on activated carbon10.1016/0008-6223(95)00030-H ↗
35. Interpretation of X-ray photoelectron spectra of carbon-nitride thin films: New insights from in situ XPS10.1016/j.carbon.2016.07.017 ↗
36. Three-dimensional nickel oxides/nickel structure by in situ electro-oxidation of nickel foam as robust electrocatalyst for oxygen evolution reaction
37. High-performance platinum-perovskite composite bifunctional oxygen electrocatalyst for rechargeable Zn–air battery10.1002/aenm.201903271 ↗
38. A Stable Rechargeable Aqueous Zn–Oxygen Battery with New Mn-Based Bifunctional Electrocatalyst
39. González-Morales, J., Mosa, J., Ishiyama, S., Rosero-Navarro, N.C., Miura, A., Tadanaga, K., and Aparicio, M. (2024). Carbon-Free Cathode Materials Based on Titanium Compounds for Zn-Oxygen Aqueous Batteries. Batteries, 10.10.3390/batteries10030094 ↗
40. Mn single-atom tuning Fe-N-C catalyst enables highly efficient and durable oxygen electrocatalysis and zinc–air batteries10.1021/acsnano.3c09100 ↗
41. High-performance bifunctional oxygen electrocatalysts for zinc-air batteries over mesoporous Fe/Co-N-C nanofibers with embedding FeCo alloy nanoparticles10.1016/j.apcatb.2018.11.039 ↗
42. Developing flexible solid-state zinc air batteries based on NiFe@NC catalyst and dual network hydrogel electrolyte10.1016/j.mtphys.2023.101288 ↗
43. A Fe-Ni-Zn triple single-atom catalyst for efficient oxygen reduction and oxygen evolution reaction in rechargeable Zn-air batteries10.1016/j.cej.2023.141868 ↗
44. Highly durable iron single-atom catalysts for low-temperature zinc-air batteries by electronic regulation of adjacent iron nanoclusters
45. Efficient iron–cobalt oxide bifunctional electrode catalysts in rechargeable high current density zinc–air batteries10.1039/D2NR01258H ↗
46. A highly durable zinc-air battery from a directly integrated FexNC@NiFe(OH)x bifunctional catalyst10.1039/D2QI02564G ↗
47. Fe single atoms encased in nanoscale ZIF-8 dodecahedra for oxygen reduction and flexible zinc–air batteries10.1021/acsanm.4c02087 ↗
48. Adhikari, A., Chhetri, K., Rai, R., Acharya, D., Kunwar, J., Bhattarai, R.M., Jha, R.K., Kandel, D., Kim, H.Y., and Kandel, M.R. (2023). (Fe-Co-Ni-Zn)-Based Metal–Organic Framework-Derived Electrocatalyst for Zinc–Air Batteries. Nanomaterials, 13.10.3390/nano13182612 ↗
49. Fe-MOF-Derived Efficient ORR/OER Bifunctional Electrocatalyst for Rechargeable Zinc–Air Batteries10.1021/acsami.0c11945 ↗
50. A Single-Crystal Open-Capsule Metal–Organic Framework10.1021/jacs.9b02417 ↗