WO2003026036A2 - Objet metallique revetu se presentant sous la forme d'une plaque et utilise en tant que composant d'un empilement de piles a combustible - Google Patents
Objet metallique revetu se presentant sous la forme d'une plaque et utilise en tant que composant d'un empilement de piles a combustible Download PDFInfo
- Publication number
- WO2003026036A2 WO2003026036A2 PCT/EP2002/010481 EP0210481W WO03026036A2 WO 2003026036 A2 WO2003026036 A2 WO 2003026036A2 EP 0210481 W EP0210481 W EP 0210481W WO 03026036 A2 WO03026036 A2 WO 03026036A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- metal object
- metal
- layer
- fuel cell
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- 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
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
-
- 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
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
-
- 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
- H01M8/023—Porous and characterised by the material
- H01M8/0241—Composites
- H01M8/0245—Composites in the form of layered or coated products
-
- 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 invention relates to a coated plate-shaped metal object as a component of a fuel cell stack, and to a method for its production.
- the plate-shaped metal object is used in particular in fuel cells as a bipolar plate, cooling layer or gas distribution structure.
- Certain types of fuel cells are made with a polymer electrolyte membrane (PEM).
- PEM polymer electrolyte membrane
- This is provided with a catalyst layer on both sides and is located between two gas diffusion layers. It is also possible for the two gas diffusion layers to be provided with the catalyst layer instead of the membrane.
- a fuel e.g. B. hydrogen gas
- an oxidizing agent e.g. B. oxygen supplied.
- Form on the anode due to of the catalyst protons, which cross the membrane acting as an electrolyte and combine with the oxygen in the cathode-side catalyst layer to form water. In this process, a potential difference arises between the two catalyst layers, which is used in an external circuit.
- the fuel cell stack may contain additional layers that are formed from plate-shaped metal objects, such as. B. a coolant layer for cooling the fuel cell stack or gas distribution structures, provided with flow channels, for improved introduction of the reaction gases to the reaction site.
- Bipolar plates, cooling layers and gas distribution layers have in common that, in order to ensure a conductive contact between the individual cells or their individual components, they must be very electrically conductive and only have a low contact resistance to the neighboring components of the fuel cell. In addition, it must be ensured that oxidation does not result in water-soluble products in the base materials used, which, when in contact with the catalyst, could block the catalyst or limit the ionic conductivity of the electrolyte. For this reason, carbon materials are often used, the contact resistances of which do not increase as a result of partial oxidation during operation of the fuel cell compared to the use of metal and which are chemically inert to blockages in the catalyst or poisoning of the electrolyte. The disadvantage of this is the high cost of the carbon materials.
- the invention is intended to avoid all of the disadvantages listed above by using inexpensive, coated metallic components.
- the use of metallic components in fuel cells is to be made possible, for which purpose simple and inexpensive coating processes are applied to these metallic coating objects, which keep the contact resistances to other components low and constant despite changing operating modes over time.
- the invention enables a cost reduction by the coating being only partially and on average not thicker than 0.04 ⁇ m. or preferably as 0.01 ⁇ m.
- a surface-covering conductive coating of the metallic coating object is not necessary for use in fuel cells in order to ensure a low contact resistance between the components used. The use of the coating material can thus be reduced.
- the risk of the formation of water-soluble oxidation products with their negative consequences for the fuel cell can be avoided by suitable selection of the material of the coating object, or a further protective layer can be added to the coating.
- components consisting of a metal can be used in fuel cells.
- These are preferably bipolar plates, but also gas distribution structures, for example made of perforated structural sheets, or cooling layers.
- the metal object to be coated it should preferably be ensured in advance that water-soluble products do not result from its oxidation, which could block the catalyst or would limit the ionic conductivity of the membrane when it comes into contact with it; otherwise this restriction of the choice of material can become unnecessary through appropriate additional protective layers.
- Stainless steel or titanium is very suitable as a base material for the metal object due to its chemical inertness in the above sense, but the latter is less preferred due to the high cost.
- an additional protective layer is advantageous due to the possible risk of water-soluble oxidation products.
- a protective layer is particularly suitable for a graphite foil.
- the coating is not applied to the entire surface of the metal object, but is a non-closed coating. This means that the entire surface of the metal object is not covered with the coating metal and its oxides.
- Suitable coating metals are metals which can have compounds with oxygen atoms to a variable degree (MO x ), although other compounds can also be covalently bonded to the oxygen atoms, for example MO x (OH) y , and their oxides have good electrical conductivity, for example tin, indium, antimony or the platinum metals ruthenium, rhodium, osmium, palladium, iridium and platinum or alloys of such metals. It is important to ensure that the metal oxide (MO x ) conducts electricity well in as many of the oxidation states that occur in different operating modes. Ruthenium and ruthenium oxide are therefore particularly preferably used.
- the oxidation levels of the coating vary depending on the place of use within the fuel cell and the respective operating mode.
- a fuel cell is supplied with hydrogen gas on the anode side and oxygen-containing gas on the cathode side; in the switched-off state, air penetrates through the membrane into the anode compartment.
- metallic components in a fuel cell stack these are alternately in an oxidizing and reducing atmosphere depending on the place of use and the selected operating mode.
- the coating of such components must therefore have a sufficiently good electrical conductivity both in elemental-metallic and in the oxidation state MO ⁇ in order to ensure the greatest possible reduction in the contact resistance to other components.
- the side of a bipolar plate facing the cathode of a fuel cell is exposed to an oxidizing atmosphere
- the side facing the anode is exposed to a reducing atmosphere on the one hand during operation of the fuel cell stack and, on the other hand, to an oxidizing atmosphere when it is at a standstill.
- the latter also applies to cooling layers which are located in the anode compartment or to gas distribution structures which are arranged in the same way and which can be produced, for example, from perforated structural sheets.
- the composition of the coating more precisely the respective oxidation state of the metal oxide MO x , therefore changes depending on the operating modes, ie on the duration of operation or standstill of the fuel cell stack and on the chosen place of use. In order to achieve a consistently low contact resistance despite this changing composition, it is advantageous if both the metal and its variable oxidation levels have sufficient electrical conductivity.
- All common application methods in particular electrolytic deposition, or the usual PVD (e.g. sputtering) or CVD methods are suitable for applying the metal layer to the coating object.
- the parameters of the corresponding coating process are selected so that a thin, non-closed layer of the coating metal is formed on the surface of the coating object.
- partial oxidation can take place. This can be done using all common methods and treatments.
- the partial oxidation of the coating could take place by treatment with atmospheric oxygen or by Tempering in an oxygen-containing atmosphere.
- the coating metal is tempered preferably in air at a temperature preferably between 100 ° C. and 800 ° C., particularly preferably between 200 ° C. and 400 ° C.
- the tempering additionally improves the adhesion of the coating, since the resultant Connects coating metal oxide with oxide layers present on the coating object before the coating.
- Further methods for partial oxidation are, for example, the electrochemical treatment of the applied coating metal or the sputtering of the coating metal in an atmosphere with a fixed oxygen content.
- an additional protective layer is expedient, as explained above.
- All materials that are highly conductive and chemically inert in the above sense are suitable as protective layers. They preferably consist of a thin, possibly gas-permeable graphite foil that can be attached to one or both surfaces of the component. Since a low contact resistance between the metal component and the protective layer is also essential here, the coating according to the invention can be used advantageously.
- the composite of coated metal component and protective layer can be produced by all common methods, for example by simply laying on or pressing on, possibly at elevated temperature. If conductive bonding is chosen as the connection method, a suitable adhesion promoter is required. Further details and embodiments of the coating according to the invention are described below using examples:
- the bipolar plates for a fuel cell stack consist of a 50 ⁇ m thick stainless steel foil, which is coated with the coating according to the invention. Ruthenium is used as the coating metal. After cleaning, degreasing and grinding the passivation layer on the surface of the stainless steel foil, the ruthenium coating is electrolytically deposited from a ruthenium chloride solution on the stainless steel foil.
- the aqueous electrolyte solution contains 0.25% by mass of ruthenium chloride and approx. 5% by mass of isopropanol. With an electrolysis voltage of 1.48 V, a current of approx. 1.5 mA / cm 2 surface of the metal object, that is the stainless steel foil, results. 60 seconds are selected as the duration of the electrolytic deposition. This creates a non-closed coating with metallic ruthenium on the stainless steel foil. After the coated bipolar plate has dried, it is annealed for 30 minutes at 300 ° C. in an oxygen-containing atmosphere for partial oxidation.
- the contact resistance of individual components can be determined using the following method:
- the component to be examined is placed between two carbon fiber papers with a thickness of 0.3 mm and this in turn between two gold-plated copper electrodes of a tensioning device.
- a defined pressure can be exerted on the component to be examined.
- the voltage falling between the copper electrodes is determined as a function of a direct current flowing through the tensioning device, from which the area-specific resistance of the component to be examined can be determined.
- a contact resistance can be created including the resistance of the carbon fiber papers of 16.3 m ⁇ cm 2 at a contact pressure of 11.5 bar, which is only slightly above the contact resistance of 13.3 m ⁇ cm 2 at the same contact pressure of a corresponding bipolar plate with elemental-metallic coating.
- an untreated bipolar plate made of 50 ⁇ m stainless steel foil has a contact resistance of 188 m ⁇ cm 2 at a contact pressure of 11.5 bar.
- the average layer thickness is less than 0.025 ⁇ m, that is to say it has less than 100 atomic layers on average. It is therefore not dense, but there are empty, uncoated areas between atomic accumulations.
- the same coating process with ruthenium can also be used for perforated structural sheets made of stainless steel, which can advantageously be used as gas distribution structures in a fuel cell stack.
- the aluminum bipolar plate or cooling layer is provided with a layer of elemental platinum or ruthenium by sputtering, which is then partially oxidized by tempering in an oxygen-containing atmosphere becomes.
- a thin 0.85 mm graphite foil which is hydrophobic, serves as a protective layer.
- the composite of coated aluminum bipolar plate or cooling layer and graphite foil is produced by means of conductive gluing.
- epoxy resin is applied in small quantities (approx. 1.5 mg / cm 2 ) to the graphite foil and cured by means of hot pressing at 110 ° C and a pressure of approx. 35 bar.
- a graphite foil according to Example 2 is not completely, but interrupted, for. B. applied in the form of individual webs or preferably connected web structures.
- the contact resistance of such a bipolar plate with gas distribution channels measured using the method shown in Example 1 is in the range of approximately 22 m ⁇ cm 2 at a contact pressure of 14 bar.
- the contact resistance of a bipolar plate with graphite foil glued to the entire surface is typically up to approx. 15 m ⁇ cm 2 at a contact pressure of also 14 bar.
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002362328A AU2002362328A1 (en) | 2001-09-18 | 2002-09-18 | Coated metal object in the form of a plate and used as component of a fuel cell stack |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10145940 | 2001-09-18 | ||
DE10145940.8 | 2001-09-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2003026036A2 true WO2003026036A2 (fr) | 2003-03-27 |
WO2003026036A3 WO2003026036A3 (fr) | 2003-10-09 |
Family
ID=7699415
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/010481 WO2003026036A2 (fr) | 2001-09-18 | 2002-09-18 | Objet metallique revetu se presentant sous la forme d'une plaque et utilise en tant que composant d'un empilement de piles a combustible |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU2002362328A1 (fr) |
WO (1) | WO2003026036A2 (fr) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004034620A1 (de) * | 2004-07-16 | 2006-02-02 | Behr Gmbh & Co. Kg | Fluiddurchströmbare Vorrichtung und Betriebsverfahren |
DE102004059691A1 (de) * | 2004-12-10 | 2006-07-20 | Daimlerchrysler Ag | Hydrophobe Separatorplatte für eine PEM-Brennstoffzelle |
EP2027621A2 (fr) * | 2006-04-14 | 2009-02-25 | Applied Materials, Inc. | Conception d'electrode de pile a combustible fiable |
US7959987B2 (en) | 2004-12-13 | 2011-06-14 | Applied Materials, Inc. | Fuel cell conditioning layer |
US8377607B2 (en) | 2005-06-30 | 2013-02-19 | GM Global Technology Operations LLC | Fuel cell contact element including a TiO2 layer and a conductive layer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1285417A (en) * | 1969-10-13 | 1972-08-16 | Int Nickel Ltd | Production of protective coatings on metals by anodic oxidation |
EP0423448A1 (fr) * | 1989-09-20 | 1991-04-24 | Asea Brown Boveri Ag | Collecteur pour la conduction du courant entre des cellules à combustible arrangées selon une pile et fonctionnant à haute température et méthode de fabrication |
EP0955686A1 (fr) * | 1998-05-07 | 1999-11-10 | Toyota Jidosha Kabushiki Kaisha | Plaque séparatrice pour cellule à combustible gazeux, pile à combustible la contenant, et procédé pour sa préparation |
US20010021470A1 (en) * | 1998-10-08 | 2001-09-13 | Barret May | Fuel cells and fuel cell plates |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07296827A (ja) * | 1994-04-27 | 1995-11-10 | Tokyo Gas Co Ltd | 複合セパレータを有する内部マニホールド方式の固体電解質型燃料電池 |
-
2002
- 2002-09-18 AU AU2002362328A patent/AU2002362328A1/en not_active Abandoned
- 2002-09-18 WO PCT/EP2002/010481 patent/WO2003026036A2/fr not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1285417A (en) * | 1969-10-13 | 1972-08-16 | Int Nickel Ltd | Production of protective coatings on metals by anodic oxidation |
EP0423448A1 (fr) * | 1989-09-20 | 1991-04-24 | Asea Brown Boveri Ag | Collecteur pour la conduction du courant entre des cellules à combustible arrangées selon une pile et fonctionnant à haute température et méthode de fabrication |
EP0955686A1 (fr) * | 1998-05-07 | 1999-11-10 | Toyota Jidosha Kabushiki Kaisha | Plaque séparatrice pour cellule à combustible gazeux, pile à combustible la contenant, et procédé pour sa préparation |
US20010021470A1 (en) * | 1998-10-08 | 2001-09-13 | Barret May | Fuel cells and fuel cell plates |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 03, 29. März 1996 (1996-03-29) & JP 07 296827 A (TOKYO GAS CO LTD), 10. November 1995 (1995-11-10) * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004034620A1 (de) * | 2004-07-16 | 2006-02-02 | Behr Gmbh & Co. Kg | Fluiddurchströmbare Vorrichtung und Betriebsverfahren |
DE102004059691A1 (de) * | 2004-12-10 | 2006-07-20 | Daimlerchrysler Ag | Hydrophobe Separatorplatte für eine PEM-Brennstoffzelle |
US7959987B2 (en) | 2004-12-13 | 2011-06-14 | Applied Materials, Inc. | Fuel cell conditioning layer |
US8377607B2 (en) | 2005-06-30 | 2013-02-19 | GM Global Technology Operations LLC | Fuel cell contact element including a TiO2 layer and a conductive layer |
EP2027621A2 (fr) * | 2006-04-14 | 2009-02-25 | Applied Materials, Inc. | Conception d'electrode de pile a combustible fiable |
EP2027621A4 (fr) * | 2006-04-14 | 2010-01-13 | Applied Materials Inc | Conception d'electrode de pile a combustible fiable |
Also Published As
Publication number | Publication date |
---|---|
WO2003026036A3 (fr) | 2003-10-09 |
AU2002362328A1 (en) | 2003-04-01 |
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