EP2070149A1 - A proton conductive membrane for a fuel cell or a reactor based on fuel cell technology and a method for making the membrane - Google Patents
A proton conductive membrane for a fuel cell or a reactor based on fuel cell technology and a method for making the membraneInfo
- Publication number
- EP2070149A1 EP2070149A1 EP07808876A EP07808876A EP2070149A1 EP 2070149 A1 EP2070149 A1 EP 2070149A1 EP 07808876 A EP07808876 A EP 07808876A EP 07808876 A EP07808876 A EP 07808876A EP 2070149 A1 EP2070149 A1 EP 2070149A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- membrane
- fuel cell
- sulfonic acid
- characteri
- reactor based
- 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.)
- Withdrawn
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- 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
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
- H01M8/0263—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant having meandering or serpentine paths
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- 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
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- 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
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- 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
- H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
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- 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
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- 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
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/881—Electrolytic membranes
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- 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
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- 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 proton conductive membrane for a fuel cell or a reactor based on fuel cell technology.
- the invention also relates to a method of manufacturing the proton conductive membrane.
- anode and cathode are used for the respective electrodes also when there is no voltage over them.
- proton conductive membrane is in this context meant a membrane having the ability on its one side to receive protons/hydroxonium ions and on its other side to emit a corresponding number of protons. When a proton enters the membrane from one side, another one is pushed out from the other side. The membrane will furthermore not allow for passage of electrons in the opposite direction and the passage of other ions than HVH 3 O + is not desired.
- DMFC is in this context further understood a fuel cell driven by liquid methanol (Direct Methanol Fuel Cell), which fuel cell comprises an anodic side having an anode and a catalyst for the anodic reaction, a cathodic side having a cathode and a catalyst for the cathodic reaction, as well as an intermediate membrane that separates the anodic and cathodic sides from each other.
- direct Methanol Fuel Cell direct Methanol Fuel Cell
- the fuel is liquid, thus enabling fast fuelling, that both the fuel cell, that can be
- Fuel cells of DMFC type are furthermore environmentally friendly, only water and carbon dioxide are discharged; no sulphur or nitrogen oxides are formed.
- the anode and the cathode in the disclosed fuel cell consist of graphite and are both provided on their respective one side with a channel system or the like, at the anode for supply of a liquid methanol-water mixture and at the cathode for supply of oxygen, neat or air oxygen.
- a channel system or the like Between the anode and the cathode there is a proton conductive membrane and between the membrane and the anode and the cathode, respectively, there is what is called a gas diffusion layer.
- the gas diffusion layers or the membrane on the anodic side carries a catalyst of Pt and Ru and on the cathodic side a catalyst of solely Pt.
- the gas diffusion layers consist of carbon cloth or carbon paper.
- the gas diffusion layer receives the CO 2 formed in connection with the oxidation of the methanol on the anodic catalyst and allows it to diffuse up to an upper end surface where CO 2 bubbles are formed.
- the supplied oxygen gas passes through the gas diffusion layer and reacts with electrons and protons passing through the membrane, to form water.
- the membrane Similar to membranes for other fuel cells driven by direct methanol, the membrane here consists of NafionTM, a sulphonated polymer of PTFE type.
- the catalysts are applied on the gas diffusion layers or on the membrane in the form of an ink of an organic solvent, finely powdered catalyst particles and a solution of NafionTM, after which the solvent is allowed to evaporate. It is stated to be essential to have a network of NafionTM for efficient transport of protons to the membrane.
- the thus prepared gas diffusion layers are furthermore used as electrodes.
- NafionTM does not have the desired methanol resistance but starts to dissolve already when exposed to 2 M (about 6 %) methanol.
- Known fuel cells of DMFC type have moreover had too low a power density, due to the slow electrochemical oxidation of methanol at the anode, and that methanol has been able to migrate through the PEM membrane (Polymer Electrolyte Membrane) to the cathode where the methanol has oxidised. This results not only in fuel loss, but also in that the platinum catalyst used at the cathode is poisoned by formed carbon monoxide, which leads to decreased efficiency. The complexity of the reactions has made it difficult to achieve a satisfying yield.
- the membrane according to the invention consisting of by sulfonic acid modified polyacrylamide.
- a membrane is not attacked by the reactants in DMFC cells, and sulfonic acids have a low pKa that allows for translation of protons/hydroxonium ions through the gel, while essentially preventing passage of other ions.
- sulfonic acids can be used that can be coupled to amide nitrogen, but e.g. 1- chlorotetrafluoroethylene sulfonic acid is costly and chlorosulfonic acid can form a product that is not completely stable.
- the sulfonic acid is preferably constituted by p-chlorobenzene sulfonic acid.
- the above mentioned object is furthermore achieved in connection with the method of manufacturing a proton conductive membrane from a by sulfonic acid modified polymer for a fuel cell or a reactor based on fuel cell technology, by, according to the invention, admixing polyacrylamide with p-chlorobenzene sulfonic acid in water and heating to the boiling point while stirring, after which the solution is allowed to slowly cool and, when the solution has reached room temperature, adding a cross-binder which gives a stable spatial configuration of the final polymer, initiating the actual polymerisation by adding a setting agent and in situ moulding the achieved mixture before it has set, to form a membrane.
- the polyacrylamide modified by p- chlorobenzene sulfonic acid solves the problem that higher contents of methanol can attack membranes of other polymeric materials and that methanol tends to migrate through the membrane and thereby impair the efficiency of the cell. If there is liquid on the other side of the membrane, the spontaneous diffusion of methanol through the membrane of said modified polyacrylamide can be almost completely eliminated, which means that this type of membrane is particularly well suited for cells that have liquid in both cell halves. Acrylamide is furthermore cheap to purchase.
