WO2007031795A1 - Electrocatalyst - Google Patents
Electrocatalyst Download PDFInfo
- Publication number
- WO2007031795A1 WO2007031795A1 PCT/GB2006/050286 GB2006050286W WO2007031795A1 WO 2007031795 A1 WO2007031795 A1 WO 2007031795A1 GB 2006050286 W GB2006050286 W GB 2006050286W WO 2007031795 A1 WO2007031795 A1 WO 2007031795A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrocatalyst
- metal particles
- carbon
- electrocatalyst according
- fuel cell
- Prior art date
Links
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 26
- 239000002923 metal particle Substances 0.000 claims abstract description 25
- 239000000446 fuel Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- 239000000976 ink Substances 0.000 abstract description 8
- 230000000712 assembly Effects 0.000 abstract description 2
- 238000000429 assembly Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- -1 catalysed electrodes Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003934 Aciplex® Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical class OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- 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
- H01M4/8605—Porous electrodes
-
- 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
- H01M4/8807—Gas diffusion layers
-
- 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
-
- 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
- H01M4/90—Selection of catalytic material
-
- 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
Definitions
- the present invention relates to an electrocatalyst that may be used in a fuel cell, and their use in catalyst inks, catalysed electrodes, catalyst coated membranes and membrane electrode assemblies.
- a fuel cell is an electrochemical cell comprising two electrodes separated by an electrolyte.
- a fuel e.g. hydrogen or methanol
- an oxidant e.g. oxygen or air
- Electrochemical reactions occur at the electrodes, and the chemical energy of the fuel and the oxidant is converted to electrical energy and heat.
- Electrocatalysts are used to promote the electrochemical oxidation of the fuel at the anode and the electrochemical reduction of oxygen at the cathode.
- Electrocatalysts used in fuel cells typically comprise platinum or a platinum alloy.
- the metal may be unsupported, but is usually supported on a high surface area carbon such as a furnace carbon black or an acetylene black. Supporting the metal increases the available surface area of the metal and reduces the amount of metal required to achieve desired activity.
- a high surface area carbon such as a furnace carbon black or an acetylene black. Supporting the metal increases the available surface area of the metal and reduces the amount of metal required to achieve desired activity.
- the present inventors have sought to prepare electrocatalysts that are suitable for use in fuel cells.
- the inventors have surprisingly found that catalysts wherein a metal particle is encapsulated by carbon are active for the anodic fuel cell reaction. This is very surprising because it is generally understood that the catalytic reactions occur at the surface of the metal.
- the inventors believe the catalysts may have advantageous properties when compared to known fuel cell catalysts, e.g. they may have better tolerance to poisons such as carbon monoxide and hydrogen sulphide.
- the present invention provides an electrocatalyst for use in a fuel cell comprising a plurality of metal particles, wherein at least 90% of the surface area of the metal particles is covered by carbon. Preferably at least 95% of the surface area is covered with a layer of carbon, most preferably all of the surface of the metal is covered with a layer of carbon.
- the carbon may be present as graphitic sheets and the term "a layer of carbon" includes both a single graphitic sheet and multiple graphitic sheets.
- the one or more metal particles suitably comprise one or more transition metals, which are optionally alloyed with further metals.
- the metal particles preferably comprise one or more metals from Groups 8 and Ib of the Periodic Table (i.e. the Groups containing platinum group metals and Fe, Co, Ni and Cu), which are optionally alloyed with further metals.
- the metal particles comprise platinum or palladium, preferably platinum, hi a particularly preferred embodiment, the metal particles consist essentially of platinum or platinum alloyed with one or more metals chosen from precious metals such as ruthenium or gold, or base metals such as molybdenum, tungsten, chromium, tin or titanium.
- the electrocatalyst consists essentially of a metal particle, wherein the particle is substantially covered with carbon.
- the particle suitably has an average diameter of from lnm to lOOnm, preferably from lnm to 50nm.
