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Vacancy Defects and Multilayer Shading in Graphene Monolayers: Enhancing Proton Transport in Centimeter-Sized Direct Methanol Fuel Cells

ACS Applied Materials & Interfaces, vol. 17, pp. 63438–63447

Abstract

High Resolution Image Download MS PowerPoint Slide Proton selectivity of monolayer graphene offers promising opportunities in energy devices. The impermeability of graphene to methanol, on the other hand, offers potential as a membrane in direct methanol fuel cells (DMFCs). The integration of graphene in DMFCs requires samples larger than 1 cm 2 and therefore must be grown via chemical vapor deposition (CVD) instead of using exfoliation. CVD graphene─as opposed to exfoliated flakes─however, contains inherent defects and multilayer patches, both of which could be harnessed to tune the fuel cell performance controllably. Here, we investigated the impact of multilayer patches on the performance of centimeter-scale graphene films in DMFCs. While single-crystalline graphene (SCG) has no multilayer patches, polycrystalline graphene (PCG) can exhibit an areal ratio of multilayer patches up to ∼4%. While multilayer patches are less reactive to plasma etching, the monolayers within SCG and PCG exhibit similar reactivity, enabling precise control over the etching process. These shaded areas of the membrane contribute to higher proton selectivity, likely due to more constrained and controlled defect sites. Our findings indicate that plasma-induced defects yield a proton conductance 10% higher than pristine graphene, and we attribute the enhanced performance of defected PCG to the shading effects provided by the multilayer patches.

Authors 6

  1. Leiden University

    Affiliation as printed

    Leiden Institute of Chemistry, Faculty of Science, Leiden University, Einsteinweg 55, Leiden 2333CC, Netherlands

  2. Peking University · Beijing Graphene Institute · Beijing National Laboratory for Molecular Sciences

    Affiliation as printed

    Beijing Graphene Institute (BGI)

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies

    Peking University

    Beijing Graphene Institute (BGI), Beijing 100095, China

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China

  3. Peking University · Beijing Graphene Institute · Beijing National Laboratory for Molecular Sciences

    Affiliation as printed

    Beijing Graphene Institute (BGI)

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies

    Peking University

    Beijing Graphene Institute (BGI), Beijing 100095, China

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China

  4. Peking University · Beijing Graphene Institute · Beijing National Laboratory for Molecular Sciences

    Affiliation as printed

    Beijing Graphene Institute (BGI)

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies

    Peking University

    Beijing Graphene Institute (BGI), Beijing 100095, China

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China

  5. Peking University · Beijing Graphene Institute · Beijing National Laboratory for Molecular Sciences

    Affiliation as printed

    Beijing Graphene Institute (BGI)

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies

    Peking University

    Beijing Graphene Institute (BGI), Beijing 100095, China

    Center for Nanochemistry, Beijing Science and Engineering Center for Nanocarbons, Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China

  6. Leiden University

    Affiliation as printed

    Leiden Institute of Chemistry, Faculty of Science, Leiden University, Einsteinweg 55, Leiden 2333CC, Netherlands

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References 31