CN108574107A - Improve fuel battery double plates carbide coating conduction and corrosion proof method - Google Patents

Improve fuel battery double plates carbide coating conduction and corrosion proof method Download PDF

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Publication number
CN108574107A
CN108574107A CN201810219089.9A CN201810219089A CN108574107A CN 108574107 A CN108574107 A CN 108574107A CN 201810219089 A CN201810219089 A CN 201810219089A CN 108574107 A CN108574107 A CN 108574107A
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coating
metal
carbide
carbide coating
plates
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易培云
黎焕明
彭林法
邱殿凯
来新民
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Priority to CN201810219089.9A priority Critical patent/CN108574107A/en
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Priority to PCT/CN2019/070161 priority patent/WO2019174373A1/en
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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
    • H01M8/0206—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
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • H01M8/021—Alloys based on iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—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
    • H01M8/0215—Glass; Ceramic 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
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Fuel Cell (AREA)
  • Physical Vapour Deposition (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The present invention relates to improve fuel battery double plates carbide coating conduction and corrosion proof method, it is included in metal bipolar plate surface and is sequentially depositing intermediate metal and metal-carbide coating, then processing is performed etching to coating cated bipolar plates, change the surface texture and constituent of carbide coating, finally through over cleaning, the carbide coating that drying obtains corrosion resistance and electric conductivity improves.Compared with prior art, the present invention uses optimization of the lithographic technique to coating performance on the basis of being coated with coating on metal polar plate, coupling influence when adjusting each parameter size when prepared by coating is avoided, therefore can be applied to further improving to reach the job requirement of fuel cell for fuel battery double plates carbide coating performance.

Description

Improve fuel battery double plates carbide coating conduction and corrosion proof method
Technical field
The invention belongs to field of fuel cell technology, more particularly, to a kind of improvement fuel battery double plates carbide coating Conductive and corrosion proof method.
Background technology
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, PEMFC) is due to its turn The features such as efficient, environmentally safe, operating temperature is low, long working life is changed, in fields such as traffic, national defence, electronic products It is widely used.In Proton Exchange Membrane Fuel Cells composed structure bipolar plates accounted for most space at This, while the Service Environment of fuel cell is that one kind containing SO4 2-,Cl-,F-High temperature (60~90 DEG C), the highly acid (pH=of plasma 1~3) environment, therefore more stringent requirements are proposed for physical property to bipolar plates and chemical property：Ideal bipolar plate material must It must be good conductor electrically and thermally, there is good gas barrier property, there is good corrosion resistant in certain operating temperature and potential range Corrosion, density is low, and intensity is high, and easily processed into type and mass production.Traditional metal material has good conduction Property, thermal conductivity, mechanical performance is excellent, be suitble to produce in enormous quantities, be the first choice of fuel battery double plates material, but metal polar plate exists Heavy corrosion can occur in fuel cell operating conditions, cause Cr in metal polar plate+,Ni+Equal metal ions are precipitated, and lead to proton Fouling membrane and catalyst degradation are exchanged, to reduce fuel cell service life, and metal surface is easily in acidic environment It forms passivating film and increases pole plate and gas diffusion layers contact resistance, lead to the decline of cell output.Therefore in metal polar plate It is the effective way for improving metal polar plate performance that surface, which prepares corrosion-resistant and high conductivity coating,.
Include at present mainly equadag coating, noble coatings, electroconductive polymer coating applied to the coating of metal double polar plates And metal-cermic coating.Although equadag coating and noble coatings have good chemical stability and electric conductivity, preceding Person's deposition rate causes time cost excessively high slowly excessively, the latter also due to its excessively high material cost and be unsuitable for producing in enormous quantities； The chemical property of electroconductive polymer coating is not sufficiently stable, and cannot be satisfied requirement with the combination degree of matrix.And metal Ceramic coating, especially metal-carbide coating since its excellent corrosion resistance and electric conductivity and deposition rate are fast, Manufacturing cost is low to be widely used in actual production, therefore the performance for further increasing coating on this basis is also Research hotspot at present.In terms of the optimization of metal-carbide coating corrosion resistance and electric conductivity, at present mainly can by with Lower three approach is realized：(1) change metal material (such as Cr, Ti, Zr, Nb etc.) and technological parameter so that it is determined that possessing optimality The ratio of each constituent in the metal carbides of energy；(2) other elements (such as N or other gold are adulterated in carbide coating Belong to)；(3) by either physically or chemically changing the surface texture and constituent of coating.First two method needs to debug again Parameter prepares new carbide coating, and a kind of last method then can be directly on the basis of existing carbide coating to its property It can be improved, a large amount of time and material cost can be saved.Wherein etching technics is a kind of by changing coating surface knot Structure is so as to improve the effective ways of coating performance, including wet etching and dry etching.Etching process includes mainly following three Step：Reactant is diffused into reaction surface, the progress of chemical reaction and the stripping of reaction product.As depicted in figs. 1 and 2, lead to Over etching changes the surface texture and constituent of metal-carbide coating, removes part metals element in coating, reduces and is on active service The effusion of metal ion in the process makes more conductive particles be exposed to surface, to effectively improve the electric conductivity of coating And corrosion resistance.
