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Hydrogen Depolarized Anodes with Liquid Anolyte: Proof of Concept

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Abstract

The development of depolarized electrodes may be considered as an improvement on economic and environmental aspects for the chemistry industry. In this regard, using a hydrogen depolarized anode (HDA) to produce protons from hydrogen oxidation could be coupled with a membrane process to concentrate valuable products. In particular, the actual standard anode used in a recent industrial lithium hydroxide electromembrane process could be replaced by an HDA. This change could lower the electric consumption and production costs. However, this evolution requires the development of an electro cell properly adaptable to the current process. In this study, we propose a proof of concept for this technology with a dedicated installation using a sulfuric acid electrolyte. Based on materials commonly used in the field of fuel cells, which share some fundamental aspects, a general understanding of hydrogen depolarized anodes will be presented. The goal is to develop an electro cell that allows anode monitoring to understand ADH operation and to compare different conditions. In this purpose, different measurements are combined to measure aspects of the ADH such as resistance, mass transfer, and kinetic overpotentials. The proposed architecture can successfully sustain the reaction at 4 kA m−1 with several mV overpotentials. But after several 10-h periods, anode operation deteriorates until reaction failure. The impact of water through the anode is identified as an important parameter to ensure long-term stability. The results obtained in this study are a first step in hydrogen depolarized anode development; they confirm the interest in this technology and identify various improvement pathways to continue its progress.

Graphical abstract

Development of a dedicated electrochemical cell allows testing the ability of a hydrogen depolarized anode to convert hydrogen to protons. The use of materials inspired by fuel cell technology was successfully adapted to a hydrogen depolarized anode. Water migration appears as a key factor, and catalytic layer flooding has to be controlled to prevent cell failure.

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References

  1. I. Moussallem, J. Jörissen, U. Kunz, S. Pinnow, T. Turek, Chlor-alkali electrolysis with oxygen depolarized cathodes: history, present status and future prospects. J. Appl. Electrochem. 38, 1177–1194 (2008)

    Article  CAS  Google Scholar 

  2. J. Clarence, A. Butler, Brine electrolysis, US Patent No. 2681884 (1950)

  3. W. Juda, Electrochemical conversion of electrolyte solutions, US Patent No. 3124520 (1959)

  4. W. Vielstich, Zur Energie-Ersparnis bei der Chloralkali-Elektrolyse mit Hilfe einer reversiblen Wasserstoff-Abscheidungs- oder Sauerstof-Lösungselektrode als Hauptkathode. Chem. Ing. Tech. 34, 346–349 (1962)

    Article  CAS  Google Scholar 

  5. G. Gritzner, Operation of a cation exchange membrane electrolytic cell for producing chlorine including feeding an oxidizing gas having a regulated moisture content to the cathode, US Patent No. 4035254 (1973)

  6. E. Yeager, P. Bindra, Sauerstoff-Verzehrkathoden für die Chloralkali-Elektrolyse. Chem. Ing. Tech. 52, 384–391 (1980)

    Article  CAS  Google Scholar 

  7. A. Tenney, A. Pavone, Bayer-ThyssenKrupp ODC (oxygen depolarized cathode) Chlor-Alkali Technology. IHS CHEMICAL Process Economics Program Review 2015–02, (2015)

  8. J. Jung, S. Postels, A. Bardow, Cleaner chlorine production using oxygen depolarized cathodes? A life cycle assessment. J. Clean Prod. 80, 46–56 (2014)

    Article  CAS  Google Scholar 

  9. O.Z. Sharaf, M.F. Orhan, An overview of fuel cell technology: fundamentals and applications. Renew. Sustain. Energy Rev. 32, 810–853 (2014)

    Article  CAS  Google Scholar 

  10. P. Symons, J.D. Genders, D. Bar, M.E. Langevin, G. Bourassa, J.F. Magnan, G. Pearse, Processes for preparing lithium hydroxide - CA2905197, Canada (2015)

  11. G. Bourassa, G. Pearse, S.C. Mackie, M. Gladkovas, P. Symons, J. D. Genders, J.F. Magnan, Processes for preparing lithium hydroxide - US20170342573A1, USA (2017)

  12. K. Fishel, G. Qian, G. Eisman, B.C. Benicewicz, Electrochemical hydrogen pumping in high temperature polymer electrolyte membrane fuel cells: approaches, status, and perspectives (Springer International Publishing, Cham, 2016)

    Google Scholar 

  13. H. Li, K. Lee, J. Zhang, Electrocatalytic H2 oxidation reaction in PEM fuel cell electrocatalysts and catalyst layers: fundamentals and applications (Springer, London, London, 2008)