- N,N' -methylene -bis-acrylamide is preferably used in combination with N,N,N',N'-tetramethylene diamine, which will give the final polymer a stable spatial configuration
- a peroxo salt is used, such as sodium percarbonate, sodium perbenzoate etc., but preferably ammonium persulfate.
- the mixture is moulded, preferably in situ, to form a membrane in the fuel cell or in the reactor based on fuel cell technology.
- the moulding which accordingly can be made in situ in the cell, can be done in a short time, about 40 sec.
- this embodiment results in improved sealing as well as elimination of the risk of damages to the thin membrane in connection with the mounting thereof, and the catalyst will better "creep" into the wall of the membrane as compared to the case in connection with pressing.
- Fig. 1 is a principle flowchart showing a fuel cell unit of DMFC type, in which liquid methanol is stepwise oxidised in fuel cells to form carbon dioxide and water.
- Fig. 2 is a view in cross-section over the fuel cell unit according to Fig. 1, showing a preferred arrangement of electrodes, intermediate membranes and flow channels.
- Figs. 3-4 are planar views over a couple of different flow patterns in which the reactants can be led inside each unit.
- Fig. 5 is a simplified cross-sectional view of a cell that has been prepared for the moulding of a proton conductive membrane between the electrodes.
- liquid methanol is stepwise oxidised in fuel cells to carbon dioxide and water.
- the shown fuel cell unit comprises three fuel cells 1 , 2 and 3 connected flow- wise in series, for conducting the stepwise oxidation in three separate steps.
- Each fuel cell comprises an anode 11, a cathode 12 and a membrane 13 that separates them from each other.
- methanol is oxidised to formaldehyde in the first step 1, in the second step 2 the obtained formaldehyde is oxidised to formic acid and in the third step 3 the obtained formic acid is oxidised to carbon dioxide.
- the three fuel cells 1, 2 and 3 are also electrically connected in series. Two electrons are going from the anode H 1 in step one to the cathode 12 3 in step three, via a load 15, shown in the form of a bulb; two electrons are going from the anode 11 3 in step three to the cathode 12 2 in step two; and two electrons are going from the anode 11 2 in step two to the cathode 12i in step one.
- formed protons/hydroxonium ions are going from the anode 11, through the membrane 13, to the cathode 12.
- Fig. 2 is a view in cross-section over the fuel cell unit according to Fig. 1 , showing a preferred arrangement of electrodes 11, 12, intermediate membranes 13 and flow channels 16.
- the anodes 11, the cathodes 12 and the membranes 13 are formed by thin plates or sheets that are attached to each other in order to form a package or a pile.
- the joining can be mechanical, e.g. by not shown connecting rods, or alternatively not shown joints of a suitable glue, e.g. of silicone type, are used in order to hold the plates/sheets together.
- a surface structure 16 is arranged that will give an optimised liquid flow over essentially the entire side of the plates.
- the flow lines shown in Fig. 1, between the individual fuel cells 1, 2 and 3, are constituted by flow connections that are formed in the plate package/pile but also by externally positioned flow connections shown in Fig. 2.
- the membrane 13 consists of a by sulfonic acid modified polyacrylamide that allows for migration of protons/hydroxonium ions from one side of the membrane 13 to the other.
- the modification by sulfonic acid of the polyacrylamide will not to any appreciable extent destroy the stability of the polymer; it will withstand attacks by many solvents and also by hydrogen peroxide.
- the material has beneficial properties such as high resistance (against electrons), high proton permeability and the ability to withstand high voltages.
- Sulfonic acids have a low pKa that allows for translation of protons/hydroxonium ions through the gel, while essentially preventing passage of other ions.
- a proton conductive membrane is accordingly achieved that in cells of DMFC type is not attacked by the reactants and that is essentially impermeable to ions other than protons/hydroxonium ions.
- sulfonic acids that can be coupled to amide nitrogen can be used, but preferably the sulfonic acid is constituted by p-chlorobenzene sulfonic acid.
- 1 -chlorotetra- fluoroethylene sulfonic acid is for example costly and chlorosulfonic acid can form a product that is not completely stable.
- the by sulfonic acid modified polyacrylamide will essentially stop the passage of other ions and molecules, such as methanol, and it is not electrically conducting, which means that electrons from the cathode 12 cannot pass through the membrane 13 to the anode 11.
- the anode 11 and the cathode 12 have thicknesses of less than 1 mm and the membrane 13 has a thickness of less than 5 mm, preferably in the magnitude of 3 mm.
- the anode 11 as well as the cathode 12 has one planar side and said surface structure 16, that gives an optimised liquid flow over essentially the entire side of the plate, is arranged on the anode 11 as well as on the cathode 12, while both sides of the intermediate membrane 13 are planar.
- the planar side of the cathode 12 1 in cell 1 in the fuel cell unit shown in Fig. 1 is then in abutting contact with the planar side of the anode 11 2 in cell 2, and so on.
- the cathode 12i in cell 1 as well as the anode 11 2 in cell 2 etc. may consist of a single plate that if desired can be provided with said surface 16 on one side or on both sides.
- the anode 11 as well as the cathode 12 is constituted of thin metal sheets of a material that is electrically conducting and resistant to the reactants, such as stainless steel, with a thickness in the magnitude of from 0.6 mm down to 0.1 mm, preferably 0.3 mm.
- the surface structure in the anode 11 and the cathode 12 may be formed by channels 16 of waved cross-section.
- the channels 16 have a width in the magnitude of 2 mm up to 3 mm and a depth in the magnitude of from 0.5 mm down to 0.05 mm.
- the surface structure 16 in the anode and cathode plates 11, 12 is preferably produced by adiabatic forming, also called High Impact Forming.
