Final Report Summary - QUASIDRY (Quasi-anhydrous and dry membranes for next generation fuel cells)
Executive Summary:
The primary objective of QuasiDry was the development of selected highly innovative approaches to polymer and membrane design to open up the possibility for fuel cells to operate at temperatures of around 120 °C, a desirable, yet currently impractical operating point with currently available materials. The QuasiDry partnership of six technical partners provided a balance between industry and academia that pooled its complementary skills and competences. The partnership was structured to cover the range of expertise required to carry the project through and achieve its objectives, for full exploitation and use of the results, and for professional project management and dissemination of project results.
The work plan comprised work packages dedicated to the main developmental RTD activities on polymers and membranes (WP2), catalyst development (WP3), and validation of the project materials in membrane electrode assemblies (MEAs, WP4). The focus of WP1 was the development of protocols for functional materials characterisation and evaluation of MEAs under project-specific conditions. WP5 and WP6 were dedicated to dissemination and use of results, and to project management, respectively.
WP2 targeted the development of new concepts for fuel cell electrolyte membranes. Its ambition with regard to conductivity values was considerable. Proton conducting materials, polymers and membranes (i) functionalised only with phosphonic acid groups (ii) incorporating polymer-bound sulfonic and phosphonic acid functionalities (iii) cross-linked high acid doping level membranes and (iv) mixed functionality membranes incorporating phosphonic and phosphoric acids, have been developed and their properties characterised, and transferred to WP4. Key outcome includes the novel properties offered by mixed functionality (sulfonic-phosphonic, and phosphoric-phosphonic), distinct from those observed for the separate components alone. Target conductivities have been achieved with two of the above membrane classes. Overall, the boundaries in the field of novel approaches to proton conducting membranes have been expanded and some very promising results achieved with significant progress over the state of the art.
In WP3, new ternary alloy catalysts for cathodes (PtXY) demonstrated improved kinetic mass activity (while retaining high stability) for operation at high temperatures from 120-180 °C and was successfully scaled-up to 200 g for further MEA development studies. A composite Pd-Pt catalyst with ultra-low Pt content produced a synergistic effect and showed a much larger activation effect for the Pd-based catalyst than a conventional Pt-alloy. This makes such composite Pd system quite appealing for application under automotive conditions characterised by intermediate temperature and low relative humidity operation. The use of heteropolyoxometalate promoters further increased the catalytic activity of a Pd catalyst under automotive conditions. Alternative non-carbon catalyst supports with specific architectures have been developed that show high electrochemical corrosion resistance.
A wide range of innovative materials from WP2 and WP3 were evaluated in WP4 using both in situ and ex situ techniques. Three new catalysts, four novel classes of membranes and the compatibiliser concept were all investigated under a wide range of conditions and constructions. Several of these new materials show significant improvements and potential compared to the initial benchmark materials. At the low RH, 120 °C, ambient pressure target conditions of the project, peak power densities >0.4 W/cm2 were achieved at useable cell voltages with the cross-linked acid doped membranes, more than doubling the initial benchmark material’s performance. Target power density could also be achieved by raising both humidification and pressure using mixed functionality sulfonic –phosphonic functionalised membrane materials. Durability was validated with one of the new catalysts and one of the new membranes demonstrating durability on par with the benchmark material. Overall some very promising practical results have been achieved from the new membrane classes, which demonstrate that significant progress has been made over the three years of the project and reveals their obvious potential.
Project results have been disseminated in conferences (25 presentations) and journal publications (9 articles).
Project Context and Objectives:
Fuel cells using oxides or polymers hold great promise in the future diversification of energy supply for applications ranging from the portable electronics market, through automotive use and stationary power generation to other niche areas related to the leisure market or military purposes. Real impact of the potential in terms of reduced emissions and alternative fuels allowed by fuel cell technology awaits introduction of a mass market application, and it is considered that the greatest bearing in this arena will be brought by fuel-cell electric vehicles.
In recent years, a vast number of polymers have been proposed and evaluated as possible materials for proton exchange membrane fuel cells (PEMFC), in particular for automotive application. Sulfonic acid functionalised perfluorinated polymers are a class of benchmark materials having excellent proton conductivity, mechanical and chemical stability. Nafion®, the 3M and Aquivion® membranes are representative perfluorosulfonic acid (PFSA) ionomers. Despite the wide use of Nafion® and other state of the art PFSAs, their maximum performance in a fuel cell is at moderate operation temperatures (80 °C). This falls significantly short of the automotive industry long-term targets, which is for a cell temperature of 120 – 130 °C, with no humidification of reactant hydrogen and air, since humidification increases systems complexity and costs. It is agreed by the automotive industry that the too low temperature of operation and the need for humidification of current polymer exchange membrane fuel cell membranes is an obstacle to widespread implementation of fuel cell vehicles (FCV). High temperature of operation is required to enable the heat generated by the fuel cell stack to be exchanged efficiently.
In the above PFSA membranes, the proton is transferred by water molecules. Over the last decade, new concepts have evolved engaging alternative proton carriers that mark a move towards reducing the need for high levels of hydration of the fuel cell membrane. The ideal protogenic group in a "quasi-anhydrous" membrane environment should be amphoteric, exhibit proton donor and acceptor properties and show a high degree of self-dissociation. It also should have a high dielectric constant to enhance the charge separation and be stable under fuel cell operation conditions. Candidate "solvents" alternative to water include nitrogen heterocycles and phosphonic acids. While initial results effectively showed that such solvents could be immobilised on to polymer backbones, the low concentration of functional groups in this first work led to rather low proton conductivity values.
The objective of QuasiDry was to develop the fuel cell electrolyte membranes of the next generation of fuel cells, satisfying the long-term automotive targets. The increase of proton conductivity with temperature, including at low RH, will allow continuous increase in fuel cell performance with temperature, rather than the drop in performance for all sulfonic acid functionalised membranes above ca. 80-90 °C. QuasiDry membranes were evaluated by electrode and MEA development, to the scale of small-scale (50 cm2) single cell demonstrators. The end result has been a step-change in the properties of these materials, as is required to underpin the future of European fuel cell research.
Several approaches to automotive fuel cell membranes were screened within the framework of Framework 6 Integrated Project Autobrane (completed 31st October 2009), including advanced perfluorosulfonic acid (PFSA) type membranes, and their composites containing an inorganic component, novel hydrocarbon type polymers with sulfonic acid functions, consideration of some novel polymers with protogenic functions other than sulfonic acid, as well as novel processing routes. Using a state-of-the-art PFSA membrane, Autobrane achieved its goal of fuel cell stack operation to 120 °C, although performance dropped severely as the temperature was increased, anode and cathode gases were hydrated, and some over-pressure was applied.
It was the intention of QuasiDry to build on some of the achievements of Autobrane by concentrating efforts on some of the most promising long-term options developed in its framework. The materials selected were those functionalised with phosphonic acid groups, since we have shown that phosphonic acid containing polymeric materials have the possibility of operating at higher temperature at low humidity conditions. Their properties are in clear contrast to those of any PFSA, or any sulfonic acid containing polymer.
The project covered the following topics:
1. Development of innovative polyphosphonic acid functionalised polymers and materials and membranes from them, phosphoric acid doped membranes and mixed functionality membranes, corresponding electrolyte dispersions, and characterisation of polymer and materials components, and membrane properties:
Despite considerable progress, in formulating and implementing new approaches leading to novel proton conducting membrane systems that have high proton conductivity at high temperature through the full range of relative humidity remains a most difficult challenge. Phosphoric and phosphonic acid derivatives in particular were considered suitable candidates as ionomers because of their efficient proton transport at high temperature that involves proton hopping via hydrogen bonds. Recent results on phosphonated polymeric membranes and their associations with sulfonic acid functionalised polymers have indicated that very high local concentrations of phosphonic acid, forming large hydrogen bonded aggregates, are needed in order to reach high proton conductivities. Innovative synthetic immobilisation strategies have to be developed to minimise local dilution effects and aggregation constraints of the acid units.
