CN101030651A - Method of depositing a nanoparticle coating on a bipolar plate and removing the nanoparticle coating from the lands of the bipolar plate - Google Patents
Method of depositing a nanoparticle coating on a bipolar plate and removing the nanoparticle coating from the lands of the bipolar plate Download PDFInfo
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- CN101030651A CN101030651A CNA2007100923613A CN200710092361A CN101030651A CN 101030651 A CN101030651 A CN 101030651A CN A2007100923613 A CNA2007100923613 A CN A2007100923613A CN 200710092361 A CN200710092361 A CN 200710092361A CN 101030651 A CN101030651 A CN 101030651A
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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
A process comprising: submerging a fuel cell bipolar plate in a bath comprising nanoparticles and a liquid phase comprising a nanoparticles dispersion agent and wherein the bipolar plate includes an upper surface having a plurality of lands and channels formed therein; removing the fuel cell bipolar plate from the bath so that a coating comprising nanoparticles adheres to the fuel cell bipolar plate; while the coating is wet and before the coating is dried and solidified, removing the coating comprising nanoparticles from the lands of the bipolar plate, leaving coating comprising nanoparticle in the channels; and drying the coating in the channels.
Description
The cross reference of related application
This application requires the priority of the temporary transient application number 60/776,363 of U.S. of submission on February 24th, 2006.
Technical field
The application relates to a kind of method of coating fuel cell assembly.
Background technology
People's such as Angelopoulos the US patent No. 6,025,057 discloses a kind of the solution and has made for example way of printed circuit plate problem of electronic building brick, and the major requirement of wherein making this assembly is to realize suitable substance P d/Sn Seed Layer (seed layer) catalyst loading.Pb catalyst deficiency will cause producing the space in copper deposition circuit layer, and generation is opened circuit.Catalyst can cause bonding failure and cross conduction too much.Bonding failure makes plated by electroless plating solution leak below photoresist and is causing deposited copper between the circuit element of short circuit.The disclosed technical scheme that addresses this problem is included on organic substrate, for example deposits the organic polymer electrolyte on the circuit board that is formed by glass fibre and epoxy resin.With colloidal palladium-Xi seed layer deposition on organic polymer electrolyte top.Then at the polymer of the top of Seed Layer deposition Photoimageable, utilize photoetching process that the polymer of this Photoimageable is carried out composition and do not cover the Seed Layer part then.The non-electrolytic deposition that uses copper is deposited on copper in the Seed Layer on the unmasked portion.Under the pH that is fit to for required seed catalyst coating, the organic polymer electrolyte is come out from aqueous solution deposition.The electrolytical example of disclosed organic polymer is the copolymer of acrylamide and Beta-methyl acryloxy (metacryloxy) ethyl trimethyl ammonium methylsulfate.Above-mentioned polymer dielectric comprises the amino group of hydrolysis and is deposited on organic substrate in pH is lower than 4 the vitriolated aqueous solution.In another disclosed embodiment, polymer dielectric pH greater than 10 the aqueous solution deposition that contains NaOH to organic substrate.Disclosed another polymer dielectric is cationic polyamide-amine.Adopt concentration neutral aqueous solution to be launched at the polymer dielectric of 0.2 to 1.2 grams per liter.Deposition Pd/Sn colloidal suspensions Seed Layer on polymer dielectric.
The people's such as Angelopoulos that published on December 7th, 1999 US patent No.5,997,997 disclose a kind of solution relates to and makes the circuit structure, the way of this problem of printed circuit board (PCB) for example, wherein traditional electroless plating method is deposited by excessive seed often.Exist excessive seed to cause leakage shorts on the circuit board, causing the bad adhesion that is used on the Seed Layer the photoresist of board circuitization because of uneven surface.Excessive Seed Layer can also cause the undesired coat of metal in ensuing operation.Disclosed technical scheme comprises provides workpiece, and this workpiece comprises the substrate that is coated with the polymeric dielectric layer.The workpiece that then this is had the polymeric dielectric layer cures in the ambient air around.After this, handle this workpiece with polymeric surfactant, this polymeric surfactant can be on the surface of polymeric dielectric with the hydrogen of weak acid group bonding.Disclosed polymeric surfactant is the cationic polymer electrolyte with amino group, for example polypropylene acid amides or cationic polyamide one amine.The molecular weight ranges of polymeric surfactant is 10
5To 10
7Disclosed polymer dielectric can use Polytech, and the trade mark of Inc is the polymer dielectric of " Polytech ".
