CN101488574A - Proton exchange film fuel cell stainless steel bi-polar plate and production thereof - Google Patents
Proton exchange film fuel cell stainless steel bi-polar plate and production thereof Download PDFInfo
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- CN101488574A CN101488574A CNA2008100101115A CN200810010111A CN101488574A CN 101488574 A CN101488574 A CN 101488574A CN A2008100101115 A CNA2008100101115 A CN A2008100101115A CN 200810010111 A CN200810010111 A CN 200810010111A CN 101488574 A CN101488574 A CN 101488574A
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 74
- 239000000446 fuel Substances 0.000 title claims abstract description 65
- 239000010935 stainless steel Substances 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000576 coating method Methods 0.000 claims abstract description 137
- 239000011248 coating agent Substances 0.000 claims abstract description 129
- 238000005260 corrosion Methods 0.000 claims abstract description 105
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 35
- 229920000767 polyaniline Polymers 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 239000011247 coating layer Substances 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 230000004087 circulation Effects 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 96
- 229910052751 metal Inorganic materials 0.000 abstract description 38
- 239000002184 metal Substances 0.000 abstract description 38
- 238000012545 processing Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 description 28
- 230000006378 damage Effects 0.000 description 21
- 230000010287 polarization Effects 0.000 description 21
- 238000002791 soaking Methods 0.000 description 21
- 230000001681 protective effect Effects 0.000 description 16
- 238000004088 simulation Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000005587 bubbling Effects 0.000 description 7
- 229940075397 calomel Drugs 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 bipolar plates Substances 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Fuel Cell (AREA)
Abstract
The invention provides a stainless steel bipolar plate of a proton exchange membrane fuel cell and the preparation thereof. The surface of the stainless steel bipolar plate is covered with a corrosion resistant and conductive complex coating of polypyrrole/polyaniline with the thickness of the coating standing at 10-25mum and the thickness ratio of a bottom polypyrrole coating and a top polyaniline coating standing between 1:1 and 1:4. The invention has the advantages of simple technique, no limitation by the shape of the workpiece structure, low processing coat, excellent corrosion resistant performance of the coating in sour environment and the like, thereby being capable of improving the corrosion resistant performance of metal and lowering contact resistance of the metal. The coating is for the first time applied to the protection of the stainless steel bipolar plate of the proton exchange membrane fuel cell.
Description
Technical field
The present invention relates to fuel cell technology, a kind of proton exchange membrane fuel cell stainless steel bipolar plate and preparation method thereof is provided especially, this bipolar plate of stainless steel has good corrosion resistance and conductivity.
Background technology
(Fuel cell FC) is a kind of efficient generating apparatus that the chemical energy in fuel and the oxidant is converted into electric energy by electrochemical reaction to fuel cell.Along with day being becoming tight and requirement on environmental protection of fossil energy, cleaning, the FC technology becomes a kind of emerging field efficiently, and is subjected to the attention of various countries day by day.Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, abbreviate PEMFC as) be to be electrolyte with the solid macromolecule proton exchange membrane, with hydrogen or reformation gas is fuel, with oxygen or air is the fuel cell of new generation of oxidant, PEMFC is subjected to the extensive concern of national governments and scientific research institution owing to have very wide development application prospect.At present, PEMFC tests in space flight, electric automobile, naval vessels, portable power source, distributed power station etc., is in development in laboratory and moves towards the practical stage gradually.International important PEMFC project comprises the national PEMFC project of USDOE's tissue and based on Canadian Ba Lade Energetics Systems Corp., by the PEMFC electric motor car plan of companies such as benz, Ford support.China classifies PEMFC as alternative energy and power project in " 95 " and " 15 " " 863 ".A PEMFC cell mainly comprises compositions such as bipolar plates, platinum catalyst, proton exchange membrane.A system is originally external except PEMFC, also should comprise the fuel and the circulatory system thereof, oxidant and auxiliary systems such as the circulatory system, water/heat management system thereof.
