[go: up one dir, main page]

WO2012020268A1 - Ensemble électrode à membrane - Google Patents

Ensemble électrode à membrane Download PDF

Info

Publication number
WO2012020268A1
WO2012020268A1 PCT/GB2011/051531 GB2011051531W WO2012020268A1 WO 2012020268 A1 WO2012020268 A1 WO 2012020268A1 GB 2011051531 W GB2011051531 W GB 2011051531W WO 2012020268 A1 WO2012020268 A1 WO 2012020268A1
Authority
WO
WIPO (PCT)
Prior art keywords
membrane
zeolite
electrode
proton exchange
mea
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2011/051531
Other languages
English (en)
Inventor
Stuart Holmes
Craig Dawson
Saravana P Shanmukham
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Manchester
Original Assignee
University of Manchester
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of Manchester filed Critical University of Manchester
Publication of WO2012020268A1 publication Critical patent/WO2012020268A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0297—Arrangements for joining electrodes, reservoir layers, heat exchange units or bipolar separators to each other
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. in situ polymerisation or in situ crosslinking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04197—Preventing means for fuel crossover
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a membrane electrode assembly, a method of making membrane electrode assemblies and direct alcohol fuel cells comprising a membrane electrode assembly of the present invention.
  • PEM fuel cells represent one of the leading fuel cell technologies. PEM fuel cells are extremely efficient, do not produce noise, and are relatively simple to manufacture and therefore are suitable for use in a broad range of applications.
  • PEM fuel cells employ an ion conducting electrolyte membrane between a positive electrode and a negative electrode.
  • the ion conducting membrane material plays a critical role in the operation of the PEM fuel cells. It acts as an ion conductor between the anode and the cathode, as a separator for the fuel and oxidant and as an insulator between the cathode and anode so that electrons conduct through an electronic circuit and not directly through the membrane.
  • a direct alcohol fuel cell e.g. a direct methanol fuel cell (DMFC)
  • a direct alcohol fuel cell has the advantage that a liquid fuel composed of an alcohol and water has the dual functionality of a coolant as well as a fuel.
  • Direct alcohol fuel cells are compact and lightweight and can operate for long periods of time. They are also very easy to refuel.
  • a direct alcohol fuel cell does have draw backs.
  • the most significant problem of a direct alcohol fuel cell is the degradation of the cell performance due to alcohol cross-over from the anode to the cathode. There had been a number of attempts to overcome this problem which are discussed in detail below.
  • Alcohol for example methanol, permeability and proton conductivity are good metrics for DMFC performance and can be used as an indication for any possible enhancement.
  • Testing data for the actual performance of a DMFC can be obtained by the method disclosed in Li, Roberts, Holmes; Evaluation of composite membranes for DMFC; JPS; 2006; 154(1 ), p1 15-123.
  • US2004/0241520 discloses a method of manufacturing a composite polymer electrolyte membrane coated with an inorganic thin film, and a use of the coated membrane in a fuel cell.
  • the invention utilises a plasma enhanced chemical vapour deposition (PECVD) method.
  • PECVD plasma enhanced chemical vapour deposition
  • the polymer electrolyte membrane could be coated with an inorganic film comprising a zeolite.
  • the preparation of a zeolite film utilising PECVD is not exemplified in this document. Furthermore, it is considered that it would not be possible to produce a zeolite film by employing the PECVD process.
  • the inorganic film exemplified in this patent application as a silica or alumina material up to 70 nm thick. It is disclosed in this document that the ionic conductivity of the composite polymer electrolyte membranes is reduced by about 20% as compared to the ionic conductivity of a bare, uncoated Nafion membrane. This is clearly disadvantageous since a high ionic conductivity is one of the most important characteristics of the membrane.
  • WO2004/015801 discloses a composite electrolyte for fuel cells that includes an inorganic cation exchange material, a silica-based binder and a polymer-based binder.
  • the problem addressed by the composite electrolyte of this disclosure is to alleviate the water management problems associated with electrolyte membranes when the membranes are used at high temperatures.
  • the types of cation exchange materials include clays, zeolites, hydroxides, and inorganic salts.
  • the amount of inorganic cation exchange material in the composite electrolyte is disclosed as being about 10 wt % to about 99 wt %. However, this level of cation exchange material reduces the power density of the fuel cell to below a workable level.
  • the actual current densities achieved by the MEA within the DMFC systems of the present invention ranged from 125-300 mAcm "2 for the temperature range 30-90°C in comparison to the standard current densities (i.e. current densities resulting from MEAs having no zeolite loading) which ranged from 100-250 mAcm "2 over the same temperature range.
  • the current density value for the fuel cell of the invention is far in excess of the current density of 5mAcm "2 obtained in WO2004/015801 .
  • the membrane of the invention yielded maximum power densities in excess of 50mWcm "2 in comparison to ⁇ 32mWcm "2 obtained for the standard Nafion cell.
  • WO2009/073055 discloses a multilayered membrane including alternating layers of hydrophilic, nano-sized particles and recast perfluorosulfonic acid (PFSA) proton conductors. This document aims to provide a membrane having a continuous internal hydration at the anode during operation by using water generated at the cathode. It is disclosed that the particle concentration in each layer is high in order to improve the mechanical strength of the hybrid multilayer film. Such a high concentration of particles is likely to reduce the power density of the MEA.
  • the concentration of the nanoparticles in one of the layers containing the nanoparticles based on the dry weight of the conductive electrolyte polymer in that layer ranges from 0.1 to 100%.
  • US2010/0038316 discloses a poly(tetrafluoroethylene) (PTFE) zeolite composite useful in processes such as filtration and separation.
  • the composite comprises from 1 to 20% zeolite by weight of the membrane. It is well known in the field of alcohol fuel cells that PTFE does not conduct protons and cannot therefore be used as a membrane in the membrane electrode assembly of a fuel cell.
  • US2008/0070094 discloses an organic/ inorganic composite electrolyte membrane formed by using zeolite as a hydrophilic organic particle in combination with a sulfonated fluorine-free polymer.
  • the method comprises the steps of dissolving a sulfonated fluorine-free hydrocarbon based polymer into a solvent to provide a polymer solution, adding a zeolite thereto to form a dispersion, and then forming the inorganic/ organic composite electrolyte membrane from the composite solution.
  • the present invention aims to overcome one or more of the above disadvantages of the prior art. It is therefore an aim to provide a proton exchange membrane having reduced alcohol (e.g. methanol) crossover as compared to conventional membranes. It is a further aim to provide a proton exchange membrane that is easy and economical to manufacture. It is a further aim to provide a proton exchange membrane having a power density value comparable to or better than a conventional membrane.
