Enhanced Anhydrous Proton Conductivity in Azole Phosphonic Acid Mixtures

Huang, Zitan; Lehmann, Michelle L.; Bhattacharya, Amit; Liu, Yifan; Cooper, Valentino R.; Clément, Raphaële J.; Saito, Tomonori; Hickner, Michael A.; Colby, Ralph H.

doi:10.1021/acsaem.4c01654

Title: Enhanced Anhydrous Proton Conductivity in Azole Phosphonic Acid Mixtures

Journal Article · 18 November 2024 · ACS Applied Energy Materials

DOI: https://doi.org/10.1021/acsaem.4c01654 · OSTI ID:2481206

Huang, Zitan ^[1]; Lehmann, Michelle L. ^[2]; Bhattacharya, Amit ^[3];

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Pennsylvania State Univ., University Park, PA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of California, Santa Barbara, CA (United States)
Michigan State Univ., East Lansing, MI (United States)

Azole molecules are investigated as potential candidates for proton conductors under anhydrous conditions. Since 1,2,3-triazole has the lowest melting point (T_m = 17 °C), it was blended with three phosphonic acid-containing molecules (small molecules with one and two phosphonic acids per molecule and a phosphonic acid polymer) to provide a source of excess protons to enhance the proton conductivity of the blends. Here we study a wide range of compositions in each system to find that these three mixtures show a maximum proton conductivity at moderate doping compositions, approximately 5–10 azole molecules per phosphonic acid group. Using NMR diffusometry, we show that the protons bonded to nitrogen move faster than the protons bonded to carbons of 1,2,3-triazole, suggesting proton hopping between azole proton carriers. Given the high proton conductivity at 90 °C of the best mixtures, in the range of 20–60 mS/cm, this work provides a path forward for future work in anhydrous proton-conducting polymer membranes. Additionally, Raman spectroscopy was used to accurately determine the molar percentage of protonated 1,2,3-triazole. Combining that with the proton diffusion results, we find that the phosphonic acid polymer shows the most proton hopping at low acid content.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Fast and Cooperative Ion Transport in Polymer-Based Materials (FaCT); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2481206

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 23 Vol. 7; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anhydrous proton conductors
azole molecules
fuel cell
phosphonic acid
proton hopping

Title: Enhanced Anhydrous Proton Conductivity in Azole Phosphonic Acid Mixtures

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