REDAEM: Anion-Exchange Membranes for Reverse Electrodialysis

Lead Research Organisation: University of Surrey
Department Name: Chemistry

Abstract

The government commitment to reduce emissions (Climate Change Act 2008 and now the Clean Growth Strategy 2017) and the resulting ambitious targets for renewable energy production requires novel approaches towards efficient production of non-intermittent electricity from renewable sources that can compensate for the closure of fossil fuel power plants around the UK. Reverse electrodialysis (RED) is a "blue" non-intermittent energy technology involving salinity gradient energy, with importance to the UK's future renewable energy mix. RED has been relatively neglected to date, hence, a systematic evaluation of its potential based on innovative materials is urgently needed. Electricity is generated when waters of different salinities (saltiness) are mixed inside an electrochemical RED cell stack (can involve industrial waste streams). A recent conservative assessment of global salinity gradient power (SGP) potential indicates that 625 TWh per year of electricity is practically extractable from river mouths globally (3% of global electricity consumption).

RED cells contain multiple pairs of anion-exchange membranes (AEM) and cation-exchange membranes (CEM). The materials development aspect of this project will focus on the development of high performance AEMs and their application in RED cells (including those supplied with real-world, non-sterile waters). These will be compared to commercial benchmark AEMs. The project will focus on AEMs because CEMs (intended for RED application) were developed as part of a previous EPSRC grant [EP/I004882/1]; there is also less diversity of chemistries available for CEMs, compared to AEMs, which is why the latter requires a more dedicated research project. A wide range of AEMs will be synthesised using the electron-beam radiation-grafting technique. We will also explore the use of sonochemistry during the grafting stage, both in combination with and without the use of the electron-beam.

The RED cell performance data will also be compared to single ion-transport data (experimental and modelling) as well as data from modelling of RED cell engineering configurations. Accurate modelling of the RED stack is crucial in order to estimate the realistic potential of RED in a future UK energy mix. The modelling activities will be further extended to take into consideration the real scalability of the process in terms of potential contribution to the UK energy demand. The integration of data on the availability and locations of fresh water and saline waste streams (e.g. waste streams from industry) with the accurate model of the RED system will produce a precise map of the technology potential at different sites. This activity will then lead to the identification of potential integrations of the process according to the available streams: i.e. once you know where you have fresh water (and how much) you can calculate how much electricity you can actually produce. Furthermore, when an alternative (e.g. industrial) saline waste stream is located close to a fresh water body, this avoids the limitations when using seawater (in terms of coastal location and the magnitude of the salinity gradient).

For cost effectiveness, this project will fully utilise membrane characterisation and RED cell testing equipment that have been purchased/established using funds from prior related EPSRC and EU projects. For maximum transparency, all resulting open access publications (CC-BY) will include DOI locators to facilitate open access to the project's (non-IP-protected) raw data. The project will be used to establish new intra-UK and UK-Dutch research collaborations that should lead to additional links to other UK and EU networks.

Planned Impact

The successful development and implementation of reverse electrodialysis (RED) in the UK will have economic, environmental and societal benefits. The extension of the UK's ability to generate its own non-intermittent renewable electricity (base load) will have great impact on quality of life and public health for people in the UK by helping reduce emissions of carbon dioxide and other pollutants. There are energy security and economic advantages with increased UK self-reliance regarding its energy needs. Reduced dependence on fossil fuels can help improve worldwide socio-economic and political stability (lower costs for all).

There will be positive impacts for the people involved in the project who will benefit from: the knowledge and expertise developed, multidisciplinary training, and acquisition of transferrable skills. The Universities involved run a wide range of continued professional development courses for researchers (e.g. project and open data management for researchers, paper and grant writing skills, research ethics, presentation and science communication skills). The people in industry who we collaborate with will benefit from interaction with academics and the university environment, through exposure to alternative capabilities, thinking, and approaches.