  • a proton exchange membrane having reduced alcohol (e.g. methanol) crossover as compared to conventional membranes. It is a further aim to provide a proton exchange membrane that is easy and economical to manufacture. It is a further aim to provide a proton exchange membrane having a power density value comparable to or better than a conventional membrane.
  • a membrane electrode assembly comprising:
  • the total zeolite content represents from 0.1 to 1.0% by weight of the sum of the sulfonated fluoropolymer proton exchange membrane and the sulfonated fluoropolymer of the one or more layers.
  • the sulfonated fluoropolymer proton exchange membrane is a perfluorosulfonic acid membrane.
  • the sulfonated fluoropolymer proton exchange membrane has a structure:
  • the sulfonated fluoropolymer proton exchange membrane has a structure:
  • the perfluorosulfonic acid membrane is a commercially available membrane selected from the group consisting of: Nafion® (Du Pont), Dow membrane (Dow Chemical), Flemion membrane (Asahi Glass Co.), Aciplex membrane (Asahi Chem.), BAM (Ballarde), Solvay Hyflon and Gore-select membrane (W.L. Gore, Inc.).
  • the sulfonated fluoropolymer proton exchange membrane is a commercially available membrane selected from the group consisting of: Nafion® (Du Pont), Dow membrane (Dow Chemical), Flemion membrane (Asahi Glass Co.), Aciplex membrane (Asahi Chem.), BAM (Ballarde), Solvay Hyflon and Gore-select membrane (W.L. Gore, Inc.).
  • the sulfonated fluoropolymer proton exchange membrane is a commercially available membrane selected from the group consisting of: Na
  • Nafion® membrane In a more preferred embodiment, the sulfonated fluoropolymer proton exchange membrane is Nafion® 1 17.
  • the perfluorosulfonic acid membrane is a membrane selected from the group consisting of: sulphonated polyetheretherketone (sPEEK), sulphonated
  • sPSU polysulphone
  • sPVA sulphonated polyvinylacetate
  • sPEI sulphonated polyetherimide
  • PBI polybenzimidazole
  • the sulfonated fluoropolymer proton exchange membrane has a thickness of from 1 to 200 ⁇ . In an embodiment, the sulfonated fluoropolymer proton exchange membrane has a thickness of from 80 to 170 ⁇ . In an embodiment, the sulfonated fluoropolymer proton exchange membrane has a thickness of less than 80 ⁇ .
  • each layer comprising a mixture of sulfonated fluoropolymer and a zeolite, provided as a mixture of the zeolite and monomer of the sulfonated fluoropolymer in one or more applications to the or each electrode independently has a thickness of from 0.5 ⁇ to 15 ⁇ , preferably 1 ⁇ to 12 ⁇ .
  • each electrode is formed from three component layers:
  • a thin porous layer e.g. a carbon cloth or carbon paper, on which the remaining two layers are fabricated;
  • a gas diffusion layer composed of carbon particles along with a hydrophobic polymer (e.g. polytetrafluoroethylene (PTFE)); and
  • a hydrophobic polymer e.g. polytetrafluoroethylene (PTFE)
  • the structure, i.e. the composition layers (1 ) and (2), of the anode is identical to the structure, i.e. the composition layers (1 ) and (2), of the cathode.
  • the catalyst material used in the catalyst layer of the anode is different from the catalyst material used in the catalyst layer of the cathode.
  • the catalyst material used in the catalyst layer of the cathode is platinum.
  • the catalyst material used in the catalyst layer of the anode is 1 :1 Pt/Ru. In an
  • the catalyst material used in the catalyst layer of the anode is 2:1 Pt/Ru.
  • the sulfonated fluoropolymer proton exchange membrane has one layer comprising a mixture of sulfonated fluoropolymer and a zeolite.
  • the face of the membrane having a layer comprising a mixture of sulfonated fluoropolymer and a zeolite is in contact with the anode.
  • the face of the membrane having a layer comprising a mixture of sulfonated fluoropolymer and a zeolite is in contact with the cathode.
  • the face of the membrane having a layer comprising a mixture of sulfonated fluoropolymer and a zeolite is in contact with the anode.
  • Results comparing the performance improvement of the layer comprising the mixture of sulfonated fluoropolymer and the zeolite being in contact with the anode and the cathode are illustrated in figures 24 and 25. It is thought that the improvement in performance for the anodic barrier placement (compared to the cathodic barrier placement) could be due to the retention of methanol at the anode which could improve performance due to increased uptake of the methanol at the anodic catalyst layer. This is particularly relevant at low molarities. The improvement could also be due to the prevention of methanol diffusion and prevention of saturation of methanol into the membrane.
  • the sulfonated fluoropolymer proton exchange membrane has two layers comprising a mixture of sulfonated fluoropolymer and a zeolite.
  • one face of the membrane having a layer comprising a mixture of sulfonated fluoropolymer and a zeolite is in contact with the cathode and the other face of the membrane having a layer comprising a mixture of sulfonated fluoropolymer and a zeolite is in contact with the anode.
  • Figures 26 and 27 illustrate the improvement of the current and power densities for the MEAs having a barrier layer at both the anode and the cathode.
  • the sulfonated fluoropolymer of the mixture of sulfonated fluoropolymer and zeolite is the same sulfonated fluoropolymer as that of the proton exchange membrane.
  • the sulfonated fluoropolymer of the mixture of sulfonated fluoropolymer and zeolite is a perfluorosulfonic acid material such as Nafion® (Du Pont), Dow membrane (Dow Chemical), Flemion membrane (Asahi Glass Co.), Aciplex membrane (Asahi Chem.), BAM (Ballarde), Solvay Hyflon or Gore-select membrane (W.L.
  • the sulfonated fluoropolymer of the mixture of sulfonated fluoropolymer and zeolite is a Nafion® material.
  • the sulfonated fluoropolymer of the mixture of sulfonated fluoropolymer and zeolite is Nafion® 1 17.
  • Zeolites are naturally occurring aluminosilicate crystals and have well defined and uniform pore size. As a result they can separate molecules based on their size and shape. They have high level of size selectivity in such separations and hence are called molecular sieves. The proportions of Si and Al atoms can be altered. This affects their
  • hydrophobic/hydrophilic characters These properties make them ideal candidates for use in the composite membranes of the present invention.
  • the zeolite is selected from the group comprising: ZSM-5, zeolite A, zeolite X, zeolite Y, mordenite, AIP0 4 , SAPO, MeAIPO, SAPO-5, AIPO-5, VPI-5, MCM-41 , chabazite, clinoptilolite, silica gel, zirconium-containing minerals, titanium-containing minerals, silicates and mixtures thereof.
  • AIP0 4 , SAPO, MeAIPO, SAPO-5, AIPO-5, VPI-5, MCM-41 are all 'zeotype' materials (analogous of zeolites with different metals other than alumina-silicate, e.g.
  • SAPO-5, AIPO-5 and VPI-5 are all analogous of zeolite ZSM-5 and have an MFI structure).
  • the titanium-containing mineral is an oxide of titanium i.e. a titanate.
  • the zeolite is mordenite. Natural mordenite has a Si/AI ratio of about 5. High purity synthesized mordenite has an increased Si/AI ratio of about 10 and high silica mordenites of having an Si/AI ratio of more than 40 are also known. Thus, in an embodiment, the mordenite has a Si/AI ratio of between about 5 and 40. In an embodiment, the mordenite has a Si/AI ratio of between about 5 and 20, preferably 10 and 15. In an embodiment, the mordenite has a Si/AI ratio of about 13.
