CN101288195A - Process for application of a hydrophilic coating to fuel cell bipolar plates - Google Patents

Process for application of a hydrophilic coating to fuel cell bipolar plates Download PDF

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Publication number
CN101288195A
CN101288195A CNA2006800382739A CN200680038273A CN101288195A CN 101288195 A CN101288195 A CN 101288195A CN A2006800382739 A CNA2006800382739 A CN A2006800382739A CN 200680038273 A CN200680038273 A CN 200680038273A CN 101288195 A CN101288195 A CN 101288195A
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coating
deposition
plasma
carrier gas
precursor
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G·温特
G·维亚斯
T·A·特拉波德
R·L·达塔
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GM Global Technology Operations LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0221—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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 comprises: depositing a coating on a fuel cell bipolar plate using plasma assisted chemical vapor deposition.

Description

Apply the method for hydrophilic coating to fuel battery double plates
Technical field
The disclosure relates generally to and prepares the fuel cell component that has coating on it.
Background technology
Hydrogen is the fuel that haves a great attraction, and produces electric power in the fuel cell effectively because its cleans and is used in.Auto industry has consumed ample resources in the exploitation as the hydrogen fuel cell of vehicle power supply.This vehicle is will be than the vehicle of present use internal combustion engine more effective and produce still less emission.
Hydrogen fuel cell has electrolytical electricity-chemical devices for comprising anode and negative electrode and their centres.Anode is accepted hydrogen-rich gas or pure hydrogen, and negative electrode is accepted oxygen or air.Hydrogen is produced free proton and electronics by disassociation in anode.Proton arrives negative electrode by electrolyte.Proton produces water with oxygen and electron reaction in negative electrode.Electronics from anode can not pass through electrolyte, therefore does work by load before being sent to negative electrode.Described merit can be used for for example operating vehicle.
It is common that Proton Exchange Membrane Fuel Cells (PEMFC) is used for vehicle.PEMFC generally includes solid-polymer-electrolyte proton conductive membrane, as perfluoro sulfonic acid membrane.Anode and negative electrode generally comprise the finely divided catalysed particulate that loads on the carbon granule and mix with ionomer, normally platinum (Pt).Catalytic mixtures is deposited on the opposite side of film.Anode-catalyzed mixture, cathode catalysis mixture and film constitute membrane electrode assembly (MEA).MEA makes relatively costly and need be used for the specified conditions of valid function.These conditions comprise appropriate water management and humidification, and the control of catalyst poisoning composition such as carbon monoxide (CO).
Usually the some fuel cells of combination produce required electric power in fuel cell pack.For above-mentioned automotive fuel cell stack mentioned, described heap can comprise about 200 or more bipolar plates.Fuel cell pack is accepted cathode reactant gas, generally is to utilize compressor to force to flow by the air of this heap.Not every oxygen is all consumed by heap, and the part air is exported as cathode exhaust, and described waste gas can comprise aqueous water as the heap accessory substance.Fuel cell pack also accepts to flow into the anode hydrogen gas reactant gas of heap anode-side.
Fuel cell pack comprises a series of flow fields or the bipolar plates between several MEA in heap.Bipolar plates comprises anode-side and the cathode side that is used for piling adjacent fuel cell.Anode gas flow channels is positioned on the bipolar plates anode-side, and it allows anodic gas to flow to the anode-side of MEA.The cathode flame passage is positioned on the cathode side of bipolar plates, and it allows cathode gas to flow to the cathode side of MEA.Bipolar plates can comprise that also cooling fluid uses the fluid passage.
Bipolar plates is generally made by electric conducting material, and as stainless steel, titanium, aluminium, polymeric carbon composites etc., thereby their electric power that fuel cell is produced is transmitted to next battery and to out-pile from a battery.Metal double polar plates generally produces native oxide so that they are corrosion-resistant on their outer surface.But this oxide skin(coating) is non-conductive, and has therefore increased the internal resistance of fuel cell, has reduced its electrical property.In addition, it is more hydrophobic that oxide skin(coating) often makes plate.
The United States Patent (USP) publication No.2003/0228512 that transfers present assignee discloses and deposited the method that prevents the plate oxidation and increase the skin of its ohmic contact on flow-field plate, and this paper introduces its disclosure as a reference.The United States Patent (USP) 6372376 that transfers present assignee equally discloses depositing electrically conductive, resistance to oxidation and acidproof coating on flow-field plate.The U.S. Patent application publication No.2004/0091768 that transfers present assignee equally discloses the flow-field plate that on flow-field plate deposition graphite and carbon black coating prepare corrosion-resistant, conduction and heat conduction.
Know all in this area that the film in the fuel cell need have certain relative humidity so that low to being enough to effective proton conducting through the ion drag force of film.During operation of fuel cells, can enter anode and cathode fluid passage from moisture and the outside moisture of MEA.Under low cell power demands, generally be lower than 0.2A/cm 2, water is in the fluid passage inner accumulated, to such an extent as to can not drive water out of passage because the flow velocity of reactant gas is too low.When water gathered, because the hydrophobic property of panel material, it formed the drop that continues expansion.The contact angle of water drop is generally about 90 °, because the drop form in the fluid passage is basically perpendicular to flowing of reactant gas.When drop size increased, the fluid passage was closed, and reactant gas is diverted into other fluid passage, because passage PARALLEL FLOW between common inlet and outlet manifold.Because reactant gas can not flow through by the passage of water blockage, so reactant gas can not be driven water out of passage.These zones of film that can not acceptable response thing gas because passage gets clogged will not produce electric power, thereby cause inhomogeneous CURRENT DISTRIBUTION and reduced the gross efficiency of fuel cell.When increasing fluid passage during by water blockage, the electric power that fuel cell produces reduces, and is regarded as battery failure less than the cell voltage of 200mV.Because fuel cell series is electrically connected, if therefore fuel cell, then whole fuel cell pack may quit work.