2. Design and development of supported electrocatalysts with high activity in the appropriate electrolyte environment:
Electrocatalyst development was required to accompany the above step-changes in high temperature, low RH properties of proton conducting membranes. Significant progress beyond the state of the art was expected by concentrating efforts in specific directions most relevant to QuasiDry objectives, including designed Pt-alloy catalyst compositions to overcome strong activation control at low current density, using stabilised carbon supports as well as non-carbon (oxide and carbide) supports to avoid high temperature corrosion, and reducing costs by developing Pt-free or ultra-low Pt loaded catalysts in conjunction with anchored heteropolyacid promoters to enhance reaction kinetics (oxygen diffusion coefficient, oxygen solubility, proton transfer at the electrode-electrolyte interface).
3. Development of electrodes and MEAs adapted for the novel polymer membranes and characterisation of the MEAs in single cells:
An MEA having an appropriate electrode structure and membrane-electrode interface was required to translate the potential of the novel membranes to proven MEA performance in a fuel cell, and thus there was a major effort on the development of appropriate electrode structures. Electrode development itself, has studied the impact of key structural and compositional variables, including electrode thickness, pore volume, pore size distribution, hydrophobicity, catalyst loading requirement, and level of ionomer incorporation. This electrode development study went hand-in-hand with developing the processes by which the catalyst layer is formulated and applied. A fundamental study of the interface involved studying the effectiveness of materials capable of electron transfer to the electrode and proton transport to the membrane (mixed ionic-electronic conductors.
The final target of QuasiDry was to achieve the development of membrane materials having conductivity at 120 °C and <25% RH of >50 mS/cm, in the range 50-100 mS/cm, and which have low dependence of conductivity on RH and also temperature (
Project Results:
See attached file for description of main S&T results/foregrounds with figures and tables.
Potential Impact:
1.4 POTENTIAL IMPACT, USE AND DISSEMINATION OF FOREGROUND
This section describes the dissemination of the results and knowledge arising from the QUASIDRY project, during all the project duration and a plan for future dissemination after the end of the project.
The following dissemination activities are described:
• Research publications in peer-reviewed journals,
• Meetings, conferences,
• Website,
• Brochure,
• Education actions.
In total 9 publications have been produced so far, in peer-reviewed scientific journals and 25 presentations (oral or posters) given at international conferences.
A complete list of journal publications, oral presentation, poster presentations and other is given.
We also provide a list of planned dissemination activities to be continued after the end of the project as well as exploitable foregrounds.
1.4.1 DISSEMINATION ACTIVITIES DURING PROJECT LIFE
1.4.1.1 Intended audience & objectives
The dissemination plan has various objectives depending on the type of audience, as detailed below:
• Scientific community & Industrial fuel cell specialists: promote the diffusion of scientific results and QUASIDRY consortium activities
• General public: fulfil project communication and dissemination needs in the direction of the scientific community and the public
• Non specialist scientists (general public and schools): promote the importance of the move to alternative energy sources, the role to be played by hydrogen as an energy carrier
1.4.1.2 Dissemination Channels
1.4.1.2.1 Dedicated Project Website
The dedicated project website is one of the main dissemination channels towards the scientific community and the public. The public section features:
• General description of the project and its objectives
• Information about the consortium and links to partners’ websites
• Public documents, such as public deliverables, publications (open-access provided), project posters and brochure.
• Contact information
1.4.1.2.2 Participation in international conferences
The consortium has attended prominent international conferences, workshops and symposia.
• Organic Pacific Grove Advances in Materials for Proton Exchange membrane Fuel Cells Systems, Asilomar Conference Grounds, California, USA, 20-23 February 2011, Crystals as proton-conducting materials, M. Klapper, Max-Planck-Institute for Polymer Research, Mainz, Germany
• 219th ECS meeting, 1st – 6th May 2011, Montreal, Canada, Investigation of Carbon Supported Pt and PtCo Electro-catalysts by Low-Energy Ion Scattering and X-ray Photoelectron Spectroscopy: Influence of the Surface characteristics on Performance and Degradation, A. Stassi, I. Gatto, G. Monforte, E. Passalacqua, V. Antonucci, A.S. Aricò, CNR-ITAE, Italy
• Fuel Cells and Hydrogen Joint Undertaking Meeting, 17-20 May 2011, Berlin, Germany, Discussion of CNR-ITAE results, A.S. Aricò, CNR-ITAE, Italy
• European Fuel Cell Forum, 28th June – 1st July 2011, Lucerne, Switzerland, Surface properties of Pt and PtCo electro-catalysts and their influence on the performance and degradation of high temperature polymer electrolyte fuel cells, A.S. Aricò, A. Stassi, I. Gatto, G. Monforte, E. Modica, E. Passalacqua, V. Antonucci, CNR-ITAE, Italy
• Fuel Cells & Hydrogen Joint Undertaking Review day, 22-23 November 2011, Brussels, Belgium, Presentation of the QUASIDRY project, D. Jones, ICGM-CNRS, Université Montpellier 2, France
• European Fuel Cell - Piero Lunghi Conference 2011 (paper EFC11013), 14-16 December 2011, Rome, Italy, Designed Electrocatalysts for High Temperature Operation of Solid Polymer Electrolyte Fuel Cells, A. S. Aricò, A. Stassi, I. Gatto, G. Monforte, E. Passalacqua, V. Antonucci, CNR-ITAE, Messina, Italy
• Fuel Cells 2012 Science & Technology, 11-12 April 2012, Berlin, Germany, Next generation high temperature PEM fuel cells incorporating quasi-anhydrous and dry membranes: from components to MEA, D. J. Jones, J. Rozière, N. Donzel , S. Cavaliere, S. Subianto, ICGM-CNRS, Université Montpellier 2, I. Gatto, A. Stassi, A. S. Arico, CNR-ITAE, Messina, S. Buche, G. Hards, Johnson Matthey Fuel Cells Ltd., M. S. Schuster, B. Bauer, fumatech GmbH, A. Sannigrahi, P. Jannasch, Lund University, J. Wegener, M. Klapper, Max-Planck-Institute for Polymer Research, Mainz, Germany.
• International Society of Electrochemistry Topic Meeting "Nanostructured Electrodes", 15-18 April 2012, Perth, Australia, Fuel cell electrodes based on electrospun nanofibres, I. Savych, S. Subianto, J. Bernard d’Arbigny, S. Cavaliere, D. J. Jones, J. Rozière, CNRS ICG-AIME, Université Montpellier 2, Montpellier, France
• E-MRS Spring meeting, 14-18 May 2012, Strasbourg, France, New catalyst supports for PEMFC electrodes, I. Savych, J. Bernard d'Arbigny, S. Cavaliere, D.J. Jones, J. Rozière , ICGM-CNRS, Université Montpellier 2, France
• GEI-ERA2012 Conference, 17-22 June 2012, Salina (Aeolian Island), Italy, A study of Different PtCo/C cathode Electrocatalysts in PEMFCs for Automotive Applications, A. Stassi, I. Gatto, G. Monforte, V. Baglio, E. Passalacqua, V. Antonucci, A.S. Aricò, CNR-ITAE, Messina, Italy
• 4th EuCheMS Chemistry Congress, 26-30 August 2012, Prague, Czech Republic, Phosphonated small molecules - a multitalent in fuel cell applications -, J. Wegener, L. Jiménez García, A. Kaltbeitzel, R. Graf, M. Klapper, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz, Germany
• International Symposium on Electrocatalysis: New concepts and approaches, 4-7 November 2012, Maragogi, Brazil, PEMFC Electrocatalyst Supports Based on Electrospun Nanofibres, I. Savych, S. Subianto, S. Cavaliere, D. J. Jones, J. Rozière, ICGM-CNRS, Université Montpellier 2, France
• MRS fall meeting, 25-30 November 2012, Boston, Massachusetts, USA, A Study on Performance and Degradation of PtCo/C Electrocatalysts for High Temperature Polymer Electrolyte Membrane Fuel Cells, A. Stassi, I. Gatto, G. Monforte, V. Baglio, E. Passalacqua, V. Antonucci, A.S. Aricò, CNR-ITAE, Messina, Italy
• ASILOMAR Conference, February 17th - 20th 2013, Pacific Grove, CA, USA, Phosphonated small molecules - a multitalent in fuel cell applications, M. Klapper, J. Wegener, L. Jiménez-Garciá, A. Kaltbeitzel, K. Müllen, Max Planck Institute for Polymer Research, Mainz, Germany
• ASILOMAR Conference, February 17th - 20th 2013, Pacific Grove, CA, USA, Proton-conducting Phosphonated Nanochannels, J. Wegener, A. Kaltbeitzel, R. Graf, M. Klapper, K. Müllen, Max Planck Institute for Polymer Research, Mainz, Germany
• Nordic polymer Days “Polymers for a Sustainable World”, 29-31 May 2013, Helsinki, Finland, Ring Opening Metathesis Polymerization - A New Pathway to Well-Defined Phosphonic Acid Functional Polymers, B. Bingöl and P. Jannash, Lund University, Sweden
• Electrochemical Society 223rd Meeting, 12-16th May 2013, Toronto, Canada, Electrospun materials as electrocatalyst supports for PEM fuel cells. S. Cavaliere, I. Savych, S. Subianto, D. J. Jones, J. Rozière, ICGM-CNRS, Université Montpellier 2, France
• European Fuel Cell Forum, 2-5 July 2013, Lucerne, Switzerland, Next Generation High Temperature PEM Fuel Cells Incorporating Quasi-Anhydrous and Dry Membranes: from Components to MEA, 1D. Jones, J. Rozière, N. Donzel and S. Cavaliere, 2I. Gatto, A. Stassi and A. Arico,; 3S. Buche and G. Hards, 4M. Schuster and B. Bauer, 5A. Sannigrahi and P. Jannasch, 6J. Wegener and M. Klapper, 1ICGM-CNRS, Université Montpellier 2, France, 2CNR-ITAE, Messina, Italy; 3Johnson Matthey Fuel Cells Ltd., Sonning Common, U.K.; 4fumatech GmbH, Germany; 5Lund University, Sweden; 6Max-Planck-Institute for Polymer Research, Mainz. Germany.