  • the zeolite is selected from the group comprising: zeolite-A (Si/AI>1 ), zeolite-Y (Si/AI>2.5), zeolite- ⁇ (Si/AI>8-20), ZSM5 (Si/AI>10), Chabazite (Si/AI>4), Clinoptilolite (Si/AI>2) and Faujasite (Si/AI>1 .5).
  • the ionic form and nature of the functionalisation of the zeolite can affect the performance of the MEA, for example, by improving methanol resistance of the MEA. This is demonstrated in example 1 1 for the zeolite, mordenite.
  • the zeolite is protonated zeolite.
  • the zeolite is silane functionalised zeolite.
  • the zeolite is sodium form zeolite.
  • the particle size of the zeolite employed in the barrier layer may be varied and may affect the performance of the MEA.
  • the particle size or the zeolite is ⁇ 500 nm, preferably ⁇ 400 nm, more preferably ⁇ 350 nm and yet more preferably ⁇ 300 nm.
  • Figures 30 and 31 demonstrate that comparable DMFC performance can be achieved with both smaller and larger particles which demonstrates the broad range of zeolite particles sizes that can be employed in the MEAs of the present invention.
  • Figures 32 (a), (b) and (c) are SEM images of composite barrier layers featuring (a) FH- mordenite, (b) supernatent FH-mordenite with a particle size ⁇ 300nm and (c) sprayed Nafion.
  • Figure 32 (a) shows a dark band across the centre of the image. This indicates the presence of a layered structure when larger FH mordenite particles are employed.
  • Figure 32 (b) shows a structure having greater homogeneity when using supernatant mordenite. It is possible that this could lead to further reductions in loading and therefore MEA resistance which in turn could give better DMFC performance.
  • Figure 32 (c) is an SEM image of plain sprayed Nafion (i.e. having no particles present). The cracks in this image appear due to the intensity of the SEM beam.
  • the total zeolite content affects the power density of the resulting membrane electrode assembly.
  • the narrow range of zeolite loading of the MEA of the present invention does not deleteriously affect the power density of the MEA.
  • the narrow range of zeolite loading of the MEA of the present invention actually improves the power density of the MEAs of the present invention when compared to conventional MEAs. This is entirely contrary to the prior art which teaches that the loading of zeolite in the MEAs actually lowers the power density.
  • Example 12 demonstrates the loading of the zeolite, mordenite, and its effects on the performance of the MEAs.
  • mordenite the performance of the MEAs is improved for loading at 0.25, 0.5 and 0.75%.
  • MEAs having a mordenite loading of 1 % perform less favourably to MEAs having a loading of 0.25, 0.5 and 0.75%.
  • the best performance improvement is achieved using a 0.5% mordenite loading.
  • the total zeolite content represents between 0.1 and 1.0% (exclusive) by weight of the sum of the sulfonated fluoropolymer proton exchange membrane and the sulfonated fluoropolymer of the one or more layers. In an embodiment, the total zeolite content represents from 0.25 to 0.75% by weight of the sum of the sulfonated
  • the total zeolite content represents from 0.4 to 0.6% by weight of the sum of the sulfonated fluoropolymer proton exchange membrane and the sulfonated fluoropolymer of the one or more layers.
  • the total zeolite content represents 0.5% by weight of the sum of the sulfonated fluoropolymer proton exchange membrane and the sulfonated fluoropolymer of the one or more layers.
  • a process for preparing a membrane electrode assembly comprising: (a) applying a mixture of a proton exchange membrane (PEM) polymer solution and a zeolite to a first electrode to form a layer of a composite on the first electrode, and optionally repeating the application of the mixture to the first electrode one or more times;
  • PEM proton exchange membrane
  • forming a membrane electrode assembly by contacting a first face of a PEM with the first electrode and contacting a second face of the PEM with the second electrode.
  • the application of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite to the first electrode is repeated once, twice, three times, four times, five times or six times.
  • two, three, four, five, six or seven layers of the mixture of the proton exchange membrane (PEM) monomer and the zeolite may be formed on the electrode.
  • the optimum number of layers of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite to a first electrode has been found to be four layers. This is illustrated in figure 28 (a1 ) and (a2).
  • the optimum number of layers of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite to a first electrode has been found to be more than four layers. For example, for 2M and 4M methanol concentration, the optimum number of layers has been found to be 5 layers. In an embodiment, therefore, the application of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite to the first electrode is repeated three times.
  • Figure 28 shows that improvements were seen with all MEAs at temperatures above 40C.
  • the first electrode is the anode and the second electrode is the cathode. In an alternative embodiment, the first electrode is the cathode and the second electrode is the anode. Preferably, the first electrode is the anode and the second electrode is the cathode.
  • the process does not include step (c).
  • only the first electrode includes the layer of a composite of the proton exchange membrane (PEM) polymer solution and the zeolite.
  • PEM proton exchange membrane
  • the process does include step (c).
  • the process involves applying a mixture of the proton exchange membrane (PEM) monomer and a zeolite to the second electrode to form a layer of a composite on the second electrode.
  • the application of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite to the second electrode is repeated once, twice, three times, four times, five times or six times.
  • two, three, four, five, six or seven layers of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite may be formed on the second electrode.
  • the optimum number of layers of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite to the second electrode has been found to be four layers. In an embodiment, therefore, the application of the mixture of the proton exchange membrane (PEM) polymer solution and the zeolite to the second electrode is repeated three times.
  • the MEA is formed by hot pressing together the first electrode, PEM and second electrode so that the PEM is between the first electrode and the second electrode.
  • the proton exchange membrane is a sulfonated fluoropolymer proton exchange membrane.
  • the sulfonated fluoropolymer proton exchange membrane is a perfluorosulfonic acid membrane.
  • the process of the second aspect of the invention can be used to produce a membrane electrode assembly having a zeolite content in the range of 0.1 to 6.0% by weight of the sum of the proton exchange membrane and the solution polymer content of the one or more layers, preferably 0.1 to 3.0% and more preferably 0.25 to 2%.
  • the total zeolite content of the final MEA represents from 0.25 to 0.75% by weight of the sum of the proton exchange membrane and the solution polymer content of the one or more layers.
  • the total zeolite content represents from 0.4 to 0.6% by weight of the sum of the proton exchange membrane and the solution polymer content of the one or more layers.
  • the total zeolite content represents 0.5% by weight of the sum of the proton exchange membrane and the solution polymer content of the one or more layers.
  • the mixture of the PEM solution and zeolite is applied to the first electrode by spraying, immersion or spreading on with a blade.