Patent publication No. CN102800871A disclose it is a kind of using non-balance magnetically controlled sputter technology prepare carbon chromium ladder plating The method of layer further improves metal bipolar by adjusting a series of technological parameter to change the constituent in coating The corrosion resistance and electric conductivity of plate.Patent publication No. CN101626082B is proposed before thin sheet surface modification using chemistry Add silver coating on its surface after erosion removal passivating film and deposition ceramic layer and coats one layer of silver-plated protective film.Specially Sharp publication number CN101918619A discloses a kind of method of manufacture highly electrically conductive surfaces, is included in corrosion resistant metal substrate or painting Layer surface deposits corrosion resistance particle, conductive particle or packet using technologies such as thermojet, selective coating, selective etch Metal containing these particles then makes these particles be exposed to improve metal surface electric conductivity.Patent publication No. CN103050712A discloses a kind of method for improving and being coated with chromium carbide bipolar plate of stainless steel corrosion resistance, i.e., to being covered with coating Bipolar plate of stainless steel carry out de-oiling, ungrease treatment and be placed in rare earth passivating solution KMnO4+Ce(NO3)3·6H2+Mg(NO3)2Middle place Reason a period of time, the corrosion electric current density of bipolar plates can be significantly reduced.Patent publication No. CN106929856A uses hydrofluoric acid Water-bath etching is carried out to nickel surface, improves its surface roughness to improve the hydrophobic performance on surface.Patent publication No. CN102051598A disclose it is a kind of by the mixed liquor of hydrofluoric acid and nitric acid ultrasound impregnate lithographic method improve titanium and nitrogen Change the binding force between titanium film.However in patent disclosed above all for the improved method technique of metal-carbide coating performance It is complex, the cost of coating preparation is increased, and there is no directly use etching technics to the resistance to of metal-carbide coating Corrosivity and electric conductivity are improved.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind passing through lithographic method Improve fuel battery double plates metal-carbide coating corrosion resistance and electric conductivity simple effective method.
The purpose of the present invention can be achieved through the following technical solutions：
Improve that fuel battery double plates carbide coatings is conductive and corrosion proof method, be included in metal bipolar plate surface according to Then secondary deposited metal transition zone and metal-carbide coating perform etching processing to coating cated bipolar plates, change carbon The surface texture and constituent of compound coating, finally through over cleaning, the carbon that drying obtains corrosion resistance and electric conductivity improves Compound coating specifically uses following steps：
1) metal double polar plates pre-process：Metal double polar plates are sequentially placed into ethyl alcohol, in acetone, using being cleaned by ultrasonic and dry It is dry；
2) prepared by coating：In metal bipolar plate surface deposited metal transition zone and metal-carbide coating；
3) coating etches：By bipolar plates be completely immersed in the good chemical etching solution of configured in advance carry out wet etching or It is placed in dry etching in etching apparatus；
4) metal double polar plates and cleaning, drying after etching are taken out and obtain the carbide painting that corrosion resistance and electric conductivity improve Layer.
The material of the metal double polar plates includes one kind in stainless steel, aluminium alloy or magnesium alloy, thickness 0.1- 2mm。
The intermediate metal is by chromium (Cr), titanium (Ti), zirconium (Zr), a kind of metal group in niobium (Nb) and molybdenum (Mo) At thickness 5-100nm.
The metal-carbide coating is steps coating or continuity coating, thickness 10-300nm.