• Euromat 2013, 8-13 September 2013, Seville, Spain, Optimization of perfluorosulphonic ionomer amount in gas diffusion electrodes for PEMFC operation under automotive conditions, I. Gatto, A. Stassi, V. Baglio, A. Carbone, E. Passalacqua, A.S. Aricò, CNR-ITAE, Messina, Italy - M. Schuster, B. Bauer, FuMA-Tech, Germany
• Euromat 2013, 8-13 September 2013, Seville, Spain, Proton conduction membranes based on highly phosphonated polymer, A. Sannigrahi, Z. Shao, B. Bingöl, P. Jannasch, Lund University, Sweden
• 64th Annual Meeting of the International Society of Electrochemistry, 8-13 September 2013, Queretaro, Mexico, PEMFC Electrocatalyst Supports Based on Electrospun Nanofibres, I. Savych, S. Subianto, S. Cavaliere, D. J. Jones, J. Rozière, ICGM-CNRS, Université Montpellier 2, France.
• 64th Annual Meeting of the International Society of Electrochemistry, 8-13 September 2013, Queretaro, Mexico, A Study of Pd-based Electrocatalysts for Automotive Applications, S. Stassi, I. Gatto, G. Monforte, A. Patti, E. Passalacqua, V. Baglio, A. S. Aricò CNR-ITAE, Messina, Italy
• 246th ACS National Meeting & Exposition, 8-12 September 2013, Indianapolis, Indiana, Proton-conducting phosphonated frameworks. J. Wegener, A. Kaltbeitzel, G. Glaber, R. Graf, M. Klapper, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany
• 246th ACS National Meeting & Exposition, 8-12 September 2013, Indianapolis, Indiana, Phosphonic acid-functionalized polymers vs. phosphonated small molecules: David vs. Goliath? M. Klapper, J. Wegener, L. Jiménez-Garcia, A. Kaltbeitzel, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany
• 246th ACS National Meeting & Exposition, 8-12 September 2013, Indianapolis, Indiana, Direct synthesis of phosphonated polymers via ring opening metathesis polymerization, B. Bingöl, A. Kröger, P. Jannasch, Lund University, Sweden
1.4.1.2.3 Journal publications & proceedings
The Consortium has submitted and will continue to submit a number of individual or joint publications to scientific journals. Each publication has followed the QUASIDRY dissemination protocol. Published articles have been made available through institutional repositories (generally the CNRS HAL repository).
1.4.1.2.3.1 Journal publications
• Electrospinning: designed architectures for energy conversion and storage devices, Energy Environ. Sci. (2011), 4, 4761-4785, S. Cavaliere, S. Subianto, I. Savych, D. J. Jones and J. Rozière, CNRS, France - DOI: 10.1039/C1EE02201F - http://hal.archives-ouvertes.fr/hal-00624576(öffnet in neuem Fenster)
• The effect of thermal treatment on structure and surface composition of PtCo electro-catalysts for application in PEMFCs operating under automotive conditions, A. Stassi, I. Gatto, G. Monforte, V. Baglio, E. Passalacqua, V. Antonucci, A. S. Aricò , CNR-ITAE, Italy - accepted in Journal Power Sources DOI: 10.1016/j.jpowsour.2012.02.014 - http://hal.archives-ouvertes.fr/hal-00753348(öffnet in neuem Fenster)
• An electro-kinetic study of oxygen reduction in polymer electrolyte fuel cells at intermediate temperatures, I. Gatto, A. Stassi, E. Passalacqua, A.S. Aricò, Int. J. Hydrogen Energy DOI: 10.1016/j.ijhydene.2012.05.155. - http://hal.archives-ouvertes.fr/hal-00753331(öffnet in neuem Fenster)
• Investigation of Pd-based electrocatalysts for oxygen reduction in PEMFCs operating under automotive conditions, A. Stassi, I. Gatto; V. Baglio; E. Passalacqua; A.S. Arico’, DOI: CNR-ITAE, Messina, Italy Journal of Power Sources (2013) 390-399 – DOI: 10.1016/j.jpowsour.2012.09.002 - http://hal.archives-ouvertes.fr/hal-00753342(öffnet in neuem Fenster)
• Oxide-supported PtCo alloy catalyst for intermediate temperature polymer electrolyte fuel cells, A. Stassi, I. Gatto, V. Baglio, E. Passalacqua, A. S. Aricò, CNR-ITAE, Messina, Italy, Applied Catalysis B: Environmental, Volumes 142–143, October–November 2013, Pages 15–24 – DOI: 10.1016/j.apcatb.2013.05.008 - http://hal.archives-ouvertes.fr/hal-00845171(öffnet in neuem Fenster)
• Block selective grafting of poly(vinylphosphonic acid) from aromatic multiblock copolymers for nanostructured electrolyte membranes, A. Sannigrahi, S. Takamuku and P. Jannasch , ULund, Polym. Chem., 2013, 4, 4207-4218- DOI: 10.1039/C3PY00513E - http://hal.archives-ouvertes.fr/(öffnet in neuem Fenster) hal-00845189
• Dopant-driven architectures of nanostructured SnO2: from dense to “loose-tube” fibers, S. Cavaliere, S. Subianto, I. Savych, M. Tillard, D. J. Jones, and J. Rozière, CNRS, France, J. Phys. Chem. C, 2013, 117 (36), pp 18298–18307 - DOI: 10.1021/jp404570d - open access in November 2014(öffnet in neuem Fenster)
• Poly(tetrafluorostyrenephosphonic acid) block copolymers for proton conducting electrolyte membranes, Z. Shao, A. Sannigrahi, P. Jannasch, ULund, Journal of Polymer Science Part A: Polymer Chemistr, Volume 51, Issue 21, pages 4657–4666, 1 November 2013 – DOI: 10.1002/pola.26887 -http://hal.archives-ouvertes.fr/ hal- 00904746
• Well-defined phosphonated polymers via direct ring opening metathesis polymerization, B. Bingöl, C. Rosenauer, P. Jannasch, ULund, Polymer, Available online 15 October 2013 – DOI: http://dx.doi.org/10.1016/j.polymer.2013.10.018 - http://hal.archives-ouvertes.fr/hal-00904767(öffnet in neuem Fenster)
1.4.1.2.4 Proceedings
1. Proton-conducting phosphonated frameworks. J. Wegener, A. Kaltbeitzel, G. Glaber, R. Graf, M. Klapper, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany, Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels 2013, 58 (2), xxxx
2. Phosphonic acid-functionalized polymers vs. phosphonated small molecules: David vs. Goliath? M. Klapper, J. Wegener, L. Jiménez-Garcia, A. Kaltbeitzel, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany, Prepr. Pap. Am. Chem. Soc., Div. Energy Fuels 2013, 58 (2), xxx
1.4.1.2.5 Education actions & brochure
Eight education actions towards non-specialist scientists (general public and schools) have been undertaken by the consortium. They mainly promote and explain the importance of the move to alternative energy sources, the role to be played by hydrogen as an energy carrier, and the role of fuel cells. A leaflet presenting the consortium activities for a more specialised public has also been released.