  • the mixture of the PEM solution and zeolite is applied to the first electrode by spraying. Spraying provides a uniform layer of the mixture on the electrode.
  • the mixture of the PEM solution and zeolite is applied to the second electrode by spraying, immersion or spreading on with a blade.
  • the mixture of the PEM solution and zeolite is applied to the second electrode by spraying.
  • the level of zeolite loading in the MEA is such that the layer allows protons through the membrane but impedes alcohol cross over through the membrane.
  • the hydrophilic particles each have a hydrophilic zone surrounding the particle.
  • the desired level of hydrophilic particle loading provides an array of hydrophilic particles having overlapping hydrophilic regions to prevent alcohol crossover but large enough gaps between the particles to allow proton conduction to occur through the membrane.
  • the amount of zeolite in the PEM monomer / zeolite mixture is chosen such that the final MEA comprises from 0.1 to 6% by weight of the sum of the proton exchange membrane and the monomer of the one or more layers.
  • This level of loading will depend on a number of factors including the thickness of the PEM including the proton conductivity/resistance, water uptake and methanol uptake of the zeolite and the polymeric material used. Other preferred ranges of the amount of zeolite in the final MEA are described above.
  • the entire procedure for fabricating the MEA (including the steps of making the anode and cathode can be divided into three steps: (1 ) application of different layers onto the electrodes, (2) membrane treatment, and (3) integrating membrane and electrodes into MEA. Individual steps involved in the preparation of MEA were:
  • a bonding layer 4. Applying a bonding layer; 5. Applying a barrier layer (i.e. a layer of a composite including zeolite);
  • Step 5 above was applied only to the composite MEA's and not to standard MEAs for comparison.
  • the bonding layer was not applied separately.
  • Application of each layer involved the same two steps. First was the
  • the second step in applying the layers was spraying the ink using the spray gun.
  • a membrane electrode assembly obtainable by the process of the second aspect described above.
  • DAFC Direct Alcohol Fuel Cell
  • the DAFC is a DMFC. In an alternate embodiment, the DAFC is a direct ethanol fuel cell (DEFC).
  • DEFC direct ethanol fuel cell
  • MEA testing was carried out for standard MEA and the MEAs with barrier layer (Composite MEAs), in order to compare their DMFC performance.
  • DMFC tests were carried out in a fuel cell testing unit, details of which are given below. The procedure followed for obtaining DMFC performance results is also given below.
  • the experimental setup can be divided into three categories for ease of explanation. First is the fuel cell testing unit where the MEAs were tested. Second is the electrical circuit which measured the voltage and current output of the MEA. Third is the reactant supply and product removal lines. Schematics of experimental setup are shown in figures 1 and 2. For the sake of clarity the electrical circuit is shown separately.
  • liquid methanol and water was fed to the anode flowfield (AF) from methanol tank (MeOH Tank) using a peristaltic pump.
  • Product stream from the anode was re-circulated back to the methanol tank.
  • Change in methanol concentration for one run (one concentration of methanol run at different temperatures) was assumed to be insignificant to affect DMFC performance.
  • Air from compressed cylinder was supplied to the cathode flowfield (CF). Its pressure and flow were measured by the flow meter and pressure gauge (see figure 1 ). Exit line from the cathode was sent to the drain.
  • a heater was used to control the cell temperature.
  • a temperature probe was used to measure the anode flowfield temperature.
  • Figure 2 shows the electrical circuit.
  • Anode flowfield of the cell (where oxidation takes place and hence electrons are generated) was connected to the positive terminal of the power supply. While the cathode flowfield (where reduction takes place and hence electrons are consumed) was connected to the negative of the power supply.
  • a load was placed in the circuit to simulate a real load.
  • An ammeter was connected in series with the power supply for measuring the current. While a voltmeter was connected in parallel to the cell to measure voltage.
  • Figure 1 Schematic of experimental setup showing testing unit and supply and removal lines.
  • Figure 2 Schematic of experimental setup showing the electrical circuit.
  • Figure 3 Plot of voltage against current density for standard MEA at 70°C and 1 M methanol concentration in feed.
  • Figure 4 Plot of voltage against current density for standard MEA at 1 M methanol concentration in feed and at different temperatures.
  • Figure 5 Plot of power density against current density for standard MEA at 1 M methanol concentration in feed at different temperatures.
  • Figure 6 Plot of voltage against current density for standard MEA at 2 M methanol concentration in feed at different temperatures.
  • Figure 7 Plot of power density against current density for standard MEA at 2 M methanol concentration in feed at different temperatures.
  • Figure 1 1 Effect of concentration on cell voltage at 90°C.
  • Figure 12 Power density curves at different temperatures for MEA 0.25% and 2M methanol concentration in feed
  • Figure 18 Power density curves for MEA 0.5% at different temperatures and 5M methanol concentration in the feed
  • Figure 19 Power density curves for MEA 0.5% at different temperatures and 6M methanol feed.
  • Figure 20 Comparison of power density curves for MEA 0% and MEA 0.5% at 60°C, 70°C and 80°C. Note that concentration of methanol feed to MEA 0% is 4M while that for MEA 0.5% is 5M.
  • Figure 21 An example procedure for silane functionalising of mordenite.
  • Figure 22 An illustration of the chemical modification of zeolite surface by silane coupling agent GPTMS.
  • Figure 23 XRD patterns of HMOR before and after silane functionalising.
  • Figure 24 Illustrates that the power densities show improvements when the barrier layer is placed at the anode or the cathode under all conditions when compared to the standard results from the application. The improvements are better when the layer is placed at the anode.
  • Figure 24 (a) is for 1 M
  • (b) is for 2M
  • (c) is for 4M methanol feeds for an MEA with 0.5% FMOR loadings at anode and cathode against standard Nafion 1 17.
  • Figure 25 Illustrates that the current densities show improvement when the barrier layer is placed at the anode for all conditions when compared to the standard results. The current density is improved when the barrier layer is placed at the cathode for 2M and 4M methanol flows, but not for 1 M methanol flow.
  • Figure 25 (a) is for 1 M, (b) is for 2M, (c) is for 4M methanol feeds for an MEA with 0.5% FMOR loadings at anode and cathode against standard Nafion 117.
  • Figure 26 Illustrates that the power densities show improvements when the barrier layer is placed at the anode and the cathode under all conditions when compared to the standard results.
  • the MEAs having a barrier layer are loaded with 3mg of Pt and 0.5% MOR.
  • Figure 26 (a) is for 1M
  • (b) is for 2M
  • (c) is for 4M
  • (d) is for 5M methanol feeds for MEA with 3mg platinum loadings against standard Nafion 117.
  • Figure 27 Illustrates that the current densities show improvements when the barrier layer is placed at the anode and the cathode under all conditions when compared to the standard results.
