CN1894813A - Fuel cell component with lyophilic surface - Google Patents
Fuel cell component with lyophilic surface Download PDFInfo
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- CN1894813A CN1894813A CNA2004800123044A CN200480012304A CN1894813A CN 1894813 A CN1894813 A CN 1894813A CN A2004800123044 A CNA2004800123044 A CN A2004800123044A CN 200480012304 A CN200480012304 A CN 200480012304A CN 1894813 A CN1894813 A CN 1894813A
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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
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- 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 fuel cell component(36) with surfaces having improved lyophilicity so that liquid on the component(36) adheres closely to the surface in relatively flat droplets or sheets. The Iyophilic surfaces may be formed with a thin layer of inherently Iyophilic polymer(38) on the surface of the component(36). The lyophilic surfaces may be selectively provided on critical areas of the component(36), such as for example on flow channel wall surfaces of bipolar plates and membrane electrode assemblies, thereby inhibiting liquid blocking of the flow channels during operation of the fuel cell.
Description
Related application
The application requires the right in the U.S. Provisional Application number 60/468,213, and this provisional application book applies for that on May 5th, 2003 therefore it can be fully with for referencial use here.
Technical field
The present invention is about some fuel cells, and in particular, it has the fuel cell component of water-wetted surface about some.
Background technology
Fuel cell technology has become the focus of recent research and development, because some environmental problems relevant with the combustion chamber with the combustion of fossil fuel engine and long-term supply of fuel problem have occurred.Fuel cell technology can be produced the more energy of cleaning usually, and they can fully compress, and weight is lighter, can use in the vehicles.In addition, when using in the fixation application environment, fuel cell can be installed near the energy and use the some place, can reduce the inefficiency problem that is caused by energy long-distance transmissions greatly like this.
Although in fuel cell, can use different reactants and raw material,, need usually to use electrolyte that positive electrode is separated with relative negative electrode for various fuel cells.Anode and negative electrode generally all have electrode hole or electrode channel, and by wherein certain hole or passage, reactant can enter in the battery, and these holes or passage are anode hole or anode passages usually; And oxidant generally enters in the battery by cathode aperture or passage.Oxidation takes place in reactant in battery, produce direct current, and is accessory substance with water and hotwork.In general, every battery can produce 1 volt electromotive force, but any amount of battery strings can be connected together, and separates by division board, can produce a fuel cell stack like this, is used to obtain the magnitude of voltage of all size.
In the modern fuels battery design, usually anode, negative electrode and electrolyte are placed in the same membrane electrode assembly, this assembly is a polyelectrolyte film, has gas diffusion layers, and separating plate and current collector are installed in one " bipolar plates " usually.This bipolar plates is used for the flow channel of the initiation material of limited reactions agent, oxidant, cooling fluid stream and power conversion reaction.Particulars about fuel cell design and operation, can be with reference to " the fuel cell handbook; 5th edition " of the USDOE national energy technology experiment chamber that is positioned at the western Morgantown in Virginia in October, 2000 publication, this handbook as the number of patent application of on April 30th, 2004 application be _ _ _ _ _ _ _ _ _ appendix A of while pending trial United States Patent (USP), this application name is called " fuel cell component that has water-wetted surface ", and described application comprises the appendix A that is used for reference herein.At United States Patent (USP) 4,988,583,5,733,678,5,798,188,5,858,569,6,071,635,6,251,308,6,436,568 and U.S.'s publication sequence number 2002/0155333 in all kinds of fuel cell components have been carried out deep introduction, these elements comprise membrane electrode assembly and bipolar plates, and these patents all are used as the reference of this patent.
Have a huge challenge aspect fuel cell design, be exactly moisture and other liquid of how controlling in the battery always.Under certain conditions, can generate moisture fast with cell reaction.If these moisture generally result from the cathode side of battery, and its constantly accumulation, may hinder or fuel limitation enters battery.This situation is " negative electrode waterflooding (cathodeflooding) " phenomenon of being familiar with of people just.In addition, inside battery gas often contains a large amount of water vapours, and these water vapours are byproduct of reaction, and because the operation cause can enter in the battery.The temperature difference between battery and the surrounding enviroment can cause the water vapour condensation occurring on negative electrode or the anolyte circulation road surface, and in running because of water vapour turnover battery, also can produce this phenomenon in whole device element or in the battery on other surfaces.And when adopting methanol fuel cell (DMFC), one or more reactants or oxidant feed exist with liquid form.
The material of making bipolar plates can be different, but under the increasing situation, adopt the interior carbon granule of polymeric binder as manufactured materials.The various common structure polymer that are applicable to binding agent have hydrophobicity to a certain degree usually.Liquid can condensation on hydrophobic surface, and this makes and relatively large intersection angle can occur between drop and the surface.Therefore, when using polymer on bipolar plates, water or other liquid can be assembled with the form of tight droplet on the bipolar plates in flow channel, thereby can cause above-mentioned flow channel to be obstructed or be restricted.
We know that polar liquid can be improved by polar group is incorporated on the polymer surfaces such as the hydrophily of the employed polymer of water usually.Polar group as used herein refers to half chemical composition that water or other polar liquid is had compatibility, these polar groups produce because of dipole, perhaps produce because of dipole polarization effect, soda acid interaction, hydrogen bond combination, ionic interaction or electrostatic interaction.These polar groups generally contain electronegative relatively element, such as oxygen, nitrogen, chlorine or sulphur, and exist with hydroxide, ether, ester, carbonyl, carboxyl, amine, acid amides, halide, sulfonyl or sulfonate form.
Splitting hair band has the polymerized fuel cell device on the improved surface of wetability, and many trials have been done in the front, and this wetability improvement is finished by polar group is incorporated on the element surface.In the technology of prior art, need to make its oxidation under the very high temperature environment by element surface is placed.And spendable material will inevitably be restricted in high-temperature technology, therefore can only use those very can resist the material that molecular structure ruptures and keeps structural intergrity under the hot environment.In addition, need the heating and cooling surface in the operating process, this has just increased complexity, production time and the producing cost of production technology.Therefore, adopt a large amount of production bipolar plates of this technology or other cell devices to be difficult to realize.