The scientific and engineering base in general will benefit from advancements in a range of areas, including: materials synthesis and characterisation, RED and reaction engineering, and computational modelling methodology from individual membranes and RED cells right through to national-scale potential RED provisions. We will engage with a wide-range of commercial, policymaker, educational stakeholders to fully exploit potential impacts stemming from the research (both expected and unanticipated) and to widen awareness of RED technologies. Government and policy makers will benefit from expert input into the debates around options for the UK future renewable energy mix (the technology delivered will provide a new option for shaping our energy future). Related to the previous point, we will set up and host a "Blue Energy" network.

Materials-chemistry-based impact will be focused on identifying the cheapest materials that can be used to synthesise non-fluorinated ion-exchange membranes. Future scale-up/cost-reduction activities will involve efforts to obtain higher TRL funding once this project identifies the most suitable chemistry/substrate configurations. Ultimately, recyclable, ion-exchange membranes costing < £1 per square metre will need to be used for longer-term commercial viability and sustainability of RED. Our close links with the Dutch leaders in RED technology will be used to evaluate select materials and to validate our models in established scaled-up RED test systems. Once the politics have settled down, and future pathways to EU-UK collaborations are clarified, we will also explore options for obtaining cross-EU- funding for a major RED development project involving our Dutch partners along with other EU commercial concerns. Even before a major RED initiative in the UK, any IP that stems from this project will be commercially exploited to facilitate development of RED systems around the world (inward investment into UK): this could be from direct sales of materials or ethically licensing our IP to relevant parties. RED should be able to play an important role in official development assistance (ODA) countries where salinity gradients are available either naturally or due to production of industrial saline outflows: The Global Challenges Research Fund (GCRF) mechanism will be explored to port the project outcomes into positive benefits to relevant ODA partner countries.

Other efforts will involve an initial exploration of the integration of project-developed RED cells with desalination systems and engagement with the ultrasound processing industry if modification of polymers using ultrasound show promise.

Publications

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Liang X (2021) 3D-Zipped Interface: In Situ Covalent-Locking for High Performance of Anion Exchange Membrane Fuel Cells. in Advanced science (Weinheim, Baden-Wurttemberg, Germany)

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Haj-Bsoul S (2022) Measuring the alkaline stability of anion-exchange membranes in Journal of Electroanalytical Chemistry

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Douglin J (2020) A high-temperature anion-exchange membrane fuel cell in Journal of Power Sources Advances

 
Description This project is focused on the identification of key anion-exchange membrane (AEM) attributes for application in Reverse Electrodialysis (RED - a sustainable salinity gradient energy technology):
(1) We have elucidated what polymer film types can be modified using the radiation-grafted route to produce anion-exchange membranes (RG-AEM) with the best balance of low resistance and high permselectivity.
(2) We have identified that cross-linking is essential and that this should be flexible ionic cross-linking. This was published in Journal of Materials Chemistry A in 2021 [https://doi.org/10.1039/D1TA05166K].
(3) We have established and validated new more accurate membrane resistance measuring cells.
(4) We have now identified what combination of head-group and crosslinking is recommended for both RG-AEMs and in future other architectures of AEM.
(5) We have also gained some important lab knowhow regarding some conditions that were previously thought unimportant but are now known to have a big effect on the properties of RG-AEMs.
Exploitation Route Cross-linking findings also being ported into EU SELECTCO2 Selective Electrochemical Reduction of CO2 to High Value Chemicals consortium grant (active until end 2022) and EPSRC grant EP/T009233/1 (ends March 2024).

The findings from this grant will help with the preparation of follow-up higher TRL level activities, with a focus on the scaled-up fabrication of anion-exchange membrane (AEM) with down-selected chemistries that look most promising in RED (or electrodialysis) application. A search for both academic and non-academic follow-on collaborations has now been instigated.

