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The role of ionic blockades in controlling the efficiency of energy recovery in forward bias bipolar membranes

Nature Energy volume 8, pages 1405–1416 (2023)Cite this article

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Abstract

Limited understanding exists about the operation of bipolar membranes (BPMs) in forward bias to convert protonic gradients into electrical work, despite their emerging role in many electrochemical devices. In these device contexts, the BPM is typically exposed to complex electrolyte mixtures, but their impact on polarization remains poorly understood. Here we develop a mechanistic model explaining the forward bias polarization behaviour of BPMs in mixed electrolytes with different acidities/basicities. This model invokes that weak acids/bases accumulate in the BPM and impose an ionic blockade that inhibits the recombination of stronger acids/bases, resulting in a substantial neutralization overpotential. We demonstrate the utility of our model for fuel cells and redox flow batteries and introduce two materials design strategies for mitigating this inhibition. Lastly, we apply our findings to enhance the energy efficiency of carbonate management in CO2 electrolysers. This work highlights how non-equilibrium local environments at membrane–membrane interfaces can define the efficiency of protonic-to-electrical energy conversion.

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Fig. 1: Existing understanding of ionic processes in BPMs.
Fig. 2: Electrochemical characterization of BPMs containing KOH–KOAc mixtures.
Fig. 3: Electrochemical characterization of BPM cells with varied electrolyte properties.
Fig. 4: Concentration and pH profiles across BPMs as a function of polarization region.
Fig. 5: Electrochemical characterization of BPMs with varying concentrations of CO2 dissolved in KOH.
Fig. 6: Materials design strategies to raise limiting current densities.
Fig. 7: Comparing pH swing and forward bias BPM CO2 electrolysers.
Fig. 8: Modes of operation for forward bias BPM CO2 electrolysers.

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The data that support the findings of this study are included in the published article and its Supplementary Information. Source data are provided with this paper.

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Acknowledgements

We thank the entire Surendranath Lab for the enriching discussions and their support. This work was supported by the Department of Energy (DOE) under award number DE-SC0021634, which also supported A.T.C. and E.R.S. This work made use of the MRSEC Shared Experimental Facilities at MIT, which is supported by the National Science Foundation under award number DMR-1419807. W.L.T. is supported by a National Science Scholarship awarded by the Agency for Science, Technology and Research (A*STAR), Singapore. H.Q.D. is supported by Undergraduate Research Opportunities Program (UROP) awards from the MIT UROP office and the MIT Energy Initiative. E.R.S. is also supported in part by a Postdoctoral Fellowship awarded by the Natural Sciences and Engineering Research Council of Canada (NSERC).

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  1. These authors contributed equally: Wei Lun Toh, Hieu Q. Dinh.

Authors and Affiliations

  1. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA

    Wei Lun Toh, Hieu Q. Dinh, An T. Chu, Ethan R. Sauvé & Yogesh Surendranath

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W.L.T., H.Q.D. and Y.S. conceptualized the project. W.L.T., H.Q.D., A.T.C. and E.R.S. conducted experiments. W.L.T., H.Q.D. and Y.S. wrote and edited the manuscript.

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Correspondence to Yogesh Surendranath.

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Toh, W.L., Dinh, H.Q., Chu, A.T. et al. The role of ionic blockades in controlling the efficiency of energy recovery in forward bias bipolar membranes. Nat Energy 8, 1405–1416 (2023). https://doi.org/10.1038/s41560-023-01404-7

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