1.4.1.2.5.1 List of Education actions
1. International Renewable Energies, Energaïa exhibition, Montpellier, France, 8 – 11 December 2010, Scientific stakes for tomorrow energies - Deborah Jones, ICGM, Montpellier, France.
This is an annual international exhibition on all renewable energies with participation and attendance by industry and research. A scientific programme aimed at an interested and energy-aware but non-specialist general public runs alongside the exhibition, and the above lecture was delivered in this context. CNRS-Université Montpellier 2 also participated in the exhibition to explain fuel cells through a series of small demonstrators including hands-on experiments.
2. Master of Renewable Energy and Energy Saving Technologies (Master T.E.R.R.E.) University of Messina, Italy, 25-26 November 2011, Lectures to graduate students on the hydrogen production, from renewable sources and not, for use in fuel cell, - S. Siracusano, CNR-ITAE, Messina, Italy
3. International Renewable Energies, Energaïa exhibition, Montpellier, France, 7 – 9 December 2011, Presentation of the UM2 Masters degree in Energy: Sources/resources, conversion, storage and energy management – Deborah Jones, ICGM, Montpellier, France. Université Montpellier 2 opened a two-year Masters course in Energy: Sources/resources, conversion, storage and energy management in 2011 and the year 1 students developed a project around an energy technology and manned a booth with small demonstrators during this exhibition.
4. International Renewable energies exhibition, Energaïa, Montpellier, france, 7 – 9 December 2011, Fuel Cells Challenges & Progress – J. Bernard d’Arbigny, ICGM, Montpellier, France.
This lecture was delivered as part of the general public oriented scientific programme of this Energaïa exhibition.
5. Master Energy – (http://www.master-energie.univ-montp2.fr(öffnet in neuem Fenster)) Montpellier, France, 2011-2012, Lecture course on Hydrogen generation & storage – Jacques Rozière, ICGM, Montpellier, France.
This is a lecture course run within the Masters course on Energy: Sources/resources, conversion, storage and energy management - 250 hours, 30 students annually.
6. UM2 open days – Montpellier, France, 3 March 2012, Visit & explanation of the Fuel Cell Experimental Platform at University Montpellier 2 – Y. Nedellec & M. Dupont, ICGM, Montpellier, France.
The Fuel Cell Experimental Platform was opened up to the general public as part of the University Open Day. This kind of event generates a lot of local interest in novel energy technologies, hydrogen and fuel cells in particular.
7. Future Materials – University of Lund, Sweden, 3 September 2012, Polymers for new energy and clean water – P. Jannasch, University of Lund, Sweden;
The lecture series “Future Materials” was aimed at high school and undergraduate students to arouse their interest into science in general and material science in particular. The talk was given 4 times on Sept. 3. to approximately 400 students.
8. Secondary schools (5th-12th grade) – Mainz, Germany - from 2010 to 2012, Markus Klapper (MPIP, Mainz, Germany) teaches frequently in secondary schools (5th-12th grade) in the local area of Mainz.
The focus is to demonstrate how modern research is done at the university and in research centres to attract young people to study chemistry for modern energy technologies, especially polymers for fuel cells.
Examples of some secondary schools are Otto-Schott-Gymnasium, Maria-Ward-Gymnasium, Mainz, berufsbildendes Gymnasium, Mainz and Gutenberg-Gymnasium, Mainz.
1.4.1.2.5.2 Brochure
To focus more on dissemination towards academic and industrial fuel cell specialists, according to the direction advised during the mid-term review meeting by the reviewers and the project officer, a leaflet presenting QUASIDRY objectives, consortium and output has been prepared by PXO & CNRS (figure 2). This brochure has been circulated among the partners for their feedback and then printed and made available for distribution during conferences, workshops … This brochure is also available for download from the QUASIDRY public web site (http://www.quasidry.eu/publications.html - bro) .
1.4.1.3 Dissemination Material
The visual identity of the QUASIDRY project has been assured at conferences, workshops, meetings etc., by the use of a project logo, presentation template and brochure.
1.4.2 FUTURE DISSEMINATION AND PLANS FOR USE OF THE RESULTS
1.4.2.1 Future Dissemination
The consortium will be engaged in conducting further activities for promoting and disseminate the project results. The following measures are planned so far in the near future to follow up the project:
1.4.2.1.1 Quasidry Website
The QUASIDRY website will be kept as an information source of the activities performed in the project. The website will also continue to receive and publish papers online related to the project. The website will be updated to reflect the current status of the project as finished. Reports and final results will be clearly communicated through relevant news items and reports.
1.4.2.1.2 Journal publications
Future academic articles and reports will be produced. This is an important component in the continuation of communicating the results from the research undertaken. Two publications are accepted for publication, and five others are in the course of preparation:
1. Proton Conductivity in Doped Aluminum Phosphonate Sponges, J. Wegener, A. Kaltbeitzel, R. Graf, M. Klapper, K. Müllen, ChemSusChem 2013, DOI 10.1002/cssc.201301055
2. On the Effect of Non-Carbon Nanostructured Supports on the Stability of Pt Nanoparticles during Voltage Cycling: a Study of TiO2 Nanofibres, I. Savych, J. Bernard d'Arbigny, S. Subianto, S. Cavaliere, D. Jones and J. Roziere, CNRS, France, accepted in J. Power Sources
3. Conductivity enhancement in mixed functionality membranes based on sulfonic and phosphonic acids, N. Donzel, D. Jones, J. Roziere, M. Schuster, P. Jannasch et al, co-authored CNRS, FUMA and ULund, to be submitted to J. Mater. Chem. A,
4. Pushing back the frontiers of phosphoric acid doped polybenzimidazole membranes. Highly conducting mixed functionality phosphonic/phosphoric acid doped PBI giving exceptional fuel cell performance. N. Donzel, K. Angjeli, D. Jones, J. Roziere, J. Wegener, M. Klapper, co-authored CNRS and MPIP, to be submitted to Angew. Chem.
5. Palladium-based electrocatalysts for oxygen reduction and hydrogen oxidation in intermediate temperature polymer electrolyte fuel cells, CNR-ITAE, Italy, to be submitted to Int. J Hydrogen Energy
6. Optimization of perfluorosulphonic ionomer amount in gas diffusion electrodes for PEMFC operation under automotive conditions, CNR-ITAE, Italy, to be submitted to Int. J. Hydrogen Energy
7. Electrochemical investigation of mixed functionality membranes for intermediate temperature polymer electrolyte fuel cells, CNR-ITAE/Partners involved to be submitted to Fuel Cells
1.4.2.1.3 Conference presentations
Conference presentations will continue to engage QUASIDRY partners. The following two planned attendances are listed below:
1. Fifth European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference December 11-13, 2013, Rome, Italy, Palladium-based electrocatalysts for oxygen reduction and hydrogen oxidation in intermediate temperature polymer electrolyte fuel cells, A.S. Aricò, A. Stassi, I. Gatto, G. Monforte, A. Patti, E. Passalacqua and V. Baglio, CNR-ITAE, Messina, Italy
2. 6th Forum on New Materials (CIMTEC 2014), 15-20 June 2014, Montecatini Terme, Italy, New polymer electrolyte membranes for fuel cells, Lund University, Sweden
1.4.2.1.4 QUASIDRY brochure
An update of the QUASIDRY brochure including the main non-confidential results and potential impacts will be edited after the agreement of all the partners and will be made available on the public website.
1.4.2.2 Exploitation of foreground
Eight exploitable foregrounds have been identified. IPR exploitable measures have been and will be taken.
1.4.2.3 Future collaborations
The QUASIDRY project work and results has established a solid base for future developments that shall be taken into account in future collaboration.