  • the MEAs having a barrier layer are loaded with 3mg of Pt and 0.5% MOR.
  • Figure 27 (a) is for 1M
  • (b) is for 2M
  • (c) is for 4M
  • (d) is for 5M methanol feeds for MEA with 3mg Pt loadings against standard Nafion 117.
  • Figure 28 Illustrates the improvement in (1) power density and (2) current density versus a standard MEA of novel MEAs using differing numbers of sprayed layers using (a) 1M, (b) 2M and (c) 4M methanol feeds.
  • Figure 29 Illustrates a comparison of the durability of a standard MEA and an MEA according to the present invention.
  • the labels (A) to (D) on the figure represent:
  • Figure 30 Max power densities for (a) 1 M, (b) 2M, (c) 4M methanol feeds for MEA with 0.5% normal (diamond) and supernatent ( ⁇ 300 nm) (square) mordenite loadings against standard Nafion 117.
  • Figure 31 Max current densities for (a) 1 M, (b) 2M, (c) 4M methanol feeds for MEA with 0.5% normal (diamond) and supernatent ( ⁇ 300 nm) (square) mordenite loadings against standard Nafion 117.
  • Figure 32 SEM images of composite barrier layer featuring: (a) functionalised H- mordenite; (b) supernatent FH-mordenite with a particle size ⁇ 300nm; (c) sprayed Nafion.
  • N.B. FH-mordenite stands for silane functionalised protonated mordenite.
  • Figure 33 (a) 1 M and (b) 2M DEFC performance using 0.5% silane functionalised mordenite as the barrier layer at various temperatures.
  • the words “comprise” and “contain” and variations of them mean “including but not limited to”, and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps.
  • the singular encompasses the plural unless the context otherwise requires.
  • the indefinite article the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.
  • Example 1 applying the gas diffusion layer (GDL)
  • Components of the GDL are ketjan black carbon and binding polymer
  • PTFE polytetrafluoroethylene
  • the binding polymer was desired to constitute 10% of GDL's weight, i.e.
  • a waste factor of 4 was used to allow for inevitable wastage of materials while spraying (maximum up to 4 times the target weight). Based on these constraints, following quantities of materials were used in preparing carbon ink,
  • Carbon ink preparation Carbon ink for GDL was prepared according to the following steps,
  • PTFE was weighed in a bottle. PTFE was added to bind the carbon particles in GDL.
  • IPA Isopropyl alcohol
  • IPA was then added in small increments. During these IPA additions any carbon on the walls of the container were drawn back into the solution.
  • step 7 The ink was sonicated for 30 minutes and the above steps 5 and 6 were repeated until all the remaining IPA was added. Note that the amount of IPA added after each sonication was incrementally raised from 2 mL to 5 mL by 1 mL at a time. Low volumes of solvent was added initially to achieve uniform dispersion of materials (same reasons as step 2).
  • Carbon and PTFE for GDL was applied by spraying according to the following steps,
  • the plain carbon paper (/backing layer) was first weighed. This is the foundation structure on which all layers of the electrodes are fabricated.
  • Airbrush was connected to the compressed nitrogen supply.
  • Carbon ink was sprayed in layers. Usually 3 mL of ink was sprayed per layer and it was dried in the oven at 1 10oC to completely remove residual solvent IPA). layer can be defined as the amount of materials deposited on the carbon paper before completely removing the solvent. This method was followed in order to achieve the target weight of materials for the whole GDL layer, by weighing each layer and calculating the required amount of ink to be sprayed after each layer. 5. Spraying was started by wetting the carbon paper with solvent. This would encourage the interaction between the first layer of the ink and the carbon paper. It was ensured that the backing layer was thoroughly wet by IPA.
  • Carbon ink was sprayed immediately following the previous step before the solvent evaporates. It was necessary to maintain right posture while spraying in order to ensure correct distance from the carbon paper and the angle of spraying. The distance between the nozzle of the airbrush and he carbon paper was approximately maintained around 2 cm and the airbrush was held at right angles to the carbon paper.
  • the backing layer was weighed. From the weight increment, density of the ink was calculated and the amount required to achieve target weight was worked out.
  • the backing layer with GDL materials was sintered at 360°C for 1 hour in oven. Temperature was increased in a controlled manner from ambient temperature to 360°Cfor 1 hour and allowed to cool naturally in the oven.
  • Components of the anode are carbon supported Pt/Ru bi metal catalyst and Nafion, for binding the catalyst particles and to form the vital 3 phase region (between electrolyte, electrode and reactants, see figure 1 .9.
  • the quantities required for anode was calculated based on two main constraints,
  • catalyst layer i.e. Nafion.
  • Table 3.2 Materials used for preparing anode catalyst ink.
  • Components of cathode layer are carbon supported Pt catalyst and Nafion, for binding the catalyst particles and to form the vital 3 phase region.
  • the quantities required for cathode was calculated based on two main constraints,
  • Both catalyst inks were prepared Both catalyst inks were sprayed in a similar manner to carbon ink. The only differences were the use of acetone as solvent instead of I PA, the platform was not heated (since acetone is more volatile than I PA), catalyst ink was sprayed on backing layer with GDL on it (not plain backing layer as for carbon ink) and eliminating the last sintering step at 360oC. When spraying was completed, the electrodes were dried in oven at 1 10oC, just like the drying step between each layer sprayed.
  • Bonding layer was applied in between the electrode and the membrane. Its component is essentially Nafion. Materials and quantity for bonding layer
  • a waste factor of 1.2 was included in the above calculations. These quantities are for one electrode of dimensions 4.5cm x 4.5cm.
  • Bonding ink was prepared according to the simple procedure given below,
  • Bonding layer was sprayed according to the steps below,
  • the electrode was wet with acetone.
  • the electrode with the bonding layer was dried in an oven at between 100 and 100°C ⁇ 5°C.
  • the barrier layer was applied only to the anodes of composite MEAs.
  • This layer was essentially a modification of the bonding layer between the anode and membrane.
  • the weight of mordenite required for this layer was too small to be measured accurately by the electronic weighing scale used.
  • a slurry containing acetone and ten times the weight of mordenite required in the ink was prepared.
  • the mordenite required for the barrier layers was transferred on a volumetric basis to a separate vial.
  • the desired quantity of Nafion and acetone were added to make the mordenite ink to be sprayed as the barrier layer.
  • Components of the barrier layer were mordenite (functionalised and hTforrn) and Nafion.
  • the weight of mordenite in the barrier layer to be sprayed on the electrode was calculated as a fraction of the weight of Nafion in the membrane, as follows,
  • the three composite MEAs had the following barrier layers, (where the % under Barrier layer column refers to the weight % of Nafion in Nafion 1 17 membrane),
  • a waste factor of 4 was included in the mordenite inks in the above calculations. These quantities are for one electrode of dimensions 4.5cm x 4.5cm.
