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Corrosion of the zinc negative electrode of zinc–cerium hybrid redox flow batteries in methanesulfonic acid

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Abstract

Corrosion of zinc in aqueous methanesulfonic acid has been evaluated over a wide range of concentrations of acid (0.5–5 mol dm−3), dissolved zinc (0.5–2 mol dm−3), and electrolyte temperature (22–50 °C). The corrosion rate of zinc, in terms of weight loss and the volume of hydrogen evolved, varied with time and it was found to be highly dependent on the surface state and electrolyte conditions. With an initial active layer of zinc present, the corrosion rate rapidly increased following a decline when the proton concentration in the solution decreased to ca. 0.56 mol dm−3. Organic and inorganic inhibitors were added to the electrolyte to suppress the zinc corrosion in 1 mol dm−3 methanesulfonic acid. The strong adsorption and blocking effects of cationic organic adsorption inhibitors, such as cetyltrimethyl ammonium bromide and butyltriphenyl phosphonium chloride, led to a significant decrease in zinc corrosion over a 10 h immersion period. With the addition of indium and lead ions inhibitors, the zinc surface showed less activity. Zinc corrosion continued to a smaller extent in the presence of these metallic inhibitors during the first few hours, but the metallic layer of the inhibitors did not cover the surface completely resulting in continued hydrogen evolution and making the inhibitors less effective at longer times.

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Abbreviations

A :

Electrode area exposed to the electrolyte (m2)

B :

Constant in the Stern–Geary equation (V)

F :

Faraday constant (C mol−1)

J :

Current density (mA cm−2)

E cell :

Cell potential (V)

E cor :

Corrosion potential (V)

I cor :

Corrosion current (A)

j cor :

Corrosion current density (mA cm−2)

M :

Molar mass of zinc (g mol−1)

R p :

Linear polarization area resistance (Ω cm2)

z :

Number of electrons involved in the reaction (dimensionless)

V m :

Molar volume of hydrogen under standard conditions (cm3 mol−1)

V i , V 0 :

Volume of hydrogen evolved in the presence, absence of corrosion inhibitor (cm3)

β a, β c :

Anodic, cathodic Tafel slope (V decade−1)

Θ :

Inhibition efficiency (dimensionless)

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Acknowledgments

Financial support has been provided by the Research Institute for Industry (RIfI) at the University of Southampton. The authors are grateful to Drs. L. Berlouis and G. Nikiforidis, University of Strathclyde for helpful discussions and particularly appreciate the training in XRD provided by Dr. Mark Light. This work represents part of P.K. Leung’s PhD research programme on the development of zinc-based flow batteries for energy storage and conversion technology.

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Author notes

  1. P. K. Leung

    Present address: Instituto IMDEA Energía, Parque Tecnológico de Móstoles, Avda. Ramón de la Sagra, 3, E-28935, Móstoles, Madrid, Spain

  2. F. J. Recio

    Present address: Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40, Correo 33, 9170022, Santiago, Chile

Authors and Affiliations

  1. Electrochemical Engineering Laboratory, Energy Technology Research Group, University of Southampton, Highfield, Southampton, SO17 1BJ, UK

    P. K. Leung, C. Ponce-de-León & F. C. Walsh

  2. Facultad de Ciencias, Departamento de Química-Física Aplicada, Universidad Autónoma de Madrid, 28049, Madrid, Spain

    F. J. Recio & P. Herrasti

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Correspondence to C. Ponce-de-León.

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Leung, P.K., Ponce-de-León, C., Recio, F.J. et al. Corrosion of the zinc negative electrode of zinc–cerium hybrid redox flow batteries in methanesulfonic acid. J Appl Electrochem 44, 1025–1035 (2014). https://doi.org/10.1007/s10800-014-0714-y

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