List of Websites:
www.quasidry.eu
Contact Information:
Dr Deborah Jones
Institut Charles Gerhardt Montpellier
Aggregates, Interfaces and Materials for Energy,
Université Montpellier 2
Place Eugène Bataillon
34095 Montpellier cedex 5
France
Deborah.Jones@univ-montp2.fr
The primary objective of QuasiDry was the development of selected highly innovative approaches to polymer and membrane design to open up the possibility for fuel cells to operate at temperatures of around 120 °C, a desirable, yet currently impractical operating point with currently available materials. The QuasiDry partnership of six technical partners provided a balance between industry and academia that pooled its complementary skills and competences. The partnership was structured to cover the range of expertise required to carry the project through and achieve its objectives, for full exploitation and use of the results, and for professional project management and dissemination of project results.
The work plan comprised work packages dedicated to the main developmental RTD activities on polymers and membranes (WP2), catalyst development (WP3), and validation of the project materials in membrane electrode assemblies (MEAs, WP4). The focus of WP1 was the development of protocols for functional materials characterisation and evaluation of MEAs under project-specific conditions. WP5 and WP6 were dedicated to dissemination and use of results, and to project management, respectively.
WP2 targeted the development of new concepts for fuel cell electrolyte membranes. Its ambition with regard to conductivity values was considerable. Proton conducting materials, polymers and membranes (i) functionalised only with phosphonic acid groups (ii) incorporating polymer-bound sulfonic and phosphonic acid functionalities (iii) cross-linked high acid doping level membranes and (iv) mixed functionality membranes incorporating phosphonic and phosphoric acids, have been developed and their properties characterised, and transferred to WP4. Key outcome includes the novel properties offered by mixed functionality (sulfonic-phosphonic, and phosphoric-phosphonic), distinct from those observed for the separate components alone. Target conductivities have been achieved with two of the above membrane classes. Overall, the boundaries in the field of novel approaches to proton conducting membranes have been expanded and some very promising results achieved with significant progress over the state of the art.
In WP3, new ternary alloy catalysts for cathodes (PtXY) demonstrated improved kinetic mass activity (while retaining high stability) for operation at high temperatures from 120-180 °C and was successfully scaled-up to 200 g for further MEA development studies. A composite Pd-Pt catalyst with ultra-low Pt content produced a synergistic effect and showed a much larger activation effect for the Pd-based catalyst than a conventional Pt-alloy. This makes such composite Pd system quite appealing for application under automotive conditions characterised by intermediate temperature and low relative humidity operation. The use of heteropolyoxometalate promoters further increased the catalytic activity of a Pd catalyst under automotive conditions. Alternative non-carbon catalyst supports with specific architectures have been developed that show high electrochemical corrosion resistance.
A wide range of innovative materials from WP2 and WP3 were evaluated in WP4 using both in situ and ex situ techniques. Three new catalysts, four novel classes of membranes and the compatibiliser concept were all investigated under a wide range of conditions and constructions. Several of these new materials show significant improvements and potential compared to the initial benchmark materials. At the low RH, 120 °C, ambient pressure target conditions of the project, peak power densities >0.4 W/cm2 were achieved at useable cell voltages with the cross-linked acid doped membranes, more than doubling the initial benchmark material’s performance. Target power density could also be achieved by raising both humidification and pressure using mixed functionality sulfonic –phosphonic functionalised membrane materials. Durability was validated with one of the new catalysts and one of the new membranes demonstrating durability on par with the benchmark material. Overall some very promising practical results have been achieved from the new membrane classes, which demonstrate that significant progress has been made over the three years of the project and reveals their obvious potential.
Project results have been disseminated in conferences (25 presentations) and journal publications (9 articles).
Project Context and Objectives:
Fuel cells using oxides or polymers hold great promise in the future diversification of energy supply for applications ranging from the portable electronics market, through automotive use and stationary power generation to other niche areas related to the leisure market or military purposes. Real impact of the potential in terms of reduced emissions and alternative fuels allowed by fuel cell technology awaits introduction of a mass market application, and it is considered that the greatest bearing in this arena will be brought by fuel-cell electric vehicles.
In recent years, a vast number of polymers have been proposed and evaluated as possible materials for proton exchange membrane fuel cells (PEMFC), in particular for automotive application. Sulfonic acid functionalised perfluorinated polymers are a class of benchmark materials having excellent proton conductivity, mechanical and chemical stability. Nafion®, the 3M and Aquivion® membranes are representative perfluorosulfonic acid (PFSA) ionomers. Despite the wide use of Nafion® and other state of the art PFSAs, their maximum performance in a fuel cell is at moderate operation temperatures (80 °C). This falls significantly short of the automotive industry long-term targets, which is for a cell temperature of 120 – 130 °C, with no humidification of reactant hydrogen and air, since humidification increases systems complexity and costs. It is agreed by the automotive industry that the too low temperature of operation and the need for humidification of current polymer exchange membrane fuel cell membranes is an obstacle to widespread implementation of fuel cell vehicles (FCV). High temperature of operation is required to enable the heat generated by the fuel cell stack to be exchanged efficiently.
In the above PFSA membranes, the proton is transferred by water molecules. Over the last decade, new concepts have evolved engaging alternative proton carriers that mark a move towards reducing the need for high levels of hydration of the fuel cell membrane. The ideal protogenic group in a "quasi-anhydrous" membrane environment should be amphoteric, exhibit proton donor and acceptor properties and show a high degree of self-dissociation. It also should have a high dielectric constant to enhance the charge separation and be stable under fuel cell operation conditions. Candidate "solvents" alternative to water include nitrogen heterocycles and phosphonic acids. While initial results effectively showed that such solvents could be immobilised on to polymer backbones, the low concentration of functional groups in this first work led to rather low proton conductivity values.
The objective of QuasiDry was to develop the fuel cell electrolyte membranes of the next generation of fuel cells, satisfying the long-term automotive targets. The increase of proton conductivity with temperature, including at low RH, will allow continuous increase in fuel cell performance with temperature, rather than the drop in performance for all sulfonic acid functionalised membranes above ca. 80-90 °C. QuasiDry membranes were evaluated by electrode and MEA development, to the scale of small-scale (50 cm2) single cell demonstrators. The end result has been a step-change in the properties of these materials, as is required to underpin the future of European fuel cell research.
Several approaches to automotive fuel cell membranes were screened within the framework of Framework 6 Integrated Project Autobrane (completed 31st October 2009), including advanced perfluorosulfonic acid (PFSA) type membranes, and their composites containing an inorganic component, novel hydrocarbon type polymers with sulfonic acid functions, consideration of some novel polymers with protogenic functions other than sulfonic acid, as well as novel processing routes. Using a state-of-the-art PFSA membrane, Autobrane achieved its goal of fuel cell stack operation to 120 °C, although performance dropped severely as the temperature was increased, anode and cathode gases were hydrated, and some over-pressure was applied.
It was the intention of QuasiDry to build on some of the achievements of Autobrane by concentrating efforts on some of the most promising long-term options developed in its framework. The materials selected were those functionalised with phosphonic acid groups, since we have shown that phosphonic acid containing polymeric materials have the possibility of operating at higher temperature at low humidity conditions. Their properties are in clear contrast to those of any PFSA, or any sulfonic acid containing polymer.
The project covered the following topics:
1. Development of innovative polyphosphonic acid functionalised polymers and materials and membranes from them, phosphoric acid doped membranes and mixed functionality membranes, corresponding electrolyte dispersions, and characterisation of polymer and materials components, and membrane properties:
Despite considerable progress, in formulating and implementing new approaches leading to novel proton conducting membrane systems that have high proton conductivity at high temperature through the full range of relative humidity remains a most difficult challenge. Phosphoric and phosphonic acid derivatives in particular were considered suitable candidates as ionomers because of their efficient proton transport at high temperature that involves proton hopping via hydrogen bonds. Recent results on phosphonated polymeric membranes and their associations with sulfonic acid functionalised polymers have indicated that very high local concentrations of phosphonic acid, forming large hydrogen bonded aggregates, are needed in order to reach high proton conductivities. Innovative synthetic immobilisation strategies have to be developed to minimise local dilution effects and aggregation constraints of the acid units.
2. Design and development of supported electrocatalysts with high activity in the appropriate electrolyte environment:
Electrocatalyst development was required to accompany the above step-changes in high temperature, low RH properties of proton conducting membranes. Significant progress beyond the state of the art was expected by concentrating efforts in specific directions most relevant to QuasiDry objectives, including designed Pt-alloy catalyst compositions to overcome strong activation control at low current density, using stabilised carbon supports as well as non-carbon (oxide and carbide) supports to avoid high temperature corrosion, and reducing costs by developing Pt-free or ultra-low Pt loaded catalysts in conjunction with anchored heteropolyacid promoters to enhance reaction kinetics (oxygen diffusion coefficient, oxygen solubility, proton transfer at the electrode-electrolyte interface).