Bipolar plates is the multipurpose multifunctional operating system of PEMFC, and it has support electrode, collected current, separation and effects such as conducting gas and draining.According to estimates, among the typical PEMFC, can reach 80% weight and volume and come from bipolar plates, the weight and volume that therefore reduces bipolar plates is the key that improves the PEMFC specific energy.Simultaneously, reducing bipolar plate material and processing charges thereof also is one of main path that reduces the PEMFC cost.Therefore, the development of bipolar plate material and manufacture craft thereof has extremely important influence to development and the commercial applications of PEMFC.
At present, bipolar plates mainly adopts graphite and composite material or metal material thereof to make.Current most popular PEMFC bipolar plate material is a graphite, it has good corrosion resisting property, conductivity and heat conductivility, but its porosity is big, mechanical strength is low, fragility is big, poor processability, for the infiltration that prevents working gas with satisfy the mechanical strength design, the thickness of graphite bi-polar plate should be thicker, this makes its volume and weight all bigger, is unfavorable for reducing battery weight specific energy and volumetric specific energy; The bipolar plates carbon composite mainly is to be mixed and solidified by macromolecule resin and graphite powder to form, it had both kept performances such as the high and contact resistance of the chemical stability of graphite material is little, overcome the deficiency of physical and mechanical properties such as the graphite porosity is big, fragility height again, but owing to utilized macromolecule resin as bonding agent, this has introduced the characteristic of macromolecular material inevitably, and wherein deterioration, the ion of its physical and mechanical properties in surrounding medium oozes out, problem such as creep all has considerable influence to the long-term operation performance of PEMFC; Compare with traditional graphite material, the intensity height of metal material, good processability can be made into very thin bipolar plates with manufacturing weight ratio and all very high PEMFC of volumetric specific energy, so metal material are the bipolar plate materials that has competitiveness.But, can produce weak acid environment during owing to PEMFC work, corrosion or passivation can take place in metal material in this environment, and both the polluted membrane electrode can increase contact resistance again, to the performance generation harmful effect of PEMFC.Therefore, adopting metal is the metallic surface modification as one of key technology of PEMFC bipolar plate material, handles with decay resistance that improves metal and the contact resistance that reduces metal by modification.
The metal material that the PEMFC bipolar plates relates to mainly contains stainless steel, titanium, nickel, aluminium, copper and carbon steel etc.Nickel, aluminium, copper and the carbon steel corrosion rate in the PEMFC environment is bigger, when selecting these material bipolar plates for use, must adopt effective coating etc. to carry out surface treatment to improve its corrosion resistance.The corrosion rate of titanium in the PEMFC environment is very low, but its surface contacted resistance is bigger, and then makes that the normal working voltage of battery is lower.Compare with the titanium material, the corrosion resistance of stainless steel in the PEMFC environment is relatively poor relatively, but it is easy to processing than titanium material, and its corrosion resisting property is apparently higher than metal materials such as nickel, aluminium, copper and carbon steels.Therefore, making stainless steel material be subjected to extensive concern just because of higher relatively intensity,, excellent machinability big than high chemical stability, alloy range of choice and relatively low cost, is the most active metal material of research at present.But stainless steel also exists corrosion (particularly in galvanic anode one side) and surface passivation (particularly at cell cathode first) in the PEMFC environment, therefore must carry out surface treatment to satisfy the practicability requirement of PEMFC.At present the metal double polar plates surface protection coating of international report mainly comprises carbon-base coating such as physical vapour deposition (PVD) diamond-film-like, conducting polymer (polypyrrole or polyaniline) coating and metal based coating such as noble coatings, cermet (metal nitride and carbide) coating and coating of metal oxides.These metal-cermic coatings preparation method mainly comprises physical vapour deposition (PVD) and chemical vapour deposition (CVD).