Usually can be by regularly forcing reactant gas to come the water that gathers in the purge fluid passage by the fluid passage with higher flow velocity.But at cathode side, this has increased the parasitic power that is applied to air compressor, thereby has reduced total system effectiveness.In addition, have many reasons not use hydrogen fuel as sweep gas, the system complexity that comprises that economy reduces, system effectiveness descends and be used for handling the exhaust flow high hydrogen concentration increases.
Also can realize reducing the water that gathers in the passage by reducing the inlet humidification.But, wish certain relative humidity is provided in anode and cathode reactant gas so that the film in the fuel cell keeps moisture.The inlet gas of doing has desiccation to film, and this can increase the ion drag force of battery, and the long durability of restriction film.
The inventor proposes to prepare hydrophilic bipolar plate for fuel cell to improve channel water transport.Hydrophilic plate is scattered the water in the passage along the surface in being called the process of spontaneous wetting.The film that obtains has the less trend that changes along the flow distribution of the channel array that is connected to shared entrance and exit collector.If panel material has sufficiently high surface energy, then the water by dispersive medium transmission is with the contact channels wall, so by capillary force, water is transferred in the base angle of passage along passage length.Support the physics of spontaneous wetting in the angle, fluid passage to require with Concus-Finn condition β+α/2＜90 ° of descriptions, wherein β is the static contact angle that forms between the liquid surface and the surface of solids, and α is the channel angle angle.For rectangular channel, α/2=45 °, this means when static contact angle and spontaneous wetting will take place during less than 45 °.For the rectangular channels of using in the existing fuel cell stack design with composite dual-electrode plates, this has set and has realized useful influence and the underload stability required contact angle approximate upper limit of hydrophilic plate surfaces to channel water transport.
The general introduction of invention typical embodiments
A kind of embodiment of the present invention comprises a kind of method, this method comprises: use precursor gases to utilize plasma auxiliary chemical vapor deposition comprising deposition first coating on the fuel cell component of substrate, this precursor gases comprises the compound that contains at least one Si-O group and contain at least one group of saturated or unsaturated carbon chains.
Another embodiment of the present invention comprises a kind of method, this method comprises uses precursor gases to utilize plasma auxiliary chemical vapor deposition comprising deposition first coating on the fuel cell component of substrate, and this precursor gases comprises and contains first at least a in siloxanes or the silanol compound.
Another embodiment of the present invention comprises a kind of method, this method comprises utilizes plasma auxiliary chemical vapor deposition comprising deposition first coating on the fuel cell component of substrate, and described plasma auxiliary chemical vapor deposition comprises makes silane gas, comprise the gas and the oxygen-containing gas that contain carbon chain compound flows.
Another embodiment of the present invention comprises a kind of method, this method comprises utilizes plasma auxiliary chemical vapor deposition deposited coatings on fuel cell component, described plasma auxiliary chemical vapor deposition comprises to be flowed in the plasma-reaction-chamber precursor gases and carrier gas is flow in the plasma-reaction-chamber, and wherein precursor is about 4-about 16% to the molar flow speed ratio of carrier gas.
Another embodiment of the present invention comprises a kind of method, and this method comprises utilizes plasma auxiliary chemical vapor deposition deposited coatings on fuel battery double plates.
To understand other embodiment of the present invention from the detailed description provided hereinafter.It should be understood that describe in detail and specific embodiment when embodiment of the present invention are described, only be used for illustration purpose and have no intention to limit the scope of the invention.
The accompanying drawing summary
The exemplary that invention will be more fully understood from the detailed description and the accompanying drawings, wherein:
Fig. 1 is the figure as a result according to the Fourier transform infrared spectroscopy of the coating of a kind of embodiment preparation according to the present invention, and this embodiment is used 4% the precursor gas ratio to carrier gas in the plasma enhanced chemical vapor deposition process.
Fig. 2 is the figure as a result according to the Fourier transform infrared spectroscopy of the coating of a kind of embodiment preparation according to the present invention, and this embodiment is used 8% the precursor gas ratio to carrier gas in the plasma enhanced chemical vapor deposition process.
Fig. 3 is the figure as a result according to the Fourier transform infrared spectroscopy of the coating of a kind of embodiment preparation according to the present invention, and this embodiment is used 12% the precursor gas ratio to carrier gas in the plasma enhanced chemical vapor deposition process.
Fig. 4 illustrates the microphoto according to the coating of one embodiment of this invention, wherein this coating be porous and comprise nano particle with brief summary shape.