In other technologies, use the concentrated sulfuric acid that element surface is handled.Can produce chemical residual after adopting this technology, unfavorable to the true(-)running of fuel cell.Therefore need to adopt complicated and expensive operating procedure remove the pollutant that brings after this chemical treatment, from and increased complexity, production time and the producing cost of production technology.
The battery industry development need be a kind of cheapness, be easy to large-scale production and the improved polymerized fuel cell device of wetability.
Summary of the invention
The present invention has satisfied battery industry to demand cheap, that be easy to large-scale production and the improved polymerized fuel cell device of wetability.In one embodiment of the invention, adopt polymeric material to make the fuel cell component main body.The surface of subelement main body at least can contact with cold plasma, can increase the hydrophily of contact surface part like this.The hydrophily on the fuel cell component surface that makes is improved, and liquid also can tightly adhere to from the teeth outwards with plane droplet-like or tabular on the element.These surfaces can selectively be used on the critical zone of this element, such as the flow channel inner wall surface of bipolar plates and membrane electrode assembly, therefore can prevent that the fluid-tight phenomenon from appearring in flow channel when operation of fuel cells.
In an alternative embodiment of the invention, element surface uses ultraviolet ray to handle under the condition that has ozone or oxygen, thereby can improve the hydrophily on the surface that generates.In other embodiments of the invention, on element surface, use the skim hydrophilic polymer, such as polyvinyl alcohol, thereby generate water-wetted surface.This thin layer polymer can be starched polymerization by electricity, film penetrates processing method, compression forming processing method or any other proper method and prepares.
No matter adopt above-mentioned which kind of a kind of method, purpose all is that element surface is carried out hydrophilic treated, and makes the element surface hydrophily obtain the expection improvement.Also can whether the needs hydrophilic properties determines whether the polymer treatment step is removed according to element.
Brief Description Of Drawings
Fig. 1 is the fuel cell stack system diagrammatic sectional view, the with good grounds bipolar plates of the present invention of this system disposition;
Fig. 2 is the enlarged partial view of Fig. 1 fuel cell stack system, has described an intrasystem flow channel;
Fig. 3 is the simplified schematic profile diagram through cold plasma treatment appts;
Fig. 4 is the polymer tabulation that is suitable for making bipolar plates and other fuel cell components;
Fig. 5 is the packing material tabulation that is used to improve polymer fuel cell element conductive performance;
Fig. 6 is the simplified schematic profile diagram through the ultraviolet irradiation processing unit;
Fig. 7 is a profile of fuel cell component, is used for the element body that depicting interior has hydrophilic polymer layer; And
Fig. 8 is the rough schematic view of plasma polymerization treatment equipment.
Summary of the invention
Purpose for the application, term " fuel cell " refers to various electrochemical fuel cell devices or system, including, but not limited to Proton Exchange Membrane Fuel Cells (PFMFC), alkaline fuel cell (AFC), phosphoric acid fuel cell (PAFC), fused carbonate type fuel cell (MCFC) and Solid Oxide Fuel Cell (SOFC).Term " fuel cell stack device " refers to one and contains a briquette fuel battery at least and contain in the fuel cell one or whole devices of elements, these independent components play different functions respectively in fuel cell, these independent components including, but not limited to, shell, insulation board, collector, pipe-line system and electric device.
Described among the present invention diagrammatic sectional view among Fig. 1 as certain fuel cell stack system 10 of embodiment.Fuel cell stack system 10 generally comprises membrane electrode assembly 12, and this assembly separates with bipolar plates 14.The one-sided bipolar plates 12 that exists with end plate 16 forms surrounds this system 10 by each terminal.Each membrane electrode assembly 12 generally is made up of an anode film structure 18, cathodic coating structure 20 and electrolyte 22.
14 and 16 plates generally include firm and hard body 23 and 25, are made by the corrosion-resistant and heat proof material of tool electrical conductance, such as filling carbon polymer.The surface 24 of plate 14 and plate 16 on the surface 26 of inside, flow channel 28 is housed, be used for reactant and oxidant are transported in the membrane electrode assembly 12, also be used for draining.There is enough big surface area plate 14 and 16 heat transfer part 30, the inside battery heat can be removed.
According to the present invention, all parts or any part of plate 14 or 16 outer surfaces can be made water-wetted surface 31.As shown in Figure 2, water-wetted surface 31 can be present in flow channel 28 on the surface 32 of inside, be used to prevent overflow phenomena occurs in the path 28.Producing water droplet in the course of reaction will stick on the flow channel inwall 33 of water-wetted surface 31 with plane drop or dull and stereotyped form, therefore can guarantee that flow channel 28 is unimpeded.
As shown in Figure 1, other parts of bipolar plates 14 or end plate 16 also can adopt the form of water-wetted surface 31 such as heat transfer part 30 and outer surface 34, can strengthen the drainage performance of assembling or being condensate in these surperficial moisture like this.Though do not describe in the drawings, other elements in the time of for many years in the fuel cell stack equipment, also should have the form of water-wetted surface 31 such as the bascule in gas diffusion layers, proton exchange membrane (PEMs) or the equipment component, can carry out better controlled to the liquid in the battery like this.
In first embodiment of the invention, to fuel cell component 36, also may be that bipolar plates 14 and 16 should be carried out " cold " plasma treatment, they are equipped with element body 37, and this main body adopts surface 39.This cold plasma is a kind of ionized gas, is made up of ion, electronics, group, atom and/or other neutrophil granules.The cold plasma of the term of Shi Yonging refers to the plasma that produces by glow discharge under the depressed gas environment herein, and this reduced pressure atmosphere vacuum degree is no more than 10 holders.Gas ion and molecule can be present under the ambient temperature, and electronics can reach the electron temperature of ten of thousands degree Kelvin.The electron temperature of plasma (Te) is measured according to the following relationship formula and is obtained:
Wherein e is the quantity of electric charge, and k is the Boltzmann constant, and E is an electric field, and λ e is the mean free path of electronics, m
mRefer to the quality of interior neutral atom of plasma and molecule, m
eRefer to the quality of electronics in the plasma.Though cold plasma is an energetic plasma, electronics can only make part ion and neutral atom have thermal mass in the plasma.Therefore, plasma still colder relatively-generally about 300 degree Kelvins (23 degrees centigrade).
