Next generation anion-exchange membranes (AEM) with covalently-bound antiradical functions for enhanced durability

Lead Research Organisation: University of Surrey
Department Name: Chemistry

Abstract

The prime motivation in the development of anion-exchange membrane-(AEM)-based fuel cells (AEMFC) and alkaline water electrolysers (AEM-AWE), that use (generate electricity) and produce sustainable hydrogen respectively, is the potential to minimise the use of precious metal electrocatalysts (cf. proton-exchange membrane equivalents); this will reduce costs and lead to systems involving only earth abundant elements (ensures sustainability). Additionally, AEM-AWEs use low-concentration aqueous-alkali or pure-water feeds (cf. traditional non-AEM alkaline water electrolysers), eliminating the need to handle large quantities of highly caustic solution (that comes with significant environmental implications related to leakage and disposal).

The AEMFCs will initially be targeted in the backup power stationary sector (including for telecoms) to replace diesel generators with the added consumer convenience of reduced noise and local emissions of pollutants: the current diesel generation market supplies 200 GW of global power demand (valued at £9B in 2015). The global hydrogen electrolyser market is estimated to register a compound annual growth rate of 7.2% between 2018-28 (market expected to reach US$426.3M by 2028), with application in the transport segment expected to grow at a significant pace in Western Europe ["Hydrogen Electrolyzer Market: Alkaline Electrolyzer Expected to Remain Dominant Product Type Through 2028: Global Industry Analysis 2013-17 and Opportunity Assessment 2018-28", Future market insights report, 2019].

The applicants are world-leaders in the development of alkaline polymer electrolyte materials (membranes and powdered forms, the latter for use in electrode manufacture), especially radiation-grafted types. Mechanically robust, alkali stable, and high performance (high conductivity, high water transport) materials have been demonstrated for use in both AEMFCs and AEM-AWEs (temperatures up to 80 degC). The recent improvements in alkali stability means that oxidative-radical degradation mechanisms become relatively significant and now need to be a research focus. The focus of this project is to develop two classes of AEM with further enhanced chemical stabilities (both alkali and radical-oxidative), but where mechanical, ion-transport and water transport properties are not sacrificed: (1) next generation radiation-grafted AEMs (RG-AEM) and (2) new dimensionally-stable, mechanically-strong pore-filled AEMs (PF-AEM).

Firstly, the focus will be on the co-incorporation of vinyl-phenolic components into RG-AEMs, where such covalently-bound phenolic components can act as radical traps to enhance radical-oxidative stabilities. Secondly, our prior RG-AEM research has also identified several new advanced monomers (such as the 3-vinylbenzyl chloride) that can form RG-AEMs with enhanced alkali stabilities but, unfortunately, poor ion conductivities and water transport properties (as such monomers cannot be made to radiation-graft at adequate levels, due to the crude radical-based nature of such grafting). Hence, these advanced monomers will be used to make PF-AEMs, which can be fabricated using alternative polymerisation methods (e.g. cationic or advanced controlled-radical polymerisation). Thirdly, co-incorporation of vinyl-phenolic monomers will also be possible with these new PF-AEMs to produce materials with maximised chemical and mechanical stabilities.

The RG-AEMs and PF-AEMs will be evaluated in both AEMFCs and AEM-AWEs, to maximise the commercialisation opportunities. This will heavily involve our industrial project partners: AFC Energy (Dunsfold, Surrey) will assist with translating the materials developments into pilot scale AEMFC demonstrator systems, using their fuel cell component integration knowhow and IP (for the backup power sector). PV3 Technologies (Cornwall) will assist with AEM-AWE developments by materials exchange and evaluation and scale-up of AEM-AWE technology in their facilities.

Planned Impact

The development of economic and sustainable technologies for energy conversion and storage is acknowledged to be one of the major milestones that will mitigate climate change and reduce our reliance on fossil fuels. The major advantage of using Anion Exchange Membranes (AEMs) in sustainable hydrogen utilising and generating systems is that they facilitate the use of a wide range of non-precious-metal (potentially Critical Raw Material-[CRM]-free) catalysts, helping to significantly lower costs and improve sustainability.

