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Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells

Nature Energy volume 7, pages 248–259 (2022)Cite this article

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Abstract

State-of-the-art automotive fuel cells that operate at about 80 °C require large radiators and air intakes to avoid overheating. High-temperature fuel cells that operate above 100 °C under anhydrous conditions provide an ideal solution for heat rejection in heavy-duty vehicle applications. Here we report protonated phosphonic acid electrodes that remarkably improve the performance of high-temperature polymer electrolyte membrane fuel cells. The protonated phosphonic acids comprise tetrafluorostyrene-phosphonic acid and perfluorosulfonic acid polymers, where a perfluorosulfonic acid proton is transferred to the phosphonic acid to enhance the anhydrous proton conduction of fuel cell electrodes. By using this material in fuel cell electrodes, we obtained a fuel cell exhibiting a rated power density of 780 mW cm–2 at 160 °C, with minimal degradation during 2,500 h of operation and 700 thermal cycles from 40 to 160 °C under load.

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Fig. 1: Protonation of phosphonic acid.
Fig. 2: Anhydride formation from phosphonic acids.
Fig. 3: Impact of protonation of phosphonic acid on fuel cell performance.
Fig. 4: H2/air fuel cell performance comparison.
Fig. 5: Performance comparison among different fuel cell technologies.
Fig. 6: Durability of the protonated HT-PEMFC under H2/air conditions.

Data availability

The data supporting the findings of this study are available within the paper, Extended Data and Supplementary Information. Source data are provided with this paper.

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Acknowledgements

PA-PBI samples were provided by E. S. De Castro (Advent Technologies). We thank A. Muenchinger (MPI) and K. D. Kreuer (MPI) for the conductivity data on PWN. This work was supported by the US Department of Energy, Energy Efficiency and Renewable Energy, Fuel Cell Technology Office (L’Innovator program) and Advanced Research Projects Agency-Energy (award number DE-AR0001003). The synthesis of the PWN polymer was developed and supported by the following German National Projects: DFG KE 673/10-1 no. 576968, BMBF 03SF0432B and 03SF0531C. A.S.L. acknowledges support from the KIST internal research program and the National R&D Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2020M3H4A3106354 and 2020M3H4A3106403). Los Alamos National Laboratory is operated by Triad National Security under US Department of Energy Contract Number 89233218CNA000001. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, a wholly owned subsidiary of Honeywell International, for the US Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. I.M. acknowledges access to the computational resources of LANL Institutional Computing Program, which is supported by the US Department of Energy National Nuclear Security Administration under contract 89233218CNA000001, NERSC, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under contract DE-AC02-05CH11231, and CARC, UNM Center for Advanced Research Computing.

Author information

Author notes

  1. These authors contributed equally: Katie H. Lim, Albert S. Lee.

Authors and Affiliations

  1. Materials Synthesis and Integrated Devices Group, Los Alamos National Laboratory, Los Alamos, NM, USA

    Katie H. Lim, Albert S. Lee, Eun Joo Park, Santosh Adhikari, Sandip Maurya, Luis Delfin Manriquez & Yu Seung Kim

  2. Materials Architecturing Research Center, Korea Institute of Science and Technology, Seoul, Republic of Korea

    Albert S. Lee & Jiyoon Jung

  3. Institute of Chemical Process Engineering, University of Stuttgart, Stuttgart, Germany

    Vladimir Atanasov & Jochen Kerres

  4. Chemical Resource Beneficiation Faculty of Natural Sciences, North-West University, Potchefstroom, South Africa

    Jochen Kerres

  5. Forschungszentrum Jülich GmbH, Helmholtz Institute Erlangen-Nürnberg for Renewable Energies, Erlangen, Germany

    Jochen Kerres

  6. Organic Materials Science, Sandia National Laboratories, Albuquerque, NM, USA

    Cy Fujimoto

  7. Department of Chemical and Biological Engineering, Center for Micro-Engineered Materials, The University of New Mexico, Albuquerque, NM, USA