Glow discharge between the electrode can produce by apply 500 low frequencies to several kilovolts (such as 60Hz) voltage between electrode.Glow discharge also can produce by gas being carried out the higher-order of oscillation.These higher-orders of oscillation can pass through spark discharger (10Hz～50Hz), radio-frequency gap (50Hz～150Hz) or microwave generator (150Hz～300Hz) generate.Can set forth in being entitled as in the 298th～336 page of " polymer interface and adhesion " literary composition of the Souheng Wu of New York Marcel Dekker Co., Ltd about the particulars of cold plasma treatment and skin effect thereof, this article is a list of references of the present invention.Take different cold plasma treatment process can increase the hydrophily of material to polymeric material, this point is at United States Patent (USP) 3,526, and 583,3,870,610,4,072,769,4,188, introduce in 426 and 5,314,539, these are list of references of the present invention.
Fig. 3 is the simplified schematic profile diagram of cold plasma processing 100 among certain embodiment.Plasma processing 100 is made of sealed compartment 102, vacuum source 104, electromagnetic energy generator 106 and processing gas supply equipment 108 usually.Electromagnetic energy generator 106 can adopt radio freqnency generator or the microwave generator of introducing previously, also can be coupled by induction coil 110 being wrapped in 102 cabin part surfaces.Vacuum source 104 can adopt any suitable use, can make the vacuum source that has enough vacuum degree in 102 cabins, desired vacuum degree be generally 10 the holder or lower, preferably be lower than 1 the holder.Handle gas supply equipment 108 and generally form, can link to each other with 102 cabins with flow controller 116 by pipeline 114 by gas supply equipment 112.
Among certain embodiment, fuel cell component 36 generally is positioned in 102 cabins of apparatus for processing plasma 100 in the present invention.Use 104 pairs 102 cabins of vacuum source to vacuumize, it is reached estimate vacuum degree (pressure of foundation).In case reach pressure of foundation, then the process gas of gas supply equipment 112 will enter in 102 cabins.Flow controller 116 is regulated, the pressure stability in 102 cabins is being set the operation pressure value, this value is generally less than 10 holders.Start the electromagnetic energy generator then, in 102 cabins, produce cold plasma.After the appropriate time, finish processing, the electromagnetic energy generator cuts out, extinguish plasma.Make the cabin return to atmospheric pressure then, and the fuel cell component of handling well 36 is shifted out.
The Plasmatec V55 type product that the commercial apparatus for processing plasma that is fit to use in the present invention can adopt the Plasmatech Co., Ltd of Kentucky State Erlanger to produce.In the scope of the invention, any apparatus for processing plasma of producing cold plasma and can keeping contacting with fuel cell component all can use.
In certain specific embodiment of the present invention, thermosetting vinyl esters (such as polyester) material can be combined such as carbon black with the graphite with electrical conductance or other conductive carbon, be used to prepare bipolar plates 14 and 16.The electricity that is used for the production bipolar plates is led " BMC-940 " product that graphite-filled vinyl esters material can adopt BulkMolding Compounds Co., Ltd, and the said firm is positioned at the 1600Powis Court (60185) in western part, Chicago, Illinois.Moulding bipolar plates 14 and 16 can adopt any suitable method, comprise with the application with the number of patent application of application in a few days for _ _ _ _ _ _ _ _ _ extrusion that provides in the United States Patent (USP) of pending trial simultaneously, name is called " squeeze bipolar plates ", for the present inventor invents jointly, and as list of references of the present invention.In case moulding finishes, should use pure oxygen bipolar plates 14 and 16 to be handled by apparatus for processing plasma 100 according to preceding method immediately as process gas.To vacuumizing processing in 102 cabins, its base pressure is reached about 0.1 holder.The speed of oxygen with 300ml/min is injected in 102 cabins, and operation pressure is stabilized in about 1 holder.In 102 cabins, can adopt enough big electromagnetic energy to form cold plasma by glow discharge.After processing is suitably long-time, to close electromagnetic energy, and make recovery atmospheric pressure in the cabin, these processing times are generally 30 seconds～1 hour, but in some embodiment, the processing time also can be 15～30 minutes.
Usually the wetness degree on bipolar plates 14 and 16 surfaces is along with increasing with the growth of cold plasma time of contact.After handling about 1 minute, the intersection angle between set water droplet and the surface can reach 25～40 degree.After handling through 1 hour, the surface shows that this intersection angle that contacts with water droplet is near 0 degree.
Also process gas force value or flow value can be changed, different results can be obtained like this.And, the processing gas that oxygen is best suited for using, but also can use other suitable gas and steam.The processing gas difference of selecting for use, the also corresponding difference of the finishing that is obtained.Gas and steam that other are suitable comprise: air; Nitrogen; Argon gas; Alkylamine; Alkyl silane; Ammonia; Carbon dioxide; Chlorine; Chlorine dioxide; The chlorine fluorine hydrocarbon material of chlorotrifluoromethane and so on; The chlorohydrocarbon that comprises chloroform, chloromethanes and chloroethanes; Nitrous oxide; Ozone; Water vapour; Alkoxy silane; Allyl alcohol; Carbon tetrachloride; Ethylene glycol; Monoethyl ether; Oxirane; Carbon monoxide; Nitroparaffin; Nitrogen; Nitrogen dioxide; Oxysulfide.
Although in above-mentioned example, used thermosetting vinyl esters material, estimate to use PROCESS FOR TREATMENT polymeric bipolar plate 14 and 16 in the present invention, and those contain the fuel cell component that can form the composition of polar group from the teeth outwards.Fig. 4 has provided other polymeric material tabulations that are applicable to shaping bipolar plates and other fuel cell components.The electrical conductance of these materials can change by adding packing material, and the form in Fig. 5 has been listed these packing materials.