Fig. 5 is the cross-sectional view of the fuel cell in fuel cell pack, and wherein fuel cell pack comprises and has the bipolar plates that makes the hydrophilic coating of plate according to embodiments of the present invention;
Fig. 6 is the cut-away cross-section that is used for the bipolar plates of fuel cell, and wherein bipolar plates comprises the coating that the island that is separated by the open area of the another embodiment according to the present invention limits;
Fig. 7 is the cut-away cross-section of the bipolar plates that is used for fuel cell that comprises coating of another embodiment according to the present invention, and wherein this coating projection between the fluid passage (land) in plate is located to be removed;
Fig. 8 is the cut-away cross-section according to the bipolar plates that is used for fuel cell of one embodiment of this invention, wherein deposited coatings on another coating that is positioned on the bipolar plates;
Fig. 9 illustrates the of the present invention a kind of embodiment that comprises a kind of method, and this method comprises that at first the high spot selectivity in bipolar plates forms mask, is comprising deposited coatings on the bipolar plates of mask then;
Figure 10 illustrates the of the present invention a kind of embodiment that comprises a kind of method, and the mask of wherein removing on the high spot only stays the coating that covers bipolar plate channels;
Figure 11 illustrates the of the present invention a kind of embodiment that comprises a kind of method, this method comprises that at first on bipolar plates deposition comprises the coating of silicon, selectivity forms mask on the passage of bipolar plates then, and eat-backs the coating on (etch back) bipolar plates high spot subsequently;
Figure 12 is the plane graph that is used for the system of the various layers of deposition on according to the bipolar plates of a kind of embodiment of the present invention; With
Figure 13 illustrates the plasma auxiliary chemical vapor deposition reative cell that is used in according in the method for one embodiment of this invention.
Exemplary describes in detail
It only is exemplary in nature that following preferred embodiment is described in, and never is used to limit invention, its application, or uses.
A kind of embodiment of the present invention comprises having substrate, such as but not limited to the fuel cell component of cated bipolar plates on it.In one embodiment, this coating is hydrophilic, and comprises at least a Si-O group, at least a polar group and at least a group that comprises saturated or unsaturated carbon chains.In one embodiment of the present invention, described polar group can comprise hydroxyl or chloride.In one embodiment of the present invention, described carbochain can be saturated or undersaturated, and can have 1-4 carbon atom.Described coating can have other element or compound and comprise that for example Au, Ag, Ru, Rh, Pd, Re, Os, Ir, Pt, rare earth metal, their alloy, polymerization carbon or graphite are to improve conductivity.
In one embodiment of the present invention, described coating comprises Si-O group and Si-R group, and wherein R comprises saturated or unsaturated carbon chains, and wherein the Si-R group is 1/8-1/2 to the mol ratio of Si-O group, preferred 1/4-1/2.In another embodiment of the present invention, described coating also comprises hydroxyl to improve the hydrophily of this coating.
Another embodiment of the present invention comprises fuel cell component, have the parts of band coating on it on these parts, and wherein said coating is derived from siloxanes.Siloxanes can be line style, branching or ring-type.In one embodiment, this siloxanes formula is R 2SiO and wherein R be alkyl.
Another embodiment of the present invention comprises fuel cell component, has the parts of band coating on it on these parts, and wherein said coating is derived from the material with following formula:
Figure A20068003827300121
R wherein 1, R 2, R 3, R 4, R 5And R 6Can be H, O, Cl separately or have the saturated or unsaturated carbon chains of 1-4 carbon atom, and R wherein 1, R 2, R 3, R 4, R 5And R 6Can be identical or different.
Another embodiment of the present invention comprises a kind of product, this product comprises the cated fuel cell component of formation on it, and wherein said coating forms by such method, this method comprises by the precursor gases that comprises the material with following formula with this coating of plasma enhanced chemical vapor deposition, and further comprises and handle plasma enhanced chemical sedimentation coating deposited so that polar group to be provided:
R wherein 1, R 2, R 3, R 4, R 5And R 6, can be H, O, Cl separately or have the saturated or unsaturated carbon chains of 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 present invention, R 1, R 2, R 3, R 4, R 5Or R 6In at least one be carbochain with at least one carbon atom.
Another embodiment of the present invention comprises reprocessing plasma enhanced chemical sedimentation coating deposited, and it comprises makes the plasma enhanced CVD coating deposited stand to wrap oxygen containing plasma to produce hydroxyl in the plasma enhanced CVD coating deposited.
Another embodiment of the present invention comprises the fuel cell component that has coating on it, wherein said coating comprises and is of a size of 1-100nm, preferred 1-50 and the nano particle of 1-10nm most preferably, and the compound of wherein said nano particle siliceous, saturated or unsaturated carbon chains and polar group in comprising.
Another embodiment of the present invention comprises fuel cell, and this fuel cell has the bipolar plates of band hydrophilic coating on it and the dispersive medium of arranging near bipolar plates.Described hydrophilic coating comprises the nano particle of brief summary shape, and the abundant porous of this coating, thereby extends to provide from the circuit of bipolar plates through coating arrival dispersive medium by coating from the fiber of position near the dispersive medium of coating on the bipolar plates.
In one embodiment of the present invention, the type siloxane (SiO of coating for applying by three step method x) material, it strengthens the bonding of panel material and material hydrophily by introducing hydroxyl (being the Si-OH key).Fourier-transform infrared (FTIR) spectrum of optimizing material is presented among Fig. 1, and the major function key is determined.The adjustment precursor can provide Si-CH the ratio of carrier gas stream 3The control of content, " shoulder " as left side, main Si-O-Si peak in Fig. 1 shows.The coating pattern that obtains has been controlled in this aspect of chemical constitution, utilizes the precursor gases HMDO (HMDSO) of carrier gas (oxygen) stream 8-10% volume flow to obtain optimization formula.The microstructure that is shown in the coating in ESEM micro-(SEM) photo among Fig. 4 is quite discontinuous, and is made up of tangible brief summary.The fiber (fibers of about 7 μ m average diameters) that this loose structure provides gas diffusion media penetrates by coating, thereby can contact closely with the substrate bipolar plate material.The additional resistance that hydrophilic coating is introduced is about 10m Ω cm 2, and obtained.This preferable material prescription has been used on the bipolar plates and has moved above 1000 hours on heap.The measured value of the coating layer thickness that obtains from plate after 534 hours in operation shows material unaccounted-for (MUF) in the cathode channel less than 20%, and known herein most of product water stops also has most important influence to the heap voltage stability under underload.Proved that this material unaccounted-for (MUF) to zero coating layer thickness can stand to surpass 5000 hours fuel cell operation.