- the electrocatalyst consists essentially of metal particles dispersed on a carbon support material, wherein the particles are substantially covered with carbon.
- the particles suitably have an average diameter of from lnm to lOOnm, preferably from lnm to 50nm, most preferably from 1 to lOnm.
- the carbon support material is suitably a high surface area carbon black, such as a furnace black or an acetylene black.
- the surface area of the carbon support is suitably at least 5OmVg, preferably at least 200m 2 /g.
- the amount of metal in the electrocatalyst is from 10 to 80wt% based on the weight of the carbon support material.
- the covering of carbon on the metal particles is suitably less than 1 Onm in thickness.
- the inventors believe that thicker carbon layers are likely to reduce the activity of the electrocatalyst.
- Methods of preparing carbon encapsulated metal particles are disclosed in, for example, WO 03/057626, WO 03/057359 and Lu et al, Chem. Commun., 2005, 98-100. These methods may be adapted for forming the electrocatalysts of the present invention.
- colloidal particles containing a source of metal are fo ⁇ ned in a liquid medium.
- the colloidal particles are stabilised by a surfactant.
- the colloidal particles contain a source of carbon such as cyanide, isocyanide, cyanate or isocyanate ligands.
- the particles are separated from the liquid medium.
- the particles are pyrolysed in an inert gas.
- the particles are dispersed on a carbon support material and are then pyrolysed in an inert gas.
- a suitable pyrolysis temperature is at least 800 0 C.
- a metal salt and a carbon source e.g. poly( vinyl alcohol)
- the solution is sprayed as a fine mist into a closed vessel containing a saturated ammonia solution.
- a solid precipitates and is collected.
- the solid is pyrolysed in an inert gas.
- the precipitate is contacted with a carbon support material, which is then pyrolysed in an inert gas.
- a suitable pyrolysis temperature is at least 800 0 C.
- a carbon forming agent e.g. polyvinyl alcohol, furfuryl alcohol or sucrose
- a pre-formed catalyst material such as platinum particles dispersed on a high surface area carbon support (e.g. HiSpecTM materials available from Johnson Matthey pic).
- the mixture is dried and then pyrolysed in an inert gas at a temperature of at least 800 0 C to form an electrocatalyst according to the second embodiment of the invention.
- the present invention provides an electrocatalyst ink comprising a catalyst according to the invention dispersed in a liquid medium.
- the ink suitably comprises aqueous and/or organic solvents, optional polymeric binders and optional proton-conducting polymers.
- Methods of making electrocatalyst inks are disclosed in EP 731 520.
- the present invention provides an electrode comprising a catalyst according to the invention deposited on an electronically conducting substrate.
- the catalyst can be deposited onto a substrate using well known techniques, such as those disclosed in EP 731 520.
- the catalyst may be formulated into an ink and the ink may be deposited onto an electronically conducting substrate using techniques such as spraying, printing and doctor blade methods.
- Suitable substrates include carbon fibre papers and filled carbon fibre non- woven webs, such as those disclosed in EP 791 974.
- the catalysed electrodes may be used in fuel cells with acid electrolytes such as proton exchange membrane (PEM) fuel cells or phosphoric acid fuel cells, or they may be used in alkaline electrolyte fuel cells.
- PEM proton exchange membrane
- the electrolyte is a proton conducting polymer membrane. Electrocatalysts may be deposited onto one or both faces of the membrane to form a catalysed membrane.
- the present invention provides a catalysed membrane comprising a catalyst according to the invention deposited on an ion-conducting polymer membrane.
- the catalyst can be deposited onto the membrane using well known techniques.
- the catalyst may be formulated into an ink and either directly deposited onto the membrane or deposited onto a decal blank for subsequent transfer to a membrane. Suitable membranes are well known to those skilled in the art and include perfluorinated sulphonic acid membranes such as Nafion®, Fleinion® and Aciplex®.
- the membrane is interposed between two catalyst layers, and each catalyst layer is in contact with an electronically conducting substrate.