- adiabatic forming also called High Impact Forming.
- porous catalyst carriers 14 preferably in the form of felts of carbon fibre, in which the catalyst adapted for the reaction desired in the cell is applied.
- Figs. 3 and 4 show a couple of different surface structures or flow patterns that will give an optimised liquid flow over essentially the entire side of the plate.
- parallel channels 16 have been repeatedly perforated laterally, such that the entire surface structure consists of shoulders arranged in a checked pattern, forming a grating pattern of channels 16.
- Fig. 4 shows that meander shaped channels 16 that run in parallel also can be used. In all cases including different possible flow paths one should strive to make them equally long from inlet to outlet.
- the membrane can, as is known per se, be moulded to form a plate or a sheet with planar sides, but it is also possible to mould the membrane 13 in a mould that will impart a surface structure 16 to one or both sides, corresponding to the one described above for the electrodes 11, 12. In both cases, the membrane is mounted in the cell after moulding. A membrane that is manufactured in this way will however risk being damaged during the mounting in the cell and problems in the sealing against the electrodes occur easily.
- the membrane 13 is accordingly manufactured by in situ moulding between the anode 11 and the cathode 12 in the cell.
- Fig. 5 is a cross-sectional view of a cell in a fuel cell unit which has been prepared for in situ moulding of the membrane 13 between the anode 11 and the cathode 12.
- the electrodes 11, 12 and the intermediate space for the membrane 13 to be moulded have been drawn with highly exaggerated thicknesses.
- the two electrodes 11, 12 are, on their sides facing each other and facing the space for the membrane, provided with a surface structure 16 in the form of channels.
- porous catalyst carrier 14 abuts against the respective sides of the two electrodes 11, 12 that are provided with the surface structure 16, which porous catalyst carrier 14 preferably is in the form of a carbon fibre felt, in which a catalyst that is optimised for the reaction desired in the cell is applied.
- each cell there is in each cell arranged an upwardly open, essentially U-shaped spacing frame 17 that has a thickness that defines the thickness of the membrane 13 to be moulded in situ in the cell.
- the material of the spacing frame 17 can be chosen from a number of different materials but preferably polyacrylate is used.
- the pile 11, 12 of electrodes and spacing frames 17 that form the basis for the fuel cell unit can be held together by gluing, but in the embodiment shown in Fig. 5 there is used four through bolts 18 (whereof two are shown), one in each corner of the electrode plates. Accordingly, a space is formed between the two catalyst carriers 14 in a cell, which space is sideways and in depth delimited by the spacing frame 17 and is upwardly open and in which the membrane 13 is to be moulded.
- the membrane 13 acrylamide is admixed with sulfonic acid, after which a cross-linking agent is added, the actual polymerisation is initiated by addition of a setting agent and the obtained mixture is in situ moulded to form a membrane in the upwardly open space between the anode and the cathode 11, 12.
- Sulfonic acids have a low pKa that allows for translation of protons/hydroxonium ions through the gel, while essentially preventing passage of other ions. All sulfonic acids that can be coupled to amide nitrogen can be used, but preferably the sulfonic acid is constituted by p-chlorobenzene sulfonic acid. 1-chlorotetrafluoroethylene sulfonic acid is for example costly and chlorosulfonic acid can form a product that is not completely stable.
- the method of manufacturing preferably comprises the use of p-chlorobenzene sulfonic acid as sulfonic acid.
- the acrylamide is admixed with p-chlorobenzene sulfonic acid in water and is heated to the boiling point while stirring, after which the solution is allowed to slowly cool and the cross-binder is added when the solution has reached room temperature.
- the cross-linking agent can however also be added earlier if desired.
- the polyacrylamide modified by p-chlorobenzene sulfonic acid solves the problem that higher contents of methanol can attack membranes of other polymeric materials and that methanol tends to migrate through the membrane and thereby impair the efficiency of the cell.
- N,N'-methylene-bis-acrylamide is preferably used in combination with N,N,N',N'-tetramethylene diamine, which will give the final polymer a stable spatial configuration
- a peroxo salt is used, such as sodium percarbonate, sodium perbenzoate etc., but preferably ammonium persulfate.
- the mixture is moulded, preferably in situ, to form a membrane in the fuel cell or in the reactor based on fuel cell technology.
- the moulding which accordingly can be made in situ in the cell, can be done in a short time, about 40 sec.
- this embodiment results in improved sealing as well as elimination of the risk of damages to the thin membrane in connection with the mounting thereof, and the catalyst will better "creep" into the wall of the membrane as compared to the case in connection with pressing.
- Optimising the catalysts for the methanol driven fuel cell unit shown in Fig. 1 will e.g. result in that said first catalyst is formed by 60-94 % Ag, 5-30 % Te and/or Ru, and 1-
- the optimised catalyst for the second step is suitably constituted by SiO 2 , TiO 2 and Ag.
- Anthraquinone (CAS no. 84-65-1) is a crystalline powder that has a melting point of 286°C and that is insoluble in water and alcohol but soluble in nitrobenzene and aniline.
- the catalyst can be produced by mixing carbon powder (carbon black), anthraquinone and silver with e.g. phenolic resin, after which it is moulded and allowed to solidify. The moulded product is then released from its support, is crushed and finely grinded, after which the obtained powder is slurried in a suitable solvent, is applied where desired, after which the solvent is allowed to evaporate.
- Example 8 g of acrylamide was admixed with 2 g of p-chlorobenzene sulfonic acid (p-CBSA) in 80 ml water and was heated to the boiling point on an electrical plate, while stirring, after which the solution was allowed slowly to cool on the plate.
- p-CBSA p-chlorobenzene sulfonic acid
- the in situ moulded membrane had excellent function in a fuel cell of DMFC type.