Should be appreciated that cold plasma treatment can selectively be used in the part outer surface of element 36, and use these outer surfaces of cold plasma treatment to need possess hydrophilic property.In certain embodiments, for the surface of the element 36 that does not need plasma treatment, use movable barrier to cover.After handling, barrier can be removed to expose unprocessed portion.In other embodiments, plasma treatment is carried out on the whole surface of element 36, and do not need the processing section should be the surface removal of handling at those.In general, surface after treatment is the skim material, and thickness is that 10nm is to 100nm.Therefore, in the present invention, during surperficial after remove handling, should remove by so thick polymeric layer, and can not damage down bedding course, removal can pass through to finish grind the finish-milling utensil, finishes such as the CNC milling machine.
In other embodiments of the invention, can use the cold plasma processing of normal pressure that element 36 selected portions are carried out plasma treatment.At United States Patent (USP) 6,502, to have introduced in 558 and be fit to a cold plasma processing of normal pressure using in the present invention, this patent is a list of references of the present invention.United States Patent (USP) 5,693 has been introduced another in 241 and has been applicable to and selects part to carry out the equipment that atmospheric plasma is handled to element 36 that this patent also is list of references of the present invention.
Above-mentioned treatment process is cold process technology, so their comparable previously used technology has more more important advantage.Need not heating and cooling and handle, this make the production technology cycle shorter, efficient is higher.In addition, because treatment temperature is lower, these technologies can not cause element the gross distortion phenomenon to occur.
And owing to need not use chemical reagent in treatment process, this greatly reduces the reprocessing needs that clean bipolar fuel cell, thereby can further raise the efficiency and reduce cost.And, used electroconductive stuffing at above-mentioned cold plasma treatment process, can strengthen the conductivity of polymer fuel cell element 34, these fillers are favourable to some fuel cell components such as bipolar plates.
By using ultraviolet ray the hydrophilicity that can improve the polymer fuel cell element surface is handled on the surface.In certain embodiments, element is contacted with oxygen, and use the high energy ultra-violet radiation to handle, ultraviolet wavelength is about 184.7nm.Ultraviolet irradiation and oxygen interact, and generate ozone and oxygen radical, the surface of their meeting oxidation polymerization construction element.In other embodiment, element is contacted with ozone, and use wavelength to handle as the ultra-violet radiation of 254nm.Ultra-violet radiation can become ozone crack molecular oxygen and elemental oxygen, thereby generates strong oxidation environment, and oxidation is carried out on the polymer element surface.And, in these embodiments, can make by the element polymer surfaces being carried out the direct ultraviolet radiation that chemical bond ruptures in the polymer, therefore when the surface and when oxidation environment contacts by force, can generate strong polarity hydroxyl, carbonyl or carboxyl, thereby improve the hydrophily on surface.About using wavelength as 140nm～and during high energy ultra-violet radiation about 400nm, the effect highly significant, and when wavelength was 184nm～365nm, effect was better.
It among Fig. 6 the simplified schematic profile diagram of a ultraviolet treatment facility 200 using in the present invention.Ultraviolet treatment facility 200 generally includes sealed compartment 202, ultraviolet source 204, vacuum source 206 and process gas supply system 208.The ultraviolet light resistant made is preferably adopted in 202 cabins.
In certain specific embodiments of the present invention, fuel cell component 36 is placed in the sealed compartment 202.Start vacuum source 206, when reaching predetermined basis pressure in 202 cabins, close, be generally 0.0001～20 holder, preferably 0.5～1 holder.Then, ozone is injected in 202 cabins by handling gas supply equipment 208, and makes that gas pressure is stabilized in a certain operation pressure place in 202 cabins, this processing pressure can be for pressure of foundation or near pressure of foundation.Open ultraviolet source 204 then, ozone and element 36 are carried out radiation.Expectation through 30 seconds～1 hour processing after, can effectively improve element 36 wettability of the surface.Also can use molecular oxygen or elemental oxygen to replace ozone as handling gas, and be the ultra-violet radiation of 184.7nm, but original position generates ozone by wavelength.
Be entitled as " being used for improving close-burning polymer and the surface treatment of a composite material ultraviolet light " literary composition what people such as Bhurke write, introduced and be fit to more particulars of the ultraviolet treatment process of use in the present invention, this paper is that the 26th nd Annual Meeting collection of bonding association of holding 23-26 day in February, 2003 included, and published in 2003 by bonding association, its ISSN is numbered 1086-9506, and this paper is as list of references of the present invention.About the additional information of UV/ozone treatment process, that can consult John R.Vig 1027-1034 delivered on J.Vac.Sci.Technol. in 1985 5/6 month is entitled as " surperficial UV/ozone cleaning " literary composition, and this article is also as list of references of the present invention.
As shown in Figure 7, the surface wettability of fuel cell component 36 can be improved by using skim 38 hydrophilic polymers from the teeth outwards, and these polymer comprise polyvinyl alcohol (PVOH).Other hydrophilic polymers that are fit to be used in thin layer 38 have: polyoxygenated alkylene class material is such as polyethylene glycol and polypropylene glycol; The plain compound of cellulose and functional fiber is such as hydroxyethylcellulose; Polyacrylonitrile; Polyacrylamide; Polyvinyl lactam; Polyethylene sugar; Poly-amino acrylates; Poly-hydroxyalkyl acrylates class material is such as hydroxy ethyl methacrylate; Polyacrylic acid; Polyacrylate; And functional styrene ionomer, such as kayexalate., can observe the wettability of its bulk polymer planar sample and assess whether applicable to making thin layer 38 for a kind of polymer by it is immersed in the water.In general, occur after the submergence scaling off and can beading, illustrate promptly that this polymer is applicable to make thin layer 38.Also can assess by drop and the intersection angle between it on the horizontal plane of observing the polymerisation in bulk matter sample.If the forward intersection angle is no more than 45 degree, can think generally that then it is suitable for making thin layer 38.
