FUEL CELL TECHNOLOGIES FOR AN AMMONIA ECONOMY

Lead Research Organisation: University College London
Department Name: Chemical Engineering

Abstract

We propose to develop a radically new system for low-temperature hydrogen fuel cells that promises a performance that can match proton-exchange membrane fuel cells but costs less and is more robust. Our system involves two new technologies, which we ourselves have developed: alkaline polymer electrolyte fuel cells (that contain alkaline anion-exchange polymer electrolytes materials that conduct hydroxide anions, and use low to zero levels of precious metal catalysts) coupled with a new effective method of hydrogen delivery based on ammonia. Our ammonia will be sourced from a low-carbon grid-balancing project that is led by Siemens AG, funded by the TSB and based at the Rutherford Appleton Laboratory. The ability of ammonia to fulfil both the role of energy buffer and energy vector (that closely mimics fossil fuel hydrocarbons such as propane and butane) indicates its potential to play a central part in a future low-carbon economy.

The proposed hydrogen store is liquid ammonia, stored at modest pressures (10 - 20 atmospheres), which is cracked at moderate temperatures (350 - 500 degC) using a novel chemical reaction mechanism that does not involve rare-metal catalysts. Our recently discovered, inexpensive approach to ammonia decomposition involves the concurrent stoichiometric decomposition and regeneration of sodium amide via sodium: it is anticipated to lead to less than a 10% loss of efficiency.

In the past decade, there has been an increased level of research into using hydroxide conducting alkaline anion-exchange polymer electrolytes in all-solid-state alkaline polymer electrolyte fuel cells. A major rationale for this is such fuel cells hold the most promise for the elimination of precious metal catalysts. Additionally, low temperature (acidic) proton-exchange membrane fuel cells are irreversibly damaged by < ppm amounts of ammonia. Alkaline fuel cells, on the other hand, can tolerate several % of ammonia in the hydrogen fuel without serious performances or durability losses. Alkaline polymer electrolyte fuel cells have even been operated with pure ammonia as the fuel.

The actively managed project (that will fully integrate into the UK's SuperGen Hydrogen and Fuel Cell Hub) will involve the development of novel amide and imide based systems for ammonia decomposition as well as the next generation of conductive and durable anion-exchange polymer electrolytes and low cost catalysts (in close partnership with Amalyst Ltd.) to produce alkaline polymer electrolyte fuel cells with improved performances over the current state-of-art. The polymer electrolyte development will include novel dual role alkaline ionomers that allows conduction of the hydroxide anions in the catalyst layers and also catalyses the decomposition of trace ammonia (to help ensure zero ammonia emissions from the fuel cell). Anode catalysts that can not only oxidise hydrogen in the presence of ammonia, but oxidise the ammonia itself (again to help eliminate ammonia emissions) will be specifically targeted. Non-precious-metal cathode catalysts will be used and ported from current and prior research programmes.

The culmination of the project will be the development of a combined system incorporating the ammonia cracker, an alkaline polymer electrolyte fuel cell incorporating developed technologies, balance-of-plant, and a control and monitoring system. Taking the systems approach beyond the test bed, a study will be performed that delivers flowsheet and device designs for a 5 kWe system to be taken forward via future projects in direct collaboration with industry.

Planned Impact

This project will advance knowledge, understanding and readiness of technologies necessary for the use of ammonia as a fuel for fuel-cell systems. This takes a materials-to-systems approach and includes development of a low-cost, high-efficiency and compact ammonia cracker, fuel cell materials that are resilient to the slippage of ammonia from the cracker and demonstration of an integrated fuel cell system composed of fuel (ammonia) processing, hydrogen buffer storage, thermal integration and control. The technological approaches proposed offer a potential step-change in fuel cell uptake, with huge associated impact. Specifically, this research project will have impact on:

- Society and the environment: Fuel cells are the most energy efficient means of converting chemical energy to electricity and thus have great promise for the replacement of heat engine technologies. This will have great impact on quality of life and public health for people in the UK and around the world by massively reducing CO2 and pollutant emissions, particularly in the automotive sector. The technology also has added technological value for a wide range of applications, where benefits over batteries allow for longer operation and more power-hungry applications to be serviced more effectively. Reducing dependence on fossil fuels also has the potential to lessen international socio-economic and political tensions, with the prospect of improved geo-political stability.