- the membrane was not dissolved by methanol, the power density was high and there were no problems with fuel loss by migration of methanol through the membrane, which meant that a high efficiency was maintained and that the yield was satisfactory.
- a suitable catalyst may e.g., if desired, be incorporated in the membrane material before the moulding, and when a prefabricated sheet or plate membrane is used it may be provided with flow channels or corresponding surface structures on one or both sides.
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Abstract
A proton conductive membrane (13) for a fuel cell or a reactor based on fuel cell technology, consists of a thin plate of by sulfonic acid modified polyacrylamide that allows for migration of protons from one side of the membrane to the other. Such a membrane is not affected by reactants that are common in DMFC cells and is not permeable to ions other than protons/hydroxonium ions and it does not conduct electrons. The sulfonic acid is preferably constituted by p-chlorobenzene sulfonic acid. As a cross-linking agent N,N'-methylene-bis-acrylamide is suitably used in combination with N,N,N',N'-tetramethylene diamine and the setting reaction is initiated by a peroxo salt, suitably ammonium persulfate. Preferably, the moulding of the membrane takes place in situ in the cell. This results in improved sealing as well as elimination of the risk of damages to the thin membrane in connection with the mounting thereof, and the catalyst will better 'creep' into the wall of the wall of the membrane as compared to the case in connection with pressing.
Description
A PROTON CONDUCTIVE MEMBRANE FOR A FUEL CELL OR A REACTOR BASED ON FUEL CELL TECHNOLOGY AND A METHOD FOR MAKING THE MEMBRANE
DESCRIPTION
TECHNICAL FIELD
The present invention relates to a proton conductive membrane for a fuel cell or a reactor based on fuel cell technology.
The invention also relates to a method of manufacturing the proton conductive membrane.
In the present context, the terms anode and cathode are used for the respective electrodes also when there is no voltage over them.
By proton conductive membrane is in this context meant a membrane having the ability on its one side to receive protons/hydroxonium ions and on its other side to emit a corresponding number of protons. When a proton enters the membrane from one side, another one is pushed out from the other side. The membrane will furthermore not allow for passage of electrons in the opposite direction and the passage of other ions than HVH3O+ is not desired.
By DMFC is in this context further understood a fuel cell driven by liquid methanol (Direct Methanol Fuel Cell), which fuel cell comprises an anodic side having an anode and a catalyst for the anodic reaction, a cathodic side having a cathode and a catalyst for the cathodic reaction, as well as an intermediate membrane that separates the anodic and cathodic sides from each other.
PRIOR ART
Fuel cells driven by direct methanol are previously known, see for example Alexandre Hacquard, Improving and Understanding Direct Methanol Fuel Cell (DMFC) Performance, (Thesis submitted to the faculty of Worcester Polytechnic Institute) published on http://www.wpi.edu/Pubs/ETD/Available/etd-051205-
151955/unrestricted/A.Hacquard.pdf. Among attainable advantages can be mentioned that the fuel is liquid, thus enabling fast fuelling, that both the fuel cell, that can be
RECORD COPY - TRANSLATION (Rule 12.4)
given a compact design, and the methanol, can be produced at low costs, and that the fuel cell can be designed for a number of different stationary or mobile/portable applications. Fuel cells of DMFC type are furthermore environmentally friendly, only water and carbon dioxide are discharged; no sulphur or nitrogen oxides are formed.
In the above mentioned publication, the anode and the cathode in the disclosed fuel cell consist of graphite and are both provided on their respective one side with a channel system or the like, at the anode for supply of a liquid methanol-water mixture and at the cathode for supply of oxygen, neat or air oxygen. Between the anode and the cathode there is a proton conductive membrane and between the membrane and the anode and the cathode, respectively, there is what is called a gas diffusion layer. Moreover, the gas diffusion layers or the membrane on the anodic side carries a catalyst of Pt and Ru and on the cathodic side a catalyst of solely Pt. The gas diffusion layers consist of carbon cloth or carbon paper. On the anodic side, the gas diffusion layer receives the CO2 formed in connection with the oxidation of the methanol on the anodic catalyst and allows it to diffuse up to an upper end surface where CO2 bubbles are formed. On the cathodic side, the supplied oxygen gas passes through the gas diffusion layer and reacts with electrons and protons passing through the membrane, to form water. Similar to membranes for other fuel cells driven by direct methanol, the membrane here consists of Nafion™, a sulphonated polymer of PTFE type. The catalysts are applied on the gas diffusion layers or on the membrane in the form of an ink of an organic solvent, finely powdered catalyst particles and a solution of Nafion™, after which the solvent is allowed to evaporate. It is stated to be essential to have a network of Nafion™ for efficient transport of protons to the membrane. The thus prepared gas diffusion layers are furthermore used as electrodes.
It has however been shown that Nafion™ does not have the desired methanol resistance but starts to dissolve already when exposed to 2 M (about 6 %) methanol. Known fuel cells of DMFC type have moreover had too low a power density, due to the slow electrochemical oxidation of methanol at the anode, and that methanol has been able to migrate through the PEM membrane (Polymer Electrolyte Membrane) to the cathode where the methanol has oxidised. This results not only in fuel loss, but also in that the platinum catalyst used at the cathode is poisoned by formed carbon monoxide, which leads to decreased efficiency. The complexity of the reactions has made it difficult to achieve a satisfying yield.