The metal carbides of the metal-carbide coating coating include chromium carbide (Cr3C2), titanium carbide (TiC), zirconium carbide (ZrC), one or more in niobium carbide (NbC) or molybdenum carbide (MoC).
The metal-carbide coating passes through magnetron sputtering method, chemical vapor deposition, multi-arc ion coating or electron beam evaporation It is prepared.
Wet etching is using hydrofluoric acid solution or the mixed liquor of hydrofluoric acid and nitric acid, and etching temperature is 10-70 DEG C, etching Time is 5s-20min.By the chemical reaction between etching liquid and coating, the conductive metal particles in coating is made to be exposed to Coating surface reduces the tenor of coat inside, effectively improves the corrosion resistance and electric conductivity of coating.When etching liquid concentration When excessive or etch period is long, the major injury of coating can be caused and expose substrate, temperature is excessively high, can cause to etch The volatilization of liquid, and etching speed not easy to control.If etching liquid concentration is too low, temperature is too low or etch period is too short, carves It is too low to lose rate, influence very little to coating composition and be unable to reach improvement.
The mass concentration of the hydrofluoric acid solution is 0.5%-10%, hydrofluoric acid in the mixed liquor of the hydrofluoric acid and nitric acid Mass concentration be 0.5%-10%, the mass concentration of nitric acid is 0.1%-20%
The process gas that dry etching uses include one kind in chlorine, carbon tetrafluoride, carbon tetrachloride, hydrogen or oxygen or It is several.Gas flow is 10-500sccm, air pressure 10-1000Pa, etch period 5min-1h.Reaction gas is put in high energy Be activated Viability particle under electric reagentia, these Particle diffusions are reacted to coating surface, formed volatile materials and Metal is removed, coating can be caused to damage if etch period is long, it is too short, it is unable to reach the effect of performance improvement.
Compared with prior art, the present invention is on the basis of one or more layers carbide coating plated, using wet method Etching or dry etching change the surface texture of coating and at being grouped as, and increase the surface roughness of coating, to further Improve the corrosion resistance and its electric conductivity of carbide coating.Preparation compared to some existing metal-carbide coatings and property Energy ameliorative way, the present invention greatly reduce technique while promoting the corrosion resistance and electric conductivity of carbide coating Complexity is executed, reduces coating manufacturing cost, and on the mechanical performance of metal polar plate almost without influence.The present invention is in metal It is coated on the basis of coating using optimization of the lithographic technique to coating performance, is adjusted when being prepared so as to avoid coating each on pole plate Coupling influence when parameter size, therefore can be applied to further improving to reach for fuel battery double plates carbide coating performance To the job requirement of fuel cell.
Description of the drawings
Fig. 1 is the schematic diagram of untreated metal polar plate；
Fig. 2 is the schematic diagram of the metal polar plate after etching；
Fig. 3 is the contact resistance of metal double polar plates after the present invention etches under different time length；
Fig. 4 is the contact resistance that metal double polar plates corrosion is front and back after the present invention etches under various concentration.
In figure, 1- metal polar plates, 2- intermediate metals, 3- metal carbide layers, 4- metal carbide particles, 5- metals The metal ion that grain, 6- etchings generate.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
Embodiment 1：
Using bipolar plate of stainless steel as matrix, titanium carbide coating is prepared on its surface, technical process is as follows：
1) pole plate pre-processes：Deionized water, acetone, absolute ethyl alcohol is used to be cleaned by ultrasonic stainless steel double polar plate surface successively And it is baked to；
2) pretreated bipolar plate of stainless steel is hung on to the planet pivoted frame in non-balance magnetically controlled sputter ion plating furnace chamber On platform, holding pivoted frame rotating speed is 4r/min, is evacuated to base vacuum 3*10-5After Torr, it is filled with argon gas and keeps operating air pressure For 4*10-4Torr, stainless steel base are biased -500V, make ion pair matrix surface constant bombardment, understand the passivation on surface Layer, scavenging period 30min；
3) 20sccm argon gas is passed through as protective gas, and is passed through 20sccm reaction gas acetylene 30min, keeps matrix inclined It is pressed in -100V, titanium target electric current is opened, in stainless steel polar plate surface reactive sputter-deposition titanium carbide coating；
4) target current and blow vent are closed, cooling 20min obtains required titanium carbide coating.