In one embodiment, powdery PVOH is mixed with water and suitable crosslinking agent, and be used in the surface of element 36.For example, PVOH solution can use 0.5%Cevol
TM325 polyvinyl alcohol and 20% glyoxal dehydrated crosslinking agent (are dissolved in 10 milliliters of Cevol with 125 microlitre crosslinking agents
TMIn 325).Cevol
TM325 can buy acquisition from the Celanese chemical company in Calvert city, the Kentucky State.By any suitable method PVOH solution thin layer is used in the surface of element 36, and dry, so just formation thin layer 38 on element 36.The thickness of the thin layer 38 for preparing usually is preferably 100 nanometers～1 millimeter, if thickness be 1 micron～100 microns better.Before using thin layer 38, adopt the cold plasma of introducing previously that the surface of element 36 is handled, can strengthen the adhesion between thin layer 38 and the element 36.
Notice that thin layer 38 can be used in selectively that those need obtain hydrophilic that part of surface (such as the inner surface of bipolar plates flow channel) on the element 36.For the surf zone that does not need to use thin layer 38 on the element 36, can selectively use thin layer 38 by using movable barrier (not describing).Take shape in barrier and element 36 not after the masked areas at thin layer 38, barrier is removed.In other embodiments, need coating portion by using automatic dispenser that thin layer 38 is used on the element 36.This automatic dispenser that is fit to use in the present invention can be a DK118 type crop dispenser, and this dispenser can be from the I﹠amp of the Fairlawn 2-07Banta Place of New Jersey; JFisnar buys acquisition.If needed, can use robot that automatic dispenser is located automatically.The robot positioning equipment that is suitable for locating automatic dispenser is I﹠amp; J7400 humanoid robot, this robot also can be from I﹠amp; J Fisnar buys acquisition.
In another embodiment of the present invention, hydrophilic polymer can thin plate form exist (such as≤1mm), and use film ejaculation processing method that it is sticked to the surface of element 36, this method is disclosed in that PCT number of patent application PCT/US02/37966 is entitled as the performance thin polymer film of the fluid control appliance " penetrate processing method " and PCT number of patent application PCT/US02/38076 was entitled as in " having the semiconductor element control device that destatics film ", these two patents are invented by the present inventor, are list of references of the present invention.By using these methods, thin layer 38 selectively can be used in needs to obtain hydrophilic surface portion (such as the inner surface of bipolar plates flow channel) on the element 36, so just no longer needs not remove not obtaining hydrophilic thin layer 38 on the element 36.
In other embodiments, can adopt known compression forming processing method thin layer 38 to be used on the surface of element 36 by the form of compression forming hydrophilic polymer with crosslinked thin plate.In other embodiments, hydrophilic polymer can be melted in and obtain thin layer 38 on the surface of element 36.
Also can adopt known plasma polymerization technology to use thin layer 38.In general, when plasma polymerization, organic substance (such as a kind of monomer) can be joined in the plasma in the reactor, make and deposit one layer of polymeric on the bottom.By inelastic collision, monomer obtains energy from plasma, and obtains activation, therefore can react with other monomers or oligomer.These micromolecule constantly are reacted into a kind of polymer, are deposited on bottom and the reactor surface.At United States Patent (USP) 3,518,108,3,666,533,4,013,532,4,188, to being applicable to that the element 36 surperficial plasma polymerization process of going up thin layer 38 depositions are described among the present invention, these patents are as list of references of the present invention in 273 and 5,447,799.
Fig. 8 is the simplified schematic profile diagram of certain embodiment ionic medium body polymerization unit 300.Plasma polymerisation device 300 is made of sealed compartment 302, vacuum source 304, electromagnetic energy generator 306 and processing gas supply equipment 308 and starting gas supply equipment 310 usually.Electromagnetic energy generator 306 can adopt radio freqnency generator that is used in apparatus for processing plasma 100 or the microwave generator of introducing previously, also can be coupled by induction coil 312 being wrapped in 302 cabin part surfaces.Vacuum source 304 can adopt any suitable use, can make the vacuum source that has enough vacuum degree in 302 cabins, desired vacuum degree be generally 10 the holder or lower, preferably be lower than 1 the holder.Process gas supply equipment 308 is general by constituting with the gas supply equipment 314 that flow controller 318 links to each other with 302 cabins by pipeline 316.Starting gas supply equipment 310 is general by constituting with the gas supply equipment 320 that flow controller 324 links to each other with 302 cabins by pipeline 322.At United States Patent (USP) 6,156, disclose in 435 and be fit to other equipment of using in the present invention, this patent is a reference of the present invention.
Among certain embodiment, fuel cell component 36 generally is positioned in 302 cabins of apparatus for processing plasma 300 in according to the present invention.Use 304 pairs 302 cabins of vacuum source to vacuumize, it is reached estimate vacuum degree (pressure of foundation).In case reach pressure of foundation, then the process gas of gas supply equipment 314 will enter in 302 cabins.Flow controller 318 is regulated, the pressure stability in 302 cabins is being set the operation pressure value, this value is generally less than 10 holders.Start electromagnetic energy generator 306 then, in 302 cabins, produce cold plasma.To come from the starting gas that starts gas supply equipment 310 then and import in 302 cabins, beginning thin layer 38 depositions.In case thin layer 38 reaches suitable thickness, the electromagnetic energy generator cuts out, extinguish plasma, and close the body supply equipment 310 of taking offence, stop supplies starting gas.Make 302 cabins return to atmospheric pressure then, and the fuel cell component 36 that will have a good thin layer 38 of deposition shift out.
Starting gas by the supply of starting gas supply equipment can be any organic or inorganic monomer that can generate hydrophilic polymer, or gaseous state or steam attitude compound.The example that is suitable as the starting gas in the starting gas supply equipment 310 comprises oxirane, nitroethane, 1-nitropropane (C
3H
7NO
2), 2-nitropropane ((CH
3)
2CHNO
2), ethene, methane and trimethylamine.And, can use silane or chlorosilane on element 36, to generate hydrophilic silicon dioxide thin layer 38 as starting gas.The silane example that is fit to use in the present invention has: and amino silane (such as aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane or two (3-trimethoxy silylation) ethylenediamine; Polyalkylene oxidation silane (such as 2-[methoxyl group (polyethyleneoxy) propyl group] trimethoxy silane; Urethanes silane is (such as N-(three ethoxy silane propyl group-o-polyethylene silicyl oxide); And silicol (such as ethoxy trimethoxy silane).