The research is timely as it responds to the use of renewable electricity generation and the mismatch between generation and use in accord with the UK renewable energy strategy of 15% renewable electricity by 2020. The government commitment to reduce emissions is evident from the recent publication of the Clean Grow Strategy. Energy security involving a diverse and resilient energy mix is at the centre of the document. The UK Industrial Strategy prioritises materials innovations, technologies of tomorrow for more convenient, carbon-friendly living, and innovation drives for affordable and clean energy. In 2016, Materials for Energy Applications was marked as a grow area by EPSRC (balancing capability). However, excluding strategic investments (Faraday and Henry Royce Institutes), there has only been a relatively small increase in the size of this research area since then. The proposed project is in full alignment with all these priorities.

Success in this project through improving the stability of AEMs will represent the required breakthrough, leading to a new era of clean power storage and generation. Our project will have wide-ranging impacts across society, academia, and industry and over a broad range of technologies such as energy conversion and storage (water and carbon dioxide electrolysers, fuel cells, metal air batteries and redox flow batteries) as well as water treatment (electrodialysis and forward osmosis). We have identified two key hydrogen technologies as our focus to demonstrate devices stability and cost savings: solid-state AEM-based alkaline water electrolysers (AEM-AWE) and AEM-based hydrogen fuel cells (AEMFC). To maximise the impact of the project and ensure that the developed materials are tested/validated in commercial configurations, we have included leading UK industrial partners, one for each application (see letters of support). A key impact activity is to embed the postdocs into these companies for 6 months at the end of the project to ensure they are exposed to industrial environments that are related to their project and the specific materials they produced. Exploitation of the potential commercial outputs of the research will be managed by the Enterprise Teams at Newcastle (NCL) and Surrey (SUR), both with extensive experience of successfully negotiating contracts in areas such as collaboration, confidentiality, material transfer and licensing.

An equally important impact is the training of researchers in AEM-related areas to facilitate the industry uptake of this technology through supplying the required skilled workforce. Since this project addresses the challenges of climate change and energy conversion, of significant interest to large sections of the general public, politicians, and industry, there will be many opportunities to communicate our science to these stakeholders. Engagement will be undertaken by the PI, Co-Is, and PDRAs via school lectures, open days, and presentations to relevant UK meetings and trade shows.

The project will help maintain a unique world leading research activity in polymer membrane-based (especially AEMs) energy systems and will provide competitive edge for hydrogen applications for power generation in the mobile, stationary, and auxiliary power sectors. Our long-term vision is to be able to use the same materials in both AEMFCs and AEM-AWEs, to facilitate commercialisation and the use of hydrogen as an energy storage vector.
 
Description Development of radiation-grafted anion-exchange membranes (RG-AEM) - elucidated:
(1) How to introduce ionic covalent crosslinking into trimethylammonium-type RG-AEMs.
(2) How to incorporate ionic-crosslinking + antiradical protection into RG-AEMs.
(3) Some very important lab knowhow regarding consistent radiation grafting and consistent fabrication of homogeneous RG-AEMs.
(4) The important of nanomorphology of RG-AEMs on ion and water transport.
(5) RG-AEMs can have surprisingly high thermal stabilities (60 - 120 degC) when kept hydrated.
Exploitation Route Potential pathways for scaled-up fabrication of lower swelling RG-AEMs with enhanced stability (both chemically and mechanically) identified for potential higher TRL (3+) projects with interested commercial stakeholders.
Initial attempts at this (BEIS low carbon bid and EPSRC prosperity partnership bid) were unsuccessful but further efforts will be made. New collaborations formed to allow for initial work to aid acquisition of funding for more formalised joint work.
Sectors Chemicals,Energy,Environment

 
Title DATESET (CC-BY): Influence of headgroups in ETFE-based radiation-grafted anion exchange membranes for CO2 electrolysis 
Description Raw data packs behind Figure 2 and Table 1 of the linked paper: Table 1 in Microsoft Excel (.xlsx) format. Figure 2 in raw Renishaw spectra files and .txt format 
Type Of Material Database/Collection of data 
Year Produced 2023 
Provided To Others? Yes  
URL https://figshare.com/articles/dataset/DATESET_CC-BY_Influence_of_headgroups_in_ETFE-based_radiation-...
 