3. Development of electrodes and MEAs adapted for the novel polymer membranes and characterisation of the MEAs in single cells:
An MEA having an appropriate electrode structure and membrane-electrode interface was required to translate the potential of the novel membranes to proven MEA performance in a fuel cell, and thus there was a major effort on the development of appropriate electrode structures. Electrode development itself, has studied the impact of key structural and compositional variables, including electrode thickness, pore volume, pore size distribution, hydrophobicity, catalyst loading requirement, and level of ionomer incorporation. This electrode development study went hand-in-hand with developing the processes by which the catalyst layer is formulated and applied. A fundamental study of the interface involved studying the effectiveness of materials capable of electron transfer to the electrode and proton transport to the membrane (mixed ionic-electronic conductors.
The final target of QuasiDry was to achieve the development of membrane materials having conductivity at 120 °C and <25% RH of >50 mS/cm, in the range 50-100 mS/cm, and which have low dependence of conductivity on RH and also temperature (
Project Results:
See attached file for description of main S&T results/foregrounds with figures and tables.
Potential Impact:
1.4 POTENTIAL IMPACT, USE AND DISSEMINATION OF FOREGROUND
This section describes the dissemination of the results and knowledge arising from the QUASIDRY project, during all the project duration and a plan for future dissemination after the end of the project.
The following dissemination activities are described:
• Research publications in peer-reviewed journals,
• Meetings, conferences,
• Website,
• Brochure,
• Education actions.
In total 9 publications have been produced so far, in peer-reviewed scientific journals and 25 presentations (oral or posters) given at international conferences.
A complete list of journal publications, oral presentation, poster presentations and other is given.
We also provide a list of planned dissemination activities to be continued after the end of the project as well as exploitable foregrounds.
1.4.1 DISSEMINATION ACTIVITIES DURING PROJECT LIFE
1.4.1.1 Intended audience & objectives
The dissemination plan has various objectives depending on the type of audience, as detailed below:
• Scientific community & Industrial fuel cell specialists: promote the diffusion of scientific results and QUASIDRY consortium activities
• General public: fulfil project communication and dissemination needs in the direction of the scientific community and the public
• Non specialist scientists (general public and schools): promote the importance of the move to alternative energy sources, the role to be played by hydrogen as an energy carrier
1.4.1.2 Dissemination Channels
1.4.1.2.1 Dedicated Project Website
The dedicated project website is one of the main dissemination channels towards the scientific community and the public. The public section features:
• General description of the project and its objectives
• Information about the consortium and links to partners’ websites
• Public documents, such as public deliverables, publications (open-access provided), project posters and brochure.
• Contact information
1.4.1.2.2 Participation in international conferences
The consortium has attended prominent international conferences, workshops and symposia.
• Organic Pacific Grove Advances in Materials for Proton Exchange membrane Fuel Cells Systems, Asilomar Conference Grounds, California, USA, 20-23 February 2011, Crystals as proton-conducting materials, M. Klapper, Max-Planck-Institute for Polymer Research, Mainz, Germany
• 219th ECS meeting, 1st – 6th May 2011, Montreal, Canada, Investigation of Carbon Supported Pt and PtCo Electro-catalysts by Low-Energy Ion Scattering and X-ray Photoelectron Spectroscopy: Influence of the Surface characteristics on Performance and Degradation, A. Stassi, I. Gatto, G. Monforte, E. Passalacqua, V. Antonucci, A.S. Aricò, CNR-ITAE, Italy
• Fuel Cells and Hydrogen Joint Undertaking Meeting, 17-20 May 2011, Berlin, Germany, Discussion of CNR-ITAE results, A.S. Aricò, CNR-ITAE, Italy
• European Fuel Cell Forum, 28th June – 1st July 2011, Lucerne, Switzerland, Surface properties of Pt and PtCo electro-catalysts and their influence on the performance and degradation of high temperature polymer electrolyte fuel cells, A.S. Aricò, A. Stassi, I. Gatto, G. Monforte, E. Modica, E. Passalacqua, V. Antonucci, CNR-ITAE, Italy
• Fuel Cells & Hydrogen Joint Undertaking Review day, 22-23 November 2011, Brussels, Belgium, Presentation of the QUASIDRY project, D. Jones, ICGM-CNRS, Université Montpellier 2, France
• European Fuel Cell - Piero Lunghi Conference 2011 (paper EFC11013), 14-16 December 2011, Rome, Italy, Designed Electrocatalysts for High Temperature Operation of Solid Polymer Electrolyte Fuel Cells, A. S. Aricò, A. Stassi, I. Gatto, G. Monforte, E. Passalacqua, V. Antonucci, CNR-ITAE, Messina, Italy
• Fuel Cells 2012 Science & Technology, 11-12 April 2012, Berlin, Germany, Next generation high temperature PEM fuel cells incorporating quasi-anhydrous and dry membranes: from components to MEA, D. J. Jones, J. Rozière, N. Donzel , S. Cavaliere, S. Subianto, ICGM-CNRS, Université Montpellier 2, I. Gatto, A. Stassi, A. S. Arico, CNR-ITAE, Messina, S. Buche, G. Hards, Johnson Matthey Fuel Cells Ltd., M. S. Schuster, B. Bauer, fumatech GmbH, A. Sannigrahi, P. Jannasch, Lund University, J. Wegener, M. Klapper, Max-Planck-Institute for Polymer Research, Mainz, Germany.
• International Society of Electrochemistry Topic Meeting "Nanostructured Electrodes", 15-18 April 2012, Perth, Australia, Fuel cell electrodes based on electrospun nanofibres, I. Savych, S. Subianto, J. Bernard d’Arbigny, S. Cavaliere, D. J. Jones, J. Rozière, CNRS ICG-AIME, Université Montpellier 2, Montpellier, France
• E-MRS Spring meeting, 14-18 May 2012, Strasbourg, France, New catalyst supports for PEMFC electrodes, I. Savych, J. Bernard d'Arbigny, S. Cavaliere, D.J. Jones, J. Rozière , ICGM-CNRS, Université Montpellier 2, France
• GEI-ERA2012 Conference, 17-22 June 2012, Salina (Aeolian Island), Italy, A study of Different PtCo/C cathode Electrocatalysts in PEMFCs for Automotive Applications, A. Stassi, I. Gatto, G. Monforte, V. Baglio, E. Passalacqua, V. Antonucci, A.S. Aricò, CNR-ITAE, Messina, Italy
• 4th EuCheMS Chemistry Congress, 26-30 August 2012, Prague, Czech Republic, Phosphonated small molecules - a multitalent in fuel cell applications -, J. Wegener, L. Jiménez García, A. Kaltbeitzel, R. Graf, M. Klapper, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz, Germany
• International Symposium on Electrocatalysis: New concepts and approaches, 4-7 November 2012, Maragogi, Brazil, PEMFC Electrocatalyst Supports Based on Electrospun Nanofibres, I. Savych, S. Subianto, S. Cavaliere, D. J. Jones, J. Rozière, ICGM-CNRS, Université Montpellier 2, France
• MRS fall meeting, 25-30 November 2012, Boston, Massachusetts, USA, A Study on Performance and Degradation of PtCo/C Electrocatalysts for High Temperature Polymer Electrolyte Membrane Fuel Cells, A. Stassi, I. Gatto, G. Monforte, V. Baglio, E. Passalacqua, V. Antonucci, A.S. Aricò, CNR-ITAE, Messina, Italy
• ASILOMAR Conference, February 17th - 20th 2013, Pacific Grove, CA, USA, Phosphonated small molecules - a multitalent in fuel cell applications, M. Klapper, J. Wegener, L. Jiménez-Garciá, A. Kaltbeitzel, K. Müllen, Max Planck Institute for Polymer Research, Mainz, Germany
• ASILOMAR Conference, February 17th - 20th 2013, Pacific Grove, CA, USA, Proton-conducting Phosphonated Nanochannels, J. Wegener, A. Kaltbeitzel, R. Graf, M. Klapper, K. Müllen, Max Planck Institute for Polymer Research, Mainz, Germany
• Nordic polymer Days “Polymers for a Sustainable World”, 29-31 May 2013, Helsinki, Finland, Ring Opening Metathesis Polymerization - A New Pathway to Well-Defined Phosphonic Acid Functional Polymers, B. Bingöl and P. Jannash, Lund University, Sweden
• Electrochemical Society 223rd Meeting, 12-16th May 2013, Toronto, Canada, Electrospun materials as electrocatalyst supports for PEM fuel cells. S. Cavaliere, I. Savych, S. Subianto, D. J. Jones, J. Rozière, ICGM-CNRS, Université Montpellier 2, France
• European Fuel Cell Forum, 2-5 July 2013, Lucerne, Switzerland, Next Generation High Temperature PEM Fuel Cells Incorporating Quasi-Anhydrous and Dry Membranes: from Components to MEA, 1D. Jones, J. Rozière, N. Donzel and S. Cavaliere, 2I. Gatto, A. Stassi and A. Arico,; 3S. Buche and G. Hards, 4M. Schuster and B. Bauer, 5A. Sannigrahi and P. Jannasch, 6J. Wegener and M. Klapper, 1ICGM-CNRS, Université Montpellier 2, France, 2CNR-ITAE, Messina, Italy; 3Johnson Matthey Fuel Cells Ltd., Sonning Common, U.K.; 4fumatech GmbH, Germany; 5Lund University, Sweden; 6Max-Planck-Institute for Polymer Research, Mainz. Germany.
