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Investigation of the properties influencing the deactivation of iron electrodes in iron-air batteries

Investigation of the properties influencing the deactivation of iron electrodes in iron-air batteries
Investigation of the properties influencing the deactivation of iron electrodes in iron-air batteries
Iron-air batteries hold the potential to be a key technology for energy storage, thanks to their energy density, low cost, safety and abundance of their materials. In order to scale the technology up and optimize the cell formulations, it is key to obtain a clear understanding of how the physical-chemical properties of the electrode influence their electrochemical behaviour, in particular, the capacity loss. In this work, we propose for the first time mathematical correlations between textural and crystallographic properties of iron electrodes and their electrochemical stability. By adjusting synthesis parameters, we were able to tune pore size and volume, surface area and crystal size of iron oxides, and found that stability is highly correlated to both surface area and pore size. Large surface area and small average pore size provide electrodes with enhanced stability. We hypothesize that the cause for deactivation is the passivation of the electrodes ascribed to the formation of a non-conductive, non-reactive iron (II) hydroxide layer during discharge, which then cannot be reduced to iron again. We validate this hypothesis with electrochemical impedance spectroscopy studies, which show that, in the more stable electrodes, the charge transfer resistance in the Fe(OH)2 to Fe reduction does not significantly change after cycling, contrary to the behaviour of the less stable electrodes, corroborating our hypothesis. Furthermore, the electrode with the best properties was cycled 100 times, retaining almost 75% of its initial capacity at the end of the 100 cycles. These results are highly relevant for the future design and operation of iron-air batteries.
deactivation, electrochemical impedance spectroscopy, iron-air batteries, porous electrodes, Porous electrodes, Deactivation, Iron-air batteries, Electrochemical impedance spectroscopy
0013-4686
Villanueva-Martínez, Nicolás I.
c02bd2d3-2621-4be1-9a9e-50533722c05e
Alegre, Cinthia
288f963e-61f3-468f-a1e5-dd7ce0fab181
Rubin, Javier
14149b97-2eff-44b9-9567-9f622201b75e
Mckerracher, Rachel
f5f9f0e7-a256-4714-b752-e3bb8dab03fc
Ponce De Leon Albarran, Carlos
508a312e-75ff-4bcb-9151-dacc424d755c
Figueredo Rodriguez, Horacio Antonio
e49f1681-45b4-4828-a217-9a507bb68791
Jesús Lázaro, María
0cb2a0ba-8874-4593-91ab-d0826d16b86f
Villanueva-Martínez, Nicolás I.
c02bd2d3-2621-4be1-9a9e-50533722c05e
Alegre, Cinthia
288f963e-61f3-468f-a1e5-dd7ce0fab181
Rubin, Javier
14149b97-2eff-44b9-9567-9f622201b75e
Mckerracher, Rachel
f5f9f0e7-a256-4714-b752-e3bb8dab03fc
Ponce De Leon Albarran, Carlos
508a312e-75ff-4bcb-9151-dacc424d755c
Figueredo Rodriguez, Horacio Antonio
e49f1681-45b4-4828-a217-9a507bb68791
Jesús Lázaro, María
0cb2a0ba-8874-4593-91ab-d0826d16b86f

Villanueva-Martínez, Nicolás I., Alegre, Cinthia, Rubin, Javier, Mckerracher, Rachel, Ponce De Leon Albarran, Carlos, Figueredo Rodriguez, Horacio Antonio and Jesús Lázaro, María (2023) Investigation of the properties influencing the deactivation of iron electrodes in iron-air batteries. Electrochimica Acta, 465, [142964]. (doi:10.1016/j.electacta.2023.142964).

Record type: Article

Abstract

Iron-air batteries hold the potential to be a key technology for energy storage, thanks to their energy density, low cost, safety and abundance of their materials. In order to scale the technology up and optimize the cell formulations, it is key to obtain a clear understanding of how the physical-chemical properties of the electrode influence their electrochemical behaviour, in particular, the capacity loss. In this work, we propose for the first time mathematical correlations between textural and crystallographic properties of iron electrodes and their electrochemical stability. By adjusting synthesis parameters, we were able to tune pore size and volume, surface area and crystal size of iron oxides, and found that stability is highly correlated to both surface area and pore size. Large surface area and small average pore size provide electrodes with enhanced stability. We hypothesize that the cause for deactivation is the passivation of the electrodes ascribed to the formation of a non-conductive, non-reactive iron (II) hydroxide layer during discharge, which then cannot be reduced to iron again. We validate this hypothesis with electrochemical impedance spectroscopy studies, which show that, in the more stable electrodes, the charge transfer resistance in the Fe(OH)2 to Fe reduction does not significantly change after cycling, contrary to the behaviour of the less stable electrodes, corroborating our hypothesis. Furthermore, the electrode with the best properties was cycled 100 times, retaining almost 75% of its initial capacity at the end of the 100 cycles. These results are highly relevant for the future design and operation of iron-air batteries.

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More information

Accepted/In Press date: 29 July 2023
e-pub ahead of print date: 30 July 2023
Published date: 10 October 2023
Additional Information: Funding Information: The authors wish to acknowledge Ministerio de Ciencia e Innovación and Agencia Estatal de Investigación (MCIN/AEI/10.13039/501100011033) for the PID2020-115848RB-C21 grant. The authors also thank the European Union and the NextGeneration EU program for the funding on grant TED2021-130279A-I00. Authors also acknowledge Gobierno de Aragón (DGA) for the financial support to Grupo de Conversión de Combustibles (T06_20R). N. Villanueva acknowledges also DGA for his pre-doctoral contract. The authors would like to acknowledge the use of the Servicio General de Apoyo a la Investigación-SAI, Universidad de Zaragoza. The authors would like to thank Dr. Javier Hernández-Ferrer for his contribution and insights during the analyses of EIS. Funding Information: The authors wish to acknowledge Ministerio de Ciencia e Innovación and Agencia Estatal de Investigación (MCIN/AEI/10.13039/501100011033) for the PID2020-115848RB-C21 grant. The authors also thank the European Union and the NextGeneration EU program for the funding on grant TED2021-130279A-I00. Authors also acknowledge Gobierno de Aragón (DGA) for the financial support to Grupo de Conversión de Combustibles (T06_20R). N. Villanueva acknowledges also DGA for his pre-doctoral contract. The authors would like to acknowledge the use of the Servicio General de Apoyo a la Investigación-SAI, Universidad de Zaragoza. The authors would like to thank Dr. Javier Hernández-Ferrer for his contribution and insights during the analyses of EIS. Publisher Copyright: © 2023 The Author(s)
Keywords: deactivation, electrochemical impedance spectroscopy, iron-air batteries, porous electrodes, Porous electrodes, Deactivation, Iron-air batteries, Electrochemical impedance spectroscopy

Identifiers

Local EPrints ID: 481402
URI: http://eprints.soton.ac.uk/id/eprint/481402
ISSN: 0013-4686
PURE UUID: 73347de0-cb48-4bb7-b60f-31e887d04602
ORCID for Carlos Ponce De Leon Albarran: ORCID iD orcid.org/0000-0002-1907-5913

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Date deposited: 25 Aug 2023 16:38
Last modified: 06 Jun 2024 01:43

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Contributors

Author: Nicolás I. Villanueva-Martínez
Author: Cinthia Alegre
Author: Javier Rubin
Author: Horacio Antonio Figueredo Rodriguez
Author: María Jesús Lázaro

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