- This five-layer assembly is known as a membrane electrode assembly.
- the present invention provides a membrane electrode assembly comprising a catalyst according to the invention.
- the membrane electrode assembly may be prepared by a process wherein an electrode according to the invention is combined with an ion-conducting membrane.
- the membrane electrode assembly may be prepared by a process wherein a catalysed membrane according to the invention is combined with an electronically conducting substrate.
- the electrocatalyst according to the invention is present in the anode of the membrane electrode assembly.
- Fig. 1 is a schematic diagram showing an electrocatalyst according to the first embodiment of the invention.
- Fig. 2 is a schematic diagram showing an electrocatalyst according to the second embodiment of the invention. The features shown in the schematic diagrams are not to scale.
- Figure 1 shows a metal particle (1) encapsulated by a layer of carbon (2).
- the diameter of the metal particle is, e.g. 1-lOOnm and the thickness of the carbon layer is less than lOnm, preferably about 2nm.
- Figure 2 shows a carbon support material (3), wherein metal particles (4) are dispersed on the support material (3).
- the metal particles (4) are encapsulated by a layer of carbon (5).
- the average diameter ofthe metal particles is, e.g. 1-lOnm and the thickness of the carbon layer is less than lOnm, preferably about 2nm.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
An electrocatalyst comprising one or more metal particles, wherein the metal particles are substantially covered by carbon, is disclosed. The electrocatalyst may be incorporated into electrocatalyst inks, catalysed electrodes; catalyst coated membranes and membrane electrode assemblies and is suitable for use in a fuel cell.
Description
ELECTROCATALYST
The present invention relates to an electrocatalyst that may be used in a fuel cell, and their use in catalyst inks, catalysed electrodes, catalyst coated membranes and membrane electrode assemblies.
A fuel cell is an electrochemical cell comprising two electrodes separated by an electrolyte. A fuel, e.g. hydrogen or methanol, is supplied to the anode and an oxidant, e.g. oxygen or air, is supplied to the cathode. Electrochemical reactions occur at the electrodes, and the chemical energy of the fuel and the oxidant is converted to electrical energy and heat. Electrocatalysts are used to promote the electrochemical oxidation of the fuel at the anode and the electrochemical reduction of oxygen at the cathode.
Electrocatalysts used in fuel cells typically comprise platinum or a platinum alloy.
The metal may be unsupported, but is usually supported on a high surface area carbon such as a furnace carbon black or an acetylene black. Supporting the metal increases the available surface area of the metal and reduces the amount of metal required to achieve desired activity.
The present inventors have sought to prepare electrocatalysts that are suitable for use in fuel cells. The inventors have surprisingly found that catalysts wherein a metal particle is encapsulated by carbon are active for the anodic fuel cell reaction. This is very surprising because it is generally understood that the catalytic reactions occur at the surface of the metal. The inventors believe the catalysts may have advantageous properties when compared to known fuel cell catalysts, e.g. they may have better tolerance to poisons such as carbon monoxide and hydrogen sulphide. Alternatively, it may be possible to use metals that are not traditionally used in fuel cell environments because the carbon encapsulation protects the metal from sintering and/or oxidation.
Accordingly, the present invention provides an electrocatalyst for use in a fuel cell comprising a plurality of metal particles, wherein at least 90% of the surface area of the metal particles is covered by carbon.
Preferably at least 95% of the surface area is covered with a layer of carbon, most preferably all of the surface of the metal is covered with a layer of carbon. The carbon may be present as graphitic sheets and the term "a layer of carbon" includes both a single graphitic sheet and multiple graphitic sheets.
The one or more metal particles suitably comprise one or more transition metals, which are optionally alloyed with further metals. The metal particles preferably comprise one or more metals from Groups 8 and Ib of the Periodic Table (i.e. the Groups containing platinum group metals and Fe, Co, Ni and Cu), which are optionally alloyed with further metals. In a preferred embodiment, the metal particles comprise platinum or palladium, preferably platinum, hi a particularly preferred embodiment, the metal particles consist essentially of platinum or platinum alloyed with one or more metals chosen from precious metals such as ruthenium or gold, or base metals such as molybdenum, tungsten, chromium, tin or titanium.