• Euromat 2013, 8-13 September 2013, Seville, Spain, Optimization of perfluorosulphonic ionomer amount in gas diffusion electrodes for PEMFC operation under automotive conditions, I. Gatto, A. Stassi, V. Baglio, A. Carbone, E. Passalacqua, A.S. Aricò, CNR-ITAE, Messina, Italy - M. Schuster, B. Bauer, FuMA-Tech, Germany
• Euromat 2013, 8-13 September 2013, Seville, Spain, Proton conduction membranes based on highly phosphonated polymer, A. Sannigrahi, Z. Shao, B. Bingöl, P. Jannasch, Lund University, Sweden
• 64th Annual Meeting of the International Society of Electrochemistry, 8-13 September 2013, Queretaro, Mexico, PEMFC Electrocatalyst Supports Based on Electrospun Nanofibres, I. Savych, S. Subianto, S. Cavaliere, D. J. Jones, J. Rozière, ICGM-CNRS, Université Montpellier 2, France.
• 64th Annual Meeting of the International Society of Electrochemistry, 8-13 September 2013, Queretaro, Mexico, A Study of Pd-based Electrocatalysts for Automotive Applications, S. Stassi, I. Gatto, G. Monforte, A. Patti, E. Passalacqua, V. Baglio, A. S. Aricò CNR-ITAE, Messina, Italy
• 246th ACS National Meeting & Exposition, 8-12 September 2013, Indianapolis, Indiana, Proton-conducting phosphonated frameworks. J. Wegener, A. Kaltbeitzel, G. Glaber, R. Graf, M. Klapper, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany
• 246th ACS National Meeting & Exposition, 8-12 September 2013, Indianapolis, Indiana, Phosphonic acid-functionalized polymers vs. phosphonated small molecules: David vs. Goliath? M. Klapper, J. Wegener, L. Jiménez-Garcia, A. Kaltbeitzel, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany
• 246th ACS National Meeting & Exposition, 8-12 September 2013, Indianapolis, Indiana, Direct synthesis of phosphonated polymers via ring opening metathesis polymerization, B. Bingöl, A. Kröger, P. Jannasch, Lund University, Sweden
1.4.1.2.3 Journal publications & proceedings
The Consortium has submitted and will continue to submit a number of individual or joint publications to scientific journals. Each publication has followed the QUASIDRY dissemination protocol. Published articles have been made available through institutional repositories (generally the CNRS HAL repository).
1.4.1.2.3.1 Journal publications
• Electrospinning: designed architectures for energy conversion and storage devices, Energy Environ. Sci. (2011), 4, 4761-4785, S. Cavaliere, S. Subianto, I. Savych, D. J. Jones and J. Rozière, CNRS, France - DOI: 10.1039/C1EE02201F - http://hal.archives-ouvertes.fr/hal-00624576(öffnet in neuem Fenster)
• The effect of thermal treatment on structure and surface composition of PtCo electro-catalysts for application in PEMFCs operating under automotive conditions, A. Stassi, I. Gatto, G. Monforte, V. Baglio, E. Passalacqua, V. Antonucci, A. S. Aricò , CNR-ITAE, Italy - accepted in Journal Power Sources DOI: 10.1016/j.jpowsour.2012.02.014 - http://hal.archives-ouvertes.fr/hal-00753348(öffnet in neuem Fenster)
• An electro-kinetic study of oxygen reduction in polymer electrolyte fuel cells at intermediate temperatures, I. Gatto, A. Stassi, E. Passalacqua, A.S. Aricò, Int. J. Hydrogen Energy DOI: 10.1016/j.ijhydene.2012.05.155. - http://hal.archives-ouvertes.fr/hal-00753331(öffnet in neuem Fenster)
• Investigation of Pd-based electrocatalysts for oxygen reduction in PEMFCs operating under automotive conditions, A. Stassi, I. Gatto; V. Baglio; E. Passalacqua; A.S. Arico’, DOI: CNR-ITAE, Messina, Italy Journal of Power Sources (2013) 390-399 – DOI: 10.1016/j.jpowsour.2012.09.002 - http://hal.archives-ouvertes.fr/hal-00753342(öffnet in neuem Fenster)
• Oxide-supported PtCo alloy catalyst for intermediate temperature polymer electrolyte fuel cells, A. Stassi, I. Gatto, V. Baglio, E. Passalacqua, A. S. Aricò, CNR-ITAE, Messina, Italy, Applied Catalysis B: Environmental, Volumes 142–143, October–November 2013, Pages 15–24 – DOI: 10.1016/j.apcatb.2013.05.008 - http://hal.archives-ouvertes.fr/hal-00845171(öffnet in neuem Fenster)
• Block selective grafting of poly(vinylphosphonic acid) from aromatic multiblock copolymers for nanostructured electrolyte membranes, A. Sannigrahi, S. Takamuku and P. Jannasch , ULund, Polym. Chem., 2013, 4, 4207-4218- DOI: 10.1039/C3PY00513E - http://hal.archives-ouvertes.fr/(öffnet in neuem Fenster) hal-00845189
• Dopant-driven architectures of nanostructured SnO2: from dense to “loose-tube” fibers, S. Cavaliere, S. Subianto, I. Savych, M. Tillard, D. J. Jones, and J. Rozière, CNRS, France, J. Phys. Chem. C, 2013, 117 (36), pp 18298–18307 - DOI: 10.1021/jp404570d - open access in November 2014(öffnet in neuem Fenster)
• Poly(tetrafluorostyrenephosphonic acid) block copolymers for proton conducting electrolyte membranes, Z. Shao, A. Sannigrahi, P. Jannasch, ULund, Journal of Polymer Science Part A: Polymer Chemistr, Volume 51, Issue 21, pages 4657–4666, 1 November 2013 – DOI: 10.1002/pola.26887 -http://hal.archives-ouvertes.fr/ hal- 00904746
• Well-defined phosphonated polymers via direct ring opening metathesis polymerization, B. Bingöl, C. Rosenauer, P. Jannasch, ULund, Polymer, Available online 15 October 2013 – DOI: http://dx.doi.org/10.1016/j.polymer.2013.10.018 - http://hal.archives-ouvertes.fr/hal-00904767(öffnet in neuem Fenster)
1.4.1.2.4 Proceedings
1. Proton-conducting phosphonated frameworks. J. Wegener, A. Kaltbeitzel, G. Glaber, R. Graf, M. Klapper, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany, Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels 2013, 58 (2), xxxx
2. Phosphonic acid-functionalized polymers vs. phosphonated small molecules: David vs. Goliath? M. Klapper, J. Wegener, L. Jiménez-Garcia, A. Kaltbeitzel, K. Müllen, Max-Planck-Institute for Polymer Research, Mainz. Germany, Prepr. Pap. Am. Chem. Soc., Div. Energy Fuels 2013, 58 (2), xxx
1.4.1.2.5 Education actions & brochure
Eight education actions towards non-specialist scientists (general public and schools) have been undertaken by the consortium. They mainly promote and explain the importance of the move to alternative energy sources, the role to be played by hydrogen as an energy carrier, and the role of fuel cells. A leaflet presenting the consortium activities for a more specialised public has also been released.