    Google Scholar 

  14. T. Wang, H. Xie, M. Chen, A. D’Aloia, J. Cho, G. Wu, Q. Li, Precious metal-free approach to hydrogen electrocatalysis for energy conversion: from mechanism understanding to catalyst design. Nano Energy 42, 69–89 (2017)

    Article  Google Scholar 

  15. N. Yuan, Q. Jiang, J. Li, J. Tang, A review on non-noble metal based electrocatalysis for the oxygen evolution reaction. Arab. J. Chem. 13, 4294–4309 (2019)

    Article  Google Scholar 

  16. J.-H. Wee, K.-Y. Lee, S.H. Kim, Fabrication methods for low-Pt-loading electrocatalysts in proton exchange membrane fuel cell systems. J. Power Sources 165, 667–677 (2007)

    Article  CAS  Google Scholar 

  17. N.M. Marković, P.N. Ross, Surface science studies of model fuel cell electrocatalysts. Surf. Sci. Rep. 45, 117–229 (2002)

    Article  Google Scholar 

  18. M.S. Wilson, J.A. Valerio, S. Gottesfeld, Low platinum loading electrodes for polymer electrolyte fuel cells fabricated using thermoplastic ionomers. Electrochim. Acta 40, 355–363 (1995)

    Article  CAS  Google Scholar 

  19. X. Cheng, B. Yi, M. Han, J. Zhang, Y. Qiao, J. Yu, Investigation of platinum utilization and morphology in catalyst layer of polymer electrolyte fuel cells. J. Power Sources 79, 75–81 (1999)

    Article  CAS  Google Scholar 

  20. L. Xiong, A. Manthiram, High performance membrane-electrode assemblies with ultra-low Pt loading for proton exchange membrane fuel cells. Electrochim. Acta 50, 3200–3204 (2005)

    Article  CAS  Google Scholar 

  21. A. Ganesan, M. Narayanasamy, Ultra-low loading of platinum in proton exchange membrane-based fuel cells: a brief review. Mater. Renew. Sustain. Energy 8, 18 (2019)

    Article  Google Scholar 

  22. R. O’Hayre, D.M. Barnett, F.B. Prinz, The triple phase boundary: a mathematical model and experimental investigations for fuel cells. J. Electrochem. Soc. 152, A439–A444 (2005)

    Article  Google Scholar 

  23. B.C.H. Steele, Material science and engineering: the enabling technology for the commercialisation of fuel cell systems. J. Mater. Sci. 36, 1053–1068 (2001)

    Article  CAS  Google Scholar 

  24. F. Hine, K. Murakami, Bubble effects on the solution IR drop in a vertical electrolyzer under free and forced convection. J. Electrochem. Soc. 127, 292–297 (1980)

    Article  CAS  Google Scholar 

  25. D.E. Gray, American Institute of Physics Handbook (McGraw-Hill Book Company Inc., New York, 1957)

    Book  Google Scholar 

  26. K. Jiao, X. Li, Water transport in polymer electrolyte membrane fuel cells. Prog. Energy Combust. Sci. 37, 221–291 (2011)

    Article  CAS  Google Scholar 

  27. M. Ji, Z. Wei, A review of water management in polymer electrolyte membrane fuel cells. Energies 2, 1057–1106 (2009)

    Article  CAS  Google Scholar 

  28. T. Romero, W. Mérida, Water transport in liquid and vapour equilibrated Nafion™ membranes. J. Membr. Sci. 338, 135–144 (2009)

    Article  CAS  Google Scholar 

  29. M. Adachi, T. Romero, T. Navessin, Z. Xie, Z. Shi, W. Mérida, S. Holdcroft, Water permeation through catalyst-coated membranes. Electrochem. Solid-State Lett. 13, B51–B54 (2010)

    Article  CAS  Google Scholar 

  30. Q. Yan, H. Toghiani, J. Wu, Investigation of water transport through membrane in a PEM fuel cell by water balance experiments. J. Power Sources 158, 316–325 (2006)

    Article  CAS  Google Scholar 

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Funding

The authors received financial support from the Fonds de recherche du Québec—Nature et technologies (FRQNT). Nicolas Sacré also received post-doctoral grant from the Mitacs and Nemaska Lithium.

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Correspondence to Régis Chenitz.

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Sacré, N., Faral, M., Chenitz, R. et al. Hydrogen Depolarized Anodes with Liquid Anolyte: Proof of Concept. Electrocatalysis 13, 139–153 (2022). https://doi.org/10.1007/s12678-021-00700-8

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