Title DATESET (CC-BY): Influence of headgroups in ETFE-based radiation-grafted anion exchange membranes for CO2 electrolysis 
Description Raw data packs behind Figure 2 and Table 1 of the linked paper: Table 1 in Microsoft Excel (.xlsx) format. Figure 2 in raw Renishaw spectra files and .txt format 
Type Of Material Database/Collection of data 
Year Produced 2023 
Provided To Others? Yes  
URL https://figshare.com/articles/dataset/DATESET_CC-BY_Influence_of_headgroups_in_ETFE-based_radiation-...
 
Description Collaboration with ICCOM at CNR (Italy) 
Organisation National Research Council
Country Italy 
Sector Public 
PI Contribution Supplied anion-exchange membranes and ionomer powders to ICCOM
Collaborator Contribution Supply of anode and cathode catalysts (developed at ICCOM) to test in Surrey Alkali Membrane Fuel Cells
Impact Led to a Royal Society - CNR International Exchange programme grant award in Jan 2018 (grant IES\R3\170134). Joint papers published: J. J. Ogada, A. K. Ipadeola, P. V. Mwonga, A. B. Haruna, F. Nichols, S. Chen, H. A. Miller, M. V. Pagliaro, F. Vizza, J. R. Varcoe, D. Motta Meira, D. M. Wamwangi, K. I. Ozoemena, "CeO2 Modulates the Electronic States of a Palladium Onion-Like Carbon Interface into a Highly Active and Durable Electrocatalyst for Hydrogen Oxidation in Anion-Exchange-Membrane Fuel Cells", ACS Catalysis, 12, 7014 (2022). R. Ren, X. Wang, H. Chen, H. A. Miller, I. Salam, J. R. Varcoe, L. Wu, Y. Chen, H.-G. Liao, E. Liu, F. Bartoli, F. Vizza, Q. Jia, Q. He, "Reshaping the Cathodic Catalyst Layer for Anion Exchange Membrane Fuel Cells: From Heterogeneous Catalysis to Homogeneous Catalysis", Angew. Chem. Int. Ed., 60, 4049 (2021). H. A. Miller, M. V. Pagliaro, M. Bellini, F. Bartoli, L. Wang, I. Salam, J. R. Varcoe, F. Vizza, "Integration of a Pd-CeO2/C Anode with Pt and Pt-Free Cathode Catalysts in High Power Density Anion Exchange Membrane Fuel Cells", ACS Appl. Energy Mater., 3, 10209 (2020). M. Bellini, M. V. Pagliaro, A. Lenarda, P. Fornasiero, M. Marelli, C. Evangelisti, M. Innocenti, Q. Jia, S. Mukerjee, J. Jankovic, L. Wang, J. R. Varcoe, C. B. Krishnamurthy, I. Grinberg, E. Davydova, D. R. Dekel, H. A. Miller, F. Vizza, "Palladium-Ceria Catalysts with Enhanced Alkaline Hydrogen Oxidation Activity for Anion Exchange Membrane Fuel Cells", ACS Appl. Energy Mater., 2, 4999 (2019). R Ren, S Zhang, HA Miller, F Vizza, JR Varcoe, Q He, "Facile preparation of novel cardo Poly (oxindolebiphenylylene) with pendent quaternary ammonium by superacid-catalysed polyhydroxyalkylation reaction for anion exchange membranes", Journal of Membrane Science, 591, 117320 (2019). L. Wang, M. Bellini, H. A. Miller, J. R. Varcoe, "A high conductivity ultrathin anion-exchange membrane with 500+ h alkali stability for use in alkaline membrane fuel cells that can achieve 2 W per square cm at 80 degC", J. Mater. Chem. A, 6, 15404 (2018). Research exchanges 2018-2022.
Start Year 2017
 