  • the required amount of mordenite for the inks was transferred from the slurry on a volumetric basis, hence it was absolutely essential to ensure homogeneity of the slurry. For this reason the slurry was stirred using a magnetic stirrer for one hour, followed by sonication for 1 hour (in the sonicator) and magnetic stirring for one hour again. Basically macro mixing and micro mixing were done alternatively. This process was not done on the basis of optimising mixing of slurry hence the elaborate mixing time. After mixing the slurry the required volume was immediately transferred into the vial for mordenite ink. The same mixing procedure was followed for mordenite ink to ensure homogeneity.
  • Mordenite ink was sprayed in multiple layers (similar to carbon and catalyst inks) according to the steps below,
  • the electrode was wet with acetone.
  • Membrane pre-treatment was carried out in order to hydrate it, clean it and functionalise it. Details of materials used and procedure followed are given below, Materials required
  • Nafion 1 17 membrane of the required size was cut.
  • MEA membrane electrode assembly
  • the MEA is then placed in a fuel cell test unit and hydrated with deionised water.
  • Performance test were carried out by varying one operating variable while holding others constant. Electrical output in terms of voltage and current were measured. Operating variables of significance were identified as methanol concentration in the feed and operating temperature of cell (Ge and Liu (2005)). All other variables including air flow rate, methanol flow rate, air and methanol pressure were held constant. These values are shown in the table below.
  • the concentration of oxygen in the air supply was assumed to be the same for
  • Figure 3 shows the polarisation curve obtained for standard MEA at 70°C and 1 M methanol concentration in the feed.
  • the curve begins at an open circuit voltage (OCV) less than the theoretical value, then there is a step drop in voltage at low current densities followed by linear drop at mid current densities and terminated by faster drop in voltage (increasing gradient) at high current densities.
  • OCV open circuit voltage
  • Figure 4 shows the polarisation curves obtained at different temperatures and 1 M methanol feed. Typical fuel cell behaviour is exhibited at all temperatures. In the figure below the curves at low temperatures appear to be linear through all the zones. This is because they are plotted together with those at higher temperatures which have large range for current density. If the low temperature curves are plotted individually then they closely represent typical fuel cell behaviour.
  • Figure 5 below is a plot of power density against current density for 1 M methanol feed at different temperatures. It can be seen that temperature affects two main values in the curve. They are maximum power density and limiting current density.
  • Figures 6 and 7 show the results obtained for 2 M methanol concentration in the feed. The same behaviour (as that for 1 M methanol feed) is evident.
  • Figure 8 shows the effect of concentration on all voltage and power at 50°C.
  • Figure 9 shows the effect of concentration on cell voltage and power at 70°C.
  • OCV decreases with increase in concentration of methanol. Also there is a decrease in voltage for the whole range. The decrease is much larger for 4 M than for 2 M. Same trends were observed for other temperatures. Thus methanol crossover affects performance at all currents and temperatures. Power density changes according to change in voltage at the same current. Hence polarisation curves for other temperatures are plotted without the power density. This also shows other features in the polarisation curves more clearly.
  • the decrease in OCV and voltage at lower current densities, with increase in methanol concentration, indicate that MCO detrimentally affects performance.
  • Figure 10 shows the effect of concentration on all voltage and power at 80°C.
  • Figure 1 1 shows the effect of concentration on all voltage and power at 90°C.
  • Membrane electrode assembly with Nafion 1 17 and a barrier layer containing 0.5% wt mordenite with respect to the weight of Nafion in the Nafion 1 17 membrane - MEA 0.5%
  • Example 10 Comparison of results for composite and standard membrane electrode assemblies.
  • Power density curves are used to present the results for different MEAs.
  • Composite MEAs showed significant improvement in performance (especially MEA 0.5%) at all temperatures and methanol concentrations compared to the standard MEA with no barrier layer.
  • MEA 0.5% had better performance then MEA 0.25%, indicating that performance improves with mordenite concentration in the barrier layer.
  • Figures 13, 14 and 15 compare the power density curves at 50°C, 70°C and 90°C for 1 M methanol concentration in the feed. These figures are an example of improvement in performance across all temperatures.
  • the composite MEA 0.5% was also run at 5M and 6M methanol concentration in the feed.
  • the standard MEA 0% performed very poorly at 4M methanol concentration in the feed due to high methanol crossover.
  • the power density results for MEA 0.5% at 5M and 6M methanol concentration in the feed is given in figures 19 and 20 below.
  • the third column shows the increase in Pmax for MEA 0.5% as a percentage of Pmax value for MEA 0%.
  • the barrier layer in composite MEAs is effective in reducing methanol crossover without adversely affecting proton conductivity. This is strongly proved by the superior performance of MEA 0.5% at 5M compared to the reasonable performance of standard MEA to a maximum concentration of 4M. Hence the research objective of reducing methanol crossover without affecting proton conductivity seems to have been achieved.
  • the performance of standard MEA was repeated by fabricating a new MEA and the results obtained at selected temperatures and
  • Example 11 effect on the performance of an MEA due to the ionic form and nature of the silane functionalisation of mordenite
  • This example demonstrates the effect on the performance of an MEA due to the mordenite ionic form and nature of the silane functionalisation of the mordenite.
  • mordenite is ground before using and undergoes an ion-exchange reaction (by treatment with cone. H 2 S0 4 ).
  • H 2 S0 4 cone.
  • better performance is obtained with all of the MEAs according to the present invention, especially at higher temperatures.
  • the improvement in performance at higher temperatures is thought to be due to more facile anode kinetics and increased amounts of methanol crossover.
  • the MEAs according to the present invention are able to reduce the increased methanol crossover at the higher temperatures relative to the methanol fuel crossover of conventional MEAs.
  • FH silane functionalised protonated mordenite: particle size ⁇ 300nm
  • Example 12 the effect of silane functionalised mordenite loading.
  • This example demonstrates the effect the level of loading of the silane functionalised mordenite has on the performance of the MEAs.
  • the performance of the MEAs is improved for loading of silane functionalised mordenite at 0.25, 0.5 and 0.75%.
  • MEAs having a silane functionalised mordenite loading of 1 % perform less favourably to MEAs having a loading of 0.25, 0.5 and 0.75%.
  • the improved performance is particularly exhibited at higher temperatures.
  • the improvement in performance at higher temperatures is thought to be due to more facile anode kinetics and increased amounts of methanol crossover.
  • the MEAs according to the present invention are able to reduce the increased methanol crossover at the higher temperatures relative to the methanol fuel crossover of conventional MEAs.
  • FH silane functionalised protonated mordenite: particle size ⁇ 300nm