    Ivana Matanovic

  8. Theoretical Division, Los Alamos National Laboratory, Los Alamos, NM, USA

    Ivana Matanovic

  9. Materials Science and Engineering Department, University of Connecticut, Storrs, CT, USA

    Jasna Jankovic

  10. Toyota Research Institute of North America, Ann Arbor, MI, USA

    Zhendong Hu & Hongfei Jia

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Contributions

A.S.L. and Y.S.K. developed the intellectual concept and designed all the experiments of this research. V.A., J.K., S.A. and C.F. prepared the polymeric materials. E.J.P., S.M., L.D.M., J. Jung, Z.H. and H.J. synthesized the model compounds and performed the electrochemical experiments. J. Jankovic performed the TEM and image analyses. K.H.L., S.M. and A.S.L. tested the fuel cells. I.M. performed the DFT calculations. K.H.L., A.S.L. and Y.S.K. analysed all the experimental data and wrote the paper.

Corresponding author

Correspondence to Yu Seung Kim.

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Competing interests

A.S.L. and Y.S.K. filed a US patent application (application no. 17/196283) on 9 March 2021 related to the ionomer composition described in this article. Z.H. and H.J. are employed by Toyota Research Institute of North America. The remaining authors declare no competing interests.

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Extended data

Extended Data Fig. 1 DFT calculations on protonation of PFPA.

(a) Linear regression fit to deprotonation energies using the difference in DFT calculated electronic energy (ΔE) of A−and HA. The ΔE values are calculated using SMD solvation model with water as solvent at the M062X/6-311 + +G(d,p) level. Equation of line is determined as \(pK_a = 0.108 \ast {\Delta}E - 28.2\) with R2 of 0.90 and rms error of 0.2 pKa units. (b) DFT structures that correspond to calculated 31P NMR shifts; M06L/6-311 + G(2d,p) level of theory and (c) Optimized structure of one perfluoroethanesulfonic acid in interaction with three PFPAs.

Source data

Extended Data Fig. 2 EIS characterization of MEA using the Nafion/PWN composite ionomer as a function of IEC of PWN at 0.6 V.

Composite ionomers: Nafion/PWN-0.9, Nafion/PWN-1.8 and Nafion/PWN-3.0 (Nafion content = 0.5). The impedance with frequency range from 1 MHz to 0.1 Hz was measured under H2/O2 conditions at 160 °C and 170 kPa backpressure.

Source data

Extended Data Fig. 3 Proton conductivity of Nafion, PWN, and Nafion/PWN mixture in DMSO (solid content: 5 wt%).

PWN-0, 0.9, 1.3, 1.8 and 3.0. The Nafion content of the ionomer = 0.5. Mean ± s.d. (n = 3) are shown. Compared to the conductivity in NMP, the conductivity of Nafion, PWN, and Nafion/PWN increased in DMSO.

Source data

Extended Data Fig. 4 H2/O2 fuel cell performance of MEAs employing Nafion/PWN-1.8 as a function of Nafion content.

MEA component: QAPOH-PA ion-pair membrane, anode (Pt-Ru/C, 0.5 mgPt cm-2), and cathode (Pt/C, 0.7 mgPt cm-2).

Source data

Extended Data Fig. 5 EIS characterization of MEA using the Nafion, (1:0), protonated phosphonic acid and non-protonated phosphonic acid ionomers.

(a) 0.8 V (b) 0.6 V and (c) 2 A cm-2. Ionomers: Nafion (Nafion content = 1), protonated phosphonic acid ionomer (Nafion content = 0.4), non-protonated phosphonic acid ionomer (Nafion content = 0). The impedance was measured with frequency range from 1 MHz to 0.1 Hz under H2/O2 condition at 160 °C and 170 kPa backpressure.

Source data

Extended Data Fig. 6 Impact of phosphoric acid and phenyl adsorption on ECSA and HOR, ORR activity.