Description Collaboration with Prof Dekel (Technion) 
Organisation Technion - Israel Institute of Technology
Department The Wolfson Department of Chemical Engineering
Country Israel 
Sector Academic/University 
PI Contribution Supply of anion-exchange membranes and ionomer powders to Technion.
Collaborator Contribution Testing of Surrey materials in Technion systems (including humidity controlled degradation set-up).
Impact Letter of support for EPSRC grant EP/X032345/1 (awaiting referee comments). Joint papers published: S. Willdorf-Cohen, A. Zhegur-Khais, J. Ponce-González, S. Bsoul-Haj, J. R. Varcoe, C. E. Diesendruck, D. R. Dekel, "Alkaline Stability of Anion-Exchange Membranes", ACS Appl. Energy Mater., 6, 1085 (2023). K. Aggarwal, N. Gjineci, A. Kaushansky, S. Bsoul, J. C. Douglin, S. Li, I. Salam, S. Aharonovich, J. R. Varcoe, D. R. Dekel, C. E. Diesendruck, "Isoindolinium Groups as Stable Anion Conductors for Anion- Exchange Membrane Fuel Cells and Electrolyzers", ACS Mater. Au, 2, 367 (2022). S. Haj-Bsoul, J. R. Varcoe, D. R. Dekel, "Measuring the alkaline stability of anion-exchange membranes", J. Electroanal. Chem., 908, 116112 (2022). J. C. Douglin, R. K. Singh, S. Haj-Bsoul, S. Li, J. Biemolt, N. Yan, J. R. Varcoe, G. Rothenburg, D. R. Dekel, "A high-temperature anion-exchange membrane fuel cell with a critical raw material-free cathode",Chem. Eng. J. Adv., 8, 100153 (2021). J. C. Douglin, J. R. Varcoe, D. R. Dekel, "A high-temperature anion-exchange membrane fuel cell", J. Power Sources Adv., 5, 100023 (2020). J. Muller, A. Zhegur, U. Krewer, J. R. Varcoe, D. R. Dekel, "A practical ex-situ technique to measure the chemical stability of anion-exchange membranes under conditions simulating fuel cell environment", ACS Mater. Lett., 2, 168 (2020). M. Bellini, M. V. Pagliaro, A. Lenarda, P. Fornasiero, M. Marelli, C. Evangelisti, M. Innocenti, Q. Jia, S. Mukerjee, J. Jankovic, L. Wang, J. R. Varcoe, C. B. Krishnamurthy, I. Grinberg, E. Davydova, D. R. Dekel, H. A. Miller, F. Vizza, "Palladium-Ceria Catalysts with Enhanced Alkaline Hydrogen Oxidation Activity for Anion Exchange Membrane Fuel Cells", ACS Appl. Energy Mater., 2, 4999 (2019). Y. Zheng, U. Ash, R. P. Pandey, A. G. Ozioko, J. Ponce-González, M. Handl, T. Weissbach, J. R. Varcoe, S. Holdcroft, M. W. Liberatore, R. Hiesgen, D. R. Dekel, "Water Uptake Study of Anion Exchange Membranes", Macromolecules, 51, 3264 (2018).
Start Year 2016
 
Description Elisabete Santiago FAPESP 
Organisation Institute of Nuclear and Energy Research (IPEN)
Country Brazil 
Sector Academic/University 
PI Contribution Hosted Dr Elisabete Santiago as visiting postdoc for 1 year research visit at Surrey (Department of Chemistry). Joint Surrey-IPEN (EPSRC-FAPESP) bid submitted 9th Sept 2022 (EPSRC EP/X032345/1): awaiting referee comments.
Collaborator Contribution FAPESP provided the funds to allow the research visit.
Impact Paper published: A. L. Gonçalves Biancolli, D. Herranz, L. Wang, G. Stehlikova, R. Bance-Soualhi, J. Ponce-Gonzalez, P. Ocon, E. A. Ticianelli, D. K. Whelligan, J. R. Varcoe, E. I. Santiago, "ETFE-based anion-exchange membrane ionomer powders for alkaline membrane fuel cells: a first performance comparison of head-group chemistry", J. Mater. Chem. A, 6, 24330 (2018).
Start Year 2016
 