As shown in figure 3, the metal double polar plates initial contact resistance is 7.84m Ω cm2, in the sulfuric acid of pH=3 Contact resistance increases to 31.07m Ω cm after constant potential 1.6V (vs.SHE) corrodes 1h2。
Embodiment 2：
Using bipolar plate of stainless steel as matrix, titanium carbide coating is prepared on its surface, and titanium carbide is promoted by wet etching The corrosion resistance and electric conductivity of coating, technical process are as follows：
1) pole plate pre-processes：Deionized water, acetone, absolute ethyl alcohol is used to be cleaned by ultrasonic stainless steel double polar plate surface successively And it is baked to；
2) pretreated bipolar plate of stainless steel is hung on to the planet pivoted frame in non-balance magnetically controlled sputter ion plating furnace chamber On platform, after being evacuated to base vacuum, it is filled with argon gas, and be biased on stainless steel base, ion pair matrix surface is made to hold Continuous bombardment, scavenging period 30min；
3) it is passed through working gas and reaction gas simultaneously into vacuum tank, by splash-proofing sputtering metal target in stainless steel polar plate table Face reactive sputter-deposition titanium carbide coating, sputtering time 30min；
4) metal double polar plates for being coated with titanium carbide coating are placed in the hydrofluoric acid of mass fraction 6% after impregnating 5s, are taken out Pole plate is cleaned and is dried, and obtains the titanium carbide coating of performance improvement.
As shown in figure 3, the metal double polar plates initial contact resistance is 2.33m Ω cm2。
Embodiment 3：
Using bipolar plate of stainless steel as matrix, titanium carbide coating is prepared on its surface, and titanium carbide is promoted by wet etching The corrosion resistance and electric conductivity of coating, technical process are as follows：
1) pole plate pre-processes：Deionized water, acetone, absolute ethyl alcohol is used to be cleaned by ultrasonic stainless steel double polar plate surface successively And it is baked to；
2) pretreated bipolar plate of stainless steel is hung on to the planet pivoted frame in non-balance magnetically controlled sputter ion plating furnace chamber On platform, after being evacuated to base vacuum, it is filled with argon gas, and be biased on stainless steel base, ion pair matrix surface is made to hold Continuous bombardment, scavenging period 30min；
3) it is passed through working gas and reaction gas simultaneously into vacuum tank, by splash-proofing sputtering metal target in stainless steel polar plate table Face reactive sputter-deposition titanium carbide coating, sputtering time 30min；
4) metal double polar plates for being coated with titanium carbide coating are placed in the hydrofluoric acid of mass fraction 6% after impregnating 10s, are taken out Pole plate is cleaned and is dried, and obtains the titanium carbide coating of performance improvement.
As shown in figure 3, the metal double polar plates initial contact resistance is 2.51m Ω cm2。
Embodiment 4：
Using bipolar plate of stainless steel as matrix, titanium carbide coating is prepared on its surface, and titanium carbide is promoted by wet etching The corrosion resistance and electric conductivity of coating, technical process are as follows：
1) pole plate pre-processes：Deionized water, acetone, absolute ethyl alcohol is used to be cleaned by ultrasonic stainless steel double polar plate surface successively And it is baked to；
2) pretreated bipolar plate of stainless steel is hung on to the planet pivoted frame in non-balance magnetically controlled sputter ion plating furnace chamber On platform, after being evacuated to base vacuum, it is filled with argon gas, and be biased on stainless steel base, ion pair matrix surface is made to hold Continuous bombardment, scavenging period 30min；
3) it is passed through working gas and reaction gas simultaneously into vacuum tank, by splash-proofing sputtering metal target in stainless steel polar plate table Face reactive sputter-deposition titanium carbide coating, sputtering time 30min；
4) metal double polar plates for being coated with titanium carbide coating are placed in the hydrofluoric acid of mass fraction 6% after impregnating 20s, are taken out Pole plate is cleaned and is dried, and obtains the titanium carbide coating of performance improvement.