In the field that does not relate to printed circuit board (PCB), the manufacturing of fuel cell stack comprises makes the bipolar plates with control water feature.The REFRIGERATION SYSTEM DRIVEN BY CAPILLARY FORCE unsteadiness of liquid film can cause the loss of hold-up and fuel battery performance in the hydrophobic bipolar plate groove.The plasma treatment of introducing hydrophilic functional groups on bipolar plate surfaces has demonstrated the elimination hold-up and has improved fuel battery performance.Yet this plasma treatment technical fee is very expensive and consuming time.Therefore, need to select alternative processing mode.Exercise question the assignee is the interim Application No. 60/707 of " fuel cell module with the coating that comprises nano particle ", disclose a kind of processing mode in 705 and selected, wherein be included in the shallow layer of spraying hydrophobic nanoparticles on the bipolar plate surfaces in the disclosed embodiment.Yet, the applicant has been found that a lot of worries to durability are present in the process that comprises following aspect under certain condition: (1) lacks coating color reflectivity hint: it is incoherent being covered by coating, (2) organic acid and surfactant residue keep with coating, and the intensity of (3) coating is bonding result rather than the bonding result who reacts to each other (that is, coating is chemically bonded on the substrate hardly or not).The invention provides the possible alternative of prior art.
Summary of the invention
One embodiment of the invention comprise a kind of method, it comprises fuel battery double plates is immersed into during the liquid phase that comprises nano particle and be made up of nanoparticie dispersion agents bathes, and wherein bipolar plates comprises having a plurality of piston ring lands that are formed on wherein and the upper surface of groove, fuel battery double plates is shifted out from bath, make in coating it is that the coating that wets and comprised nano particle before coating is dry and curing sticks on the fuel battery double plates, the coating that will comprise nano particle is removed from the piston ring land of bipolar plates, and the coating that will comprise nano particle is stayed in the groove and dry coating.
Become apparent in the detailed description that another embodiment of the invention will provide hereafter.Be to be understood that detailed description and specific embodiment in expression representative embodiment of the present invention, purpose only is explanation and is not to limit the scope of the invention.
Description of drawings
From following detailed and accompanying drawing, will understand the present invention more all sidedly, wherein:
Fig. 1 is the process chart that method according to an embodiment of the invention is described.
Fig. 2 is the process chart that another kind of method according to another embodiment of the invention is described.
Fig. 3 explanation fuel assembly according to an embodiment of the invention with ground floor polyelectrolyte polymers and second coating material on it.
Fig. 4 explanation fuel assembly according to another embodiment of the invention with ground floor polyelectrolyte polymers and second coating material on it.
Fig. 5 explanation method according to an embodiment of the invention.
Fig. 6 explanation method according to another embodiment of the invention.
Fig. 7 explanation method according to another embodiment of the invention.
Fig. 8 explanation method according to another embodiment of the invention.
Fig. 9 explanation product according to an embodiment of the invention.
Figure 10 explanation method according to an embodiment of the invention.
Embodiment
The description of following embodiment only is exemplary in essence and is not to limit invention, its application, or uses.
One embodiment of the invention comprise a kind of method, and it comprises that the aqueous solution that will comprise polyelectrolyte polymers is coated on the fuel cell module.Polyelectrolyte polymers can comprise Cationic functional groups and/or anionic functional group.The example of suitable cationic polyelectrolyte polymer is including, but not limited to following: the copolymer of acrylamide and doped quaternary ammonium salt; Polyamide-amide, polypropylene amine hydroxide, based on the azobenzene polymer of epoxy radicals and based on acrylic acid azobenzene polymer.The example of suitable fuel cell module is including, but not limited to bipolar plates, dispersive medium and membrane electrode assembly.Second coating material can be applied on the polyelectrolyte polymers that adheres on the fuel cell module.As an example, second coating can be including, but not limited to hydrophilic or hydrophobic material.In one embodiment, second coating material can comprise nano particle.Be that 60/707,705 exercise question is for disclosing the second suitable coating material in " fuel cell module with the coating that comprises nano particle ", at this in conjunction with its disclosed content as a reference at assignee's u.s. patent application serial number.In one embodiment of the invention, second coating material comprises the water wetted material that has the negative electrical charge group, and wherein this group that has negative electrical charge can form strong ionic bond with the cationic polymer (polyelectrolyte) that applies on the fuel cell module.