Description International partner of ARC Centre of Excellence for Green Electrochemical Transformation of Carbon Dioxide - GetCO2 (led by Uni of Queensland, Austrial) 
Organisation University of Queensland
Country Australia 
Sector Academic/University 
PI Contribution Letter of support for successful ARC Centre of Excellence for Green Electrochemical Transformation of Carbon Dioxide (GetCO2) bid Plan for materials and researcher exchanges, joint papers etc.
Collaborator Contribution Plan for materials and researcher exchanges, joint papers etc.
Impact None atm
Start Year 2022
 
Description Letter of support for Lorenz Gubler (Paul Scherrer Institute, Switzerland) 
Organisation Paul Scherrer Institute
Country Switzerland 
Sector Academic/University 
PI Contribution Letter of support for Lorenz Gubler bid to the Swiss National Science Foundation (SNSF). Envisage materials exchanges and joint testing (for radical stability) for joint future papers.
Collaborator Contribution Future joint testing of materials.
Impact Joint papers envisaged.
Start Year 2022
 
Description NDA with INEOS Electrochemical Solutions (IES, Runcorn, UK) 
Organisation INEOS
Country United Kingdom 
Sector Private 
PI Contribution Various meeting and co-authorship of an EPSRC prosperity partnership (PP) bid (EP/X000850/1, unsuccessful). NDA and MTA agreed for supply of materials to INEOS to establish a working relationship to move towards a future PP bid.
Collaborator Contribution Various meeting and co-authorship of an EPSRC prosperity partnership bid. Letter of support for EPSRC application EP/X032345/1 (awaiting referee comments). Discussions of INEOS Support for future bid to University of Surrey Impact Acceleration Account (EP/X525832/1) for anion-exchange membrane scale-up.
Impact EPSRC prosperity partnership (PP) bid (EP/X000850/1, unsuccessful).
Start Year 2022
 
Description Surrey - Bramble Energy 
Organisation Bramble Energy Ltd
Country United Kingdom 
Sector Private 
PI Contribution Partner on a joint bid to BEIS Low Carbon Hydrogen Supply 2 competition (Stream 1 Phase 2)
Collaborator Contribution Partner on a joint bid to BEIS Low Carbon Hydrogen Supply 2 competition (Stream 1 Phase 2). Unsuccesfull.
Impact None to date. Possible future bids to other TRL3+ funding schemes.
Start Year 2022
 
Description Surrey - Hungyen Lin (Lancaster Uni) collaboration 
Organisation Lancaster University
Country United Kingdom 
Sector Academic/University 
PI Contribution Supply of Surrey materials.
Collaborator Contribution THz characterisation of Surrey supplied materials.
Impact 1 joint paper in preparation. Further papers being planned.
Start Year 2021
 
Description Surrey - UCL (Fabrizia Foglia - ESPRC Fellow) collaboration on neutron scattering work 
Organisation University College London
Country United Kingdom 
Sector Academic/University 
PI Contribution Characterisation of membranes. Supply of membranes.
Collaborator Contribution Characterisation of Surrey supplied membranes using X-ray and neutron facilities.
Impact Joint paper published: F. Foglia, Q. Berrod, A. J. Clancy, K. Smith, G. Gebel, V. García Sakai, M. Appel, J.-M. Zanotti, M. Tyagi, N. Mahmoudi, T. S. Miller, J. R. Varcoe, A. P. Periasamy, D. J. L. Brett, P. R. Shearing, S. Lyonnard, P. F. McMillan, "Disentangling water, ion and polymer dynamics in an anion exchange membrane",Nature Mater., 21, 555 (2022). 3 more papers in preparation.
Start Year 2021
 