US-B 16,444,343 (Prakash et al.) reviews a number of different PEM membranes, starting already at 1959 when it was suggested to manufacture such membranes for H2/θ2 fuel cells by condensation of phenol sulfonic acid and formaldehyde. For membranes in such fuel cells it was also possible to use partially sulfonated polystyrene, and the membranes could also be manufactured from a cross-linked styrene- divinylbenzene with an inert fluorocarbon matrix followed by sulfonation or from homopolymers of α,β,β-trifluorostyrene-sulfonic acid. Considering the drawbacks mentioned for such materials, especially in connection with the use of fuel cells of DMFC type, it is suggested in '343 to manufacture the membrane from a cross-linked polystyrene sulfonic acid within an inert matrix of poly(vinylidene fluoride).
BRIEF ACCOUNT OF THE INVENTION
It is an object of the present invention to provide a proton conductive membrane that is not affected by the reactants in DMFC cells and that is essentially not permeable to ions other than protons/hydroxonium ions.
In the membrane mentioned in the introduction, this object is achieved by the membrane according to the invention consisting of by sulfonic acid modified polyacrylamide. Such a membrane is not attacked by the reactants in DMFC cells, and sulfonic acids have a low pKa that allows for translation of protons/hydroxonium ions through the gel, while essentially preventing passage of other ions.
All sulfonic acids can be used that can be coupled to amide nitrogen, but e.g. 1- chlorotetrafluoroethylene sulfonic acid is costly and chlorosulfonic acid can form a product that is not completely stable. Hence, the sulfonic acid is preferably constituted by p-chlorobenzene sulfonic acid.
The above mentioned object is furthermore achieved in connection with the method of manufacturing a proton conductive membrane from a by sulfonic acid modified polymer for a fuel cell or a reactor based on fuel cell technology, by, according to the invention, admixing polyacrylamide with p-chlorobenzene sulfonic acid in water and heating to the boiling point while stirring, after which the solution is allowed to slowly cool and, when the solution has reached room temperature, adding a cross-binder which gives a stable spatial configuration of the final polymer, initiating the actual polymerisation by adding a setting agent and in situ moulding the achieved mixture before it has set, to form a membrane. The polyacrylamide modified by p- chlorobenzene sulfonic acid solves the problem that higher contents of methanol can
attack membranes of other polymeric materials and that methanol tends to migrate through the membrane and thereby impair the efficiency of the cell. If there is liquid on the other side of the membrane, the spontaneous diffusion of methanol through the membrane of said modified polyacrylamide can be almost completely eliminated, which means that this type of membrane is particularly well suited for cells that have liquid in both cell halves. Acrylamide is furthermore cheap to purchase.
As a cross-linking agent N,N' -methylene -bis-acrylamide is preferably used in combination with N,N,N',N'-tetramethylene diamine, which will give the final polymer a stable spatial configuration, and as the setting agent that initiates the actual polymerization a peroxo salt is used, such as sodium percarbonate, sodium perbenzoate etc., but preferably ammonium persulfate.
After the addition of the setting agent, the mixture is moulded, preferably in situ, to form a membrane in the fuel cell or in the reactor based on fuel cell technology. The moulding, which accordingly can be made in situ in the cell, can be done in a short time, about 40 sec. In comparison with individually manufactured membranes that are built into a fuel cell or a reactor, this embodiment results in improved sealing as well as elimination of the risk of damages to the thin membrane in connection with the mounting thereof, and the catalyst will better "creep" into the wall of the membrane as compared to the case in connection with pressing.
BRIEF DESCRIPTION OF THE ENCLOSED DRAWINGS
In the following, the invention will be described in greater detail with reference to the preferred embodiments and the enclosed drawings.
Fig. 1 is a principle flowchart showing a fuel cell unit of DMFC type, in which liquid methanol is stepwise oxidised in fuel cells to form carbon dioxide and water.
Fig. 2 is a view in cross-section over the fuel cell unit according to Fig. 1, showing a preferred arrangement of electrodes, intermediate membranes and flow channels.
Figs. 3-4 are planar views over a couple of different flow patterns in which the reactants can be led inside each unit.
Fig. 5 is a simplified cross-sectional view of a cell that has been prepared for the moulding of a proton conductive membrane between the electrodes.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS In the fuel cell unit of DMFC type shown in the principle flowchart in Fig. 1 , liquid methanol is stepwise oxidised in fuel cells to carbon dioxide and water. The shown fuel cell unit comprises three fuel cells 1 , 2 and 3 connected flow- wise in series, for conducting the stepwise oxidation in three separate steps. Each fuel cell comprises an anode 11, a cathode 12 and a membrane 13 that separates them from each other. On the anodic side, methanol is oxidised to formaldehyde in the first step 1, in the second step 2 the obtained formaldehyde is oxidised to formic acid and in the third step 3 the obtained formic acid is oxidised to carbon dioxide. On the cathodic side, freshly supplied hydrogen peroxide is reduced in each step 1-3, to form water. The supply of oxidant to the different steps is suitably controlled such that the reactions on the anodic and the cathodic sides are in stoichiometric balance with each other in every separate step. Thereby, the reactions can be more reliably refined and controlled in order to increase yield.
The three fuel cells 1, 2 and 3 are also electrically connected in series. Two electrons are going from the anode H1 in step one to the cathode 123 in step three, via a load 15, shown in the form of a bulb; two electrons are going from the anode 113 in step three to the cathode 122 in step two; and two electrons are going from the anode 112 in step two to the cathode 12i in step one. In all three cells 1, 2 and 3, formed protons/hydroxonium ions are going from the anode 11, through the membrane 13, to the cathode 12.
Fig. 2 is a view in cross-section over the fuel cell unit according to Fig. 1 , showing a preferred arrangement of electrodes 11, 12, intermediate membranes 13 and flow channels 16. The anodes 11, the cathodes 12 and the membranes 13 are formed by thin plates or sheets that are attached to each other in order to form a package or a pile. In conventional fuel cell units, the joining can be mechanical, e.g. by not shown connecting rods, or alternatively not shown joints of a suitable glue, e.g. of silicone type, are used in order to hold the plates/sheets together. Between the membrane 13 and the anode 11 and between the membrane 13 and the cathode 12, a surface structure 16 is arranged that will give an optimised liquid flow over essentially the entire side of the plates. The flow lines shown in Fig. 1, between the individual fuel cells 1, 2 and 3, are constituted by flow connections that are formed in the plate package/pile but also by externally positioned flow connections shown in Fig. 2.
