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Fuel cells with an operational range of –20 °C to 200 °C enabled by phosphoric acid-doped intrinsically ultramicroporous membranes

Nature Energy volume 7, pages 153–162 (2022)Cite this article

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Abstract

Conventional proton exchange membrane fuel cells (PEMFCs) operate within narrow temperature ranges. Typically, they are run at either 80‒90 °C using fully humidified perfluorosulfonic acid membranes, or at 140‒180 °C using non-humidified phosphoric acid (PA)-doped membranes, to avoid water condensation-induced PA leaching. However, the ability to function over a broader range of temperature and humidity could simplify heat and water management, thus reducing costs. Here we present PA-doped intrinsically ultramicroporous membranes constructed from rigid, high free volume, Tröger’s base-derived polymers, which allow operation from −20 to 200 °C. Membranes with an average ultramicropore radius of 3.3 Å show a syphoning effect that allows high retention of PA even under highly humidified conditions and present more than three orders of magnitude higher proton conductivity retention than conventional dense PA-doped polybenzimidazole membranes. The resulting PA-doped PEMFCs display 95% peak power density retention after 150 start-up/shut-down cycles at 15 °C and can accomplish over 100 cycles, even at −20 °C.

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Fig. 1: Chemical structures and properties of TB polymers.
Fig. 2: Solid-state 31P NMR spectra of PA-saturated samples.
Fig. 3: Conductivity and PA loss for PA-doped membranes under different conditions.
Fig. 4: i‒V curves, power density and HFR of MEAs without backpressure or external humidification.
Fig. 5: Durability of cell performance.

Data availability

Source data are provided with this paper. The authors declare that the data supporting the findings of this study are available within the paper and Supplementary information. Further data beyond the immediate results presented here are available from the corresponding authors on reasonable.

Code availability

This study did not generate any datasets.

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Acknowledgements

We thank T. Yan and Z. He from Nankai University for the computational study the alkalinity of N atoms. We also thank Y. Li from Soochow University (computational chemistry materials simulation and design) for the molecular dynamics simulation and X. Ma from Tiangong University for the synthesis of Trip-TB polymer. We are grateful to the National Natural Science Foundation of China (grant nos. 21835005 and 52G15023), Science and Technology Major Projects of Shanxi Province of China (grant no. 20181102019), the Hundred Talents Program of the Shanxi Province and the autonomous research project of SKLCC (grant no. 2020BWZ001).

Author information

Author notes

  1. These authors contributed equally: Hongying Tang, Kang Geng.

Authors and Affiliations

  1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, China

    Hongying Tang, Kang Geng, Lei Wu & Nanwen Li

  2. Tianjin Key Laboratory of Water Resources and Environment, Tianjin Normal University, Tianjin, China

    Hongying Tang

  3. Hubei Nuclear Solid Physics Key Laboratory, Department of Physics, Wuhan University, Wuhan, China

    Junjie Liu & Zhiquan Chen

  4. Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    Wei You

  5. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, China

    Feng Yan

  6. State Key Laboratory of Engines, Tianjin University, Tianjin, China

    Michael D. Guiver

  7. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, China

    Michael D. Guiver

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Contributions

H.T. and K.G. designed the experiments, performed the polymer characterization, MEA fabrication, testing experiments of fuel cells and data collection. F.Y. helped with data collection. L.W. aided in the synthesis of TB polymers. J.L. and Z.C. measured the PALS of the membranes. W.Y. and M.D.G. supervised and guided the work. N.L. developed the concept and supervised the research. H.T., W.Y., N.L. and M.D.G. analysed all experimental data and wrote the paper.

Corresponding authors

Correspondence to Wei You, Michael D. Guiver or Nanwen Li.

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Competing interests

The authors declare no competing interests.

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Peer review information Nature Energy thanks Dirk Henkensmeier and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–14 and Tables 1–4.

Supplementary Data 1

Calculated Cartesian coordinates for TB polymers.

Supplementary Data 2

Source Data for Supplementary Figs. 7 and 8 and Table 3.

Source data

Source Data Fig. 1

Chemical structures and properties of TB polymers.

Source Data Fig. 2

Solid-state 31P NMR spectra of PA-saturated samples.

Source Data Fig. 3

Conductivity and PA loss for PA-doped membranes under different conditions.

Source Data Fig. 4

i‒V curves, power density and HFR of MEAs without backpressure or external humidification.

Source Data Fig. 5

Figure 5: durability of cell performance.

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Tang, H., Geng, K., Wu, L. et al. Fuel cells with an operational range of –20 °C to 200 °C enabled by phosphoric acid-doped intrinsically ultramicroporous membranes. Nat Energy 7, 153–162 (2022). https://doi.org/10.1038/s41560-021-00956-w

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