Volume 9 Issue 11
Nov.  2024
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Article Navigation >  Green Energy&Environment  > 2024  >  9(11): 1734-1746
Xu Li, Dongwei Zhang, Si Chen, Yingzhao Geng, Yong Liu, Libing Qian, Xi Chen, Jingjing Li, Pengfei Fang, Chunqing He. Outstanding proton conductivity over wide temperature and humidity ranges and enhanced mechanical, thermal stabilities for surface-modified MIL-101-Cr-NH2/Nafion composite membranes. Green Energy&Environment, 2024, 9(11): 1734-1746. doi: 10.1016/j.gee.2023.10.007
Citation: Xu Li, Dongwei Zhang, Si Chen, Yingzhao Geng, Yong Liu, Libing Qian, Xi Chen, Jingjing Li, Pengfei Fang, Chunqing He. Outstanding proton conductivity over wide temperature and humidity ranges and enhanced mechanical, thermal stabilities for surface-modified MIL-101-Cr-NH2/Nafion composite membranes. Green Energy&Environment, 2024, 9(11): 1734-1746. doi: 10.1016/j.gee.2023.10.007
shu

Outstanding proton conductivity over wide temperature and humidity ranges and enhanced mechanical, thermal stabilities for surface-modified MIL-101-Cr-NH2/Nafion composite membranes

doi: 10.1016/j.gee.2023.10.007

  • a. Key Laboratory of Nuclear Solid-State Physics Hubei Province, School of Physics and Technology, Wuhan University, Wuhan, 430072, China;

  • b. School of Nuclear Technology and Chemistry & Biology, Hubei University of Science and Technology, Xianning, 437100, China;

  • c. Guangdong Key Laboratory for Hydrogen Energy Technologies, School of Materials Science and Hydrogen Energy, Foshan University, Foshan, 528000, China

Funds:

This work was supported by the National Natural Science Foundation of China (NSFC) (Nos. 12075172, 12375288, 12205089, and 12105048), National Key R&D Program of China (Grant No. 2019YFA0210003), Guangdong Basic and Applied Basic Research Foundation (No.2020A1515110817). We thank the Core Facility of Wuhan University for supporting the characterization and analysis of the materials. Dr. Y. Ma was appreciated for the AFM measurement.

  • Received date 21 September 2023, Accepted date 30 October 2023, RevRecd date 22 October 2023, Publish date 31 October 2023,
    Abstract
  • High-performance proton exchange membranes are of great importance for fuel cells. Here, we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH2 (PCP-MCN), a kind of hybrid metal-organic framework, which exhibits a superior proton conductivity. PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes. Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated. Significant enhancement in proton conduction for PCP-MCN around 55 ℃ is interestingly found due to the thermal motion of the PCP molecular chains. Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains, i.e., the formation of substantial acid-base pairs (-SO3-···+H-NH-), which further improves compatibility between additive and Nafion matrix. At the same humidity and temperature condition, the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion. Proton conductivity (σ) over wide ranges of humidities (30 - 100% RH at 25 ℃) and temperatures (30 - 98 ℃ at 100% RH) for prepared membranes is measured. The σ in PCP-MCN/Nafion composite membranes is remarkably enhanced, i.e. 0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98 ℃ and 100% RH, because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation-deprotonation processes. The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN. In particular, when 3 wt.% PCP-MCN was added to Nafion, the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480, 1.098 W/cm2 under 40% RH, 100% RH at 60 ℃, respectively, guaranteeing it to be a promising proton exchange membrane.

     

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