Summary of the invention
The object of the present invention is to provide a kind of proton exchange membrane fuel cell stainless steel bipolar plate and preparation method thereof.
The invention provides a kind of proton exchange membrane fuel cell stainless steel bipolar plate, surface coverage one deck polypyrrole/polyaniline of described bipolar plate of stainless steel is anti-corrosion, the conduction composite coating, coating layer thickness 10～25 μ m., the polyaniline coating thickness of bottom polypyrrole coating and top layer is than between 1:1～1:4.
The preparation of proton exchange membrane fuel cell stainless steel bipolar plate provided by the invention, described coating adopt electrochemical method synthetic, and the polypyrrole of bottom synthesizes at 0.1～0.4mol/dm
3Pyrroles+0.05～0.3mol/dm
3Carry out in the aqueous solution of lauryl sodium sulfate, wherein 0.4mol/dm
3Pyrroles+0.15mol/dm
3The coating performance optimum that lauryl sodium sulfate obtains, coating layer thickness is by regulating the control of generated time and resultant current density; Synthesizing of the polyaniline coating of top layer at 0.1～1mol/dm
3Aniline+0.1～1mol/dm
3Carry out in the aqueous solution of sulfuric acid, wherein at 0.5mol/dm
3Aniline+1mol/dm
3The synthetic polyaniline coating performance that obtains is best in the sulfuric acid, and coating layer thickness is by regulating synthetic cycle-index; Top layer and bottom all use the method for ice-water bath that synthesis temperature is remained on about 0～5 ℃, synthesize in camera bellows to avoid illumination.
The preparation of proton exchange membrane fuel cell stainless steel bipolar plate provided by the invention, the electric potential scanning interval of bottom is-0.2～1V, and sweep speed is 30mV/s, and resultant current is constant in 0.5～10mA/cm
-2, wherein working as resultant current is 3～5mA/cm
-2, coating performance optimum, coating layer thickness 2～15 μ m; The synthetic cycle-index of top layer polyaniline coating is 2～6, and thickness is 2～15 μ m;
The preparation of proton exchange membrane fuel cell stainless steel bipolar plate provided by the invention, the polyaniline coating thickness of bottom polypyrrole coating and top layer compares functional between 1:1～1:4, is optimum when the thickness of the two compares at 1:3 wherein.
The preparation of proton exchange membrane fuel cell stainless steel bipolar plate provided by the invention, what preparation bottom polypyrrole coating adopted is the bipolar electrode system, is auxiliary electrode with platinized platinum or stainless steel substrates promptly, stainless steel is a work electrode; What preparation top layer polyaniline coating adopted is three-electrode system, promptly is reference electrode with the saturated calomel electrode, and platinized platinum or stainless steel substrates are auxiliary electrode, and stainless steel/polypyrrole is a work electrode.
The preparation of proton exchange membrane fuel cell stainless steel bipolar plate provided by the invention, synthesized on the proton exchange membrane fuel cell stainless steel bipolar plate surface a kind of polypyrrole/polyaniline anti-corrosion, the conduction composite coating.It can be applied to all types of stainless steels (as 304,316,310 type stainless steels) surface.When reaching the 15 μ m left and right sides, the thickness of coating can play long-term protective effect to the base material stainless steel.
With 304 stainless steels is example, at 25 ℃ of following 0.3mol/dm
3In the HCl aqueous solution, matrix stainless steel corrosion potential pact-360mV (relative saturation calomel electrode, down together), pitting potential pact-80mV, coating can make its corrosion potential bring up to more than the 100mV, simultaneously can suppress the active dissolution of parent metal, and not find matrix stainless steel generation spot corrosion at the corrosion potential place; Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good corrosion resisting property and higher conductivity after long period of soaking.
Simulation fuel battery cathode with proton exchange film environment (80 ℃, 0.1M H
2SO
4The aqueous solution, bubbling air) in, the stainless corrosion potential pact-300mV of matrix, coating can make corrosion potential bring up to more than the 110mV.Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good corrosion resisting property and higher conductivity after long period of soaking.