Also may need hydrophilic coating on the bipolar plates anode-side, influence operational stability because known anode water accumulates under some conditions, and under a cloud because hydrogen deficient influences electrode and film durability.But,, therefore can reckon with that the coating dissolution velocity on the anode-side will be faster than on cathode side because HF concentration is higher in the water.Therefore, anodic coating can be thicker than cathode, to realize durability when fuel battery service life finishes.In one embodiment of the present invention, average anodic coating thickness is than average cathode thickness thick about 15%.Although the plasma enhanced CVD condition remains unchanged in the entire coating process, anodic coating is thicker naturally, because passage is less in the active area, this has reduced total plate surface area.The visual examination afterwards of band hydrophilic coating plate shows that the loss antianode side of SiOx material has a significant impact, especially 90 ΩNeighbouring in the bending of anode export collector upstream end.Therefore, preferred anodic coating will surpass 15% than cathode is thick, and this may need to adjust the CVD application parameters.
Between plate manufacturing and coating process, need preprocessing process to remove owing to organic pollution on the base sheet material is stayed in board manufacturing process or processing.In addition, should select pretreatment operation that polar group is connected to and strengthen the effect of deposition process subsequently on the base sheet material.This preprocessing process comprises oxygen plasma environment 0-5 minute that is exposed to microwave and produces, preferred 0.5-3 minute and most preferably 1 minute.
In one embodiment of the present invention, precursor gases is preferably HMDO (HMDSO), but can be selected from the inorganic or organic derivative of siloxanes, silanol or silanes chemical substance or the gas and/or the liquid of other carbon containing and/or silicon.In one embodiment of the present invention, coating method comprises and uses HMDO (HMDSO) precursor and purity oxygen to strengthen chemical vapor deposition (CVD) as the microwave plasma of carrier gas that this produces type siloxane (SiOx) coating.Microwave frequency can be fixed on 2.45GHz.This process temperature can be lower, in the scope of room temperature to 45 ℃, thereby can apply the bipolar plate material of any practicality, and need not consider cause thermal damage or distortion.By chemistry and the physical structure that relevant with applying device six adjustable technological parameters control hydrophilic coating materials actual applies and it obtains, in this case, device is PLASMAtechModel110, for volume is 110 liters CVD reactor, at 0-500Pa, preferred 10-100Pa with most preferably under the pressure of 30Pa and at 50W-10kW, preferred 100W-1kW with most preferably work under the microwave power of 200-300W.As mentioned above, precursor gases is preferably HMDO (HMDSO), but can be selected from the inorganic or organic derivative of siloxanes, silanol or silanes chemical substance or the gas and/or the liquid of other carbon containing and/or silicon.Carrier gas is preferably oxygen, but can comprise nitrogen, nitrous oxide, argon gas, argon gas-oxygen or their mixture and with the mixture of other gas of proper proportion at least a.
Precursor has material impact to the ratio of the volume flow rate of carrier gas to the chemical constitution that obtains and the pattern of overlay.Usually, especially use the precursor that contains siloxanes, little precursor will produce near pure SiO the carrier gas ratio 2Chemical constitution than dense coating.When this ratio increased, the organic content of coating increased, the porosity that this has reduced hydrophily (promptly having increased static contact angle) probably and has improved coating structure.In order to obtain required contact angle, also make the resistance minimum of increase simultaneously, the balance of these characteristics is critical for fuel cells applications.
Can be appreciated that SiO by observed variation in illustrated fourier-transform infrared (FTIR) spectrum among Fig. 1 to 3 xVariation when the chemical constitution of coating changes the carrier gas ratio with precursor.In Fig. 1, for the gas ratio of 4-5%, coating does not have tangible Si-CH near the structure of pure quartz 3Content.When precursor stream was increased to the 8-10% of carrier current, little " shoulder " peak appeared at the left side at main Si-O-Si peak, represented low relatively Si-CH 3Content (Fig. 2).When this gas ratio further is increased to about 12-15%, Si-CH 3Content is increased to more (Fig. 3) significantly.In this three kinds of air-flows combination, determine the 10m Ω cm that only has an appointment that the 8-10% ratio provides very low static contact angle (＜10 °) and caused because of discontinuous physical structure 2The additional resistance preferred characteristics.
In one embodiment of the present invention, precursor is 2-16% to the carrier current ratio, is preferably 4-12%, and most preferably is 8-10%.
Absolute gas flow rates will be the function of total reactor volume.For the PLASMAtech Model 110 that is used to prepare bipolar plate coating described herein, airflow range (being assumed to be the air-flow ratio of 8-10% recited above) is as follows: the scope of application: precursor=2-50ml/min; Carrier=20-625ml/min; Preferably: precursor=10-30ml/min; Carrier=100-375ml/min; Most preferably: precursor=15-20ml/min; Carrier=150-250ml/min.