Fig. 1 is the process chart that method according to an embodiment of the invention is described.In this embodiment, the first step 100 of this method comprises the polyelectrolyte polymers aqueous solution is coated to the fuel tank assembly, for example on the bipolar plates.Second step 102 of this method comprises by for example purge fuel battery component in deionized water, any polyelectrolyte polymers that does not adhere to is removed from fuel cell module.The 3rd step 104 of this method comprises second coating material is coated on the polyelectrolyte polymers that sticks on the fuel cell module.Second coating material can be for example to comprise the material of nano particle.
The 4th step 106 of this method comprises by for example purge fuel cell panel in deionized water, will remove on any second coating material that does not adhere on the polyelectrolyte polymers.Step 1 to 4 (100-106) can be repeated several times to make up multi-layer polyelectrolyte polymer and adhesion second coating material thereon.
In one embodiment of the invention, fuel cell module is a bipolar plates, and it comprises the gas flowfield that is limited by a plurality of piston ring lands that form and groove in the bipolar plates upper surface.The 5th step 107 of the present invention is included in that coating remains wet and coating material is removed from the piston ring land of bipolar plates when not having dry solidification.Coating is stayed in the groove of bipolar plates.One embodiment of the invention comprise discovery the coating that comprises nano particle remain wet in, even be coated on the bipolar plates when strengthening onboard adhesion of nanoparticle coating in the polyelectrolyte coating, still can have easily removed from bipolar plates.
Fig. 2 is the process chart that method according to another embodiment of the invention is described.The first step 108 of this method comprises bipolar plates is immersed in the preprocessing solution, for example 65 ℃ of following submergences three minutes, grease and/or impurity is removed from fuel battery double plates.An embodiment of preprocessing solution comprises K2-level (FDA microelectronics level) degreasing agent.Second step 110 of this method is included in and cleans this bipolar plates in the first deionization water-bath, for example cleans one minute down at 57 ℃.The 3rd step 112 of this method is included in and cleans this bipolar plates in the second deionization water-bath, for example cleans one minute down at 57 ℃, thereby finishes the cleaning flushing.The 4th step 114 of this method comprises and this bipolar plates is immersed in first aqueous solution that comprises first polyelectrolyte polymers for example about two minutes.In one embodiment of the invention, first polyelectrolyte polymers is a PAMC, for example Superfloc C-442 or the C-446 that is obtained by CYTEC.Another example of cationic polyacrylamide polymer is by Polytech, the Polytech 7M that Inc obtains.The 5th step 116 of this method is included in and cleans this bipolar plates in the 3rd deionization water-bath, for example cleans one minute down to remove any first polyelectrolyte polymers that does not adhere at 57 ℃.The 6th step 118 of this method is included in and cleans this bipolar plates in the 4th deionization water-bath, for example cleans one minute down at 57 ℃, thereby finishes the cleaning flushing.The 7th step 120 of this method comprises this bipolar plates is immersed in second aqueous solution that comprises second coating material, for example 57 ℃ of following submergences three minutes.Second coating material can comprise hydrophilic nano, for example the X-Tec 4014 or 3408 that is obtained by Nano-X.The 8th step 122 of this method is included in and cleans this bipolar plates in the 5th deionization water-bath, for example cleans one minute to remove any second coating material that does not adhere on first polyelectrolyte polymers down at 57 ℃.The 9th step 124 of this method is included in and cleans this bipolar plates in the 6th deionization water-bath, for example cleans one minute down at 57 ℃, thereby finishes the cleaning flushing.The tenth step 126 of this method comprises that repeating step 4 to 9 (114-124) amounts to three circulations, makes up multi-layer polyelectrolyte polymer and second coating material on it.The 11 step 127 of this method is included in coating and remains wet and be not dried and when solidifying, remove coating material from the piston ring land of bipolar plates.Coating is stayed in the groove of bipolar plates.After this, the 12 step 128 of this method for example comprises made the bipolar plates drying in 10-15 minute by bipolar plates is placed on drying table.
Assignee's u.s. patent application serial number is the suitable example that discloses second coating material that comprises nano particle in 60/707705, below the example of this second coating material is described.One embodiment of the invention comprise the fuel cell module with substrate, such as, but be not limited to the bipolar plates that has polyelectrolyte polymers on it and second coating material that comprises nano particle on polyelectrolyte polymers.The size range of nano particle can be about 2 to about 100 nanometers; Preferably arrive about 20 nanometers about 2; And most preferably arrive about 5 nanometers about 2.Nano particle can comprise inorganic and/or organic material.Second coating material can comprise the compound that comprises hydroxyl, halogen, carbonyl, ketone and/or aldehyde functional group.Second coating material can make fuel cell module, and for example bipolar plates becomes hydrophilic.