For element 34,, can make thin layer 38 have relative electrical conductance such as bipolar plates 14 and 16.In the plasma polymerization process, can join such as carbon and prepare thin layer 38 in 302 cabins by electricity being led particulate with electrical conductance.At United States Patent (USP) 4,422, in 915, a kind of equipment and the method that generate conductive polymer membrane by plasma polymerization on fuel cell component are disclosed, this patent is a list of references of the present invention.
Simultaneously in other embodiments, need also selectively plasma polymerization thin layer 38 is used in that those need obtain hydrophilic part on the element 36.As mentioned above, for the surf zone that does not need to use thin layer 38 on the element 36, can selectively use thin layer 38 by using movable barrier (not describing).Take shape in barrier and element 36 not after the masked areas at thin layer 38, barrier is removed, expose and do not conform to thin layer 38 zones.Also can will need not strengthen thin layer 38 removals of hydrophilic part by the conventional mechanical processing method such as grinding or milling.
The present invention also can be used in other particular instances, and can not change the critical nature that provides among the present invention, the embodiment that is therefore introduced see in all its bearings all have illustrative, and unrestricted.Expectation can be to disclosed character in the application's book, and make up or revise as the character that provides in the list of references of the present invention, to be fit to specific environment for use.The various modifications and variations of being done need be carried out according to general knowledge.
Claims
(according to the modification of the 19th of treaty)
1. fuel cell polymer bipolar plates, bipolar plates comprises the plate main body with hydrophilic polymer segment layer, the plate main body is obtained by a kind of polymeric material manufacturing in following one group of material at least, and this group material comprises alkyd resins, dially phthalate, epoxides, phenolic plastics, melamine, polyester, urea, acrylate, polyolefin, polystyrene, polystyrene copolymer, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, the polytetrafluoroethyl-ne alkene copolymer, polyimides, polysulfones, polyphenylene sulfide, polyester, nylon, liquid crystal polymer and mixture, poly-aryl ketones, natural rubber, polyisoprene, polybutadiene, chlorobutadiene, butyl rubber, acrylonitrile-butadiene rubber, silicone, ethylene-propylene rubber, polyolefin, polyester, polyurethane, the caprolactam block copolymer, and styrene-olefin block copolymers; The plate main body also contains a kind of filler that selection obtains from following one group of material, and this group material comprises glass fibre, bead, stainless steel fibre, metal particle, mineral matter, carbon dust, carbon fiber, graphite, carbon fiber and carbon nano-tube; The method manufacturing that it is made up of the following step:
The plate main body is prepared by polymeric material, and the plate main body has an outer surface;
The plate main body is contained in the sealed compartment;
To start gas is injected in the sealed compartment;
Apply enough big electromagnetic energy, make starting gas generate a kind of cold plasma; And
Make starting gas on the plate main body, deposit a polymeric layer by cold plasma polymerization.
2. (deletion)
3. bipolar plates according to claim 1, wherein, the plate main body adopts the manufacturing of thermosetting vinyl esters.
4. (deletion)
5. bipolar plates according to claim 1, wherein, starting gas can be selected from following one group of material, and this group material comprises oxirane, nitroethane, 1-nitropropane (C
3H
7NO
2), 2-nitropropane ((CH
3)
2CHNO
2), ethene, methane and trimethylamine.
6. bipolar plates according to claim 1, wherein, production technology comprises the following steps, be about to the electrically conductive particles material and add in the back seal cabin, and the electrically conductive particles material that will have a polymeric layer is deposited on the plate main body.
7. bipolar plates according to claim 1, wherein, production technology comprises the following steps, is about to silane or chlorosilane and joins in the sealed compartment, and by plasma polymerization process silicon dioxide is deposited upon on the plate main body.
8. bipolar plates according to claim 1, wherein, production technology comprises the following steps, is about at least a portion polymeric layer and removes.
9. a manufacturing has the method for the polymer fuel cell element of water-wetted surface part, comprises the following steps:
Use polymeric material that element is shaped, this element has an outer surface;
Element is contained in the sealed compartment;
To start gas is injected in the sealed compartment;
Apply enough big electromagnetic energy, make starting gas generate a kind of cold plasma; And
Make starting gas on the plate main body, deposit the sedimentary deposit of a hydrophilic polymer own by cold plasma polymerization.
10. method according to claim 9, wherein, this element is a bipolar plates.
11. method according to claim 9, wherein, this element is obtained by a kind of polymeric material manufacturing in following one group of material at least, and this group material comprises alkyd resins, dially phthalate, epoxides, phenolic plastics, melamine, polyester, urea, acrylate, polyolefin, polystyrene, polystyrene copolymer, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, the polytetrafluoroethyl-ne alkene copolymer, polyimides, polysulfones, polyphenylene sulfide, polyester, nylon, liquid crystal polymer and mixture, poly-aryl ketones, natural rubber, polyisoprene, polybutadiene, chlorobutadiene, butyl rubber, acrylonitrile-butadiene rubber, silicone, ethylene-propylene rubber, polyolefin, polyester, polyurethane, the caprolactam block copolymer, and styrene-olefin block copolymers.
12. method according to claim 9, wherein, element adopts the manufacturing of thermosetting vinyl esters.
13. method according to claim 9, wherein, element contains a kind of filler that selection obtains from following one group of material, and this group material comprises glass fibre, bead, stainless steel fibre, metal particle, mineral matter, carbon dust, carbon fiber, graphite, carbon fiber and carbon nano-tube.
14. method according to claim 9, wherein, starting gas can be selected from following one group of material, and this group material comprises oxirane, nitroethane, 1-nitropropane (C
3H
7NO
2), 2-nitropropane ((CH
3)
2CHNO
2), ethene, methane and trimethylamine.
15. method according to claim 9, wherein, this method also comprises the following steps, be about to the electrically conductive particles material and add in the back seal cabin, and the electrically conductive particles material that will have a polymeric layer is deposited on the element.
16. method according to claim 9, wherein, this method also comprises the following steps, is about to silane or chlorosilane and joins in the sealed compartment, and by plasma polymerization process silicon dioxide is deposited upon on the element.
