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Conductive Polymer Grafting Platinum Nanoparticles as Efficient Catalysts for the Oxygen Reduction Reaction: Influence of the Polymer Structure

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Abstract

Pt nanoparicles supported on a carbon powder  Pt-NPs/C were synthesized by a polyol method and modified by grafting of different non-fluorinated and fluorinated proton conducting polymers. In the case of fluorinated polymers, the sulfonyl functions were attached either directly or through spacers (-O-PSA and -S-PSA) to the tetrafluorovinylic groups. Results in three-electrode electrochemical cell showed that the nature and structure of the grafted proton-conducting polymer influenced mass transport in the catalytic film towards the oxygen reduction active sites, the limiting current density in the catalytic film decreasing from ca. 97 mA cm−2 for Pt-NPs/C to ca. 80 mA cm−2 for Pt-NPs-(PSSA)/C and less than 60 mA cm−2 for Pt-NPs-(PTFV-O-PSA)/C and Pt-NPs-(PTFV-S-PSA)/C. This influence was directly linked to the hydrophobic character of the polymers. The importance of the spacer on the electrochemicaly active surface area (ECSA), kinetic current density (jk), and mass activity (MA) at 0.9 V was pointed out. The jk at 0.9 V vs RHE increased from 2.8 to 3.6 mA cm−2 for the nanocomposite catalysts without spacer and with a -O-PSA spacer, respectively. However, the best performance was obtained with Pt-NPs-(PSSA)/C with jk = 8.6 mA cm−2 (Pt-NPs/C leading to 4.6 mA cm−2). Fuel cell tests also showed the influence of the grafted polymer on the water management in cathodes. Maximum power density of ca. 1 W cm−2 at ca. 2.1 A cm−2 was obtained with a Pt-NPS-(Nafion)/C cathode and a Pt-NPs-(PSSA)/C cathode without Nafion and ca. 0.85 W cm−2 with a Pt-NPs-(PTFV-O-PSA)/C cathode. Durability under fuel cell working conditions revealed that the presence of the grafted conducting polymers in the cathode catalytic layer led to comparable electrical performances, but to better stabilities of the fuel cell performances than in the case of a classical Pt-NPs-(25 wt% Nafion)/C cathode: the potential losses at 38 °C were two and four times lower with a Pt-NPs-(PTFV-O-PSA)/C (16 μV h−1) cathode than with Pt-NPs-(PSSA)/C (40 μV h−1) and Pt-NPs-(Nafion)/C (80 μV h−1) cathodes, respectively. At 60 °C, the potential loss with a Pt-NPs-(PTFV-O-PSA)/C cathode remained twice lower than with a Pt-NPs-(Nafion)/C cathode.

New architectures of the active layer of fuel cell electrodes for higher fuel cell performance durability

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Funding

We acknowledge the ADEME (French Environment and Energy Management Agency) for its financial support through the EXALAME project. Some authors (SB and CC) thank the European communities (FEDER) and the “Région Nouvelle Aquitaine” for financial supports.

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Authors and Affiliations

  1. CEA, DAM, Le Ripault, F-37260, Monts, France

    Delphine Dru, Patrick Urchaga, Agathe Frelon, Janick Bigarré & Pierrick Buvat

  2. IC2MP, UMR CNRS No. 7285, Université́ de Poitiers, 86022, Poitiers, France

    Delphine Dru, Stève Baranton & Christophe Coutanceau

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  1. Delphine Dru
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Correspondence to Christophe Coutanceau.

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Dru, D., Urchaga, P., Frelon, A. et al. Conductive Polymer Grafting Platinum Nanoparticles as Efficient Catalysts for the Oxygen Reduction Reaction: Influence of the Polymer Structure. Electrocatalysis 9, 640–651 (2018). https://doi.org/10.1007/s12678-018-0479-x

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