The reactor time will be stipulated the thickness of overlay, but also can influence the coating pattern.But select time is thick in being enough to provide in the fuel cell in rare HF environment material dissolves speed to the coating of end of lifetime to prepare.On the contrary, coating should be thinned to the resistance minimum that is enough to make increase, and has preferred discontinuous pattern.By using the combination of 4 minutes the time-optimized coating characteristic of reactor of the every side of bipolar plates, be the coating of 80-100nm with the preparation average thickness.Illustrate the stereoscan photograph of preferred coatings among Fig. 4.
Be mainly the plane if apply the workpiece of coating, can obtain uniform coating layer thickness on the space by using steady-state plasma.But,,, then can reckon with to have plasma density difference and so gained coating layer thickness difference as the situation of bipolar plate channels if existence is apart from the part of plasma source different distance on workpiece.In one embodiment of the present invention, for the stable state microwave plasma, (the degree of depth=290 μ m of the coating layer thickness in the channel bottom; Width-degree of depth aspect ratio=1.9) is protruding about 60% of the coating layer thickness of going up.By using microsecond to the plasma electrical source pulse of nanosecond can further improve this coating layer thickness difference between projection and the passage.In addition, when passage aspect ratio and/or absolute depth diminish (this just is being considered for following heap design at present), it is more remarkable that the coating layer thickness inhomogeneities will become.That can use plasma electrical source littlely avoids these coating difference to nanosecond pulse.
May need last handling process to introduce polar functional part (mainly being hydroxyl) to substrate SiO xOn the structure, thus further reinforcing material hydrophily.In one embodiment of the present invention, this is by exposing SiO xFilm is finished to active-oxygen plasma, and described active-oxygen plasma activates SiO by having interrupted switch and having formed hydroxyl, carboxyl and aldehyde radical functional group xCoating.Thisly utilize the activation of reprocessing also to increase the material porosity, it can further reduce resistance.In another embodiment, make coating and chemical reaction polarization group.In yet another embodiment, introduce polar group by the thin layer that applies hydrophilic coating.
In one embodiment of the present invention, last handling process comprises and is exposed in the oxygen plasma environment that microwave produces 0-5 minute, preferred 0.5-3 minute and most preferably 1.5 minutes.
Fig. 5 is the cross-sectional view as the fuel cell 10 of a above-mentioned type fuel assembly part.Fuel cell 10 comprises the cathode side 12 and the anode-side 14 of being separated by dielectric film 16.Cathode side diffusion media layer 20 is positioned at cathode side 12, and cathode-side catalytic layer 22 is between film 16 and diffusion media layers 20.Equally, anode side diffusion media layer 24 is positioned at anode-side 14, and anode side catalyst layer 26 is between film 16 and diffusion media layers 24.Catalyst layer 22 and 26 and film 16 constitute MEA. Diffusion media layers 20 and 24 is input gas transmission that is provided to MEA and the porous layer that leaves the water transmission of MEA.Known various technology are used for respectively at deposited catalyst layer 22 and 26 on diffusion media layers 20 and 24 or on film 16 in this area.Fuel cell 10 can comprise other the layer and/or coating, as but be not limited to microporous layers.
Cathode side flow field plate or bipolar plates 18 are provided on cathode side 12, anode-side flow-field plate or bipolar plates 30 are provided on anode-side 14.Between the fuel cell of bipolar plates 18 and 30 in fuel cell pack.Hydrogen gas reactant air-flow and catalyst layer 26 from fluid passage 28 in the bipolar plates 30 react to be dissociated into hydrogen ion and electronics.Air stream and catalyst layer 22 reactions from fluid passage 32 in the bipolar plates 18.Hydrogen ion can transmit by film 16, and the oxygen during they flow with air there and the return electron generation electricity in the catalyst layer 22-chemical reaction produce the water as accessory substance.
In this non-limiting embodiments, bipolar plates 18 comprises by nip drum and two sheets 34 welded together and 36.Sheet 36 limits fluid passages 32, and sheet 34 is defined for the fluid passage 38 of the anode-side of the fuel cell adjacent with fuel cell 10.Cooling fluid fluid passage 40 is between sheet 34 and 36, as shown.Equally, bipolar plates 30 comprise the sheet 42 that limits fluid passage 28, the sheet 44 and the cooling fluid fluid passage 48 of the fluid passage 46 of the cathode side that is defined for adjacent fuel cell.In the embodiment that this paper discusses, sheet 34,36,42 and 44 is made by electric conducting material, described electric conducting material such as stainless steel, titanium, aluminium, polymeric carbon composites etc.
According to a kind of embodiment of the present invention, bipolar plates 18 and 30 comprises makes plate 18 and 30 hydrophilic coatings 50.The hydrophily of coating 50 makes the water in fluid passage 28 and 32 form film rather than water droplet, thereby water can significantly not block the fluid passage.Especially, the hydrophily of coating 50 has reduced the contact angle of the water of fluid passage 32,38,28 and 46 inner accumulated, preferably is lower than 40 °, thereby reactant gas still can flow through passage 28 and 32 under underload.In one embodiment, coating 50 is a film, and for example, in the 5-50nm scope, thereby the conductivity of sheet 34,36,42 and 44 still allows electricity to be derived fuel cell 10 effectively.
According to another embodiment of the present invention, coating 50 and the electric conducting material that can increase coating 50 conductivity such as ruthenium-oxide or golden the combination.By bipolar plates 18 and 30 is more conducted electricity, that has reduced fuel cell 10 electrically contacts resistance and ohmic loss, thereby improves battery efficiency.In addition, can provide the reduction of compression stress in the heap, solve some endurance issues in the heap.