According to the invention, the membrane 13 consists of a by sulfonic acid modified polyacrylamide that allows for migration of protons/hydroxonium ions from one side of the membrane 13 to the other. The modification by sulfonic acid of the polyacrylamide will not to any appreciable extent destroy the stability of the polymer; it will withstand attacks by many solvents and also by hydrogen peroxide. Also in terms of electricity, the material has beneficial properties such as high resistance (against electrons), high proton permeability and the ability to withstand high voltages. Sulfonic acids have a low pKa that allows for translation of protons/hydroxonium ions through the gel, while essentially preventing passage of other ions. By the modification by sulfonic acid, a proton conductive membrane is accordingly achieved that in cells of DMFC type is not attacked by the reactants and that is essentially impermeable to ions other than protons/hydroxonium ions.
All sulfonic acids that can be coupled to amide nitrogen can be used, but preferably the sulfonic acid is constituted by p-chlorobenzene sulfonic acid. 1 -chlorotetra- fluoroethylene sulfonic acid is for example costly and chlorosulfonic acid can form a product that is not completely stable. Moreover, the by sulfonic acid modified polyacrylamide will essentially stop the passage of other ions and molecules, such as methanol, and it is not electrically conducting, which means that electrons from the cathode 12 cannot pass through the membrane 13 to the anode 11. Accordingly, no appreciable migration of methanol can take place from the anode 11 to the cathode 12, which means that there is no appreciable fuel loss due to migration of methanol and no formation of carbon monoxide at the cathode 12, which could otherwise decrease the efficiency of a platinum catalyst that is optionally used there.
In the preferred embodiment shown in Fig. 2, the anode 11 and the cathode 12 have thicknesses of less than 1 mm and the membrane 13 has a thickness of less than 5 mm, preferably in the magnitude of 3 mm. The anode 11 as well as the cathode 12 has one planar side and said surface structure 16, that gives an optimised liquid flow over essentially the entire side of the plate, is arranged on the anode 11 as well as on the cathode 12, while both sides of the intermediate membrane 13 are planar. The planar side of the cathode 121 in cell 1 in the fuel cell unit shown in Fig. 1 is then in abutting contact with the planar side of the anode 112 in cell 2, and so on. Naturally, the cathode 12i in cell 1 as well as the anode 112 in cell 2 etc. may consist of a single plate that if desired can be provided with said surface 16 on one side or on both sides.
Suitably, the anode 11 as well as the cathode 12 is constituted of thin metal sheets of a material that is electrically conducting and resistant to the reactants, such as stainless steel, with a thickness in the magnitude of from 0.6 mm down to 0.1 mm, preferably 0.3 mm. The surface structure in the anode 11 and the cathode 12 may be formed by channels 16 of waved cross-section. Suitably, the channels 16 have a width in the magnitude of 2 mm up to 3 mm and a depth in the magnitude of from 0.5 mm down to 0.05 mm. The surface structure 16 in the anode and cathode plates 11, 12 is preferably produced by adiabatic forming, also called High Impact Forming. One example of such forming is disclosed in US-B2-6,821,471.
Between the anode 11 and the membrane 13 and between the cathode 12 and the membrane 13, there are thin, porous catalyst carriers 14, preferably in the form of felts of carbon fibre, in which the catalyst adapted for the reaction desired in the cell is applied. In that way the constructing of a compact pile of fuel cells 1, 2, 3 with electrodes 11, 12 of the same thin sheet shape having one planar side and one side with surface structure is facilitated, whereby a high power density can be achieved.
Figs. 3 and 4 show a couple of different surface structures or flow patterns that will give an optimised liquid flow over essentially the entire side of the plate. In Fig. 3, parallel channels 16 have been repeatedly perforated laterally, such that the entire surface structure consists of shoulders arranged in a checked pattern, forming a grating pattern of channels 16. Finally, Fig. 4 shows that meander shaped channels 16 that run in parallel also can be used. In all cases including different possible flow paths one should strive to make them equally long from inlet to outlet.
If desired, the membrane can, as is known per se, be moulded to form a plate or a sheet with planar sides, but it is also possible to mould the membrane 13 in a mould that will impart a surface structure 16 to one or both sides, corresponding to the one described above for the electrodes 11, 12. In both cases, the membrane is mounted in the cell after moulding. A membrane that is manufactured in this way will however risk being damaged during the mounting in the cell and problems in the sealing against the electrodes occur easily.
In a preferred embodiment of the invention, the membrane 13 is accordingly manufactured by in situ moulding between the anode 11 and the cathode 12 in the cell. This is shown in greater detail in Fig. 5 that is a cross-sectional view of a cell in a fuel cell unit which has been prepared for in situ moulding of the membrane 13 between the
anode 11 and the cathode 12. In order better to illustrate the invention, the electrodes 11, 12 and the intermediate space for the membrane 13 to be moulded have been drawn with highly exaggerated thicknesses. In the shown cell in the fuel cell unit, the two electrodes 11, 12 are, on their sides facing each other and facing the space for the membrane, provided with a surface structure 16 in the form of channels. The porous catalyst carrier 14 abuts against the respective sides of the two electrodes 11, 12 that are provided with the surface structure 16, which porous catalyst carrier 14 preferably is in the form of a carbon fibre felt, in which a catalyst that is optimised for the reaction desired in the cell is applied.