On the academic front, a follow-up EPSRC grant (FAPESP joint funded international collaboration with IPEN in Sao Paulo Brazil) was submitted [EP/X032345/1] but unfunded. The findings from this grant were also instrumental in the provision of a International Project Partner Letter of Support that helped the University of Queensland obtain Australian Research Council funding for a Centre of Excellence for Green Electrochemical Transformation of Carbon Dioxide. Some of the RG-AEMs developed in REDAEM will be evaluated in CO2 electrochemical systems once this ARC CofE is up and running.
Sectors Chemicals

Energy

Environment

 
Title DATASET (CC-BY): Changes in permselectivity of radiation-grafted anion-exchange membranes with different cationic headgroup chemistries are primarily due to water content differences 
Description The raw data behind Figures 1 in both native Renishaw file formats and in .xlsx Microsoft Excel formats. An .xlsx file of an example ETFE-g-poly(VBC) membrane with a degree of grafting = 46% is also presented. 
Type Of Material Database/Collection of data 
Year Produced 2023 
Provided To Others? Yes  
URL https://figshare.com/articles/dataset/DATASET_CC-BY_Changes_in_permselectivity_of_radiation-grafted_...
 
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 the Eindhoven University of Technology (Netherlands) 
Organisation Eindhoven University of Technology
Department Department of Chemical Engineering and Chemistry
Country Netherlands 
Sector Academic/University 
PI Contribution Joint EPSRC grant awarded (EP/R044163/1). Supply of Surrey materials expected in 2019-2021
Collaborator Contribution To test Surrey materials in reverse electrodialysis. This group formally at University of Twente.
Impact J. R. Varcoe, P. Atanassov, D. R. Dekel, A. M. Herring, M. A. Hickner, P. A. Kohl, A. R. Kucernak, W. E. Mustain, K. Nijmeijer, K. Scott, T. Xu, L. Zhuang, "Anion-exchange membranes in electrochemical energy systems", Energy Environ. Sci., 7, 3135 (2014). Joint EPSRC grant awarded (EP/R044163/1 ): REDAEM: Anion-Exchange Membranes for Reverse Electrodialysis (Duration Oct 2018 - Sept 2021 Value £430k to Surrey): A 3-partner consortium led by Surrey. Joint papers planned.
Start Year 2012
 
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 Faraday Technology Inc (collaborative project with NASA) 
Organisation Faraday Technology
Country United States 
Sector Private 
PI Contribution To date: a supply of Surrey-developed anion-exchange membranes for testing in peroxide generating electrochemical cells. These membranes are performing well compared to commercial types.
Collaborator Contribution The partners are developing a peroxide generating system for use on the international space station. They are evaluating Surrey-developed anion-exchange membranes. Things are moving forward now, and a more formal collaboration (via a consultancy agreement and materials transfer agreement) being finalised.
Impact None to date, but Surrey will supply more anion-exchange membranes for larger scale evaluations (under a consultancy agreement).
Start Year 2023
 
Description Faraday Technology Inc (collaborative project with NASA) 
Organisation National Aeronautics and Space Administration (NASA)
Department Johnson Space Center (JSC)
Country United States 
Sector Public 
PI Contribution To date: a supply of Surrey-developed anion-exchange membranes for testing in peroxide generating electrochemical cells. These membranes are performing well compared to commercial types.
Collaborator Contribution The partners are developing a peroxide generating system for use on the international space station. They are evaluating Surrey-developed anion-exchange membranes. Things are moving forward now, and a more formal collaboration (via a consultancy agreement and materials transfer agreement) being finalised.
Impact None to date, but Surrey will supply more anion-exchange membranes for larger scale evaluations (under a consultancy agreement).
Start Year 2023
 