Go forward coating 50 being deposited on bipolar plates 18 and 30, can clean bipolar plates 18 and 30 by suitable method such as ion beam sputtering, with remove bipolar plates 18 and 30 outside may established resistive oxide films.Can coating 50 materials be deposited on bipolar plates 18 and 30 by any suitable technique, described suitable technique includes but not limited to physical gas-phase deposition, chemical vapor deposition (CVD) technology, thermal spraying craft, sol-gel, spraying, dip-coating, brushing, spin coating or silk screen printing.The suitable example of physical gas-phase deposition comprises electron beam evaporation, magnetron sputtering and pulse plasma body technology.Suitable chemical vapor deposition method comprises plasma enhanced CVD and atom layer deposition process.The CVD depositing operation may be more suitable for the thin layer of coating 50.
Fig. 6 is the cut-away cross-section of the bipolar plates 60 that comprises reactant gas flow channels 62 and projection therebetween 64 according to another embodiment of the invention.Bipolar plates 60 is suitable for replacing the bipolar plates 18 or 30 in the fuel cell 10.In this embodiment, coating 50 is deposited on the plate 60 as random islands 68, thereby the electric conducting material of plate 60 is exposed on 70 places, zone between the island 68.Coating island 68 provides plate 60 required hydrophily, and exposed region 70 provides plate 60 required conductivity.In this embodiment, preferably can be by physical gas-phase deposition such as electron beam evaporation, magnetron sputtering and pulsed plasma process deposits island 68.In one embodiment, the thickness between deposition island 68 to 50 and the 100nm.
Fig. 7 is the cut-away cross-section of the bipolar plates 72 that comprises reactant gas flow channels 74 and projection therebetween 76 according to another embodiment of the invention.In this embodiment, coating 78 is deposited on the bipolar plates 72.Then by any suitable method as polishing or grind the coating 78 of removing on the projection 76 to expose the electric conducting material of plate 72 at protruding 76 places.Therefore, fluid passage 74 comprises hydrophilic coating, projection 76 conductions, thus electricity is derived fuel cell.In this embodiment, coating 78 can be deposited thicklyer than above-mentioned embodiment, as 100nm-1 μ m, because plate 72 can not too conduct electricity in passage 74.
Fig. 8 is the cut-away cross-section of the bipolar plates 82 that comprises reactant gas flow channels 74 and projection 76 according to another embodiment of the invention.In this embodiment, bipolar plates 82 has conductive protecting layer 52 thereon.Provide according to 78 passages 74 that cover bipolar plates 82 of coating of the present invention.
Fig. 9 illustrates a kind of embodiment of the method according to this invention, and this method comprises at first selectivity formation mask 200 on the projection 76 of bipolar plates 18, deposits the coating 50 that can comprise silicon then on the bipolar plates 18 that comprises mask 200.Mask 200 can be hard physical mask, viscous liquid or gel-like material maybe can remove material such as photoresist.As shown in Figure 10, remove the mask 200 of projection on 76 to stay the coating 50 of the passage 74 that only covers bipolar plates 18.
Figure 11 illustrates the of the present invention a kind of embodiment that comprises method, this method comprises that at first on the bipolar plates 18 that comprises projection 76 and passage 74 deposition comprises the coating 50 of silicon, selectivity forms mask 200 as photoresist or water-soluble material on the passage 74 of bipolar plates then, eat-backs the coating 50 on the projection 76 of bipolar plates then.Can use wet or dry etching process is finished etching, as long as this etching does not destroy bipolar plates 18.In one embodiment, can remove coating 50 on the projection, remove any remainder of mask then by argon plasma.
Figure 12 is the plane graph that is used for the system 100 of the various layers of deposition on above-mentioned bipolar plates.System 100 is used to represent any above-mentioned technology, includes but not limited to sandblast (blasting), physical gas-phase deposition, chemical vapor deposition method, thermal spraying craft and sol-gel.In system 100, on the substrate 106 that electron gun 102 heating materials 104 make material 104 be evaporated and be deposited on to represent bipolar plates, form coating 108 thereon.In other method, system 100 comprises the ion gun 110 of guiding ion beam to sputtering surface 112, and described sputtering surface 112 releasable material such as metal oxide are with deposited coatings 108.In another embodiment, can apply coating 50 by spraying, dip-coating, brushing, spin coating or silk screen printing.
Figure 13 illustrates a kind of embodiment of using plasma auxiliary chemical vapor deposition reactor 400 in the method according to the invention.Reactor 400 comprises a plurality of walls 402 and top board 404.A plurality of inflation inlets 406,408,410 can be set up by wall 402 or top board 404 and be used to charge into reaction gas and carrier gas in reactor chamber 412.Dress liquid distributor 414 also can be provided.This reactor can comprise that microwave generation device 416 and Rf generation device 418 are to produce plasma in reactor chamber 412.Can provide chuck 420 with supported fuel cell parts such as bipolar plates.
In another embodiment of the invention, selective deposition has the coating of Si-O and Si-R (wherein R is saturated or unsaturated carbon chains) group on flat substrate such as stainless steel foil, for example form bipolar plates then, and wherein said coating is deposited in the passage with the gas flowfield that comprises a large amount of projectioies and passage by nip drum.