Simulation Proton Exchange Membrane Fuel Cells anode-context (80 ℃, 0.1M H
2SO
4The aqueous solution feeds hydrogen) in, the stainless corrosion potential pact-320mV of matrix, coating can make corrosion potential bring up to more than the 60mV.Be higher than Proton Exchange Membrane Fuel Cells anode working current potential-240mV under polarization do not cause the destruction and the corrosion of metal of coating in 4 hours.In above-mentioned medium, coating still can keep good corrosion resisting property after long period of soaking.
It is simple that the present invention has technology, not limited by the Workpiece structure shape, and processing cost is low, and coating has excellent advantages such as corrosion resistance in sour environment, can improve the decay resistance of metal and the contact resistance of reduction metal.This coating first Application is in the protection of proton exchange membrane fuel cell stainless steel bipolar plate.
Embodiment
Embodiment 1
Before synthetic, stainless steel surfaces needs with being polished to 240# with silicon carbide paper, and cleans and dry through distilled water, acetone, so that coatings prepared and stainless steel base have good combination.The synthetic employing bipolar electrode system of bottom polypyrrole coating promptly is auxiliary electrode with the platinized platinum, and 304 stainless steels are work electrode.Preparation is at 0.4mol/dm
3Pyrroles+0.15mol/dm
3Carry out in the aqueous solution of lauryl sodium sulfate, use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, resultant current is constant in 3mAcm
-2, generated time 20 minutes, coating layer thickness are about 12 μ m; The synthesized polyaniline coating adopts three-electrode system on the 304SS/ polypyrrole, and reference electrode is a saturated calomel electrode, and auxiliary electrode is a platinized platinum, and synthetic preparation is at 0.5mol/dm
3Aniline and 1mol/dm
3H
2SO
4Carry out in the solution, the scanning potential region is-0.2～1.0V
SCE, sweep speed is 30mV/s.Use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, circulate 3 times, coating layer thickness is about 4 μ m, final formed on stainless surface a layer thickness be about polypyrrole/polyaniline of 16 μ m anti-corrosion, conduct electricity composite coating.
At 25 ℃ of following 0.3mol/dm
3In the HCl aqueous solution, matrix stainless steel corrosion potential pact-360mV (relative saturation calomel electrode, down together), pitting potential pact-80mV, coating can make its corrosion potential bring up to more than the 110mV, simultaneously can suppress the active dissolution of parent metal, and not find matrix stainless steel generation spot corrosion at the corrosion potential place; Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good corrosion resisting property and higher conductivity after long period of soaking, do not degenerate.
Simulation fuel battery cathode with proton exchange film environment (80 ℃, 0.1M H
2SO
4The aqueous solution, bubbling air) in, matrix stainless steel corrosion potential pact-300mV, coating can make corrosion potential bring up to more than the 110mV.Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good corrosion resisting property and higher conductivity after long period of soaking.
Simulation Proton Exchange Membrane Fuel Cells anode-context (80 ℃, 0.1M H
2SO
4The aqueous solution feeds hydrogen) in, the stainless corrosion potential pact-320mV of matrix, coating can make corrosion potential bring up to more than the 60mV.Be higher than Proton Exchange Membrane Fuel Cells anode working current potential-240mV under polarization do not cause the destruction and the corrosion of metal of coating in 4 hours.In above-mentioned medium, coating still can keep good corrosion resisting property after long period of soaking.