One embodiment of the invention comprise the fuel cell module that has polyelectrolyte polymers on it and be included in the permanent hydrophilic coating of the nano particle that has hydrophilic side chain on the polyelectrolyte polymers.
In one embodiment of the invention, the permanent hydrophilic coating that comprises nano particle comprises the inorganic structure of 10 to 90 weight %, hydrophilic side chain and the organic side chain with functional group 0 to 50 weight % of 5 to 70 weight %.In one embodiment of the invention, hydrophilic side chain is amino, sulfonate radical, sulfate radical, inferior sulfate radical, sulfonamide, sulfoxide, carboxylate radical, polyalcohol, polyethers, phosphate radical or phosphonyl group.
In one embodiment of the invention, second coating material can comprise organic side chain, and wherein the functional group of organic side chain be epoxy radicals, acryloxy, methacryloxy, glycidoxypropyl, pi-allyl, vinyl, carboxyl, sulfydryl, hydroxyl, acid amides or amino, isocyano group, hydroxyl or silanol groups.The pH of coating is 3 to 10 in one embodiment of the invention.
Another embodiment of the invention is included in the pulp-like solution that deposition on the polyelectrolyte polymers on the fuel cell module comprises nano particle and carrier, then carrier is expelled.Carrier can comprise water, alcohol and/or other suitable solvents.In one embodiment, slurry comprises the nano particle of 4-5 weight %, and remainder is a carrier.In one embodiment, carrier can be ejected away under about 180 ℃ temperature at about 80 ℃.In the scope in 10 seconds of cure cycle scope under can 10 minutes to 180 ℃ under from 80 ℃.
Suitable grout material can obtain with trade (brand) name HP 3408 and HP 4014 from Nano-X Gmbh.Grout material can provide the permanent hydrophilic coating that can preserve more than 2500 hours under the fuel cell operation condition.Durable coatings can for example aluminium and high level stainless steel, polymerizable substrate and conduction composite base plate for example form on the bipolar plates at metal.
Application No. 2004/0237833 at this in conjunction with its disclosure as a reference, has been described the several different methods of making useful in the present invention slurry, below it is carried out repetition.
Embodiment 1.221.29g (1mol) 3-aminopropyltriethoxywerene werene is added in the 444.57g sulfosuccinic acid, stir simultaneously and be heated to 120 ℃, in silicone oil bath, kept 5 hours.After the reactant mixture cooling, 20g viscous fluid and 80g (0.38mol) tetraethoxysilane are mixed, be absorbed in then in the 100g ethanol.Then the HCl solution of this solution with 13.68g (0.76mol) 0.1N is mixed, tempering is spent the night in water-bath under 40 ℃.This has obtained the hydrophilic nano that about 2nm has reactive terminal group.It is 5% that the mixture of water with 1/3 and 2/3 N-methyl pyrrolidone (NMP) is diluted to solid matter content with the solution that obtains, then by spray coating to glass substrate, wet-film thickness is 10 to 20 μ m.Then, with this substrate in the drying by circulating air case 150 ℃ of following compactings 3 hours.
Embodiment 2.221.29g (1mol) 3-aminopropyltriethoxywerene werene is added in the 444.57g sulfosuccinic acid, stir simultaneously.Then this solution is heated to 150 ℃ in silicone oil bath.After 1 little the reaction time, the aqueous solution of silica gel (pH=10) of 332.93g Levasil 300/30% type alkali stabilisation adds in this reaction solution, stirs simultaneously.After reaction 12 hours, water is 5% with this mixture diluted to solid matter content.This has obtained the hydrophilic nano that about 15nm has reactive terminal group.By flooding this system is coated on the plasma-activated polycarbonate sheet, follows in the drying by circulating air case 130 ℃ of following compactings 5 hours.
Embodiment 3.123.68g (0.5mol) 3-NCO propyl-triethoxysilicane is added in 600g (1mol) Macrogol 600, in silicone oil bath, be heated to 130 ℃ then, adding 0.12g dibutyl tin dilaurate (is 0.1wt% with respect to 3-NCO propyl-triethoxysilicane) afterwards, 25g (0.12mol) tetraethoxysilane and 33.4g (0.12mol) 3-glycidoxypropyl (glycidyloxy) propyl group tetraethoxysilane are added in the solution that 50g obtains (solution A), stir simultaneously.After adding 15.12g (0.84mol) 0.1NHCl solution, mixture is hydrolyzed and condensation at room temperature 24 hours.This has obtained the hydrophilic nano that about 5nm has reactive terminal group.