Between the anode 11 and the cathode 12 and in sealing contact therewith, there is in each cell arranged an upwardly open, essentially U-shaped spacing frame 17 that has a thickness that defines the thickness of the membrane 13 to be moulded in situ in the cell. The material of the spacing frame 17 can be chosen from a number of different materials but preferably polyacrylate is used. The pile 11, 12 of electrodes and spacing frames 17 that form the basis for the fuel cell unit can be held together by gluing, but in the embodiment shown in Fig. 5 there is used four through bolts 18 (whereof two are shown), one in each corner of the electrode plates. Accordingly, a space is formed between the two catalyst carriers 14 in a cell, which space is sideways and in depth delimited by the spacing frame 17 and is upwardly open and in which the membrane 13 is to be moulded.
For the manufacturing of the membrane 13 acrylamide is admixed with sulfonic acid, after which a cross-linking agent is added, the actual polymerisation is initiated by addition of a setting agent and the obtained mixture is in situ moulded to form a membrane in the upwardly open space between the anode and the cathode 11, 12.
Sulfonic acids have a low pKa that allows for translation of protons/hydroxonium ions through the gel, while essentially preventing passage of other ions. All sulfonic acids that can be coupled to amide nitrogen can be used, but preferably the sulfonic acid is constituted by p-chlorobenzene sulfonic acid. 1-chlorotetrafluoroethylene sulfonic acid is for example costly and chlorosulfonic acid can form a product that is not completely stable.
The method of manufacturing preferably comprises the use of p-chlorobenzene sulfonic acid as sulfonic acid. The acrylamide is admixed with p-chlorobenzene sulfonic acid in water and is heated to the boiling point while stirring, after which the solution is
allowed to slowly cool and the cross-binder is added when the solution has reached room temperature. The cross-linking agent can however also be added earlier if desired. The polyacrylamide modified by p-chlorobenzene sulfonic acid solves the problem that higher contents of methanol can attack membranes of other polymeric materials and that methanol tends to migrate through the membrane and thereby impair the efficiency of the cell. If there is liquid on the other side of the membrane, as in cells of DMFC type, the spontaneous diffusion of methanol through the membrane of said modified polyacrylamide can be almost completely eliminated, which means that this type of membrane is particularly well suited for cells that have liquid in both cell halves. Acrylamide is furthermore cheap to purchase.
As a cross-linking agent N,N'-methylene-bis-acrylamide is preferably used in combination with N,N,N',N'-tetramethylene diamine, which will give the final polymer a stable spatial configuration, and as the setting agent that initiates the actual polymerization a peroxo salt is used, such as sodium percarbonate, sodium perbenzoate etc., but preferably ammonium persulfate.
After the addition of the setting agent, the mixture is moulded, preferably in situ, to form a membrane in the fuel cell or in the reactor based on fuel cell technology. The moulding, which accordingly can be made in situ in the cell, can be done in a short time, about 40 sec. In comparison with prefabricated membranes that are built into a fuel cell or a reactor, this embodiment results in improved sealing as well as elimination of the risk of damages to the thin membrane in connection with the mounting thereof, and the catalyst will better "creep" into the wall of the membrane as compared to the case in connection with pressing.
Optimising the catalysts for the methanol driven fuel cell unit shown in Fig. 1 will e.g. result in that said first catalyst is formed by 60-94 % Ag, 5-30 % Te and/or Ru, and 1-
10 % Pt alone or in combination with Au and/or TiO2, preferably at the ratio of about 90:9:1 for the reaction
CH3OH <→ HCHO + 2 H+ + 2 e" (a) of SiO2 and TiO2 in combination with Ag for the reaction
HCHO + H2O <→ HCOOH + 2 H+ + 2 e" (b) of Ag alone or in combination with TiO2 and/or Te for the reaction HCOOH <→ CO2 + 2 H+ + 2 e" (c) said second catalyst is then formed by e.g. carbon powder (carbon black), anthraquinone and Ag and phenolic resin, for the reaction
H2O2 + 2 H+ + 2 e" <→ 2 H2O (d)
As is mentioned above, the optimised catalyst for the second step is suitably constituted by SiO2, TiO2 and Ag.
Anthraquinone (CAS no. 84-65-1) is a crystalline powder that has a melting point of 286°C and that is insoluble in water and alcohol but soluble in nitrobenzene and aniline. The catalyst can be produced by mixing carbon powder (carbon black), anthraquinone and silver with e.g. phenolic resin, after which it is moulded and allowed to solidify. The moulded product is then released from its support, is crushed and finely grinded, after which the obtained powder is slurried in a suitable solvent, is applied where desired, after which the solvent is allowed to evaporate.
Example 8 g of acrylamide was admixed with 2 g of p-chlorobenzene sulfonic acid (p-CBSA) in 80 ml water and was heated to the boiling point on an electrical plate, while stirring, after which the solution was allowed slowly to cool on the plate. Hereby, a coupling product was formed between the acrylamide and p-CBSA, via the amide nitrogen in the acrylamide, and HCl was also formed that was degassed during the boiling. When the solution had reached room temperature a cross-linking agent was added, in this case 2 g of N,N'-methylene-bis-acrylamide in combination with 0.5 ml of N,N,N',N'- tetramethylene diamine, which gave the final polymer a stable structure. In order to mould a membrane, a quarter of the obtained product was withdrawn and the actual polymerisation was initiated by a peroxo salt, in this case ammonium persulfate, of which the tip of a spatula was enough. The polymerisation started after 40 sec, which meant that there was plenty of time to transfer the product to the already assembled fuel cell, in which the moulding of the membranes took place in an upright position. The membranes moulded in the fuel cell were shown to give impeccable sealing. It was also shown that the catalyst better "crept" into the wall of the membrane than the case in connection with pressing, and there were no damages to the membrane.