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Sustainable Development (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention concerne un ensemble électrode à membrane, un procédé de fabrication d'ensembles électrodes à membranes et des piles à combustible à utilisation directe d'alcool comportant un ensemble électrode à membrane selon la présente invention. Du fait de sa structure, l'ensemble électrode à membrane selon la présente invention présente un transfert d'alcool réduit par comparaison à des membranes conventionnelles.
PCT/GB2011/051531 2010-08-12 2011-08-12 Ensemble électrode à membrane Ceased WO2012020268A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1013526.7 2010-08-12
GBGB1013526.7A GB201013526D0 (en) 2010-08-12 2010-08-12 Membrane electrode assembly

Publications (1)

Publication Number Publication Date
WO2012020268A1 true WO2012020268A1 (fr) 2012-02-16

Family

ID=42937867

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2011/051531 Ceased WO2012020268A1 (fr) 2010-08-12 2011-08-12 Ensemble électrode à membrane

Country Status (2)

Country Link
GB (1) GB201013526D0 (fr)
WO (1) WO2012020268A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811771A (zh) * 2014-01-20 2014-05-21 哈尔滨工业大学深圳研究生院 一种用于直接甲醇燃料电池的质子交换膜的改性方法
WO2015021278A3 (fr) * 2013-08-09 2015-04-23 Junhang Dong Membranes d'échange ionique microporeuses inorganiques pour batteries à écoulement redox
WO2020252435A1 (fr) * 2019-06-14 2020-12-17 University Of Maryland, College Park Systèmes et procédés de synthèse à haute température de dispersions à atome unique et de dispersions à atomes multiples

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003282095A (ja) * 2002-03-26 2003-10-03 Rikogaku Shinkokai 燃料電池用電解質膜およびその製造方法
WO2004015801A1 (fr) 2002-08-13 2004-02-19 Hoku Scientific, Inc. Electrolyte composite pour piles a combustible
US20040241520A1 (en) 2003-05-31 2004-12-02 Korea Institute Of Science And Technology Method to manufacture composite polymer electrolyte membranes coated with inorganic thin films for fuel cells
EP1648047A1 (fr) * 2004-10-14 2006-04-19 Samsung SDI Co., Ltd. Electrolyte polymère pour pile à combustible à combustion directe, méthode pour sa préparation et pile à combustible à oxydation directe le comprenant
WO2008030198A1 (fr) * 2006-09-07 2008-03-13 Nanyang Technological University Matériau composite d'électrode
US20080070094A1 (en) 2006-06-20 2008-03-20 Lg Chem, Ltd. Organic/inorganic composite electrolyte membranes using zeolite and fuel cell comprising the same
US20080182154A1 (en) * 2007-01-30 2008-07-31 Cheil Industries Inc. Coating Slurry for Cation-Conducting Polymer Composite Membrane, Method for Producing Cation-Conducting Polymer Composite Membrane Using the Coating Slurry, Membrane-Electrode Assembly, and Fuel Cell
WO2009073055A1 (fr) 2007-09-04 2009-06-11 Chemsultants International, Inc. Membrane échangeuse de protons composite multicouche et son procédé de fabrication
US20100038316A1 (en) 2008-08-12 2010-02-18 General Electric Company Poly(tetrafluoroethylene) zeolite composite and methods

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003282095A (ja) * 2002-03-26 2003-10-03 Rikogaku Shinkokai 燃料電池用電解質膜およびその製造方法
WO2004015801A1 (fr) 2002-08-13 2004-02-19 Hoku Scientific, Inc. Electrolyte composite pour piles a combustible
US20040241520A1 (en) 2003-05-31 2004-12-02 Korea Institute Of Science And Technology Method to manufacture composite polymer electrolyte membranes coated with inorganic thin films for fuel cells
EP1648047A1 (fr) * 2004-10-14 2006-04-19 Samsung SDI Co., Ltd. Electrolyte polymère pour pile à combustible à combustion directe, méthode pour sa préparation et pile à combustible à oxydation directe le comprenant
US20080070094A1 (en) 2006-06-20 2008-03-20 Lg Chem, Ltd. Organic/inorganic composite electrolyte membranes using zeolite and fuel cell comprising the same
WO2008030198A1 (fr) * 2006-09-07 2008-03-13 Nanyang Technological University Matériau composite d'électrode
US20080182154A1 (en) * 2007-01-30 2008-07-31 Cheil Industries Inc. Coating Slurry for Cation-Conducting Polymer Composite Membrane, Method for Producing Cation-Conducting Polymer Composite Membrane Using the Coating Slurry, Membrane-Electrode Assembly, and Fuel Cell
WO2009073055A1 (fr) 2007-09-04 2009-06-11 Chemsultants International, Inc. Membrane échangeuse de protons composite multicouche et son procédé de fabrication
US20100038316A1 (en) 2008-08-12 2010-02-18 General Electric Company Poly(tetrafluoroethylene) zeolite composite and methods