- Economy and the commercial sector: Use of ammonia as an energy carrier overcomes the key challenge of hydrogen storage and thus accelerates the market uptake of fuel cells, with benefits for the whole supply chain. The production of ammonia using excess electricity produced by renewables will accelerate its large-scale uptake. Use of greater efficiency power generation technologies could reduce energy bills and consequently feed the economy with greater expendable income. The UK is at the forefront of commercial fuel cell development, with some of the largest and best fuel cell companies in the world. Ammonia for fuel cells stands to remove a key barrier to fuel cell uptake and therefore shortens the distance to wide-scale market penetration, with consequent economic benefit to our companies. Also, by developing the IP necessary to underpin ammonia fuel fuelled fuel cells, the UK will have a major advantage if this promising energy vector is adopted.

- People: Positive impact for the people involved in the project will be derived from the expertise developed by the research team, training and transferrable skills acquired. The people who we will work with in industry will benefit from interaction with academics and the university environment through alternative approaches and highly creative ideas. General career progression will ensue for all those involved in the project as a result of the learning, outputs and advances made.

- Knowledge and science base: The scientific and engineering base will benefit from advancements in a range of areas, including: materials, catalysts, polymers, fuel cell and reaction engineering.

- Government: Finally, the Government and policy makers will benefit from expert input into the 'ammonia as a fuel' debate and the technology delivered will provide a new option and dimension for shaping our energy future. DECC are considering ammonia as a component of their 2050 Pathways Calculator after discussions of our research.


Ultimately, we will be considering the automotive sector in the longer term. However, we will be initially targeting back-up power which is a multi-million dollar market for the telecoms sector alone. Cost is a prime concern here, while operational lifetimes need not be long. Lifetimes in the order of 500 to several 1000s hours are that is needed because only intermittent operation is required for power resilience.

Publications

10 25 50
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Abdulaziz R (2016) Predominance Diagrams of Spent Nuclear Fuel Materials in LiCl-KCl and NaCl-KCl Molten Salt Eutectics in International Journal of Electrochemical Science

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Abouelamaiem D (2018) Integration of supercapacitors into printed circuit boards in Journal of Energy Storage

 
Description We have developed a new ammonia cracking technology capable of producing hydrogen for use in low temperature fuel cells. This cracking technology is remarkable as it is very low cost and his a high conversion efficiency.
UCL have provided innovation funding to commercialise our findings and we plan to spin out a company in 2017/18.
Exploitation Route U. Oxford have patented this technology.
UCL have provided innovation funding to commercialise our findings and we plan to spin out a company in 2017/18.
Sectors Aerospace, Defence and Marine,Energy,Environment,Transport

 
Description Findings support a patent held by U. Oxford
First Year Of Impact 2016
Sector Aerospace, Defence and Marine,Energy,Environment,Transport
Impact Types Societal,Economic

 
Description Design and Regulation of Anion Exchange Membranes for Alkaline Polyelectrolyte Fuel Cells (collaboration with USTC Hefei)
Amount ¥2,430,000 (CNY)
Funding ID 21720102003 
Organisation National Natural Science Foundation of China 
Sector Public
Country China
Start 01/2018 
End 12/2022
 
Description HAPEEL: collaboration with SINTEF (Trondheim)
Amount kr 10,427,000 (NOK)
Funding ID 268019 
Organisation Research Council of Norway 
Sector Public
Country Norway
Start 09/2017 
End 09/2020
 