As shown in figure 3, the metal double polar plates initial contact resistance is 2.72m Ω cm2。
Embodiment 5：
Using bipolar plate of stainless steel as matrix, titanium carbide coating is prepared on its surface, and titanium carbide is promoted by wet etching The corrosion resistance and electric conductivity of coating, technical process are as follows：
1) pole plate pre-processes：Deionized water, acetone, absolute ethyl alcohol is used to be cleaned by ultrasonic stainless steel double polar plate surface successively And it is baked to；
2) pretreated bipolar plate of stainless steel is hung on to the planet pivoted frame in non-balance magnetically controlled sputter ion plating furnace chamber On platform, after being evacuated to base vacuum, it is filled with argon gas, and be biased on stainless steel base, ion pair matrix surface is made to hold Continuous bombardment, scavenging period 30min；
3) it is passed through working gas and reaction gas simultaneously into vacuum tank, by splash-proofing sputtering metal target in stainless steel polar plate table Face reactive sputter-deposition titanium carbide coating, sputtering time 30min；
4) metal double polar plates for being coated with titanium carbide coating are placed in the hydrofluoric acid of mass fraction 6% after impregnating 30s, are taken out Pole plate is cleaned and is dried, and obtains the titanium carbide coating of performance improvement.
As shown in figure 3, the metal double polar plates initial contact resistance is 2.73m Ω cm2。
Embodiment 6：
Using bipolar plate of stainless steel as matrix, titanium carbide coating is prepared on its surface, and titanium carbide is promoted by wet etching The corrosion resistance and electric conductivity of coating, technical process are as follows：
1) pole plate pre-processes：Deionized water, acetone, absolute ethyl alcohol is used to be cleaned by ultrasonic stainless steel double polar plate surface successively And it is baked to；
2) pretreated bipolar plate of stainless steel is hung on to the planet pivoted frame in non-balance magnetically controlled sputter ion plating furnace chamber On platform, after being evacuated to base vacuum, it is filled with argon gas, and be biased on stainless steel base, ion pair matrix surface is made to hold Continuous bombardment, scavenging period 30min；
3) it is passed through working gas and reaction gas simultaneously into vacuum tank, by splash-proofing sputtering metal target in stainless steel polar plate table Face reactive sputter-deposition titanium carbide coating, sputtering time 30min；
4) metal double polar plates for being coated with titanium carbide coating are placed in the hydrofluoric acid of mass fraction 2% after impregnating 10s, are taken out Pole plate is cleaned and is dried, and obtains the titanium carbide coating of performance improvement.
As shown in figure 4, the metal double polar plates initial contact resistance is 2.77m Ω cm2, in the sulfuric acid of pH=3 Contact resistance increases to 15.82m Ω cm after constant potential 1.6V (vs.SHE) corrodes 1h2。
Embodiment 7：
Using bipolar plate of stainless steel as matrix, titanium carbide coating is prepared on its surface, and titanium carbide is promoted by wet etching The corrosion resistance and electric conductivity of coating, technical process are as follows：
1) pole plate pre-processes：Deionized water, acetone, absolute ethyl alcohol is used to be cleaned by ultrasonic stainless steel double polar plate surface successively And it is baked to；
2) pretreated bipolar plate of stainless steel is hung on to the planet pivoted frame in non-balance magnetically controlled sputter ion plating furnace chamber On platform, after being evacuated to base vacuum, it is filled with argon gas, and be biased on stainless steel base, ion pair matrix surface is made to hold Continuous bombardment, scavenging period 30min；
3) it is passed through working gas and reaction gas simultaneously into vacuum tank, by splash-proofing sputtering metal target in stainless steel polar plate table Face reactive sputter-deposition titanium carbide coating, sputtering time 30min；
4) metal double polar plates for being coated with titanium carbide coating are placed in the hydrofluoric acid of mass fraction 4% after impregnating 10s, are taken out Pole plate is cleaned and is dried, and obtains the titanium carbide coating of performance improvement.
As shown in figure 4, metal double polar plates initial contact resistance is 2.32m Ω cm2, by perseverance in the sulfuric acid of pH=3 Contact resistance increases to 17.16m Ω cm after current potential 1.6V (vs.SHE) corrosion 1h2。
Above-described embodiment is implemented based on the technical solution of the present invention, gives detailed embodiment and specific Operating process, wherein under the conditions of example 3 --- after 6% hf etching 10s, metal-carbide coating has best Corrosion resistance and electric conductivity, the contact resistance before corrosion are 2.51m Ω cm2, contact resistance is 6.72m Ω cm after corrosion2, It is satisfied by fuel battery double plates contact resistance and is less than 10m Ω cm2Requirement.