Embodiment 2
Before synthetic, stainless steel surfaces needs with being polished to 240# with silicon carbide paper, and cleans and dry through distilled water, acetone, so that coatings prepared and stainless steel base have good combination.The synthetic employing bipolar electrode system of bottom polypyrrole coating promptly is auxiliary electrode with the platinized platinum, and 304 stainless steels are work electrode.The coating preparation is at 0.4mol/dm
3Pyrroles and 0.15mol/dm
3Carry out in the aqueous solution of lauryl sodium sulfate, use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, resultant current is constant in 3mAcm
-2, generated time 12 minutes, coating layer thickness are 8 μ m; The synthesized polyaniline coating adopts three-electrode system on the 304SS/ polypyrrole, and reference electrode is a saturated calomel electrode, and auxiliary electrode is a platinized platinum, and synthetic preparation is at 0.1mol/dm
3Aniline and 1mol/dm
3H
2SO
4Carry out in the solution.The scanning potential region is-0.2～1.0V
SCE, sweep speed is 30mV/s.Use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, circulate 3 times, coating layer thickness is 4 μ m, and the final layer thickness that formed on stainless surface is anti-corrosion, the conduction composite coating of polypyrrole/polyaniline of about 12 μ m.
At 25 ℃ of following 0.3mol/dm
3In the HCl aqueous solution, matrix stainless steel corrosion potential pact-360mV (relative saturation calomel electrode, down together), pitting potential pact-80mV, coating can make its corrosion potential bring up to more than the 100mV, simultaneously can suppress the active dissolution of parent metal, and not find matrix stainless steel generation spot corrosion at the corrosion potential place; Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking, do not degenerate.
Simulation fuel battery cathode with proton exchange film environment (80 ℃, 0.1mol/dm
3H
2SO
4The aqueous solution, bubbling air) in, the stainless corrosion potential pact-300mV of matrix, coating can make corrosion potential bring up to more than the 110mV.Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking.
Simulation Proton Exchange Membrane Fuel Cells anode-context (80 ℃, 0.1M H
2SO
4The aqueous solution feeds hydrogen) in, the stainless corrosion potential pact-320mV of matrix, coating can make corrosion potential bring up to more than the 60mV.Be higher than Proton Exchange Membrane Fuel Cells anode working current potential-240mV under polarization do not cause the destruction and the corrosion of metal of coating in 4 hours.In above-mentioned medium, coating still can keep good protective after long period of soaking.
Embodiment 3
Before synthetic, stainless steel surfaces needs with being polished to 240# with silicon carbide paper, and cleans and dry through distilled water, acetone, so that coatings prepared and stainless steel base have good combination.The synthetic employing bipolar electrode system of bottom polypyrrole coating promptly is auxiliary electrode with the platinized platinum, and 304 stainless steels are work electrode.The coating preparation is at 0.1mol/dm
3Pyrroles and 0.1mol/dm
3Carry out in the aqueous solution of lauryl sodium sulfate, use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, resultant current is constant in 1.5mAcm
-2, generated time 30 minutes, coating layer thickness are 10 μ m; The synthesized polyaniline coating adopts three-electrode system on the 304SS/ polypyrrole, and reference electrode is a saturated calomel electrode, and auxiliary electrode is a platinized platinum, and synthetic preparation is at 1mol/dm
3Aniline and 0.5mol/dm
3H
2SO
4Carry out in the solution.The scanning potential region is-0.2～1.0V
SCE, sweep speed is 30mV/s.Use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, circulate 2 times, coating layer thickness is 2 μ m, final formed on stainless surface a layer thickness be about polypyrrole/polyaniline of 12 μ m anti-corrosion, conduct electricity composite coating.
At 25 ℃ of following 0.3mol/dm
3In the HCl aqueous solution, matrix stainless steel corrosion potential pact-360mV (relative saturation calomel electrode, down together), pitting potential pact-80mV, coating can make its corrosion potential bring up to more than the 100mV, simultaneously can suppress the active dissolution of parent metal, and not find matrix stainless steel generation spot corrosion at the corrosion potential place; Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking, do not degenerate.
Simulation fuel battery cathode with proton exchange film environment (80 ℃, 0.1mol/dm
3H
2SO
4The aqueous solution, bubbling air) in, the stainless corrosion potential pact-300mV of matrix, coating can make corrosion potential bring up to more than the 110mV.Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking.