Description University of Surrey - University of South Carolina (USA) 
Organisation University of South Carolina
Country United States 
Sector Academic/University 
PI Contribution Surrey has supplied anion-exchange membranes and powder ionomers for Prof William Mustain's group at USC to evaluate performance and durability in alkaline membarne fuel cells.
Collaborator Contribution Produced durability data that cannot be done at Surrey.
Impact Several joint papers have been produced and several more planned for 2019/2020: Published to date: H. Adabi, A. Shakouri, N. U. Hassan, J. R. Varcoe, B. Zulevi, A. Serov, J. R. Regalbuto, W. E. Mustain, "High-performing commercial Fe-N-C cathode electrocatalyst for anion-exchange membrane fuel cells", Nature Energy, 6, 834 (2021). Y. Zheng, G. Huang, M. Mandal, J. R. Varcoe, P. A. Kohl, W. E. Mustain, "Editors' Choice-Power-Generating Electrochemical CO2 Scrubbing from Air Enabling Practical AEMFC Application", J. Electrochem. Soc., 168, 024504 (2021). X. Peng, D. Kulkarni, Y. Huang, T. J. Omasta, B. Ng, Y. Zheng, L. Wang, J. M. LaManna, D. S. Hussey, J. R. Varcoe, I. V. Zenyuk, W. E. Mustain, "Using operando techniques to understand and design high performance and stable alkaline membrane fuel cells", Nature Commun., 11, 3561 (2020). L. Wang, X. Peng, W. E. Mustain, J. R. Varcoe, "Radiation-grafted anion-exchange membranes: the switch from low- to high-density polyethylene leads to remarkably enhanced fuel cell performance", Energy Environ. Sci., 12, 1575 (2019). [Raw data (CC-BY) is available at DOI: 10.15126/surreydata.8050274] Y. Zheng, T. J. Omasta, X. Peng, L. Wang, J. R. Varcoe, B. S. Pivovar, W. E. Mustain, "Quantifying and elucidating the effect of CO2 on the thermodynamics, kinetics and charge transport of AEMFCs", Energy Environ. Sci., 12, 2806 (2019). X. Peng, T. J. Omasta, E. Magliocca, L. Wang, J. R. Varcoe, W. E. Mustain, "N-doped Carbon CoOx Nanohybrids: The First Precious Metal Free Cathode to Achieve 1.0 W/cm2 Peak Power and 100 h Life in Anion-Exchange Membrane Fuel Cells" Angew. Chem. Intl. Ed., 58, 1046 (2019). T. J. Omasta, A. M. Park, J. M. LaManna, Y. Zhang, X. Peng, L. Wang, D. L. Jacobson, J. R. Varcoe, D. S. Hussey, B. S. Pivovar, W. E. Mustain, "Beyond Catalysis and Membranes: Visualizing and Solving the Challenge of Electrode Water Accumulation and Flooding in AEMFCs", Energy Environ. Sci., 11, 551 (2018). T. J. Omasta, L. Wang, X. Peng, C. A. Lewis, J. R. Varcoe, W. E. Mustain, "Importance of balancing membrane and electrode water in anion exchange membrane fuel cells", J. Power Sources, 375, 205 (2018). Travis J. Omasta, Yufeng Zhang, Andrew M. Park, Xiong Peng, Bryan Pivovar, John R. Varcoe,4 and William E. Mustain, "Strategies for Reducing the PGM Loading in High Power AEMFC Anodes", Journal of the Electrochemical Society, 165, F710 (2018). Travis J. Omasta, Xiong Peng, Hamish A. Miller, Francesco Vizza, Lianqin Wang, John R. Varcoe, Dario R. Dekel, and William E. Mustain, "Beyond 1.0Wcm-2 Performance without Platinum: The Beginning of a New Era in Anion Exchange Membrane Fuel Cells", Journal of Electrochemical Society, 165, J3039 (2018).
Start Year 2017