GB2484886A - Membrane - Google Patents
Membrane Download PDFInfo
- Publication number
- GB2484886A GB2484886A GB1011904.8A GB201011904A GB2484886A GB 2484886 A GB2484886 A GB 2484886A GB 201011904 A GB201011904 A GB 201011904A GB 2484886 A GB2484886 A GB 2484886A
- Authority
- GB
- United Kingdom
- Prior art keywords
- membrane
- polymer
- particulate material
- acid groups
- porous particulate
- 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- Withdrawn
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000011236 particulate material Substances 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 3
- 239000011147 inorganic material Substances 0.000 claims abstract description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004693 Polybenzimidazole Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 6
- 229920002480 polybenzimidazole Polymers 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- -1 poly(2,5-benzimidazole) Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H01M2/166—
-
- 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
- H01M8/0289—Means for holding the electrolyte
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Fuel Cell (AREA)
Abstract
A membrane for use in a proton exchange membrane fuel cell at a temperature in excess of 100°C comprises a membrane formed from a polymer capable of being doped with one or more acid groups or which is pre-complexed with one or more acid groups, and a porous particulate material is disclosed. The polymer may be a polyazole. The porous particulate material may be 20-80 % by weight of the polymer and may be a stable, non-electrically conducting inorganic material.
Description
MEMBRANE
The present invention relates to a proton-conducting polymer electrolyte membrane, suitable for use in fuel cells, and in particular a polyelectrolyte membrane formed from a polyazole, wherein the membrane further comprises a porous particulate material.
It is known that membranes comprising polymers which are capable of complexing with acid groups or being doped with acid groups can be used in proton exchange membrane (PEM) fuel cells and can provide a viable alternative to PEM fuel cells comprising a perfluorosulfonic acid polymer, for example Nafion®, for use at temperatures in excess of 100°C. For example, membranes formed from polybenzimidazole and doped with phosphoric acid are well known (US 5,525,436).
However, it has been found that such membranes are susceptible to compression when used in the fuel cell, which can lead to membrane thinning and eventually shorting of the fuel cell electrodes. This leads to failure of the fuel cell and therefore a much shorter lifetime than is required for practical applications.
Tt is therefore an object of the invention to provide a membrane which is resistant to compression and which overcomes the problems of shorting of the electrodes.
Accordingly, the present invention provides a membrane, suitably for use in a proton exchange membrane fuel cell at a temperature in excess of 100°C, said membrane being formed from a polymer capable of being doped with one or more acid groups or which is pre-complexed with one or more acid groups, and a porous particulate material.
Pre-complexing of the polymer with the acid groups may be carried out by a polycondensation reaction of the monomer and acid components, such as described in U52006/0079392.
I
In one particular embodiment, the polymer is based on a polyazole structure, for example: polybenzimidazole; polyimidazole; polybenzthiazole; polybenzoxazole; polyoxadiazole; polythiadiazole; polythiazole; preferably the polymer is a polybenzimidazole. A number of polymers comprising a polybenzimidazole structure are known, for example: poly(2,5-benzimidazole) (AB-PBI); poly(2,2 -m-phenylene-5,5 - bibenzimidazole) (m-PBI); poly-[(l -(4,4 -diphenylether)-S-oxybenzimidazole)- benzimidazole] (PBI-OO); poly[( 1-93,3 -phthalide-p-phenylene)-5-oxybenzimidazoleO-benzimidazolel (PBT-OPh). Most preferably, the polymer is in-PBI or AB-PBI.
The acid groups with which the polymer is capable of being doped or which are pre-complexed to the polymer are suitably sulphuric acid groups, polyphosphonic acid groups or phosphoric acid groups, preferably phosphoric acid groups. Suitably, the polymer is capable of being doped by, or is pre-complexed to at least two, preferably at least three acid groups (molecules) per repeating polymer unit. Suitably, there are no more than six, preferably no more than five acid molecules per repeating unit, although much higher levels of doping or pre-complexing of up to 50 mols acid per repeat polymer unit are possible and are within the scope of the invention.
The membrane has a thickness suitably in the region of 50-200 microns, more suitably 70-150 microns, and preferably 70-100 microns.
The porous particulate material is present in a suitable amount such that compression of the membrane leading to shortage of the electrodes is prevented. Suitably, it is present in an amount of from 20-80 % by weight of the polymer component of the membrane, more suitably in an amount of from 30 -70% by weight and preferably from -70% by weight.
The particle size of the porous particulate material is dependent upon the thickness of the membrane. The porous particulate material has a maximum dimension that is smaller than the thickness of the membrane.
The particulate material is preferably porous such that acid groups can be held within the pores of the particulate material, thus not reducing the proton conductivity of the membrane. The porous particulate material is suitably a stable, non-electrically conducting, inorganic material. In one preferred embodiment of the invention, the particulate material is silicon carbide.
In one embodiment, the porous particulate material is added to the polymer solution prior to casting of the membrane.
Membranes of the present invention are suitable for use in proton exchange membrane fuel cells, in particular those that operate at temperatures in excess of 100°C and preferably in excess of 140°C. If the membrane of the invention has been pre-complexed with acid groups, then no further processing is required before it is combined with anode and cathode catalyst layers and anode and cathode gas diffusion layers to form a membrane electrode assembly (MEA), However, if the membrane has not been pre-complexed with acid groups, doping of the membrane is required. This is carried out according to methods known in the art, for example by immersing the membrane in a suitable acid, for example sulphuric acid or phosphoric acid. The doped membrane may then be combined with the various layers as described above to form the MEA.