Simulation Proton Exchange Membrane Fuel Cells anode-context (80 ℃, 0.1M H
2SO
4The aqueous solution feeds hydrogen) in, the stainless corrosion potential pact-320mV of matrix, coating can make corrosion potential bring up to more than the 60mV.Be higher than Proton Exchange Membrane Fuel Cells anode working current potential-240mV under polarization do not cause the destruction and the corrosion of metal of coating in 4 hours.In above-mentioned medium, coating still can keep good protective after long period of soaking.
Embodiment 4
Before synthetic, stainless steel surfaces needs with being polished to 240# with silicon carbide paper, and cleans and dry through distilled water, acetone, so that coatings prepared and stainless steel base have good combination.The synthetic employing bipolar electrode system of bottom polypyrrole coating promptly is auxiliary electrode with the platinized platinum, and 304 stainless steels are work electrode.The coating preparation is at 0.4mol/dm
3Pyrroles and 0.15mol/dm
3Carry out in the aqueous solution of lauryl sodium sulfate, use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, resultant current is constant in 5mAcm
-2, generated time 9 minutes, coating layer thickness are 10 μ m; The synthesized polyaniline coating adopts three-electrode system on the 304SS/ polypyrrole, and reference electrode is a saturated calomel electrode, and auxiliary electrode is a platinized platinum, and synthetic preparation is at 0.5mol/dm
3Aniline and 1mol/dm
3H
2SO
4Carry out in the solution.The scanning potential region is-0.2～1.0V
SCE, sweep speed is 30mV/s.Use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, circulate 5 times, coating layer thickness is 10 μ m, final formed on stainless surface a layer thickness be about polypyrrole/polyaniline of 20 μ m anti-corrosion, conduct electricity composite coating.
At 25 ℃ of following 0.3mol/dm
3In the HCl aqueous solution, matrix stainless steel corrosion potential pact-360mV (relative saturation calomel electrode, down together), pitting potential pact-80mV, coating can make its corrosion potential bring up to more than the 90mV, simultaneously can suppress the active dissolution of parent metal, and not find matrix stainless steel generation spot corrosion at the corrosion potential place; Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking, do not degenerate.
Simulation fuel battery cathode with proton exchange film environment (80 ℃, 0.1mol/dm
3H
2SO
4The aqueous solution, bubbling air) in, the stainless corrosion potential pact-300mV of matrix, coating can make corrosion potential bring up to more than the 100mV.Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking.
Simulation Proton Exchange Membrane Fuel Cells anode-context (80 ℃, 0.1M H
2SO
4The aqueous solution feeds hydrogen) in, the stainless corrosion potential pact-320mV of matrix, coating can make corrosion potential bring up to more than the 60mV.Be higher than Proton Exchange Membrane Fuel Cells anode working current potential-240mV under polarization do not cause the destruction and the corrosion of metal of coating in 4 hours.In above-mentioned medium, coating still can keep good protective after long period of soaking.
Embodiment 5
Before synthetic, stainless steel surfaces needs with being polished to 240# with silicon carbide paper, and cleans and dry through distilled water, acetone, so that coatings prepared and stainless steel base have good combination.The synthetic employing bipolar electrode system of bottom polypyrrole coating promptly is auxiliary electrode with the platinized platinum, and 304 stainless steels are work electrode.The coating preparation is at 0.4mol/dm
3Pyrroles and 0.15mol/dm
3Carry out in the aqueous solution of lauryl sodium sulfate, use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, resultant current is constant in 3mAcm
-2, generated time 15 minutes, coating layer thickness are 10 μ m; The synthesized polyaniline coating adopts three-electrode system on the 304SS/ polypyrrole, and reference electrode is a saturated calomel electrode, and auxiliary electrode is a platinized platinum, and synthetic preparation is at 0.5mol/dm
3Aniline and 1mol/dm
3H
2SO
4Carry out in the solution.The scanning potential region is-0.2～1.0V
SCE, sweep speed is 30mV/s.Use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, circulate 3 times, coating layer thickness is 4 μ m, final formed on stainless surface a layer thickness be about polypyrrole/polyaniline of 25 μ m anti-corrosion, conduct electricity composite coating.