1.4.1.2.5.1 List of Education actions
1. International Renewable Energies, Energaïa exhibition, Montpellier, France, 8 – 11 December 2010, Scientific stakes for tomorrow energies - Deborah Jones, ICGM, Montpellier, France.
This is an annual international exhibition on all renewable energies with participation and attendance by industry and research. A scientific programme aimed at an interested and energy-aware but non-specialist general public runs alongside the exhibition, and the above lecture was delivered in this context. CNRS-Université Montpellier 2 also participated in the exhibition to explain fuel cells through a series of small demonstrators including hands-on experiments.
2. Master of Renewable Energy and Energy Saving Technologies (Master T.E.R.R.E.) University of Messina, Italy, 25-26 November 2011, Lectures to graduate students on the hydrogen production, from renewable sources and not, for use in fuel cell, - S. Siracusano, CNR-ITAE, Messina, Italy
3. International Renewable Energies, Energaïa exhibition, Montpellier, France, 7 – 9 December 2011, Presentation of the UM2 Masters degree in Energy: Sources/resources, conversion, storage and energy management – Deborah Jones, ICGM, Montpellier, France. Université Montpellier 2 opened a two-year Masters course in Energy: Sources/resources, conversion, storage and energy management in 2011 and the year 1 students developed a project around an energy technology and manned a booth with small demonstrators during this exhibition.
4. International Renewable energies exhibition, Energaïa, Montpellier, france, 7 – 9 December 2011, Fuel Cells Challenges & Progress – J. Bernard d’Arbigny, ICGM, Montpellier, France.
This lecture was delivered as part of the general public oriented scientific programme of this Energaïa exhibition.
5. Master Energy – (http://www.master-energie.univ-montp2.fr(öffnet in neuem Fenster)) Montpellier, France, 2011-2012, Lecture course on Hydrogen generation & storage – Jacques Rozière, ICGM, Montpellier, France.
This is a lecture course run within the Masters course on Energy: Sources/resources, conversion, storage and energy management - 250 hours, 30 students annually.
6. UM2 open days – Montpellier, France, 3 March 2012, Visit & explanation of the Fuel Cell Experimental Platform at University Montpellier 2 – Y. Nedellec & M. Dupont, ICGM, Montpellier, France.
The Fuel Cell Experimental Platform was opened up to the general public as part of the University Open Day. This kind of event generates a lot of local interest in novel energy technologies, hydrogen and fuel cells in particular.
7. Future Materials – University of Lund, Sweden, 3 September 2012, Polymers for new energy and clean water – P. Jannasch, University of Lund, Sweden;
The lecture series “Future Materials” was aimed at high school and undergraduate students to arouse their interest into science in general and material science in particular. The talk was given 4 times on Sept. 3. to approximately 400 students.
8. Secondary schools (5th-12th grade) – Mainz, Germany - from 2010 to 2012, Markus Klapper (MPIP, Mainz, Germany) teaches frequently in secondary schools (5th-12th grade) in the local area of Mainz.
The focus is to demonstrate how modern research is done at the university and in research centres to attract young people to study chemistry for modern energy technologies, especially polymers for fuel cells.
Examples of some secondary schools are Otto-Schott-Gymnasium, Maria-Ward-Gymnasium, Mainz, berufsbildendes Gymnasium, Mainz and Gutenberg-Gymnasium, Mainz.
1.4.1.2.5.2 Brochure
To focus more on dissemination towards academic and industrial fuel cell specialists, according to the direction advised during the mid-term review meeting by the reviewers and the project officer, a leaflet presenting QUASIDRY objectives, consortium and output has been prepared by PXO & CNRS (figure 2). This brochure has been circulated among the partners for their feedback and then printed and made available for distribution during conferences, workshops … This brochure is also available for download from the QUASIDRY public web site (http://www.quasidry.eu/publications.html - bro) .
1.4.1.3 Dissemination Material
The visual identity of the QUASIDRY project has been assured at conferences, workshops, meetings etc., by the use of a project logo, presentation template and brochure.
1.4.2 FUTURE DISSEMINATION AND PLANS FOR USE OF THE RESULTS
1.4.2.1 Future Dissemination
The consortium will be engaged in conducting further activities for promoting and disseminate the project results. The following measures are planned so far in the near future to follow up the project:
1.4.2.1.1 Quasidry Website
The QUASIDRY website will be kept as an information source of the activities performed in the project. The website will also continue to receive and publish papers online related to the project. The website will be updated to reflect the current status of the project as finished. Reports and final results will be clearly communicated through relevant news items and reports.
1.4.2.1.2 Journal publications
Future academic articles and reports will be produced. This is an important component in the continuation of communicating the results from the research undertaken. Two publications are accepted for publication, and five others are in the course of preparation:
1. Proton Conductivity in Doped Aluminum Phosphonate Sponges, J. Wegener, A. Kaltbeitzel, R. Graf, M. Klapper, K. Müllen, ChemSusChem 2013, DOI 10.1002/cssc.201301055
2. On the Effect of Non-Carbon Nanostructured Supports on the Stability of Pt Nanoparticles during Voltage Cycling: a Study of TiO2 Nanofibres, I. Savych, J. Bernard d'Arbigny, S. Subianto, S. Cavaliere, D. Jones and J. Roziere, CNRS, France, accepted in J. Power Sources
3. Conductivity enhancement in mixed functionality membranes based on sulfonic and phosphonic acids, N. Donzel, D. Jones, J. Roziere, M. Schuster, P. Jannasch et al, co-authored CNRS, FUMA and ULund, to be submitted to J. Mater. Chem. A,
4. Pushing back the frontiers of phosphoric acid doped polybenzimidazole membranes. Highly conducting mixed functionality phosphonic/phosphoric acid doped PBI giving exceptional fuel cell performance. N. Donzel, K. Angjeli, D. Jones, J. Roziere, J. Wegener, M. Klapper, co-authored CNRS and MPIP, to be submitted to Angew. Chem.
5. Palladium-based electrocatalysts for oxygen reduction and hydrogen oxidation in intermediate temperature polymer electrolyte fuel cells, CNR-ITAE, Italy, to be submitted to Int. J Hydrogen Energy
6. Optimization of perfluorosulphonic ionomer amount in gas diffusion electrodes for PEMFC operation under automotive conditions, CNR-ITAE, Italy, to be submitted to Int. J. Hydrogen Energy
7. Electrochemical investigation of mixed functionality membranes for intermediate temperature polymer electrolyte fuel cells, CNR-ITAE/Partners involved to be submitted to Fuel Cells
1.4.2.1.3 Conference presentations
Conference presentations will continue to engage QUASIDRY partners. The following two planned attendances are listed below:
1. Fifth European Fuel Cell Technology & Applications Conference - Piero Lunghi Conference December 11-13, 2013, Rome, Italy, Palladium-based electrocatalysts for oxygen reduction and hydrogen oxidation in intermediate temperature polymer electrolyte fuel cells, A.S. Aricò, A. Stassi, I. Gatto, G. Monforte, A. Patti, E. Passalacqua and V. Baglio, CNR-ITAE, Messina, Italy
2. 6th Forum on New Materials (CIMTEC 2014), 15-20 June 2014, Montecatini Terme, Italy, New polymer electrolyte membranes for fuel cells, Lund University, Sweden
1.4.2.1.4 QUASIDRY brochure
An update of the QUASIDRY brochure including the main non-confidential results and potential impacts will be edited after the agreement of all the partners and will be made available on the public website.
1.4.2.2 Exploitation of foreground
Eight exploitable foregrounds have been identified. IPR exploitable measures have been and will be taken.
1.4.2.3 Future collaborations
The QUASIDRY project work and results has established a solid base for future developments that shall be taken into account in future collaboration.
List of Websites:
www.quasidry.eu
Contact Information:
Dr Deborah Jones
Institut Charles Gerhardt Montpellier
Aggregates, Interfaces and Materials for Energy,
Université Montpellier 2
Place Eugène Bataillon
34095 Montpellier cedex 5
France
Deborah.Jones@univ-montp2.fr