(a) CV scan of MEAs with protonated or non-protonated ionomer. (b) CV scan of Pt/C as a function of the concentration of phosphoric acid. Each electrode (Pt/C) was conditioned in O2 saturated 0.1 M HClO4 solution before transferred into HClO4-H3PO4 mixture solution for ECSA measurement. (c) Effect of phosphoric acid on ECSA. Total concentration of HClO4-H3PO4 was kept the same as 0.5 M for the tests. (d) Effect of pentafluorophenyl phosphonic acid (PPA) on ECSA. Electrolyte for PPA: 0.1 M HClO4 + PPA. (e) HOR mass activity retention of catalysts in presence of phosphoric acid or PPA. Total used for PPA test. Red square: equivalent phenyl concentration of the protonated PtRu/C anode. Blue diamond: equivalent phenyl concentration of the non-protonated PtRu/C anode. (f) ORR mass activity retention of catalysts in presence of phosphoric acid or FPA. Total concentration of HClO4-H3PO4 was kept the same as 0.5 M for the phosphoric acid tests. 0.1 M HClO4 + FPA was used for FPA test. Red square: equivalent phenyl concentration of the protonated Pt/C cathode. Blue diamond: equivalent phenyl concentration of the non-protonated Pt/C cathode.

Source data

Extended Data Fig. 7 H2/air fuel cell performance of Nafion-based LT-PEMFCs at 100 °C as a function of RH.

i-V curve, power density and HFR of Nafion LT-PEMFC at 100 °C and 148 kPa (absolute) backpressure and high H2/air flows (500/500 sccm). Nafion MEA component: Nafion 211 membrane (25 µm thickness), Nafion ionomer, anode and cathode (TEC10E40E, Pt/C, 0.1 mgPt cm-2).

Source data

Extended Data Fig. 8 Effect of cathode catalyst loading on H2/air fuel cell performance.

Cathode catalyst: (a) HiSPEC 9100: Pt 60% on high surface area carbon (Johnson Matthey). (b) TEC10E40E: Pt 40% on high surface area carbon. (c) TEC10E20E: Pt 20% on high surface area carbon. The other MEA components: QAPOH-PA membrane (35 µm thick), anode catalyst (Pt-Ru/C, 0.5 mgPt cm-2), cathode catalyst (Pt/C, 0.1, 0.3, and 0.6 mgPt cm-2), and Nafion/PWN-1.8 ionomer (Nafion content: 0.5). The performance was measured at 160 °C under anhydrous conditions.

Source data

Extended Data Fig. 9 Comparison of H2/air fuel cell performance of different MEAs at 120 °C.

Protonated ionomer-bonded MEA: QAPOH-PA membrane (35 µm thickness), Nafion/ PWN-1.8 ionomer (Nafion content: 0.5), anode (Pt-Ru/C, 0.5 mgPt cm-2), and cathode (Pt/C, 0.3 mgPt cm-2). Commercial PA−PBI: PA-PBI membrane (50 µm thickness), PTFE binder, anode (Pt/C, 1.0 mgPt cm-2), and cathode (Pt-alloy, 0.75 mgPt cm-2). Nafion MEA: Nafion 211 membrane (25 µm thickness), Nafion ionomer, anode (Pt/C, 0.2 mgPt cm-2) and cathode (Pt/C, 0.3 mgPt cm-2).

Source data

Extended Data Fig. 10 Fuel cell performance of the protonated HT-PEMFC at 80 °C.

MEA components: QAPOH-PA membrane, anode catalyst (Pt-Ru/C, 0.5 mgPt cm–2), cathode catalyst (Pt/C, 0.6 mgPt cm–2), and Nafion/PWN-1.8 ionomer (Nafion content: 0.5). The performance was measured under anhydrous conditions.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–9 and Table 1.

Supplementary Data 1

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Lim, K.H., Lee, A.S., Atanasov, V. et al. Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells. Nat Energy 7, 248–259 (2022). https://doi.org/10.1038/s41560-021-00971-x

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