Embodiment 4.20%CeO with 12.5g (0.05mol) 3-methacryloxypropyl trimethoxy silane, 12.5g
2The aqueous solution (from Aldrich) and 50g ethanol add in the solution A of describing in the 50g exemplary 3, stir so that mixture is even simultaneously, carry out hydrophiling 48 hours.After adding the Ingacure 184 of 0.375g from Ciba Spezialitaten Chemie (is 3wt% with respect to the 3-methacryloxypropyl trimethoxy silane), by spraying mixture is coated on the polycarbonate sheet that burnt, wet-film thickness is at most 30 μ m, at first in the drying by circulating air case 130 ℃ of following heated dryings 10 minutes.Be output as 1-2J/cm with radiation subsequently
2The Hg reflector carry out the photochemistry drying.
Scope of the present invention is not limited to second coating material and the manufacture method thereof of foregoing description, but also comprises other second coating materials, is included in the nano particle that forms on the polyelectrolyte polymers on the fuel cell module.Other embodiments to second coating material and manufacture method thereof are described below.
Suitable nano particle for example still is not limited to SiO
2, other metal oxides HfO for example
2, ZrO
2, Al
2O
3, SnO
2, Ta
2O
5, Nb
2O
5, MoO
2, IrO
2, RuO
2, metastable nitrogen oxide, non-stoichiometric metal oxide, nitrogen oxide and comprise carbochain or comprise the derivative of carbon and their mixture.
In one embodiment, second coating material is hydrophilic and comprises at least one Si-O group, at least one polar group and at least one comprises the group of saturated or unsaturated carbon chains.In one embodiment of the invention, polar group can comprise hydroxyl, halogen, carbonyl, ketone or aldehyde functional group.In one embodiment of the invention, carbochain can be saturated or undersaturated and can have 1 to 4 carbon atom.Second coating material can have the element of interpolation or compound, comprises that for example Au, Ag, Ru, Rh, Pd, Re, Os, Ir, Pt, rare earth metal and alloy thereof, polymer carbon or graphite are to improve conductivity.
In one embodiment of the invention, second coating material comprises Si-O group and Si-R group, and wherein R comprises saturated or unsaturated carbon chains, and wherein the Si-R group is 1/8 to 1/2 to the molar ratio range of Si-O group, preferably 1/4 to 1/2.In another embodiment of the invention, second coating material comprises that also oh group is to improve the hydrophily of coating.
Another embodiment of the invention comprises fuel cell module, and it has the assembly that has polyelectrolyte polymers on it and be positioned at second coating material above the polyelectrolyte polymers, and wherein coating source from siloxanes.This siloxanes can be straight chain, side chain or ring-type.In one embodiment, this siloxanes has general formula R
2SiO and wherein R be alkyl.
In another embodiment of the invention, second coating material is from the material with following general formula:
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Each can be H, O, Cl or the saturated or unsaturated carbon chains with 1-4 carbon atom, and R wherein
1, R
2, R
3, R
4, R
5And R
6Can be identical or different.
In another embodiment of the invention, second coating material is derived from the material with following general formula:
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Each can be H, O, Cl or the saturated or unsaturated carbon chains with 1-4 carbon atom, and R wherein
1, R
2, R
3, R
4, R
5And R
6Can be identical or different, and R
1, R
2, R
3, R
4, R
5 orR
6In at least one is the carbochain with at least one carbon atom.
Another embodiment of the invention comprises fuel cell module, it has the assembly that has polyelectrolyte polymers on it and be positioned at second coating material above the polyelectrolyte polymers, and wherein second coating material comprises that size range is 1 to 100 nanometer, be preferably the 1-50 nanometer, most preferably be the nano particle of 1-10 nanometer, and wherein nano particle comprises the compound that comprises silicon, saturated or unsaturated carbon chains and polar group.In one embodiment, second coating can have the average thickness of 80-100nm.
As shown in Figure 3, fuel cell module can be the bipolar plates that comprises the substrate 12 of relative thin, and wherein this substrate 12 is pressed into and defines the gas flowfield that is defined by a plurality of piston ring lands 16 and groove 14 (gas stream is crossed wherein).The aqueous solution that comprises polyelectrolyte polymers can be deposited on the upper surface 18 of bipolar plates, and feasible sticking to the small part polyelectrolyte polymers forms ground floor 20 on the substrate 12.Can the compacting substrate 12 before or afterwards, the solution deposition that will comprise polyelectrolyte polymers is on the upper surface 18 of bipolar plates.After this, the aqueous solution that comprises second coating material can be applied on the ground floor 20 of polyelectrolyte in combination thing, and makes its drying, forms second coating material 22 on the ground floor 20 of polyelectrolyte in combination thing.Substrate 12 can be a for example stainless steel of metal.