17. method according to claim 9, wherein, this method comprises the following steps, is about at least a portion polymeric layer and removes.
(18. deletion)
(19. deletion)
20. a fuel cell component comprises:
The element body that the manufacturing of employing polymeric material obtains also has outer surface; The polymeric material flitch is selected from a kind of by in following one group of material, and this group material comprises alkyd resins, dially phthalate, epoxides, phenolic plastics, melamine, polyester, urea, acrylate, polyolefin, polystyrene, polystyrene copolymer, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, the polytetrafluoroethyl-ne alkene copolymer, polyimides, polysulfones, polyphenylene sulfide, polyester, nylon, liquid crystal polymer and mixture, poly-aryl ketones, natural rubber, polyisoprene, polybutadiene, chlorobutadiene, butyl rubber, acrylonitrile-butadiene rubber, silicone, ethylene-propylene rubber, polyolefin, polyester, polyurethane, the caprolactam block copolymer, and styrene-olefin block copolymers; Element body also contains a kind of filler that selection obtains from following one group of material, this group material comprise glass fibre, bead, stainless steel fibre, metal particle, mineral matter, carbon dust, carbon fiber, graphite, carbon fiber and carbon nano-tube and
At least the thin layer that on subelement main body outer surface, has hydrophilic polymer materials formation.
21. fuel cell component according to claim 20, it is characterized in that, the hydrophilic polymer that uses in the element can be selected from following one group of material, and this group material comprises: poly-alkylene ethylene glycol, cellulose, the plain compound of functional fiber, polyacrylonitrile, polyacrylamide, polyvinyl lactam, polyethylene sugar, poly-amino acrylates, poly-hydroxyalkyl acrylates, polyacrylic acid, polyacrylate and functional styrene ionomer.
22. fuel cell component according to claim 20, wherein, hydrophilic polymer is a polyvinyl alcohol in the element.
23. fuel cell component according to claim 20, wherein, adopt the method for the following step to use hydrophilic polymer materials: it is crosslinked lamellar that hydrophilic polymer materials is made one deck, then with this thin plate extrusion forming to element surface.
24. fuel cell component according to claim 20 wherein, adopts the method for the following step to use hydrophilic polymer materials: hydrophilic polymer materials is made thin film, then with the film ejection formation to element surface.
25. fuel cell component according to claim 20 wherein, adopts the method for the following step to use hydrophilic polymer materials: with the liquid solution mixing that hydrophilic polymer materials is made, solution is coated in forms a shallow layer on the element surface then.
26. fuel cell component according to claim 20, wherein, adopt the method for the following step to use hydrophilic polymer materials: element is packed in the sealed compartment, make its inside reach the pressure of foundation that is lower than atmospheric pressure gas emptying in the sealed compartment, air gas is injected in the sealed compartment, to start gas then and inject in the cabin, and apply enough big electromagnetic energy, and make starting gas generate a kind of cold plasma.
Claims (26)
1. fuel cell polymer bipolar plates, the method manufacturing that it is made up of the following step:
The plate main body is prepared by polymeric material, and the plate main body has an outer surface;
The plate main body is contained in the sealed compartment;
To start gas is injected in the sealed compartment;
Apply enough big electromagnetic energy, make starting gas generate a kind of cold plasma; And
Make starting gas on the plate main body, deposit a polymeric layer by cold plasma polymerization.
2. bipolar plates according to claim 1, wherein, the plate main body is obtained by a kind of polymeric material manufacturing in following one group of material at least, and this group material comprises alkyd resins, dially phthalate, epoxides, phenolic plastics, melamine, polyester, urea, acrylate, polyolefin, polystyrene, polystyrene copolymer, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, the polytetrafluoroethyl-ne alkene copolymer, polyimides, polysulfones, polyphenylene sulfide, polyester, nylon, liquid crystal polymer and mixture, poly-aryl ketones, natural rubber, polyisoprene, polybutadiene, chlorobutadiene, butyl rubber, acrylonitrile-butadiene rubber, silicone, ethylene-propylene rubber, polyolefin, polyester, polyurethane, the caprolactam block copolymer, and styrene-olefin block copolymers.
3. bipolar plates according to claim 2, wherein, the plate main body adopts the manufacturing of thermosetting vinyl esters.
4. bipolar plates according to claim 2, wherein, the plate main body contains a kind of filler that selection obtains from following one group of material, and this group material comprises glass fibre, bead, stainless steel fibre, metal particle, mineral matter, carbon dust, carbon fiber, graphite, carbon fiber and carbon nano-tube.
5. bipolar plates according to claim 1, wherein, starting gas can be selected from following one group of material, and this group material comprises oxirane, nitroethane, 1-nitropropane (C
3H
7NO
2), 2-nitropropane ((CH
3)
2CHNO
2), ethene, methane and trimethylamine.
6. bipolar plates according to claim 1, wherein, production technology comprises the following steps, be about to the electrically conductive particles material and add in the back seal cabin, and the electrically conductive particles material that will have a polymeric layer is deposited on the plate main body.
7. bipolar plates according to claim 1, wherein, production technology comprises the following steps, is about to silane or chlorosilane and joins in the sealed compartment, and by plasma polymerization process silicon dioxide is deposited upon on the plate main body.
8. bipolar plates according to claim 1, wherein, production technology comprises the following steps, is about at least a portion polymeric layer and removes.
9. polymer fuel cell element that has water-wetted surface part, wherein, this element is by the method manufacturing that comprises the following steps:
Use polymeric material that element is shaped, this element has an outer surface;
Element is contained in the sealed compartment;
To start gas is injected in the sealed compartment;
Apply enough big electromagnetic energy, make starting gas generate a kind of cold plasma; And
Make starting gas on the plate main body, deposit a polymeric layer by cold plasma polymerization.
10. fuel cell component according to claim 9, wherein, this element is a bipolar plates.