Description High Spec Raman Spectrometer Regional Facility (Equipment Business Case)
Amount £350,780 (GBP)
Funding ID EP/M022749/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 08/2015 
End 08/2018
 
Description ISIS BeamTime Application - RB1620449 (SANS2D 1 day)
Amount £10,000 (GBP)
Funding ID RB1620449 
Organisation Rutherford Appleton Laboratory 
Sector Public
Country United Kingdom
Start 02/2017 
End 02/2017
 
Description Muon Level Crossing Resonance Studies of Anion-exchange Membranes under Different Humidities
Amount £70,000 (GBP)
Funding ID RB1520483 
Organisation Science and Technologies Facilities Council (STFC) 
Department ISIS Neutron and Muon Source
Sector Public
Country United Kingdom
Start 09/2015 
End 10/2015
 
Description Prof Mustain Fulbright Scholarship
Amount $12,000 (USD)
Funding ID Prof William Mustain Scholarship 
Organisation US-UK Fulbright Commission 
Sector Charity/Non Profit
Country United Kingdom
Start 04/2016 
End 08/2016
 
Description RAEng Distinguishing Visiting Fellowship (Round 5)
Amount £4,495 (GBP)
Funding ID Prof Mohamed Nasef DVF 
Organisation Royal Academy of Engineering 
Sector Learned Society
Country United Kingdom
Start 08/2016 
End 10/2016
 
Description Ana-Laura Biancolli (FAPESP) 
Organisation University of Sao Paulo
Department Institute of Chemistry
Country Brazil 
Sector Academic/University 
PI Contribution Hosted Ana-Laura Biancolli as a visiting research student (PhD) at Surrey (Department of Chemistry).
Collaborator Contribution FAPESP provided the funds to allow the visit.
Impact Joint papers envisaged.
Start Year 2016
 
Description Collaboration iwith STFC (ISIS) 
Organisation STFC Laboratories
Country United Kingdom 
Sector Public 
PI Contribution Supply of membranes for testing on ISIS SANS and Muon facilities
Collaborator Contribution Experimental design, membrane testing and results analysis.
Impact SANS and Muon data to date (results being analysed).
Start Year 2015
 
Description Collaboration with AFC Energy 
Organisation AFC Energy Ltd
Country United Kingdom 
Sector Private 
PI Contribution Supply of anion-exchange membranes and ionomers to AFC Energy
Collaborator Contribution Testing of Surrey materials in AFC Energy small alkaline fuel cell test set-ups.
Impact Innovate UK Feasibility Study grant submitted in Feb 2017 (not awarded). Innovate UK grant submitted Jan 2018 for 2 year project (awaiting outcome). AFC Energy and Surrey have signed a non-exclusive agreement giving AFC Energy first option on any commercial use of Surrey's radiation-grafted polymer electrolytes in fuel cells or hydrogen electrolysers.
Start Year 2016
 
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 We have collected joint data that will be published in 2018. This has also led to a Royal Society - CNR International Exchange programme grant application in Oct 2017 (awaiting outcome).
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 Joint papers envisaged.
Start Year 2016
 
Description Collaboration with Prof Nasef (UTM) 
Organisation University of Technology, Malaysia
Country Malaysia 
Sector Academic/University 
PI Contribution Scientific discussion on Radiation-grafted. Testing of UTM materials in Surrey's fuel cells and Raman Instrument. Hosted Prof Nasef at Surrey (see outputs)
Collaborator Contribution Discussion of Surrey results and input into a paper on Surrey's materials.
Impact L. Wang, E. Magliocca, E. L. Cunningham, W. E. Mustain, S. D. Poynton, R. Escudero-Cid, M. M. Nasef, J. Ponce-Gonzalez, R. Bance-Souahli, R. C. T. Slade, D. K. Whelligan, J. R. Varcoe, "An optimised synthesis of high performance radiation-grafted anion-exchange membranes", Green Chem., 19, 831-843 (2017). Prof Nasef being awarded a RAEng Distinguished Visting Fellowship in May 2016 for his 1 month research visit to Surrey in Aug 2016.
Start Year 2016
 