In another embodiment of the invention, can use the various chemical substances that contain Si material and carbonaceous material that comprise on substrate, to form coating with Si-O and Si-R (wherein R is saturated or unsaturated carbon chains) group.For example, can utilize silane (SiH 4), the gas of oxygen and carbon back liquid utilizes plasma assisted CVD to produce coating.In another embodiment, can utilize TEOS is tetraethyl orthosilicate or tetraethoxysilane (Si (C 2H 5O) 4), or MTEOS be methyl triethoxysilane and oxygen or ozone and randomly the gas of carbon back liquid use plasma assisted CVD to prepare coating.
Term " plasma auxiliary chemical vapor deposition " refers to use the chemical vapour deposition (CVD) of plasma, and comprises plasma enhanced CVD and high-density plasma CVD.When term " ... top ", when " covering " etc. is used for layer the relative position of each other in this article, this class term should refer to that each other the layer of directly contact maybe can be inserted in other single or multiple lift between the layer.
Being described in of this paper only is exemplary in nature, and therefore, its variation is not regarded as a departure from the spirit and scope of the present invention.

Claims (74)

1. method, this method comprises:
Use precursor gases to utilize plasma auxiliary chemical vapor deposition comprising deposition first coating on the fuel cell component of substrate, this precursor gases comprises the compound that contains at least one Si-O group and contain at least one group of saturated or unsaturated carbon chains.
2. the method for claim 1 also is included in the preceding pre-processed substrate of deposition first coating to remove pollutant from substrate.
3. the method for claim 1 also is included in the preceding pre-processed substrate of deposition first coating to connect polar group to substrate.
4. method as claimed in claim 3, wherein said polar group comprises hydroxyl.
5. method, this method are included in pre-processed substrate before deposition first coating, and described preliminary treatment comprises and exposes this substrate to containing oxygen plasma.
6. method, this method are included in pre-processed substrate before deposition first coating, and described preliminary treatment comprises and exposes the contain oxygen plasma of this substrate to the microwave generation.
7. method as claimed in claim 6, wherein said exposing as is up to 5 minutes time.
8. method as claimed in claim 6, the wherein said time that exposes as 0.5-3 minute.
9. the method for claim 1 is wherein carried out described plasma auxiliary chemical deposition under the pressure of 0-500Pa.
10. the method for claim 1 is wherein carried out described plasma auxiliary chemical deposition under the pressure of 10-100Pa.
11. the method for claim 1 is wherein carried out described plasma auxiliary chemical deposition under the pressure of 30-100Pa.
12. the method for claim 1 wherein produces described plasma by microwave energy.
13. as claim 12 described methods, wherein said microwave energy is 50W-10kW.
14. method as claimed in claim 12, wherein said microwave energy are 100W-1kW.
15. method as claimed in claim 12, wherein said microwave energy are 200W-300W.
16. method as claimed in claim 15, the volume of wherein said reactor are about 110 liters.
17. the method for claim 1 also comprises carrier gas.
18. method as claimed in claim 17, wherein said carrier gas comprise at least a in air, nitrogen, argon gas, alkylamine, alkyl silane, ammonia, carbon dioxide, chloride, chlorine dioxide, chlorocarbon, nitrous oxide, oxygen, ozone, the steam or their mixture.
19. method as claimed in claim 17, wherein precursor is 4-16% to the carrier gas volume flow ratio.
20. method as claimed in claim 17, wherein precursor is 4-12% to the carrier gas volume flow ratio.
21. method as claimed in claim 17, wherein precursor is 8-10% to the carrier gas volume flow ratio.
22. method as claimed in claim 17, wherein said carrier gas comprises oxygen.
23. method as claimed in claim 22, wherein precursor is 4-16% to the carrier gas volume flow ratio.
24. method as claimed in claim 22, wherein precursor is 4-12% to the carrier gas volume flow ratio.
25. method as claimed in claim 22, wherein precursor is 8-10% to the carrier gas volume flow ratio.
26. method as claimed in claim 22, wherein said carrier gas comprises O 2
27. method as claimed in claim 17, wherein said precursor gases flow velocity is 2-50ml/min, and flow rate of carrier gas is 20-625ml/min.
28. method as claimed in claim 17, wherein said precursor gases flow velocity is 10-30ml/min, and flow rate of carrier gas is 100-375ml/min.
29. method as claimed in claim 17, wherein said precursor gases flow velocity is 15-20ml/min, and flow rate of carrier gas is 150-250ml/min.
30. the method for claim 1, wherein said plasma remains on stable state.
31. method as claimed in claim 12 wherein uses microsecond to nanosecond pulse to make microwave power produce pulse.
32. the method for claim 1 comprises that also reprocessing first coating is to increase polar group to compound.
33. the method for claim 1 also comprises reprocessing first coating, described reprocessing comprises that exposure first coating is to containing oxygen plasma.
34. method as claimed in claim 33 wherein exposes and is up to 5 minutes time.
35. method as claimed in claim 33 wherein exposes 0.5-3 minute time.
36. method as claimed in claim 32, wherein said polar group comprise hydroxyl, halide, carboxyl, ketone group or aldehyde radical functional group.
37. the method for claim 1, wherein said carbochain have 1-4 carbon atom.
38. the method for claim 1, wherein said coating also comprises electric conducting material.
39. product as claimed in claim 38, wherein said electric conducting material comprise at least a in Au, Ag, Ru, Rh, Pd, Re, Os, Ir, Pt, rare earth metal, their alloy, polymerization carbon or the graphite.
40. product as claimed in claim 1, wherein said parts comprise bipolar plates.
41. product as claimed in claim 1, wherein said substrate comprises metal.
42. product as claimed in claim 1, wherein said substrate comprises polymer composite material.