The in situ moulded membrane had excellent function in a fuel cell of DMFC type. The membrane was not dissolved by methanol, the power density was high and there were no problems with fuel loss by migration of methanol through the membrane, which meant that a high efficiency was maintained and that the yield was satisfactory.
Although the invention has been described above with reference to a preferred embodiment shown in the drawings, it is clear that a person skilled in the art and without any inventive work can come up with a number of modifications of the invention within the scope of the appended claims. A suitable catalyst may e.g., if desired, be incorporated in the membrane material before the moulding, and when a prefabricated sheet or plate membrane is used it may be provided with flow channels or corresponding surface structures on one or both sides.
Claims
1. A proton conductive membrane (13) for a fuel cell or a reactor based on fuel cell technology, which membrane (13) consists of a thin sheet of by sulfonic acid modified polyacrylamide, that allows for migration of protons from one side of the membrane to the other, characte ri se d in that the sulfonic acid is p- chlorobenzene sulfonic acid.
2. A membrane according to claim 1, characteri s ed in that the membrane (13) of by sulfonic acid modified polyacrylamide is in situ moulded in the fuel cell or in the reactor based on fuel cell technology.
3. Method for the manufacturing of a proton conductive membrane (13) from a by sulfonic acid modified polymer, for a fuel cell or a reactor based on fuel cell technology, characteri s e d i n that - acrylamide is admixed with p-chlorobenzene sulfonic acid in water and is heated to the boiling point while stirring, after which the solution is allowed to slowly cool,
- a cross-linking agent is added when the solution has reached room temperature, which cross-linking agent gives the final polymer a stable spatial configuration,
- the actual polymerisation is initiated by the addition of a setting agent, and - the obtained mixture is, before it has set, moulded to form a membrane (13).
4. A method according to claim 3, characteri s e d in that N,N' -methyl ene-bis- acrylamide in combination with N,N,N',N'-tetramethylene diamine is used as said cross-linking agent.
5. A method according to claim 3 or 4, characteri s e d i n that a peroxo salt is used as said setting agent.
6. A method according to claim 5, characteri s e d in that said peroxo salt is ammonium persulfate.
7. A method according to any one of claims 3-6, characteri s ed in that after the addition of the setting agent, the mixture is in situ moulded to form a membrane (13) between an anode (11) and a cathode (12) in the fuel cell or in the reactor based on fuel cell technology.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE0602128A SE530389C2 (en) | 2006-10-06 | 2006-10-06 | Proton Conductive Membrane for a Fuel Cell or a Fuel Cell Technology Reactor and Process for Preparing the Membrane |
| PCT/SE2007/050639 WO2008041923A1 (en) | 2006-10-06 | 2007-09-11 | A proton conductive membrane for a fuel cell or a reactor based on fuel cell technology and a method for making the membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2070149A1 true EP2070149A1 (en) | 2009-06-17 |
| EP2070149A4 EP2070149A4 (en) | 2011-01-05 |
Family
ID=39268697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP07808876A Withdrawn EP2070149A4 (en) | 2006-10-06 | 2007-09-11 | PROTON CONDUCTIVE MEMBRANE FOR FUEL CELL OR REACTOR DERIVED FROM FUEL CELL TECHNOLOGY, AND METHOD FOR MANUFACTURING THE MEMBRANE |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2070149A4 (en) |
| JP (1) | JP2010506358A (en) |
| CN (1) | CN101589501A (en) |
| SE (1) | SE530389C2 (en) |
| TW (1) | TW200935645A (en) |
| WO (1) | WO2008041923A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6444343B1 (en) * | 1996-11-18 | 2002-09-03 | University Of Southern California | Polymer electrolyte membranes for use in fuel cells |
| US7361729B2 (en) * | 2000-09-20 | 2008-04-22 | Virginia Tech Intellectual Properties, Inc. | Ion-conducting sulfonated polymeric materials |
| US6503378B1 (en) * | 2001-04-23 | 2003-01-07 | Motorola, Inc. | Polymer electrolyte membrane and method of fabrication |
| US7318972B2 (en) * | 2001-09-07 | 2008-01-15 | Itm Power Ltd. | Hydrophilic polymers and their use in electrochemical cells |
| JP2005108604A (en) * | 2003-09-30 | 2005-04-21 | Canon Inc | Membrane electrode assembly, method for producing the same, and polymer electrolyte fuel cell |
| WO2005111103A1 (en) * | 2004-05-13 | 2005-11-24 | Mitsubishi Gas Chemical Co., Inc. | Solid polymer electrolyte membrane and fuel cell |
| CN100499231C (en) * | 2004-07-06 | 2009-06-10 | 东亚合成株式会社 | Electrolyte membrane and fuel cell utilizing the electrolyte membrane |
-
2006
- 2006-10-06 SE SE0602128A patent/SE530389C2/en unknown
-
2007
- 2007-09-11 CN CNA2007800374173A patent/CN101589501A/en active Pending
- 2007-09-11 JP JP2009531352A patent/JP2010506358A/en active Pending
- 2007-09-11 EP EP07808876A patent/EP2070149A4/en not_active Withdrawn
- 2007-09-11 WO PCT/SE2007/050639 patent/WO2008041923A1/en not_active Ceased
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2008041923A1 (en) | 2008-04-10 |
| EP2070149A4 (en) | 2011-01-05 |
| SE530389C2 (en) | 2008-05-20 |
| CN101589501A (en) | 2009-11-25 |
| JP2010506358A (en) | 2010-02-25 |
| TW200935645A (en) | 2009-08-16 |
| SE0602128L (en) | 2008-04-07 |
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