11. fuel cell component according to claim 9, wherein, element is obtained by a kind of polymeric material manufacturing in following one group of material at least, and this group material comprises alkyd resins, dially phthalate, epoxides, phenolic plastics, melamine, polyester, urea, acrylate, polyolefin, polystyrene, polystyrene copolymer, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, the polytetrafluoroethyl-ne alkene copolymer, polyimides, polysulfones, polyphenylene sulfide, polyester, nylon, liquid crystal polymer and mixture, poly-aryl ketones, natural rubber, polyisoprene, polybutadiene, chlorobutadiene, butyl rubber, acrylonitrile-butadiene rubber, silicone, ethylene-propylene rubber, polyolefin, polyester, polyurethane, the caprolactam block copolymer, and styrene-olefin block copolymers.
12. fuel cell component according to claim 9, wherein, element adopts the manufacturing of thermosetting vinyl esters.
13. fuel cell component according to claim 9, wherein, element contains a kind of filler that selection obtains from following one group of material, and this group material comprises glass fibre, bead, stainless steel fibre, metal particle, mineral matter, carbon dust, carbon fiber, graphite, carbon fiber and carbon nano-tube.
14. fuel cell component according to claim 9, wherein, starting gas can be selected from following one group of material, and this group material comprises oxirane, nitroethane, 1-nitropropane (C
3H
7NO
2), 2-nitropropane ((CH
3)
2CHNO
2), ethene, methane and trimethylamine.
15. fuel cell component according to claim 9, wherein, this method also comprises the following steps, be about to the electrically conductive particles material and add in the back seal cabin, and the electrically conductive particles material that will have a polymeric layer is deposited on the element.
16. fuel cell component according to claim 9, wherein, this method also comprises the following steps, is about to silane or chlorosilane and joins in the sealed compartment, and by plasma polymerization process silicon dioxide is deposited upon on the element.
17. fuel cell component according to claim 9, wherein, this method also comprises the following steps, is about at least a portion polymeric layer and removes.
18. suppressing the method for negative electrode waterflooding phenomenon in fuel cell is made up of the following step:
A fuel cell that comprises polylith bipolar plates and a plurality of membrane electrode assemblies is provided, is used to control a plurality of flow channels, each flow channel is subjected to a flow channel inner wall limit;
On each flow channel part inwall, generate a hydrophilic polymer layer, make the moisture that during operation of fuel cells, condenses in the flow channel can stick on the flow channel inwall, can't the plugging fluid circulation flow path.
19. method according to claim 18, wherein, the technology that generates hydrophilic polymer layer is that the using plasma polymerization technique deposits one deck hydrophilic polymer on part flow channel inner wall surface.
20. a fuel cell component comprises:
The element body that the manufacturing of employing polymeric material obtains also has outer surface; And
At least the thin layer that on subelement main body outer surface, has hydrophilic polymer materials formation.
21. fuel cell component according to claim 20, it is characterized in that, the hydrophilic polymer that uses in the element can be selected from following one group of material, and this group material comprises: poly-alkylene ethylene glycol, cellulose, the plain compound of functional fiber, polyacrylonitrile, polyacrylamide, polyvinyl lactam, polyethylene sugar, poly-amino acrylates, poly-hydroxyalkyl acrylates, polyacrylic acid, polyacrylate and functional styrene ionomer.
22. fuel cell component according to claim 20, wherein, hydrophilic polymer is a polyvinyl alcohol in the element.
23. fuel cell component according to claim 20, wherein, adopt the method for the following step to use hydrophilic polymer materials: it is crosslinked lamellar that hydrophilic polymer materials is made one deck, then with this thin plate extrusion forming to element surface.
24. fuel cell component according to claim 20 wherein, adopts the method for the following step to use hydrophilic polymer materials: hydrophilic polymer materials is made thin film, then with the film ejection formation to element surface.
25. fuel cell component according to claim 20 wherein, adopts the method for the following step to use hydrophilic polymer materials: with the liquid solution mixing that hydrophilic polymer materials is made, solution is coated in forms a shallow layer on the element surface then.
26. fuel cell component according to claim 20, wherein, adopt the method for the following step to use hydrophilic polymer materials: element is packed in the sealed compartment, make its inside reach the pressure of foundation that is lower than atmospheric pressure gas emptying in the sealed compartment, air gas is injected in the sealed compartment, to start gas then and inject in the cabin, and apply enough big electromagnetic energy, and make starting gas generate a kind of cold plasma.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46821303P | 2003-05-05 | 2003-05-05 | |
| US60/468,213 | 2003-05-05 | ||
| US10/837,030 | 2004-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1894813A true CN1894813A (en) | 2007-01-10 |
Family
ID=37598282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800123044A Pending CN1894813A (en) | 2003-05-05 | 2004-05-03 | Fuel cell component with lyophilic surface |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1894813A (en) |
| TW (2) | TW200501494A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110010938A (en) * | 2011-12-22 | 2019-07-12 | 希乐克公司 | Processing biomass for use in fuel cells |
| CN110577390A (en) * | 2019-10-25 | 2019-12-17 | 四川信敏绿色新建筑材料科技有限公司 | Concrete preparation process |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI416791B (en) * | 2007-07-04 | 2013-11-21 | Wistron Corp | A coupling structure of fuel cells is disclosed |
| TWI394313B (en) * | 2009-10-12 | 2013-04-21 | Toplus Energy Corp | Bipolar plate of fuel cell |
| TWI464952B (en) * | 2012-10-03 | 2014-12-11 | Ind Tech Res Inst | Manufacturing method of bipolar plate |
-
2004
- 2004-05-03 CN CNA2004800123044A patent/CN1894813A/en active Pending
- 2004-05-05 TW TW093112582A patent/TW200501494A/en unknown
- 2004-05-05 TW TW093112581A patent/TW200501493A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110010938A (en) * | 2011-12-22 | 2019-07-12 | 希乐克公司 | Processing biomass for use in fuel cells |
| CN110577390A (en) * | 2019-10-25 | 2019-12-17 | 四川信敏绿色新建筑材料科技有限公司 | Concrete preparation process |
| CN110577390B (en) * | 2019-10-25 | 2022-01-18 | 四川信敏绿色新建筑材料科技有限公司 | Concrete preparation process |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200501493A (en) | 2005-01-01 |
| TW200501494A (en) | 2005-01-01 |
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