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 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 Science and Technology of China (Hefei, PR China) 
Organisation University of Science and Technology of China USTC
Country China 
Sector Academic/University 
PI Contribution Developing new membrane chemistries for alkaline anion-exchange membrane fuel cells. Exchange of materials. Testing of USTC Hefei membranes in Surrey Fuel Cell Test Stations
Collaborator Contribution Supply of USTC Hefei membranes to test in Surrey Fuel Cell Test Stations
Impact NSFC joint grant awarded (NSFC grant 21720102003). Joint papers published: J. Zhang, Y. He, K. Zhang, X. Liang, R. Bance-Soualhi, Y. Zhu, X. Ge, M. A. Shehzad, W. Yu, Z. Ge, L. Wu, J. R. Varcoe, T. W. Xu, "Cation-dipole interaction that creates ordered ion channels in an anion exchange membrane for fast OH- conduction", AIChE J., 67, e17133 (2021). X. Liang, M. A. Shehzad, Y. Zhu, L. Wang, X. Ge, J. Zhang, Z. Yang, L. Wu, J. R. Varcoe, T. Xu, "Ionomer Cross-linking Immobilization of Catalyst Nanoparticles for High Performance Alkaline Membrane Fuel Cell", Chemistry of Materials, 31, 7812 (2019).Y. Zhu, L. Ding, X. Liang, M. A. Shehzad, L. Wang, X. Ge, Y. He, L. Wu, J. R. Varcoe, T. Xu, "Beneficial use of rotatable-spacer side-chains in alkaline anion exchange membrane fuel cells" Energy Environ. Sci., 11, 3472 (2018). L. Wu, Q. Pan, J. R. Varcoe, D. Zhou, J. Ran, Z. Yang, T. Xu, "Thermal Crosslinking of an Alkaline Anion Exchange Membrane Bearing Unsaturated Side Chains", J. Membr. Sci., 490, 1 (2015). X. Lin, X. Liang, S. D. Poynton, J. R. Varcoe, A. Ong, J. Ran, Y. Li, Q. Li, T. Xu, "Alkaline anion exchange membranes containing pendant benzimidazolium groups for alkaline fuel cells", J. Membr. Sci., 443, 193 (2013). X. Lin, J. R. Varcoe, S. D. Poynton, X. Liang, A. Ong, J. Ran, Y. Li, T. Xu, "Alkaline polymer electrolytes containing pendant dimethylimidazolium groups for alkaline membrane fuel cells", J. Mater. Chem. A, 1, 7262 (2013). X. Lin, Y. Liu, S. D. Poynton, A. Ong, J. R. Varcoe, L. Wu, Y. Li, X. Liang, Q. Li, T. Xu, "Cross-linked anion exchange membranes for alkaline fuel cells synthesized using a solvent free strategy", J. Power Sources, 233, 259 (2013). Z. Zhang, L. Wu, J. Varcoe, C. Li, A. Ong, S. Poynton, T. Xu, "Aromatic polyelectrolytes via polyacylation of pre-quaternized monomers for alkaline fuel cells.", J. Mater. Chem. A, 1, 2595 (2013). X. Lin, L. Wu, Y. Liu, A. L. Ong, S. D. Poynton, J. R. Varcoe, T. Xu, "Alkali resistant and conductive guanidinium-based anion-exchange membranes for alkaline polymer electrolyte fuel cells", J. Power Sources, 217, 373 (2012). J. Ran, L. Wu, J. R. Varcoe, A. L. Ong, S. D. Poynton, T. Xu, "Development of imidazolium-type alkaline anion exchange membranes for fuel cell application", J. Membr. Sci., 415-416, 242 (2012). Y. Wu, C. Wu, J. R. Varcoe, S. D. Poynton, T. Xu, Y. Fu, "Novel silica/poly(2,6-dimethyl-1,4-phenylene oxide) hybrid anion exchange membranes for alkaline fuel cells: effect of silica content and the single cell performance", J. Power Sources, 195, 3069 (2010).
Start Year 2010
 
Description Radiation-grafted anion-exchange polymer electrolytes for electrochemical applications (Invited Lecture EUPOC 2015) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Type Of Presentation keynote/invited speaker
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Talked sparked Q&amp;amp;A

I was invited by a participant to examine a PhD student in Sweden in Sept 2015
Year(s) Of Engagement Activity 2015
URL https://www1.dcci.unipi.it/eupoc2015/speakers.html