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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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.
This study did not generate any datasets.
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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).
The authors declare no competing interests.
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 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 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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