With reference now to Fig. 4,, another embodiment of the invention comprises the fuel battery double plates 10 that comprises substrate 12, and wherein this substrate 12 is machined into and defines the gas flowfield that is defined by a plurality of piston ring lands 16 and groove 14 (gas stream is crossed wherein).The aqueous solution that comprises polyelectrolyte polymers can be deposited on the upper surface 18 of bipolar plates, and feasible sticking to the small part polyelectrolyte polymers forms ground floor 20 on the substrate 12.After this, the aqueous solution that comprises second coating material can be coated on the ground floor 20 of polyelectrolyte polymers, thereby can dryly on the ground floor 20 of polyelectrolyte polymers, form second coating material 22 then.Substrate 12 can be a for example stainless steel of metal.
With reference now to Fig. 5,, in one embodiment of the invention, substrate 12 can be coated with the ground floor 20 of polyelectrolyte polymers, and mask material 24 can be deposited on the ground floor 20 selectively.After this, second coating material 22 can be deposited on ground floor 20 and the mask material 24.As shown in Figure 6, can and directly overlay second coating material on the mask material 24 with mask material 24 removes and stay part second coating material 22 selectively on ground floor 20.Substrate 12 can be pressed into and make second coating material be positioned at the groove 14 of gas flowfield.The aqueous solution that comprises the aqueous solution of polyelectrolyte polymers and comprise second coating material all can be by coating such as dipping, spraying, roll-in, brush are smeared or being deposited on the substrate 12.
With reference now to Fig. 7,, in another embodiment, mask material 24 can be deposited on the upper surface 18 of substrate 12 selectively.The ground floor 20 of polyelectrolyte polymers can be formed on the part of not covering in the upper surface of mask material 24 and substrate 12.Second coating material 22 can be formed on the ground floor 20 then.After this, can with mask material 24 and directly overlay part ground floor 20 on the mask material 24 and second coating material 22 remove and stay the expose portion 18 of substrate 12 upper surfaces ', as shown in Figure 8.Can use similar mask technique to come the machining substrate.
In another embodiment of the invention, coating processes can utilize or the above-mentioned use of unfavorable usefulness comprises the coating processes of the aqueous solution of polyelectrolyte.In this embodiment of the present invention, fuel assembly is immersed in the bath that comprises above-mentioned nano particle and liquid phase, wherein liquid phase comprises the nanoparticie dispersion agents that accounts for liquid phase volume at least 30%.Liquid phase can comprise 30-100 volume % or between the nanoparticie dispersion agents of wherein any volume %.Liquid phase also can comprise and accounts for liquid phase 0.1-7.0 volume % or between the water of wherein any volume %.Suitable nanoparticie dispersion agents is including, but not limited to alcohols, comprises at least a in methyl alcohol, ethanol or the propyl alcohol.Form solution with water and provide any organic solvent of disperse properties can deemed appropriate dispersant.When using X-Tec 3408 or 4014, nano particle constitutes the 4-5 weight % of X-Tec material.In one embodiment of the invention, the content of nano particle can be the 0.2-5 weight % of body lotion.
Fuel cell module is being immersed in the above-mentioned bath and after wherein shift out, randomly fuel cell module is cleaned to remove any coating that does not stick on the fuel cell module in water (for example DI water), then fuel cell module is exposed at least a drying in surrounding air, convection oven, infrared ray or the microwave energy.Submergence, cleaning and the dry thick nanoparticle coating of 25nm at least that produced.In one embodiment of the invention, submergence, cleaning and drying have produced nano coating on fuel cell module, have the silicon of 0.4 atomic wts % in this nano coating.
After this, submergence several times repeatedly, cleaning and dry on fuel cell module, to make up the multi-layer nano grain coating.For example, can carry out submergence, cleaning and dry to same fuel cell module at least to produce the thick nanoparticle coating of 100nm at least.In one embodiment of the invention, carry out submergence, cleaning and drying repeatedly, thereby on fuel cell module, produce nanoparticle coating, wherein have the silicon of 1.5 atomic wts % in this coating.Material suitable for nano particle was described in the above, particularly the X-Tec3408 that obtains from Nano-X and/or 4014 or the silica nanometer powder that obtains from Sigma-Aldrich.One embodiment of the invention comprise the X-Tec 3408 of at least 1 parts by volume and/or the solvent of 4014 pairs 19 parts by volume, and wherein this solvent is the water that comprises the alcohol of at least 30 volume %.