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
LI X ET AL: "Evaluation of composite membranes for direct methanol fuel cells", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 154, no. 1, 9 March 2006 (2006-03-09), pages 115 - 123, XP025083760, ISSN: 0378-7753, [retrieved on 20060309], DOI: 10.1016/J.JPOWSOUR.2005.03.222 *
LI, ROBERTS, HOLMES: "Evaluation of composite membranes for DMFC", JPS, vol. 154, no. 1, 2006, pages 115 - 123, XP025083760, DOI: doi:10.1016/j.jpowsour.2005.03.222
SCHULTZ ET AL., CHEMICAL ENGINEERING AND TECHNOLOGY, vol. 24, no. 12, 2001, pages 1223 - 1233
T.S ZHAO, MICRO FUEL CELLS: PRINCIPLES AND APPLICATIONS, 2009, pages 10
TRICOLI V ET AL: "Zeolite-Nafion composites as ion conducting membrane materials", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 48, no. 18, 1 August 2003 (2003-08-01), pages 2625 - 2633, XP004435009, ISSN: 0013-4686, DOI: 10.1016/S0013-4686(03)00306-2 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015021278A3 (fr) * 2013-08-09 2015-04-23 Junhang Dong Membranes d'échange ionique microporeuses inorganiques pour batteries à écoulement redox
CN106163805A (zh) * 2013-08-09 2016-11-23 辛辛那提大学 适于氧化还原液流电池的无机微孔离子交换膜
US9911985B2 (en) 2013-08-09 2018-03-06 University Of Cincinnati Inorganic microporous ion exchange membranes for redox flow batteries
CN103811771A (zh) * 2014-01-20 2014-05-21 哈尔滨工业大学深圳研究生院 一种用于直接甲醇燃料电池的质子交换膜的改性方法
CN103811771B (zh) * 2014-01-20 2016-04-13 哈尔滨工业大学深圳研究生院 一种用于直接甲醇燃料电池的质子交换膜的改性方法
WO2020252435A1 (fr) * 2019-06-14 2020-12-17 University Of Maryland, College Park Systèmes et procédés de synthèse à haute température de dispersions à atome unique et de dispersions à atomes multiples
US12201964B2 (en) 2019-06-14 2025-01-21 University Of Maryland, College Park Systems and methods for high temperature synthesis of single atom dispersions and multi-atom dispersions

Also Published As

Publication number Publication date
GB201013526D0 (en) 2010-09-29

Similar Documents

Publication Publication Date Title
Vinothkannan et al. Potential bifunctional filler (CeO2–ACNTs) for nafion matrix toward extended electrochemical power density and durability in proton-exchange membrane fuel cells operating at reduced relative humidity
Ercelik et al. Investigation of Nafion based composite membranes on the performance of DMFCs
Shao et al. Hybrid Nafion–inorganic oxides membrane doped with heteropolyacids for high temperature operation of proton exchange membrane fuel cell
Xiang et al. Layer-by-layer self-assembly in the development of electrochemical energy conversion and storage devices from fuel cells to supercapacitors
Niluroutu et al. A copper–trimesic acid metal–organic framework incorporated sulfonated poly (ether ether ketone) based polymer electrolyte membrane for direct methanol fuel cells
EP2161770A1 (fr) Ensemble film-électrode, ensemble film-électrode-couche de diffusion de gaz comprenant cet ensemble, pile à combustible à polymère semi-conducteur et procédé de fabrication de l'ensemble film-électrode
WO2005124911A1 (fr) Membrane polyélectrolyte solide pour pile à combustible, procédé de production de cette même membrane et assemblage électrodes-membrane pour pile à combustible à polymère solide
KR20150135116A (ko) 복합 전해질 막, 이의 제조방법 및 이의 용도
Lee et al. Nafion based organic/inorganic composite membrane for air-breathing direct methanol fuel cells
KR20100098528A (ko) 고 안정성 연료 전지 막 및 그의 제조 방법
WO2013064640A1 (fr) Procédé pour la préparation de membranes revêtues par catalyseur
CN104852003A (zh) 聚合物电解质膜、包括它的膜电极组件和燃料电池
KR20090054875A (ko) 불소가스를 이용한 직접불소화법에 의해 표면처리된수소이온전도성 고분자막, 이를 포함하는 막-전극 어셈블리및 연료전지
CN1764001B (zh) 用于直接氧化燃料电池的聚合物电解液及其制备方法以及包含它的直接氧化燃料电池
EP2169751A1 (fr) Ensemble d'électrode à membrane, son procédé de production et pile à combustible polymère solide
You et al. High performance membrane electrode assemblies by optimization of coating process and catalyst layer structure in direct methanol fuel cells
TW200921978A (en) Membrane-electrode assembly, method for production thereof, and solid polymer fuel cell
CN1981400B (zh) 固体高分子型燃料电池用电解质膜、其制造方法以及固体高分子型燃料电池用膜电极接合体
KR102093536B1 (ko) 고분자 전해질막, 이를 포함하는 막 전극 접합체 및 상기 막 전극 접합체를 포함하는 연료 전지
JP2025525301A (ja) 膜
WO2012020268A1 (fr) Ensemble électrode à membrane
US8163438B2 (en) Composite electrolyte membrane, production method thereof, membrane-electrode assembly, and fuel cell
JP2009021231A (ja) 触媒インク、触媒インクの製造方法、膜−電極接合体の製造方法及びこれにより得られる膜−電極接合体、並びに、燃料電池
EP4473147A2 (fr) Membranes revêtues de catalyseur pour électrolyseurs d'eau
CN101432915A (zh) 燃料电池用电解质膜和膜电极接合体、燃料电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11763752

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11763752

Country of ref document: EP

Kind code of ref document: A1