In a first embodiment of the invention, the electrocatalyst consists essentially of a metal particle, wherein the particle is substantially covered with carbon. The particle suitably has an average diameter of from lnm to lOOnm, preferably from lnm to 50nm.
In a second and preferred embodiment of the invention, the electrocatalyst consists essentially of metal particles dispersed on a carbon support material, wherein the particles are substantially covered with carbon. The particles suitably have an average diameter of from lnm to lOOnm, preferably from lnm to 50nm, most preferably from 1 to lOnm. The carbon support material is suitably a high surface area carbon black, such as a furnace black or an acetylene black. The surface area of the carbon support is suitably at least 5OmVg, preferably at least 200m2/g. Suitably, the amount of metal in the electrocatalyst is from 10 to 80wt% based on the weight of the carbon support material.
The covering of carbon on the metal particles is suitably less than 1 Onm in thickness. The inventors believe that thicker carbon layers are likely to reduce the activity of the electrocatalyst.
Methods of preparing carbon encapsulated metal particles are disclosed in, for example, WO 03/057626, WO 03/057359 and Lu et al, Chem. Commun., 2005, 98-100. These methods may be adapted for forming the electrocatalysts of the present invention.
In a first method, colloidal particles containing a source of metal are foπned in a liquid medium. The colloidal particles are stabilised by a surfactant. The colloidal particles contain a source of carbon such as cyanide, isocyanide, cyanate or isocyanate ligands. The particles are separated from the liquid medium. To form an electro catalyst according to the first embodiment of the invention, the particles are pyrolysed in an inert gas. To form an electrocatalyst according to the second embodiment of the invention, the particles are dispersed on a carbon support material and are then pyrolysed in an inert gas. A suitable pyrolysis temperature is at least 8000C.
In a second method, a metal salt and a carbon source (e.g. poly( vinyl alcohol)) are mixed together in deionised water at room temperature. The solution is sprayed as a fine mist into a closed vessel containing a saturated ammonia solution. A solid precipitates and is collected. To form an electrocatalyst according to the first embodiment of the invention, the solid is pyrolysed in an inert gas. To foπn an electrocatalyst according to the second embodiment of the invention, the precipitate is contacted with a carbon support material, which is then pyrolysed in an inert gas. A suitable pyrolysis temperature is at least 8000C.
In a third method, a carbon forming agent (e.g. polyvinyl alcohol), furfuryl alcohol or sucrose) is mixed with a pre-formed catalyst material such as platinum particles dispersed on a high surface area carbon support (e.g. HiSpec™ materials available from Johnson Matthey pic). The mixture is dried and then pyrolysed in an inert gas at a temperature of at least 8000C to form an electrocatalyst according to the second embodiment of the invention.
In a further aspect the present invention provides an electrocatalyst ink comprising a catalyst according to the invention dispersed in a liquid medium. The ink suitably comprises aqueous and/or organic solvents, optional polymeric binders and optional proton-conducting polymers. Methods of making electrocatalyst inks are disclosed in EP 731 520.
In a further aspect the present invention provides an electrode comprising a catalyst according to the invention deposited on an electronically conducting substrate. The catalyst can be deposited onto a substrate using well known techniques, such as those disclosed in EP 731 520. The catalyst may be formulated into an ink and the ink may be deposited onto an electronically conducting substrate using techniques such as spraying, printing and doctor blade methods. Suitable substrates include carbon fibre papers and filled carbon fibre non- woven webs, such as those disclosed in EP 791 974. The catalysed electrodes may be used in fuel cells with acid electrolytes such as proton exchange membrane (PEM) fuel cells or phosphoric acid fuel cells, or they may be used in alkaline electrolyte fuel cells.