With reference now to Fig. 9,, one embodiment of the invention comprise fuel cell module 10, and for example bipolar plates comprises the substrate 12 with the gas flowfield that is defined by a plurality of piston ring lands 16 and groove 14.Ground floor 20 polyelectrolyte polymers are positioned on the upper surface 18 of substrate.Ground floor 20 comprises a plurality of layers 19,21, and every layer all comprises the polyelectrolyte polymers that forms according to above-mentioned aqueous solution coating processes.The second layer 22 nano particles are set at above the ground floor 20 of polyelectrolyte polymers.The second layer 22 nano particles can be formed by multilayer 200,202,204,206, and each layer all comprises the nano particle that technology forms of dipping that is used for the deposit nanometric particles pantostrat by above-mentioned.In one embodiment of the invention, layer 200,202,204,206 amounts to that to be at least 100nm thick and amount to the silicon with at least 1.5 atomic wts %.
With reference now to Figure 10,, in one embodiment of the invention, fuel cell module is a bipolar plates 12, and this bipolar plates 12 has the substrate 12 of the gas flowfield that forms, defined by a plurality of piston ring lands 16 and groove 14 in upper surface.As implied above, polyelectrolyte coating 20 and nanoparticle coating 22 all are deposited on piston ring land 16 and the groove 14.Coating 20,22 is taken out from cleaner bath remain wet and do not have dry solidification in, remove the coating 22,22 that is arranged in the coatings 20,22 above the piston ring land 16 and stays groove 14.Can be by coating 20,22 being wiped, scrape off, is rubbed or coating above the piston ring land 16 being removed in slight abrasion.In one embodiment of the invention, scraper 300 crosses piston ring land 16 and moves coating 20,22 to wipe piston ring land 16.Scraper 300 can be made by metal, polymer (for example plastics), elastomeric material (for example rubber) or compound.In one embodiment of the invention, scraper 300 is a rubber squeegee.In one embodiment of the invention, can come from piston ring land 16, to remove coating 20,22 by fabric or the elastomeric material of removing piston ring land 16 tops.
Description of the invention only is exemplary in essence, therefore can will fall within the scope of the present invention in the change that does not break away from main points of the present invention.This change does not think to depart from the spirit and scope of the present invention.
Claims (31)
1. method comprises:
Fuel battery double plates is immersed in the bath that comprises nano particle and liquid phase, and wherein this liquid phase comprises nanoparticie dispersion agents, and wherein bipolar plates is included in the upper surface that wherein is formed with a plurality of piston ring lands and groove;
Fuel battery double plates is taken out from bath, make the coating that comprises nano particle stick on the fuel battery double plates;
Coating be wet and before with the coating dry solidification, the coating that will comprise nano particle is removed from the piston ring land of bipolar plates, the coating that will comprise nano particle is stayed in the groove;
And the coating in the dry groove.
2. according to the process of claim 1 wherein that removing coating from piston ring land comprises the coating that wipes out on the piston ring land.
3. according to the method for claim 2, wherein said wiping comprises that crossing piston ring land moves scraper.
4. according to the method for claim 3, wherein said scraper comprises metal.
5. according to the method for claim 3, wherein said scraper comprises elastomeric material.
6. according to the method for claim 3, wherein said scraper comprises rubber
7. according to the method for claim 3, wherein said scraper comprises compound.
8. according to the method for claim 2, wherein said wiping comprises that crossing piston ring land moves rubber squeegee.
9. according to the method for claim 2, wherein said wiping comprises crosses the piston ring land moving fabric.
10. according to the method for claim 2, wherein said wiping comprises that crossing piston ring land moves elastomeric material.
11. according to the method for claim 1, also be included in the groove floating coat is carried out before the drying, the purge fuel battery component is to remove any nano particle that does not fully adhere on the fuel cell module.
12. according to the process of claim 1 wherein that described dispersant comprises alcohol.
13. according to the method for claim 3, the content of wherein said alcohol is to account at least 30% of liquid phase volume.
14. according to the method for claim 4, wherein liquid phase also comprises the water of the 0.1-70% that accounts for liquid phase volume.