Embodiment 8：
Without the structure of wet etching or the metal polar plate of dry etching as shown in Figure 1, including metal polar plate 1, apply The intermediate metal 2 and metal carbide layer 3 on metal polar plate 1 are overlayed on, contains metal carbides in metal carbide layer 3 Particle 4 and metallic particles 5.
By the structure of wet etching or the metal polar plate of dry etching as shown in Fig. 2, compared to Figure 1, through over etching Afterwards, most of metallic particles 5 in metal carbide layer 3 forms metal ion 6 and enters etching liquid or form volatility object Matter and be removed, cause conductive metal particles to be exposed to coating surface and be improved to electric conductivity.And metal carbides The suffered etching influence of grain 4 is smaller, causes the increase of metal carbides content in coating, further increases the corrosion resistance of coating Energy.
Embodiment 9：
Improve that fuel battery double plates carbide coatings is conductive and corrosion proof method, be included in metal bipolar plate surface according to Then secondary deposited metal transition zone and metal-carbide coating perform etching processing to coating cated bipolar plates, change carbon The surface texture and constituent of compound coating, finally through over cleaning, the carbon that drying obtains corrosion resistance and electric conductivity improves Compound coating specifically uses following steps：
1) metal double polar plates pre-process：Metal double polar plates are sequentially placed into ethyl alcohol, in acetone, using being cleaned by ultrasonic and dry It is dry；
2) prepared by coating：In metal bipolar plate surface deposited metal transition zone and metal-carbide coating, wherein metal carbon Compound coating is steps coating, and the metal carbides of thickness 10nm, coating include chromium carbide (Cr3C2), titanium carbide (TiC), lead to Magnetron sputtering method is crossed to be prepared；
3) coating etches：By bipolar plates be completely immersed in the good mass concentration of configured in advance be 0.5% hydrofluoric acid solution in into Row wet etching, etching temperature are 10 DEG C, etch period 20min；
4) metal double polar plates and cleaning, drying after etching are taken out and obtain the carbide painting that corrosion resistance and electric conductivity improve Layer.
Embodiment 10：
Improve that fuel battery double plates carbide coatings is conductive and corrosion proof method, be included in metal bipolar plate surface according to Then secondary deposited metal transition zone and metal-carbide coating perform etching processing to coating cated bipolar plates, change carbon The surface texture and constituent of compound coating, finally through over cleaning, the carbon that drying obtains corrosion resistance and electric conductivity improves Compound coating specifically uses following steps：
1) metal double polar plates pre-process：Metal double polar plates are sequentially placed into ethyl alcohol, in acetone, using being cleaned by ultrasonic and dry It is dry；
2) prepared by coating：In metal bipolar plate surface deposited metal transition zone and metal-carbide coating, wherein metal carbon Compound coating is steps coating, and the metal carbides of thickness 80nm, coating are zirconium carbide (ZrC), pass through chemical vapor deposition It is prepared；
3) coating etches：Bipolar plates are completely immersed in mass concentration to be made of 10% hydrofluoric acid and 0.1% nitric acid Chemical etching solution in carry out wet etching；
4) metal double polar plates and cleaning, drying after etching are taken out and obtain the carbide painting that corrosion resistance and electric conductivity improve Layer.
Embodiment 11：
Improve that fuel battery double plates carbide coatings is conductive and corrosion proof method, be included in metal bipolar plate surface according to Then secondary deposited metal transition zone and metal-carbide coating perform etching processing to coating cated bipolar plates, change carbon The surface texture and constituent of compound coating, finally through over cleaning, the carbon that drying obtains corrosion resistance and electric conductivity improves Compound coating specifically uses following steps：
1) metal double polar plates pre-process：Metal double polar plates are sequentially placed into ethyl alcohol, in acetone, using being cleaned by ultrasonic and dry It is dry；
2) prepared by coating：In metal bipolar plate surface deposited metal transition zone and metal-carbide coating, wherein metal carbon Compound coating is continuity coating, and the metal carbides of thickness 200nm, coating are niobium carbide, are prepared by multi-arc ion coating It arrives；
3) coating etches：Bipolar plates are placed in etching apparatus and carry out dry etching, the process gas used is chlorine, gas Body flow is 10sccm, air pressure 10Pa, etch period 1h；
4) metal double polar plates and cleaning, drying after etching are taken out and obtain the carbide painting that corrosion resistance and electric conductivity improve Layer.