Description Collaboration with Swansea University 
Organisation Swansea University
Department College of Engineering
Country United Kingdom 
Sector Academic/University 
PI Contribution Supply of Surrey anion-exchange polymer electrolyte powders to Dr Paolo Bertoncello's group.
Collaborator Contribution Testing Surrey's ionomer powders in electrochemical sensor applications.
Impact None to date. A possible joint grant is envisaged if initial results look promising.
Start Year 2017
 
Description Collaboration with Universidad Autónoma de Madrid  
Organisation Autonomous University of Madrid
Country Spain 
Sector Academic/University 
PI Contribution Hosted UAM students and postdocs for joint reserch projects at Surrey.
Collaborator Contribution Paid for some of the costs for student and postdoc visits to Surrey.
Impact L. Wang, E. Magliocca, E. L. Cunningham, W. E. Mustain, S. D. Poynton, R. Escudero-Cid, M. M. Nasef, J. Ponce-Gonzalez, R. Bance-Souahli, R. C. T. Slade, D. K. Whelligan, J. R. Varcoe, "An optimised synthesis of high performance radiation-grafted anion-exchange membranes", Green Chem., 19, 831-843 (2017). S. D. Poynton, R. C. T. Slade, T. Omasta, W. E. Mustain, R. Escudero Cid, P. Ocón, J. R. Varcoe, "Preparation of radiation-grafted powders for use as anion exchange ionomers in alkaline polymer electrolyte fuel cells", J. Mater. Chem. A, 2, 5124 (2014).
Start Year 2014
 
Description Collaboration with Wuhan University 
Organisation Wuhan University
Country China 
Sector Academic/University 
PI Contribution Supplied polymer electrolyte membranes and powders to Wuhan University for testing in their fuel cell systems with their ionomers.
Collaborator Contribution Testing Surrey membranes in their alkaline fuel cell systems. Obtained Chinese funding to allow John Varcoe (Fellow) to visit Wuhan in 2015.
Impact J. Ponce-Gonzalez, D. K. Whelligan, L. Wang, R. Bance-Soualhi, Y. Wang, Y. Peng, H. Peng, D. C. Apperley, H. N. Sarode, T. P. Pandey, A. G. Divekar, S. Seifert, A. M. Herring, L. Zhuang, J. R. Varcoe, "High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes", Energy Environ. Sci., 9, 3724 (2016). 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).
Start Year 2013
 
Description Colloboration with Colorado School of Mines (Golden, CO, USA) 
Organisation Colorado School of Mines
Country United States 
Sector Academic/University 
PI Contribution Membrane supply and CSM conducting experiments on membranes
Collaborator Contribution Extensive specialist testing of Surrey membranes and ionomers (DSC, dielectric, IR microscopy, SAXS, specialist NMR)
Impact Joint papers: J. Ponce-Gonzalez, D. K. Whelligan, L. Wang, R. Bance-Soualhi, Y. Wang, Y. Peng, H. Peng, D. C. Apperley, H. N. Sarode, T. P. Pandey, A. G. Divekar, S. Seifert, A. M. Herring, L. Zhuang, J. R. Varcoe, "High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes", Energy Environ. Sci., 9, 3724 (2016). M. A. Vandiver, B. R. Caire, J. R. Carver, K. Waldrop, M. R. Hibbs, J. R. Varcoe, A. M. Herring, M. W. Liberatore, "Mechanical characterization of anion exchange membranes by extensional rheology under controlled hydration", J. Electrochem. Soc., 161, H677 (2014). 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). T. P. Pandey, A. M. Maes, H. N. Sarode, B. D Peters, S. Lavinia, Ki Vezzu, Y. Yang, S. Poynton, J. R. Varcoe, S. Seifert, M. Liberatore, V. Di Noto, A. Herring, "Interplay between water uptake, ion interactions, and conductivity in an e-beam grafted poly(ethylene-co-tetrafluoroethylene) anion exchange membrane", Phys. Chem. Chem. Phys., 17, 4367 (2015).
Start Year 2011
 