In PEM fuel cells, the electrolyte is a proton conducting polymer membrane. Electrocatalysts may be deposited onto one or both faces of the membrane to form a catalysed membrane. In a further aspect the present invention provides a catalysed membrane comprising a catalyst according to the invention deposited on an ion-conducting polymer membrane. The catalyst can be deposited onto the membrane using well known techniques. The catalyst may be formulated into an ink and either directly deposited onto the membrane or deposited onto a decal blank for subsequent transfer to a membrane. Suitable membranes are well known to those skilled in the art and include perfluorinated sulphonic acid membranes such as Nafion®, Fleinion® and Aciplex®.
In PEM fuel cells, the membrane is interposed between two catalyst layers, and each catalyst layer is in contact with an electronically conducting substrate. This five-layer assembly is known as a membrane electrode assembly. In a yet further aspect the present invention provides a membrane electrode assembly comprising a catalyst according to the invention. The membrane electrode assembly may be prepared by a process wherein an electrode according to the invention is combined with an ion-conducting membrane. Alternatively, the membrane electrode assembly may be prepared by a process wherein a catalysed membrane according to the invention is combined with an electronically conducting substrate. Preferably the electrocatalyst according to the invention is present in the anode of the membrane electrode assembly.
For a more complete understanding of the invention, reference is made to the schematic drawings wherein:
Fig. 1 is a schematic diagram showing an electrocatalyst according to the first embodiment of the invention. Fig. 2 is a schematic diagram showing an electrocatalyst according to the second embodiment of the invention. The features shown in the schematic diagrams are not to scale.
Figure 1 shows a metal particle (1) encapsulated by a layer of carbon (2). The diameter of the metal particle is, e.g. 1-lOOnm and the thickness of the carbon layer is less than lOnm, preferably about 2nm.
Figure 2 shows a carbon support material (3), wherein metal particles (4) are dispersed on the support material (3). The metal particles (4) are encapsulated by a layer of carbon (5). The average diameter ofthe metal particles is, e.g. 1-lOnm and the thickness of the carbon layer is less than lOnm, preferably about 2nm.
Claims
1. An electrocatalyst for use in a fuel cell comprising a plurality of metal particles, wherein at least 90% of the surface area of the metal particles is covered by carbon.
2. An electrocatalyst according to claim 1 , wherein the metal particles comprise one or more transition metals.
3. An electrocatalyst according to claim 2, wherein the metal particles comprise one or more metals from groups 8 and Ib of the period table.
4. An electrocatalyst according to claim 3, wherein the metal particles comprise platinum or palladium.
5. An electrocatalyst according to claim 4, wherein the metal particles consist essentially of platinum or platinum alloyed with one or more metals chosen from ruthenium, gold, molybdenum, tungsten, chromium, tin or titanium.
6. An electrocatalyst according to any preceding claim, consisting essentially of metal particles dispersed on a carbon support material, wherein at least 90% of the area of the particles is covered with carbon.
7. The use of an electrocatalyst according to any one of the preceding claims dispersed in a liquid medium, to form an electrocatalyst ink.
8. The use of an electrocatalyst according to any one of claims 1 to 6 deposited on an electronically conducting substrate to form a fuel cell electrode.
9. The use of an electrocatalyst according to any of claims 1 to 6 deposited on a polymer electrolyte membrane to form a catalysed membrane for a fuel cell.