Alternatively the anode and cathode catalyst layers may be pre-doped with acid groups, and the acid is transferred and doped into the membrane during the assembly process to form the MEA and in the conditioning of the MEA in the fuel cell. Still alternatively, a combination of doping the membrane and the anode and/or cathode may be used.
Accordingly, a further aspect of the invention provides an MEA comprising a membrane of the invention.
The anode and cathode catalyst layers each comprise an electrocatalyst, which may be a finely divided unsupported metal powder, or may be a supported catalyst wherein small metal particles are dispersed on electrically conducting particulate carbon supports. The electrocatalyst metal is suitably selected from (i) the platinum group metals (platinum, palladium, rhodium, ruthenium, iridium and osmium), (ii) gold or silver, (iii) a base metal, or an alloy or mixture comprising one or more of these metals or their oxides.
The preferred electrocatalyst metal is platinum, which may be alloyed with other precious metals or base metals. If the electrocatalyst is a supported catalyst, the loading of metal particles on the carbon support material is suitably in the range lO-9Owt%, preferably 15- 75wt% of the weight of resulting electrocatalyst. Suitably the carbon support used for the cathode catalyst is a carbon black that has been treated at high temperature to impart a high level of corrosion resistance, or is produced as a highly corrosion resistant carbon black in its production process.
The anode and cathode gas diffusion layers are suitably based on conventional gas diffusion substrates. Typical substrates include non-woven papers or webs comprising a network of carbon fibres and a thermoset resin binder (e.g. the TGP-H series of carbon fibre paper available from Toray Industries Inc., Japan or the 112315 series available from Freudenberg FCCT KG, Germany, or the Sigracet® series available from SQL Technologies GmbH, Germany or AvCarb® series from Ballard Power Systems Inc, or woven carbon cloths. The carbon paper, web or cloth may be provided with a further treatment prior to being incorporated into a MEA either to make it more wettable (hydrophilic) or more wet-proofed (hydrophobic). The nature of any treatments will depend on the type of fuel cell and the operating conditions that will be used. The substrate can be made more wettable by incorporation of materials such as carbon blacks via impregnation from liquid suspensions, or can be made more hydrophobic by impregnating the pore structure of the substrate with a colloidal suspension of a polymer such as PTFE or polyfluoroethylenepropylene (FEP), followed by drying and heating above the melting point of the polymer. A microporous layer may also be applied to the gas diffusion substrate on the face that will contact the electrocatalyst layer. The microporous layer typically comprises a mixture of a carbon black, which is suitably a corrosion resistant material, and a polymer such as polytetrafluoroethylene (PTFE).
Claims (6)
- CLAIMS1. A membrane, suitably for use in a proton exchange membrane fuel cell at a temperature in excess of 100°C, said membrane being formed from a polymer capable of being doped with one or more acid groups or which is pre-complexed with one or more acid groups, and a porous particulate material.
- 2. A membrane according to claim 1, wherein the polymer is a polyazole.
- 3. A membrane according to claim 1 or claim 2, wherein the porous particulate material is present in an amount of from 20-80 % by weight of the polymer.
- 4. A membrane according to any preceding claim, wherein the porous particulate material is a stable, non-electrically conducting, inorganic material.
- 5. A membrane according to claim 4, wherein the porous particulate material is silicon carbide.
- 6. A membrane electrode assembly comprising a membrane according to any one of claims ito 5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1011904.8A GB2484886A (en) | 2010-07-15 | 2010-07-15 | Membrane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1011904.8A GB2484886A (en) | 2010-07-15 | 2010-07-15 | Membrane |
Publications (2)
Publication Number | Publication Date |
---|---|
GB201011904D0 GB201011904D0 (en) | 2010-09-01 |
GB2484886A true GB2484886A (en) | 2012-05-02 |
Family
ID=42734984
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1011904.8A Withdrawn GB2484886A (en) | 2010-07-15 | 2010-07-15 | Membrane |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB2484886A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003069708A2 (en) * | 2002-02-13 | 2003-08-21 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Electrolyte membrane comprising a diffusion barrier, membrane electrode units containing said membranes, method for the production thereof and specific uses of the same |
EP1624519A1 (en) * | 2004-08-03 | 2006-02-08 | Air Products And Chemicals, Inc. | Proton conducting mediums for electrochemical devices and electrochemical devices comprising the same |
-
2010
- 2010-07-15 GB GB1011904.8A patent/GB2484886A/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003069708A2 (en) * | 2002-02-13 | 2003-08-21 | Creavis Gesellschaft Für Technologie Und Innovation Mbh | Electrolyte membrane comprising a diffusion barrier, membrane electrode units containing said membranes, method for the production thereof and specific uses of the same |
EP1624519A1 (en) * | 2004-08-03 | 2006-02-08 | Air Products And Chemicals, Inc. | Proton conducting mediums for electrochemical devices and electrochemical devices comprising the same |
Also Published As
Publication number | Publication date |
---|---|
GB201011904D0 (en) | 2010-09-01 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) |
Free format text: REGISTERED BETWEEN 20120913 AND 20120919 |
|
WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |