CN1326278C - Flexible graphite article and fuel cell electrode with enhanced electrical and thermal conductivity - Google Patents
Flexible graphite article and fuel cell electrode with enhanced electrical and thermal conductivity Download PDFInfo
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- CN1326278C CN1326278C CNB008196400A CN00819640A CN1326278C CN 1326278 C CN1326278 C CN 1326278C CN B008196400 A CNB008196400 A CN B008196400A CN 00819640 A CN00819640 A CN 00819640A CN 1326278 C CN1326278 C CN 1326278C
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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
- H01M4/8605—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/536—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite based on expanded graphite or complexed graphite
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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
- H01M4/96—Carbon-based electrodes
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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
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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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
- H01M8/026—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant characterised by grooves, e.g. their pitch or depth
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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
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
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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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/94—Products characterised by their shape
- C04B2235/945—Products containing grooves, cuts, recesses or protusions
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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
Abstract
The present invention provides a graphite product (20) which can be used for manufacturing a membrane electrode component (6), and the component comprises a pair of electrodes and an ion exchange membrane (550) arranged between the electrodes. At least one electrode is formed by the flake of the compressed bodies of expanded graphite particles, the electrode is provided with a plurality of transverse fluid flow passages (20) of the flake, and the fluid flow passages are penetrated through the first opposite surface and the second opposite surface of the flake. When the present invention is used in the membrane electrode component (6), one opposite surface is adjacent to the ion exchange membrane (550), and at least a part of the fluid flow passages (20) are mutually communicated to cause fluid to flow through inside.
Description
Technical field
The present invention relates to a kind of goods that are used for the electrode assemblie of electrochemical fuel cell.Assembly of the present invention comprises a kind of goods that formed by flexible graphite sheet, and it is that fluid is permeable and have an isotropism of raising for thermal conductivity and conductivity.
Background of invention
Graphite is that the aspect by hexagonal array or netted carbon atom is constituted.The carbon atom aspect of these hexagonal arraies is substantially flats, and is directed or rule, so that they are substantially parallel and equidistant each other.Carbon atom thin slice described substantially flat, parallel equidistant or layer are referred to as basal plane usually, and they connect or are bonded together, and their combination is arranged with microcrystalline form.The graphite of height rule is made up of quite large-sized crystallite: described crystallite is highly alignment or directed each other, and the carbon-coating with good rule.In other words, the graphite of height rule has highly preferred crystallite orientation.Should be noted that graphite has anisotropic structure, thereby show or have many character, particularly thermal conductivity, conductivity and diffuse fluid that they all are short transverses.In brief, graphite is characterised in that the layer structure of its carbon, that is, and and the structure that carbon atomic layer that comes out one after another that is combined by weak model ylid bloom action power or thin layer are formed.When considering graphite-structure, need two axles or direction usually, promptly described " c " axle or direction and described " a " axle or direction.Briefly, described " c " axle or direction can be thought the direction perpendicular to described carbon-coating.Described " a " axle or direction can think to be parallel to the direction of described carbon-coating, or perpendicular to the direction of described " c " direction.Be fit to be used for making the native graphite of flexible graphite, have the very orientation of height.
As mentioned above, the adhesion that parallel carbon atomic layer is fixed together only is weak Van der Waals force.Can handle graphite, make described space of coming out one after another between carbon-coating or the thin layer open slightly a little, so just can (promptly described " c " direction) provide significant expansion on perpendicular to the direction of described layer, thereby form graphite-structure a kind of expansion or enlargement, the stratiform feature of wherein said carbon-coating is to keep substantially.
Natural graphite flake, it expanded widely and more specifically expand into make its final thickness or " c " direction be of a size of its original " c " direction size at least about 80 times or bigger, do not need to adopt binding agent, just can be shaped as adhesion or the whole flexible graphite sheet of expanded graphite, for example, fabric, paper, band, tape etc.Expand into about 80 times graphite particulate that final thickness or " c " direction size are at least original " c " direction size, form the forming process of whole flexible flake by compression, do not need to adopt any binding material to be considered to possible, because it has good mechanical interlocking or cohesive force (it is to obtain) between the graphite particulate of huge expansion yet.
Except flexibility; as mentioned above; find that also described sheeting has the anisotropy of height for thermal conductivity and conductivity and diffuse fluid; can be comparable to the native graphite raw material, this is because described expanded graphite particulate is basically parallel to the apparent surface's of the thin slice that is obtained by very high compression such as roll-in orientation.The sheeting that makes like this has good flexibility, good strength and orientation very highly.
In brief, the method of described preparation anisotropy graphite flake material flexible, binder free such as fabric, paper, band, tape, paillon foil, mat etc., be included under the predetermined load and do not have binding agent lower compression or a compacting expanded graphite particulate, " c " direction size that described expansion particulate has is at least about 80 times of its primary particle, thereby forms the graphite flake of a kind of substantially flat, flexibility, integral body.Described expanded graphite particulate, its outward appearance is vermiform or lumbricoid normally, in case compressed, will maintain the compressive deformation and the arrangement of the corresponding main surfaces of described thin slice.The density of described sheeting and thickness can change by controlling described compression degree.The density of described sheeting can be between about 5-125 pound/cubic feet scope.Described flexible graphite sheet material has the anisotropy of obvious degree, and this is because the arrangement of graphite particulate is parallel to the main opposing parallel surface of described thin slice, also improves in the described sheeting of roll-in anisotropic degree when improving density.In the anisotropy sheeting of roll-in, thickness (being described direction perpendicular to described parallel sheet surface relatively) comprises described " c " direction, with described along length and width variation direction, promptly along or the direction of parallel described corresponding main surfaces comprise described " a " direction, for described " c " and " a " direction, according to its order of magnitude, the thermal property of described thin slice, electrical property and diffuse fluid character are very inequality.
This qualitative notable difference is referred to as anisotropy, and it is very disadvantageous by the direction decision in some applications.For example, as in the gasket applications of gasket material, in use, it is tightly to be fixed between the metal surface in flexible graphite sheet, the diffusion of fluid such as gas or liquid can more easily be parallel to and carry out between the first type surface of described flexible graphite sheet.In most of situations, if the mobile resistance that is parallel to the first type surface (" a " direction) of described graphite flake of fluid increases, even is cost to reduce diffuse fluid transverse to the mobile resistance of first type surface (" c " direction) of described graphite flake, it also needs better packing ring performance.For electrical property, the resistance coefficient of anisotropic flexible graphite sheet, in the direction (" c " direction) transverse to the first type surface of described flexible graphite sheet is very high, and be parallel to and described flexible graphite sheet first type surface between direction (" a " direction) be low-down basically.In application as the fluid flow fields battery lead plate that is used for fuel cell and the sealing that is used for fuel cell and so on, if the resistance transverse to described flexible graphite sheet first type surface (" c " direction) reduces, even to improve in the resistivity that is parallel to the first type surface direction of described flexible graphite sheet (" a " direction) is cost, also will be favourable.
For thermal property, the thermal conductivity of flexible graphite sheet is relative high on the upper surface that is parallel to described flexible graphite sheet and lower surface direction, and is relative very low on described " c " direction transverse to described upper surface and lower surface.
Aforesaid situation can be by the invention provides.
Summary of the invention
According to the present invention, a kind of membrane electrode assembly that is used for electrochemical fuel cell is provided, comprise pair of electrodes and be arranged on amberplex between described two electrodes, at least one described electrode is formed by the thin slice of the compression body of expanded graphite particulate, have numerous lateral fluid passages and pass thin slice between first and second apparent surfaces of described thin slice, an apparent surface engages described amberplex.Advantageously, described lateral fluid passage is that the graphite of preposition forms in described thin slice to discharge for apparent surface by the described thin slice of mechanical stamping.Adjacent setting of described lateral fluid passage and compressed expanded graphite wall are separated, and at least a portion in them can allow to form be interconnected (for example by groove is set therein) between adjacency channel, to guarantee that fluid is from flowing through therebetween.
Brief description of drawings
Figure 1 shows that a kind of plane graph that laterally can see through thin slice of the present invention with flexible graphite of the interconnection that is interconnected;
Fig. 1 (A) is a kind of schematic diagram that is used for making the terminal smooth outstanding element of perforated sheet passage shown in Figure 1;
Fig. 2 is the end view of the described thin slice section of Fig. 1;
Fig. 2 (A), (B), (C) are for being used for laterally the be interconnected schematic diagram of multiple different suitable terminal flat structures of passage of the present invention;
Fig. 3,3 (A), 3 (B) are a kind of schematic diagram that is used to make the mechanical device of goods shown in Figure 1;
Fig. 3 (C), 3 (D) are the enlarged perspective that laterally can see through the flexible graphite sheet part of the present invention;
Fig. 3 (E) is the picture that laterally can see through the part of flexible graphite sheet of corresponding diagram 3 (C);
Fig. 4 is the enlarged diagram of front view of the directional expansion graphite particulate of flexible graphite sheet material;
Fig. 5 is a kind of schematic diagram of amplification front elevation of the goods that formed by flexible graphite sheet of the present invention;
Fig. 5,6,7 and 7 (A) comprise that for a kind of a kind of fluid that laterally can see through goods of the present invention can see through the electrode assemblie schematic diagram;
Fig. 8 is the schematic diagram of the part of corresponding schematic side view shown in Figure 5 at the picture that amplifies 100 times (original enlargement ratios).
Detailed description of the present invention
Graphite is a kind of carbon of crystalline form, is included in covalently bound atom in the smooth layering plane, has weak adhesion between described plane.By adopting a kind of insertion agent (intercalant) as sulfuric acid and salpeter solution to handle graphite particulate, as natural graphite flake, then described the crystal structure of graphite can react the compound that forms a kind of graphite and described insertion agent.After this graphite particulate after the described processing is called " insertion graphite particulate ".When being exposed to high temperature, described insertion graphite particulate expands, and is collapsible form in described " c " direction direction of the crystal plane of described graphite (promptly perpendicular to) usually, and dilation dimension reaches about 80 times or bigger of its initial volume.Exfoliate graphite particulate outward appearance is vermiform, and therefore they often be called as worm.Described worm is the boil down to flexible flake together, and is different with described original graphite flakes, and they are plastic or cut into various shape, and can provide very little lateral opening by distortion mechanical stamping.
A kind ofly make graphite flake such as paillon foil method commonly used by flexible graphite, be disclosed in people's such as Shane US3, among 404,061, the disclosure of this patent can be introduced and be made for reference herein.In the typical case of people's methods such as described Shane implemented, natural graphite flake was by disperseing described thin slice to insert among a kind of solution that contains just like the oxidant of nitric acid and sulfuric acid mixture.Described insertion solution contains oxidant well known in the art and other inserts agent.Instantiation comprises that those contain the material of oxidant and oxidation mixture, as contain the solution of nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, dichromic acid, perchloric acid etc., perhaps mixture, for example, red fuming nitric acid (RFNA) and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid or a kind of strong organic acid are as the mixture of the strong oxidizer in the organic acid as described in trifluoroacetic acid and a kind of the dissolving in.
In a preferred implementation, described insertion agent is that sulfuric acid or sulfuric acid and phosphoric acid and oxidant are the solution of the mixture of nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, acid iodide or periodic acid etc.Although be not preferred,, described insertion solution can contain metal halide such as iron chloride and be mixed with sulfuric acid or halide as with the solution form of bromine and sulfuric acid or be present in the iron chloride of the bromine form in a kind of organic solvent.
Through after inserting processing, all excess solutions are discharged from described thin slice, and water washs described thin slice at described thin slice.Remain in the amount of the insertion solution on the described thin slice after discharging step, its scope is 20-150 weight portion (pph) with respect to the graphite flake of per 100 weight portions, more typically about 50-120pph.A kind of replacement scheme is, the amount of described insertion solution can be limited in per relatively 100 weight portion graphite (pph) between the 10-50 weight portion (pph), according to the instruction and the explanation of US4895713 (its disclosure also can be introduced and be made for reference herein), this solution amount scope can allow to omit described washing step.Graphite particulate through this processing is referred to as " insertion graphite particulate " sometimes.When being exposed to high temperature for example about 700-1000 ℃ or higher temperature, described insertion graphite particulate expands, be collapsible form in described " c " direction direction of the crystal plane of described graphite (promptly perpendicular to), dilation dimension reaches the about 80-1000 of its initial volume doubly or higher.The graphite particulate outward appearance of described expansion (or scaling off) is vermiform, and therefore they often be called as worm.Described worm is the boil down to flexible flake together, and is different with described original graphite flakes, and they are plastic or cut into various shape, and can provide very little lateral opening by the distortion mechanical stamping that below will describe.
Flexible graphite sheet and paillon foil are to be adhered together, and have good manipulation strength, and they can compatibly compress (as by roll-in) density to the thickness and the 0.1-1.5 gram/cubic centimetre of 0.003-0.15 inch.Described in US5902762 (it can be introduced and be made for reference herein), the ceramic additive of about 1.5-30wt.% can mix with described insertion graphite flake, thereby the resin impregnated performance of enhancing is provided in final flexible graphite product.Described additive comprises having the ceramic fibre particulate that length is 0.15-1.5mm.The width of described particulate is 0.04-0.004mm suitably.Described ceramic fibre particulate is nonactive for graphite, and also inadhesion is on graphite, and they are being stable up to 2000 during preferably up to the high temperature of 2500 .Suitable ceramic fibre particulate be by the quartz glass fibre of macerating, carbon and graphite fibre, zirconia, boron nitride, carborundum and magnesia fibers, it is natural that to form mineral fibres such as ca silicate fibre, aluminosilicate calcium fiber, alumina fibre etc. formed.
Referring to Fig. 1 and Fig. 2, a kind of compression body of expanded graphite particulate is the flexible graphite sheet form, shown in mark among the figure 10.Described flexible graphite sheet 10 has passage 20, and preferably side is level and smooth for they, and shown in the mark in Fig. 5 and 8 67, they pass between the described parallel facing surfaces 30,40 of flexible graphite sheet 10, and the wall 3 of compressed expanded graphite is separated.Described wall 3 advantageously has groove 5, and its degree of depth is the 1/10-1/3 of channel depth of the present invention.Described passage 20 preferably has perforate 50 in an apparent surface 30, they are greater than the perforate 60 in another apparent surface 40.Described passage 20 can have different structures, shown in 20 '-20 ' among Fig. 2 (A), 2 (B), 2 (C), they be adopt as Fig. 1 (A) and 2 (A), 2 (B), 2 (C), 2 (D) in the smooth outstanding element formation of the difform end face shown in the mark 75,175,275,375, they are formed as steel by metal suitably, and constitute an integral body with the pressure roller 70 of decompressor shown in Figure 3 and stretched out by it.The outstanding element 75 of described formation passage, 175,275,375 level and smooth flat end, as mark among the figure 77,177,277, shown in 377, outstanding element 675 with described formation groove, 775,875,975 level and smooth flat end, as among the figure 677,777,877, shown in 977, level and smooth bearing surface 73 with described pressure roller 70, with the level and smooth bearing surface 78 of described pressure roller 72 (perhaps, can select flat metal sheets 79), can guarantee the distortion and the displacement of graphite in the described flexible graphite sheet, preferably, so just can not exist owing to form the Roughen Edges that punching press brought or the fragment of passage.The outstanding element 675,775,875,975 of described formation groove can cause that also the graphite among the described flexible graphite sheet deforms and is shifted.The preferred outstanding element 77 that forms passage has the cross section that reduces in the direction away from described pressure roller 70, thereby provides bigger channel aperture at the end that described thin slice initially carries out punching press.Around level and smooth straightway surperficial 63 the expansion of channel aperture 60, can guarantee that fluid flows freely into and flows through level and smooth (mark 67) passage 20 in described side.
In a preferred implementation, one of described apparent surface's perforate is greater than the channel aperture among another apparent surface, for example area is its 1-200 times, and this is owing to the outstanding element (shown in 76,276,376) that uses the side with convergence forms.Described interconnection 20 is that the precalculated position in thin slice 10 forms by mechanical stamping a plurality of precalculated positions in described flexible graphite sheet 10, be to adopt a kind of mechanical device as shown in Figure 3 to carry out, this device comprises a pair of steel rider 70,72, one of them roller has (being that end face is smooth) the prismatic ledge 75 that blocks, thereby thereby the surface 30 that it can stamping flexible graphite flake 10 makes graphite that displacement take place and penetrates thin slice 10 and forms open channels 20.In the present invention, the ledge 75 of described formation passage by ledge 675 bridgings that form groove together, form the groove 5 be interconnected between their passages 20 in alignment channel in a row, form passage 20 simultaneously, shown in the picture of the schematic diagram of Fig. 3 (C) and Fig. 3 (E).In addition, the outstanding element 675 ' that forms groove is includable, shown in Fig. 3 (A), 3 (B), thereby forms the groove 5 ' that is interconnected in the interconnection 20 that is arranged in parallel, shown in Fig. 3 (D).In fact, two rollers 70,72 all can have the ledge of " not lining up ", and a flat metal sheets with 79 expressions can be used for substituting the roller 72 of surface smoothing.Fig. 4 is the enlarged diagram of flexible graphite 110 thin slices, and the orientation of the typical prior art of the expanded graphite particulate 80 of its explanation compression is parallel to described apparent surface 130,140 basically.This orientation of described expanded graphite particulate 80 causes the anisotropy in flexible graphite sheet, be the conductivity and the thermal conductivity of described thin slice, on direction (" c " direction), be lower than the direction (" a " direction) that is parallel to apparent surface 130,140 significantly transverse to apparent surface 130,140.In the process of stamping flexible graphite flake 10 with formation passage 20, as shown in Figure 3, the smooth surface 73 of shifting to and lean against roller 70 when it is to destroy and during distortion expanded graphite particulate 80 parallel-oriented, shown in 800 among Fig. 5, graphite is pushed away peripheral graphite by the ledge 75 of end face smooth (at 77 places) formation passage and is subjected to displacement in flexible graphite sheet 10.The ledge 675 that forms groove makes the parallel-oriented of described expanded graphite particulate deform simultaneously.The zone 800 of this adjacent channel 20 and groove 5 has illustrated a kind of inclination, the nonparallel orientation of described parallel-oriented destroyed formation, amplify 100 times and more high magnification just can be clear that.In fact, the described graphite that has been shifted is to carry out the punch die moulding by the side 76 of contiguous ledge 75 and the smooth surface 73 of described roller 70, as shown in Figure 5.This will reduce the anisotropy of flexible graphite sheet 10, thereby improves described thin slice 10 transverse to conductivity and thermal conductivity on described apparent surface's 30,40 directions.Adopt the smooth ledge 275 and 175 of end face of the peg shape of conical butt and parallel sided, also can obtain similar effect.The gas permeable flexible graphite sheet of perforation shown in Figure 1 can be used as the electrode of electrochemical fuel cell 500, shown in Fig. 6,7 and 7 (A).
Fig. 6, Fig. 7 and Fig. 7 (A) illustrate a kind of primary element of electrochemical fuel cell 500, its more comprehensively detailed content be disclosed among patent document US4988583 and US5300370 and the PCT WO95/16287 (June 15 nineteen ninety-five), each in them all can be introduced and be made for reference herein.
Referring to Fig. 6, Fig. 7 and Fig. 7 (A), by the fuel cell of 500 expressions, comprise the electrolyte that is plastic form generally, for example a kind of solid polymer ion exchange membrane 550, catalyst coated for example is coated with platinum 600, as shown in Fig. 7 (A) on surface 601,603; The flexible graphite sheet electrode 10 of perforation of the present invention; With flow field plates plate 1000,1100, they are adjacent electrode 10 respectively.Pressurized fuel circulates in the groove 1400 of fuel flow field battery lead plate 1100, and pressurized oxidant circulates in groove 1200.At work, described fuel flow field battery lead plate 1100 becomes anode, and described oxidant flow field battery lead plate 1000 becomes negative electrode, and consequently, forming electromotive force between described fuel flow field battery lead plate 1000 and described oxidant flow field battery lead plate 1100 is voltage.Above-mentioned electrochemical fuel cell can combine with other fuel battery, to produce electric current and electrical power as expection level as described in the above-mentioned US5300370 is provided.
Fig. 8 is the picture (original enlargement ratio 100X) of the flexible graphite body of corresponding diagram 5 schematic diagram parts.
Fig. 1 and 5 goods and the material shown in the picture shown in Figure 8 (100X), with compare transverse to the direction on the described material of Fig. 4 (wherein with the nonaligned expansion native graphite in described relatively flat surface be perusal less than) surface 130,140, with regard to thermal conductivity and conductivity, they have the thermal conductivity and the conductivity of raising on the flat surfaces 30,40 transverse to opposing parallel.
A kind of thickness is 0.01 inch and has the sample that density is the flexible graphite sheet of 0.3g/cc, as shown in Figure 4, by adopting a kind of device similar to Fig. 3, provides the passage of different size through mechanical stamping in described flexible graphite sheet.Measure the resistance of horizontal (" c " direction) of described sheeting sample, the gained result is as shown in the table.
And the horizontal gas permeability of the flexible graphite sheet sample of described groove according to the present invention, is by using a kind of Gurley Model 4118 that is used for the gas permeability measurement to measure.
The sample of the flexible graphite sheet of groove of the present invention is placed on the bottom opening (diameter is 3/8 inch) of vertical cylinder (diameter cross is 3 inches).Described cylinder is filled with the 300cc air, and a load piston (5oz.) is placed on the suitable place at the top of described cylinder.The speed that gas stream is crossed the sample of described groove is to measure as the function of piston fall time, and the gained result is as shown in the table.
Flexible graphite sheet
(thickness is 0.01 inch; Density=0.3g/cc)
| No passage | 0.020 inch in 1600 passages/square inch-top width; 0.005 inch of bottom width | 0.020 inch in 250 passages/square inch-top width; 0.007 inch of bottom width | |
| Lateral resistance (micro-ohm) | 80 | 8 | 0.3 |
| Diffusion rate-second | - | 8 seconds | 3 seconds |
In the present invention, for having contiguous described passage of the about 0.003-0.015 inch of thickness and the about 0.5-1.5g/cm of density
3Flexible graphite sheet, preferred channel density be about 1000-3000 passage/square inch, preferably channel size is such passage, wherein the area of major path perforate is 50 with the ratio of the area of passage aisle perforate: 1-150: 1.
In enforcement of the present invention, flexible graphite sheet can advantageously adopt resin to handle sometimes, and the resin of absorption can improve humidity-proof ability and manipulation strength, promptly described hardness of scratching graphite flake after solidifying.Appropriate resin content preferably is about 20-30wt%, compatibly can be up to about 60wt%.
Goods of the present invention can be among the integrated circuit of computer application as electricity and coupling element heat, among defroster as conformal electrically contacting pad and excite grid as electricity.
Above-mentioned explanation is to be used for making those skilled in the art can implement the present invention.It is not to be used for enumerating all possible modification and improvement, as long as those skilled in the art have read described explanation, these all will become cheer and bright.But it is intended that, and all these classes are improved and modification all should be included within the scope of the invention that is limited by appended claims.Described claims will cover can satisfy effectively the object of the invention, with any arrangement or the order element and step, unless clear and definite opposite explanation is arranged in the context.