15. according to the method for claim 3, wherein said alcohol comprises at least a in methyl alcohol, ethanol or the propyl alcohol.
16. according to the process of claim 1 wherein that described nanoparticie dispersion agents comprises the organic solvent that can form solution with water.
17. according to the method for claim 7, wherein said liquid phase also comprises water.
18. the method according to claim 1 also comprises:
Before submergence, the aqueous solution that will comprise polyelectrolyte polymers is coated on the bipolar plates, makes polyelectrolyte polymers stick on the bipolar plates.
19. according to the method for claim 18, wherein polyelectrolyte polymers comprises Cationic functional groups.
20. according to the method for claim 18, wherein polyelectrolyte polymers comprises the anionic functional group.
21., also comprise second coating material is coated on the polyelectrolyte polymers that sticks on this assembly according to the method for claim 18.
22. according to the method for claim 19, also comprise being coated on the polyelectrolyte polymers that sticks on this assembly, make this have negative electrical charge functional group and have positive charge functional group to form ionic bond with comprising second coating material that has negative electrical charge functional group.
23. according to the method for claim 18, wherein nano particle comprises and has negative electrical charge functional group.
24. according to the method for claim 18, wherein nano particle comprises siloxanes.
25. according to the method for claim 18, wherein nano particle comprises silicon dioxide.
26. a method comprises:
(a) the polyelectrolyte polymers aqueous solution is coated on the fuel battery double plates with upper surface, makes this polyelectrolyte polymers stick on the bipolar plates, wherein the upper surface of bipolar plates comprises a plurality of piston ring lands and groove;
(b) remove any polyelectrolyte polymers that does not adhere on the bipolar plates;
(c) second coating material is coated on the polyelectrolyte polymers that sticks on the bipolar plates;
(d) remove any second coating material that does not adhere on the polyelectrolyte polymers that sticks on the bipolar plates;
(e) fuel battery double plates is immersed in the bath that comprises nano particle and liquid phase, wherein this liquid phase comprises nanoparticie dispersion agents;
(f) fuel battery double plates is taken out from bath, make nanoparticle coating stick on this fuel cell module and dry coating;
(g) the purge fuel cell bipolar plate is to remove any nano particle that does not fully adhere on this fuel cell module;
(h) coating be wet and before with the coating dry solidification, the coating that will comprise nano particle is removed from the piston ring land of bipolar plates, the coating that will comprise nano particle is stayed in the groove; And
(i) coating in the dry groove.
27., wherein remove coating and comprise the coating that wipes out on the piston ring land from piston ring land according to the method for claim 26.
28. according to the method for claim 27, wherein said wiping comprises that crossing piston ring land moves scraper.
29., also comprise repetition (a-d) for several times according to the method for claim 26.
30., also comprise repetition (f-g) for several times according to the method for claim 26.
31. a method comprises:
(a) by bipolar plates being immersed in the predetermined solution to remove degrease and impurity from fuel battery double plates;
(b) in the first deionization water-bath, clean this bipolar plates;
(c) in the second deionization water-bath, clean this bipolar plates;
(d) this bipolar plates is immersed in first aqueous solution of first polyelectrolyte polymers;
(e) in the 3rd deionization water-bath, clean this bipolar plates to remove any first polyelectrolyte polymers that does not adhere on this bipolar plates;
(f) in the 4th deionization water-bath, clean this bipolar plates;
(g) this bipolar plates is immersed in second dispersion liquid that comprises second coating material, wherein second dispersion liquid comprises nano particle and alcohol;
(h) in the 4th deionization water-bath, clean this bipolar plates to remove any second coating material that does not adhere on first polyelectrolyte polymers that sticks on this bipolar plates;
(i) in the 5th deionization water-bath, clean this bipolar plates;
(j) repeat (d-1) three times;
(k) remain in coating and remove any coating from piston ring land in wet from cleaning beginning;
(l) dry bipolar plates.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77636306P | 2006-02-24 | 2006-02-24 | |
| US60/776363 | 2006-02-24 | ||
| US11/669465 | 2007-01-31 |
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| CN100565993C CN100565993C (en) | 2009-12-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111129475A (en) * | 2020-01-15 | 2020-05-08 | 扬州大学 | Preparation method of molybdenum dioxide/carbon/silicon dioxide nanospheres and negative electrode material of lithium ion battery |
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| CN111129475A (en) * | 2020-01-15 | 2020-05-08 | 扬州大学 | Preparation method of molybdenum dioxide/carbon/silicon dioxide nanospheres and negative electrode material of lithium ion battery |
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