10. A polymer electrolyte membrane fuel cell wherein the anode comprises an electrocatalyst according to any one of claims 1 to 6.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0518635.8A GB0518635D0 (en) | 2005-09-13 | 2005-09-13 | Catalyst |
GB0518635.8 | 2005-09-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007031795A1 true WO2007031795A1 (en) | 2007-03-22 |
Family
ID=35221379
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2006/050286 WO2007031795A1 (en) | 2005-09-13 | 2006-09-12 | Electrocatalyst |
Country Status (2)
Country | Link |
---|---|
GB (1) | GB0518635D0 (en) |
WO (1) | WO2007031795A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4137373A (en) * | 1977-11-23 | 1979-01-30 | United Technologies Corporation | Platinum catalyst and method for making |
EP0731520A1 (en) * | 1995-03-09 | 1996-09-11 | Johnson Matthey Public Limited Company | Materials for use in catalytic electrode manufacture |
US5593740A (en) * | 1995-01-17 | 1997-01-14 | Synmatix Corporation | Method and apparatus for making carbon-encapsulated ultrafine metal particles |
US6037072A (en) * | 1996-09-27 | 2000-03-14 | Regents Of The University Of California | Fuel cell with metal screen flow field |
US6069107A (en) * | 1998-06-17 | 2000-05-30 | Aer Energy Resources, Inc. | Recharge catalyst with thin film carbon coating, metal-air electrode including said catalyst and methods for making said catalyst and electrode |
-
2005
- 2005-09-13 GB GBGB0518635.8A patent/GB0518635D0/en active Pending
-
2006
- 2006-09-12 WO PCT/GB2006/050286 patent/WO2007031795A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4137373A (en) * | 1977-11-23 | 1979-01-30 | United Technologies Corporation | Platinum catalyst and method for making |
US5593740A (en) * | 1995-01-17 | 1997-01-14 | Synmatix Corporation | Method and apparatus for making carbon-encapsulated ultrafine metal particles |
EP0731520A1 (en) * | 1995-03-09 | 1996-09-11 | Johnson Matthey Public Limited Company | Materials for use in catalytic electrode manufacture |
US6037072A (en) * | 1996-09-27 | 2000-03-14 | Regents Of The University Of California | Fuel cell with metal screen flow field |
US6069107A (en) * | 1998-06-17 | 2000-05-30 | Aer Energy Resources, Inc. | Recharge catalyst with thin film carbon coating, metal-air electrode including said catalyst and methods for making said catalyst and electrode |
Non-Patent Citations (1)
Title |
---|
AN-NUI ET AL.: "Highly stable carbon-protected cobalt nanoparticles and graphite shells", CHEM. COMMUN., November 2004 (2004-11-01), pages 98 - 100, XP002411566 * |
Also Published As
Publication number | Publication date |
---|---|
GB0518635D0 (en) | 2005-10-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8173324B2 (en) | Catalyst | |
US9923210B2 (en) | Ternary platinum alloy catalyst | |
JP5270098B2 (en) | Improved electrode | |
KR101350865B1 (en) | Supported catalyst for fuel cell, method for preparing the same, electrode for fuel cell comprising the same, membrane electrode assembly comprising the electrode and fuel cell comprising the membrane electrode assembly | |
US9054384B2 (en) | Electrode catalyst with improved longevity properties and fuel cell using the same | |
CA2171386C (en) | Improved materials for use in electrode manufacture | |
US7572543B2 (en) | Supported catalyst and fuel cell | |
US11264624B2 (en) | Electrocatalyst | |
EP2168187B1 (en) | Catalyst layer | |
KR20050083660A (en) | Fuel cell electrode | |
EP1771903B1 (en) | Ruthenium-rhodium alloy electrode catalyst and fuel cell comprising the same | |
CA2591040C (en) | Electrode catalyst for fuel cell | |
CA2353761A1 (en) | A membrane electrode unit for polymer electrolyte fuel cells and a process for the production thereof | |
KR101273314B1 (en) | Platinum alloy catalyst | |
KR20110129627A (en) | Electrode catalyst for fuel cell, manufacturing method thereof and fuel cell using same | |
US9299991B2 (en) | Electrochemical deposition of nanoscale catalyst particles | |
WO2007031795A1 (en) | Electrocatalyst | |
KR20070031133A (en) | Electrode catalyst with increased oxygen reduction activity and fuel cell using same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 06794969 Country of ref document: EP Kind code of ref document: A1 |