43. product as claimed in claim 1 also comprises second coating that includes electric conducting material, and wherein said second coating covers substrate and first coating covers second coating.
44. product as claimed in claim 1, wherein said carbochain are straight chain, side chain or ring-type.
45. the method for claim 1 also is included in selective deposition mask on the substrate part, does not have mask on a part of substrate, and is to expose before deposition first coating on the fuel cell component.
46. method as claimed in claim 45, wherein said mask be hardmask, can wash a kind of in mask or the photoresist mask.
47. method as claimed in claim 45, wherein said parts are the bipolar plates with a plurality of projectioies and passage, wherein said mask only is deposited on the described projection by selectivity.
48. the method for claim 1, wherein said parts are the bipolar plates with a plurality of projectioies and passage, be that wherein the preceding selective deposition mask of deposition first coating is removed first coating layer portion of mask and any coverage mask then on the fuel cell component on the part bipolar plates.
49. the method for claim 1, wherein said parts are the bipolar plates with a plurality of projectioies and passage, and wherein first coating is deposited on projection and the passage, remove the selection part of first coating then.
50. the method for claim 1, wherein said parts are the bipolar plates with a plurality of projectioies and passage, and wherein first coating is deposited on projection and the passage, removes first coating on the projection then.
51. the method for claim 1, wherein said parts are the bipolar plates with a plurality of projectioies and passage, and wherein first coating is deposited on projection and the passage, and also be included in selective deposition mask on part first coating, stay part first coating and expose, remove the expose portion of first coating then.
52. method as claimed in claim 51 is wherein removed described expose portion by etching.
53. the method for claim 1 wherein only deposits described mask on passage.
54. the method for claim 1, wherein said precursor gases comprises the material with following formula:
Figure A20068003827300051
R wherein 1, R 2, R 3, R 4, R 5And R 6Can be H, O, Cl or saturated or unsaturated carbon chains separately, and R wherein 1, R 2, R 3, R 4, R 5And R 6Can be identical or different.
55. method as claimed in claim 32, wherein said polar group comprise at least a in hydroxyl, carboxyl or the aldehyde radical functional group.
56. the method for claim 1, wherein said precursor comprises HMDO.
57. a method, this method comprises:
Use precursor gases to utilize plasma auxiliary chemical vapor deposition comprising deposition first coating on the fuel cell component of substrate, described precursor gases comprises and contains first at least a in siloxanes or the silanol compound.
58. method as claimed in claim 57, wherein said plasma auxiliary chemical vapor deposition also comprise oxygen containing second gas.
59. method as claimed in claim 58, wherein said coating comprises second compound, and comprises that also processing first coating is to increase polar group to second compound.
60. a method, this method comprises:
Utilize plasma auxiliary chemical vapor deposition comprising deposition first coating on the fuel cell component of substrate, wherein said plasma auxiliary chemical vapor deposition comprises makes silane gas, comprise the gas and the oxygen-containing gas that contain carbon chain compound flows.
61. a method, this method comprises:
Utilize plasma auxiliary chemical vapor deposition comprising on the fuel cell component of substrate deposition first coating, wherein said plasma auxiliary chemical vapor deposition comprises makes the gas that comprises the first siliceous compound, comprise second gas of second compound that contains carbochain and comprise the 3rd gas flow of oxygenatedchemicals.
62. a method, this method comprises:
Utilize plasma auxiliary chemical vapor deposition deposited coatings on fuel cell component, precursor gases is flowed in the plasma-reaction-chamber and carrier gas is flow in the plasma-reaction-chamber, wherein said precursor is about 4-about 16% to the molar flow speed ratio of carrier gas.
63. method as claimed in claim 62, wherein said precursor is about 4-about 12% to the molar flow speed ratio of carrier gas.
64. method as claimed in claim 62, wherein said precursor is about 8-about 10% to the molar flow speed ratio of carrier gas.
65. method as claimed in claim 62, wherein said precursor gases comprises HMDO, and carrier gas comprises oxygen.
66. method as claimed in claim 62 comprises that also post-treatment coatings is to increase polar group.
67. method as claimed in claim 62 also comprises post-treatment coatings, described reprocessing comprises the plasma of this coating of exposure to oxygen-carrying ion.
68. method as claimed in claim 62 also is included in the preceding preliminary treatment fuel cell component of deposition, described preliminary treatment comprises that the connection polar group is to fuel cell component.
69. a method, this method comprises:
Use plasma auxiliary chemical vapor deposition deposited coatings on fuel battery double plates.
70. one kind as the described method of claim 69, forms mask before also being included in deposition on the part of bipolar plates.
71. as the described method of claim 69, wherein said use plasma auxiliary chemical vapor deposition comprises flows in the plasma-reaction-chamber precursor gases, and wherein said precursor gases comprises at least a in carbon or the silicon.
72. as the described method of claim 69, wherein said use plasma auxiliary chemical vapor deposition comprises flows in the plasma-reaction-chamber precursor gases, and wherein said precursor gases comprises carbon and silicon.
73. as the described method of claim 72, comprise also carrier gas is flow in the plasma-reaction-chamber that wherein said carrier gas comprises oxygen.
74. method as claimed in claim 54, wherein R 1, R 2, R 3, R 4, R 5Or R 6In at least one be carbochain with at least one carbon atom.
CNA2006800382739A 2005-08-12 2006-08-08 Process for application of a hydrophilic coating to fuel cell bipolar plates Pending CN101288195A (en)

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