Claims (20)
1. membrane electrode assembly, comprise pair of electrodes and be arranged on amberplex between described two electrodes, at least one electrode is that the thin slice by the compression body of expanded graphite particulate forms, a plurality of lateral fluid passages with thin slice between first and second apparent surfaces that pass described thin slice, and compressed expanded graphite particulate wall is separated, at least a portion of described wall allows to form between the adjacency channel and is interconnected, and one of described apparent surface is adjacent to described amberplex.
2. assembly as claimed in claim 1, wherein said lateral fluid passage be by the apparent surface of the described thin slice of a plurality of precalculated position mechanical stampings so that the displacement of the graphite in the described thin slice form.
3. assembly as claimed in claim 1 wherein, is to realize via the groove that forms in the described wall to small part to being interconnected of the described adjacent channel of small part.
4. assembly as claimed in claim 3, the groove of wherein said connection be by the apparent surface of the described thin slice of wall place mechanical stamping of separating adjacent passage so that fluid flows between adjacency channel forms.
5. assembly as claimed in claim 1, the compression body of wherein said expanded graphite particulate are characterised in that the expanded graphite particulate is adjacent to described passage and extends obliquely with respect to the apparent surface of described thin slice.
6. assembly as claimed in claim 1, wherein the channel aperture of described thin slice second surface by smooth graphite surface around.
7. assembly as claimed in claim 1, wherein in the channel aperture of described first surface greater than channel aperture at described second surface.
8. assembly as claimed in claim 7 is at the 50-150 of second surface place channel aperture doubly at the area of the channel aperture of described first surface wherein.
9. assembly as claimed in claim 1 wherein, has 1000-3000 passage/square inch in described thin slice.
10. assembly as claimed in claim 1, wherein the described graphite flake of contiguous described passage has thickness 0.003-0.015 inch, and its density is 0.5-1.5 gram/cubic centimetre.
11. graphite product, the thin slice that comprises the compression body of expanded graphite particulate, it has a plurality of lateral fluid passages of the thin slice that passes between its first and second apparent surface, and compressed expanded graphite particulate wall separates, at least a portion of described wall allow and adjacency channel between form and be interconnected.
12. goods as claimed in claim 11, wherein said lateral fluid passage be by the apparent surface of the described thin slice of a plurality of precalculated position mechanical stampings so that the displacement of the graphite in the described thin slice form.
13. goods as claimed in claim 11 wherein, are realized via the groove that forms in the described wall to small part to being interconnected of the described adjacent channel of small part.
14. goods as claimed in claim 13, the groove of wherein said connection be by the apparent surface of the described thin slice of wall part mechanical stamping of separating adjacent passage so that fluid flows between adjacency channel forms.
15. goods as claimed in claim 11, the compression body of wherein said expanded graphite particulate are characterised in that the expanded graphite particulate is adjacent to described passage and extends obliquely with respect to the apparent surface of described thin slice.
16. goods as claimed in claim 11, wherein the channel aperture of described thin slice second surface by smooth graphite surface around.
17. goods as claimed in claim 11, wherein in the channel aperture of described first surface greater than channel aperture at described second surface.
18. goods as claimed in claim 17 are at the 50-150 of second surface place channel aperture doubly at the area of the channel aperture of described first surface wherein.
19. goods as claimed in claim 11 wherein, have 1000-3000 passage/square inch in described thin slice.