Description Elisabete Santiago FAPESP 
Organisation Institute of Nuclear and Energy Research (IPEN)
Country Brazil 
Sector Public 
PI Contribution Hosted Dr Elisabete Santiago as visiting postdoc for 1 year research visit at Surrey (Department of Chemistry)
Collaborator Contribution FAPESP provided the funds to allow the research visit.
Impact Joint papers envisaged
Start Year 2016
 
Description NREL collaboration 
Organisation U.S. Department of Energy
Department National Renewable Energy Laboratory (NREL)
Country United States 
Sector Public 
PI Contribution Supply of anion-exchange membranes and ionomers powders.
Collaborator Contribution NREL is conducting some performance and durability testing on Surrey materials.
Impact None to date but joint papers envisages.
Start Year 2017
 
Description Parajito Powder 
Organisation Pajarito Powder, LLC
PI Contribution Supply of anion-exchange polymer electrolytes.
Collaborator Contribution Testing of Surrey materials in electrochemical systems like alkaline electrolysers.
Impact None to date but joint papers planned.
Start Year 2017
 
Description SINTEF 
Organisation SINTEF
Country Norway 
Sector Multiple 
PI Contribution Letter of support written for SINTEFs grant application.
Collaborator Contribution SINTEF to apply for a grant to Norwegian Research Council for a joint project on anion-exchange membranes for hydrogen electrolysers.
Impact Grant application submitted and funded. The award includes funds for travel and testing of Surrey's anion-exchange polymer electrolytes in SINTEF electrolyser systems.
Start Year 2016
 
Description University of Surrey - University of Connecticut (USA) 
Organisation University of Connecticut
Country United States 
Sector Academic/University 
PI Contribution Development of low temperature carbonate fuel cells containing anion-exchange membranes. Materials exchange; Planned future researcher exchange; Testing UConn catalysts in Surrey fuel cell systems
Collaborator Contribution Testing of Surrey materials in fuel cells and electrochemical devices for the electroreduction of carbon dioxide.
Impact Prof Mustain (lead collaborator at the University of Connecticut) has been awarded a Fulbright Scholarship and will be working at Surrey for 4 months in 2016. L. Wang, E. Magliocca, E. L. Cunningham, W. E. Mustain, S. D. Poynton, R. Escudero-Cid, M. M. Nasef, J. Ponce-Gonzalez, R. Bance-Souahli, R. C. T. Slade, D. K. Whelligan, J. R. Varcoe, "An optimised synthesis of high performance radiation-grafted anion-exchange membranes", Green Chem., 19, 831-843 (2017). 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).
Start Year 2011
 
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 (see further funding entry). Joint papers published: 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 A talk to the sixth form of the Oratory School (Reading) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact A talk on "Chemistry's role in future clean energy technologies".
Year(s) Of Engagement Activity 2017
 
Description Departmental Colloquia at UClan (Jan 2016) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Undergraduate students
Results and Impact Presentation on the use of anion-exchange membranes in electrochemical devices.
Year(s) Of Engagement Activity 2016
 
Description Guildford College Talk (June 2016) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact Discussion on what studying Chemistry is like at University as well as discussing various forms of electrochemical clean energy technologies.
Year(s) Of Engagement Activity 2016
 
Description Radiation-grafted polymer electrolytes for electrochemical energy technologies (Invited Talk - 7th International Fuel Cell Workshop, Kofu Japan) 
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 Talk sparked Q&A.

Nothing to date.
Year(s) Of Engagement Activity 2015
URL http://fc-nano.yamanashi.ac.jp/english/ifcw/index2015.html