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Effect of Lithium and Potassium Cations on the Electrocatalytic Properties of Carbon and Manganese Oxide Electrocatalysts Towards the Oxygen Reduction Reaction in Concentrated Alkaline Electrolyte

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Abstract

The impact of alkaline cations (Li+ and K+) on the electrocatalytic properties of high-surface-area carbon (HSAC) and nanometric manganese oxides (MnOx) deposited onto HSAC (MnOx/C) used as oxygen reduction reaction (ORR) electrodes has been studied in concentrated LiOH or KOH media. The electrochemical characterizations firstly reveal that HSAC have good ORR electrocatalytic properties in these strong alkaline electrolytes, in agreement with the literature. However, although MnOx/C exhibits high ORR activity in NaOH and KOH media below 1 M (Roche et al., J Phys Chem C 111:1434, 2007), the present study reveals their deactivation in concentrated LiOH or KOH electrolytes because of an insufficient activity of water. The latter is indeed not compatible with a sufficient presence of protons in solution, thereby limiting the necessary proton insertion into the MnOx lattice, a prerequisite for ORR activity (Roche et al., J Phys Chem C 111:1434, 2007). In addition, when LiOH electrolyte is used, another effect penalizes the electrode performances; Li+ ions may insert into the MnOx lattice and stabilize both the Mn atoms at the oxidation state 3 and the oxygen groups at the carbon surface, which prevents their role of redox mediating species and further blocks the catalytic process, eventually yielding increased ORR overpotential.

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Notes

  1. Accurately measuring the surface area of MnOx or MnOx/C catalysts is very difficult, and therefore current densities are usually normalized to the mass of active material in such case.

  2. Nevertheless, effects of the carbon pretreatments (chemical, thermal, etc.) are hardly predictable because of their dependence to various parameters [48].

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Acknowledgments

Financial support from Agence Nationale de la Recherche et de la Technologie (ANRT) is gratefully acknowledged. MC thanks Jiri Vondràk for providing the (Ni)MnOx/C materials and Fabio H. B. Lima for fruitful discussions.

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Authors and Affiliations

  1. Electricité de France, R&D, Laboratoire des matériels électriques, LME, Groupe des batteries et gestionnaires d’énergie, M29, Avenue des Renardières, 77818, Moret-sur-Loing, France

    Florian Moureaux & Philippe Stevens

  2. Laboratoire d’Electrochimie et de Physicochimie des Matériaux et des Interfaces, LEPMI, UMR 5279 CNRS/Grenoble-INP/Université de Savoie/Université Joseph Fourier, 1130 rue de la piscine, BP75, 38402, Saint-Martin-d’Hères Cedex, France

    Florian Moureaux & Marian Chatenet

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Correspondence to Marian Chatenet.

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Appendix

Appendix

The oxygen transport parameters of the electrolyte were measured in the two electrolytes investigated in this study. The data, given in Table 5, were acquired with a Pt rotating ring disk electrode, by following the procedure described by Chatenet et al. [23].

Table 5 Electrolyte parameters measured on a Pt rotating ring disk electrode (T = 25 °C; \( {P_{{{{\mathrm{O}}_2}}}} = 1{0^5}\ \mathrm{Pa} \))
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Moureaux, F., Stevens, P. & Chatenet, M. Effect of Lithium and Potassium Cations on the Electrocatalytic Properties of Carbon and Manganese Oxide Electrocatalysts Towards the Oxygen Reduction Reaction in Concentrated Alkaline Electrolyte. Electrocatalysis 4, 123–133 (2013). https://doi.org/10.1007/s12678-013-0127-4

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