20. goods as claimed in claim 11, wherein the described graphite of the contiguous described passage of thin slice has thickness 0.003-0.015 inch, and its density is 0.5-1.5 gram/cubic centimetre.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2000/009508 WO2001078179A1 (en) | 2000-04-10 | 2000-04-10 | Flexible graphite article and fuel cell electrode with enhanced electrical and thermal conductivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1454399A CN1454399A (en) | 2003-11-05 |
| CN1326278C true CN1326278C (en) | 2007-07-11 |
Family
ID=21741248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008196400A Expired - Fee Related CN1326278C (en) | 2000-04-10 | 2000-04-10 | Flexible graphite article and fuel cell electrode with enhanced electrical and thermal conductivity |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1273063A4 (en) |
| CN (1) | CN1326278C (en) |
| AU (2) | AU2000243369B2 (en) |
| BR (1) | BR0017202B1 (en) |
| CA (1) | CA2405303C (en) |
| MX (1) | MXPA02009995A (en) |
| WO (1) | WO2001078179A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA02010087A (en) * | 2000-04-14 | 2003-09-10 | Graftech Inc | Graphite article useful as an electrode for an electrochemical fuel cell. |
| DE102004035309A1 (en) * | 2004-07-21 | 2006-02-16 | Pemeas Gmbh | Membrane electrode units and fuel cells with increased service life |
| US7687090B2 (en) | 2004-11-30 | 2010-03-30 | Corning Incorporated | Fuel cell device assembly and frame |
| KR100658756B1 (en) | 2006-02-16 | 2006-12-15 | 삼성에스디아이 주식회사 | Membrane-electrode assembly for mixed reactant fuel cell and mixed reactant fuel cell system comprising same |
| KR100709222B1 (en) | 2006-02-20 | 2007-04-18 | 삼성에스디아이 주식회사 | Stack for mixed reactant fuel cell and mixed reactant fuel cell system comprising same |
| EP2020696B1 (en) | 2007-07-20 | 2013-10-16 | NGK Insulators, Ltd. | Reactor |
| CN102044677A (en) * | 2009-10-15 | 2011-05-04 | 鼎佳能源股份有限公司 | Conductive bipolar plate of fuel cell |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5707755A (en) * | 1996-12-09 | 1998-01-13 | General Motors Corporation | PEM/SPE fuel cell |
| US5981098A (en) * | 1997-08-28 | 1999-11-09 | Plug Power, L.L.C. | Fluid flow plate for decreased density of fuel cell assembly |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4752518A (en) * | 1986-07-31 | 1988-06-21 | Polycarbon, Inc. | Flexible surface deformation-resistant graphite foil |
| US6087034A (en) * | 1998-07-09 | 2000-07-11 | Ucar Graph-Tech Inc. | Flexible graphite composite |
-
2000
- 2000-04-10 BR BRPI0017202-2A patent/BR0017202B1/en not_active IP Right Cessation
- 2000-04-10 AU AU2000243369A patent/AU2000243369B2/en not_active Ceased
- 2000-04-10 CN CNB008196400A patent/CN1326278C/en not_active Expired - Fee Related
- 2000-04-10 MX MXPA02009995A patent/MXPA02009995A/en active IP Right Grant
- 2000-04-10 WO PCT/US2000/009508 patent/WO2001078179A1/en active IP Right Grant
- 2000-04-10 CA CA002405303A patent/CA2405303C/en not_active Expired - Fee Related
- 2000-04-10 EP EP00923203A patent/EP1273063A4/en not_active Withdrawn
- 2000-04-10 AU AU4336900A patent/AU4336900A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5707755A (en) * | 1996-12-09 | 1998-01-13 | General Motors Corporation | PEM/SPE fuel cell |
| US5981098A (en) * | 1997-08-28 | 1999-11-09 | Plug Power, L.L.C. | Fluid flow plate for decreased density of fuel cell assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2405303C (en) | 2009-02-03 |
| WO2001078179A1 (en) | 2001-10-18 |
| CA2405303A1 (en) | 2001-10-18 |
| BR0017202A (en) | 2004-01-06 |
| AU4336900A (en) | 2001-10-23 |
| EP1273063A4 (en) | 2009-04-01 |
| AU2000243369B2 (en) | 2005-11-24 |
| BR0017202B1 (en) | 2010-11-03 |
| CN1454399A (en) | 2003-11-05 |
| MXPA02009995A (en) | 2003-02-12 |
| EP1273063A1 (en) | 2003-01-08 |
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Address after: The United States Delaware Patentee after: Graftech Inc. Address before: The United States Delaware Patentee before: Graftech Inc. |
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Granted publication date: 20070711 Termination date: 20140410 |