Embodiment 12：
Improve that fuel battery double plates carbide coatings is conductive and corrosion proof method, be included in metal bipolar plate surface according to Then secondary deposited metal transition zone and metal-carbide coating perform etching processing to coating cated bipolar plates, change carbon The surface texture and constituent of compound coating, finally through over cleaning, the carbon that drying obtains corrosion resistance and electric conductivity improves Compound coating specifically uses following steps：
1) metal double polar plates pre-process：Metal double polar plates are sequentially placed into ethyl alcohol, in acetone, using being cleaned by ultrasonic and dry It is dry；
2) prepared by coating：In metal bipolar plate surface deposited metal transition zone and metal-carbide coating, wherein metal carbon Compound coating is continuity coating, and the metal carbides of thickness 300nm, coating are molybdenum carbide (MoC), by electron beam evaporation system It is standby to obtain；
3) coating etches：Bipolar plates are placed in etching apparatus and carry out dry etching, the process gas used is tetrafluoride Carbon and carbon tetrachloride, gas flow 500sccm, air pressure 1000Pa, etch period 5min；
4) metal double polar plates and cleaning, drying after etching are taken out and obtain the carbide painting that corrosion resistance and electric conductivity improve Layer.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (8)

1. improving fuel battery double plates carbide coating conduction and corrosion proof method, which is characterized in that this method is included in Metal bipolar plate surface is sequentially depositing intermediate metal and metal-carbide coating, is then carried out to coating cated bipolar plates Etching processing changes the surface texture and constituent of carbide coating, finally through over cleaning, drying obtain corrosion resistance and The carbide coating that electric conductivity improves.
2. improvement fuel battery double plates carbide coating conduction according to claim 1 and corrosion proof method, special Sign is that this method specifically uses following steps：
1) metal double polar plates pre-process：Metal double polar plates are sequentially placed into ethyl alcohol, in acetone, using being cleaned by ultrasonic and dry；
2) prepared by coating：In metal bipolar plate surface deposited metal transition zone and metal-carbide coating；
3) coating etches：Bipolar plates are completely immersed in chemical etching solution and carry out wet etching or be placed in etching apparatus to do Method etches；
4) metal double polar plates and cleaning, drying after etching are taken out and obtain the carbide coating that corrosion resistance and electric conductivity improve.
3. improvement fuel battery double plates carbide coating conduction according to claim 2 and corrosion proof method, special Sign is that the metal-carbide coating is steps coating or continuity coating, thickness 10-300nm.
4. improvement fuel battery double plates carbide coating conduction according to claim 2 and corrosion proof method, special Sign is that the metal carbides of the metal-carbide coating coating include chromium carbide (Cr3C2), titanium carbide (TiC), zirconium carbide (ZrC), one or more in niobium carbide (NbC) or molybdenum carbide (MoC).
5. improvement fuel battery double plates carbide coating conduction according to claim 2 and corrosion proof method, special Sign is that the metal-carbide coating passes through magnetron sputtering method, chemical vapor deposition, multi-arc ion coating or electron beam evaporation system It is standby to obtain.
6. improvement fuel battery double plates carbide coating conduction according to claim 2 and corrosion proof method, special Sign is that wet etching is using hydrofluoric acid solution or the mixed liquor of hydrofluoric acid and nitric acid, and etching temperature is 10-70 DEG C, etching Time is 5s-20min.
7. improvement fuel battery double plates carbide coating conduction according to claim 6 and corrosion proof method, special Sign is, the mass concentration of the hydrofluoric acid solution is 0.5%-10%, hydrofluoric acid in the mixed liquor of the hydrofluoric acid and nitric acid Mass concentration be 0.5%-10%, the mass concentration of nitric acid is 0.1%-20%.
8. improvement fuel battery double plates carbide coating conduction according to claim 2 and corrosion proof method, special Sign is, the process gas that dry etching uses include one kind in chlorine, carbon tetrafluoride, carbon tetrachloride, hydrogen or oxygen or It is several, gas flow 10-500sccm, air pressure 10-1000Pa, etch period 5min-1h.
CN201810219089.9A 2018-03-16 2018-03-16 Improve fuel battery double plates carbide coating conduction and corrosion proof method Pending CN108574107A (en)

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