At 25 ℃ of following 0.3mol/dm
3In the HCl aqueous solution, matrix stainless steel corrosion potential pact-360mV (relative saturation calomel electrode, down together), pitting potential pact-80mV, coating can make its corrosion potential bring up to more than the 100mV, simultaneously can suppress the active dissolution of parent metal, and not find matrix stainless steel generation spot corrosion at the corrosion potential place; Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking, do not degenerate.
At simulation fuel battery cathode with proton exchange film environment (80 ℃ of 0.1mol/dm
3H
2SO
4The aqueous solution, bubbling air) in, the stainless corrosion potential pact-300mV of matrix, coating can make corrosion potential bring up to more than the 100mV.Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking.
At simulation Proton Exchange Membrane Fuel Cells anode-context (80 ℃ of 0.1M H
2SO
4The aqueous solution feeds hydrogen) in, the stainless corrosion potential pact-320mV of matrix, coating can make corrosion potential bring up to more than the 60mV.Be higher than Proton Exchange Membrane Fuel Cells anode working current potential-240mV under polarization do not cause the destruction and the corrosion of metal of coating in 4 hours.In above-mentioned medium, coating still can keep good protective after long period of soaking.
Embodiment 6
Before synthetic, stainless steel surfaces needs with being polished to 240# with silicon carbide paper, and cleans and dry through distilled water, acetone, so that coatings prepared and stainless steel base have good combination.The synthetic employing bipolar electrode system of bottom polypyrrole coating promptly is auxiliary electrode with the platinized platinum, and 304 stainless steels are work electrode.The coating preparation is at 0.3mol/dm
3Pyrroles and 0.3mol/dm
3Carry out in the aqueous solution of lauryl sodium sulfate, use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, resultant current is constant in 10mAcm
-2, generated time 3 minutes, coating layer thickness are 6 μ m; The synthesized polyaniline coating adopts three-electrode system on the 304SS/ polypyrrole, and reference electrode is a saturated calomel electrode, and auxiliary electrode is a platinized platinum, and synthetic preparation is at 0.5mol/dm
3Aniline and 1mol/dm
3H
2SO
4Carry out in the solution.The scanning potential region is-0.2～1.0V
SCE, sweep speed is 30mV/s.Use the method for ice-water bath that synthesis temperature is remained on about 5 ℃ in building-up process, circulate 3 times, coating layer thickness is 4 μ m, final formed on stainless surface a layer thickness be about polypyrrole/polyaniline of 10 μ m anti-corrosion, conduct electricity composite coating.
At 25 ℃ of following 0.3mol/dm
3In the HCl aqueous solution, matrix stainless steel corrosion potential pact-360mV (relative saturation calomel electrode, down together), pitting potential pact-80mV, coating can make its corrosion potential bring up to more than the 100mV, simultaneously can suppress the active dissolution of parent metal, and not find matrix stainless steel generation spot corrosion at the corrosion potential place; Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking, do not degenerate.
At simulation fuel battery cathode with proton exchange film environment (80 ℃ of 0.1mol/dm
3H
2SO
4The aqueous solution, bubbling air) in, the stainless corrosion potential pact-300mV of matrix, coating can make corrosion potential bring up to more than the 110mV.Polarization did not cause the destruction and the corrosion of metal of coating in 4 hours under the 600mV that is higher than the fuel battery cathode with proton exchange film operating potential.In above-mentioned medium, coating still can keep good protective and higher conductivity after long period of soaking.
At simulation Proton Exchange Membrane Fuel Cells anode-context (80 ℃ of 0.1M H
2SO
4The aqueous solution feeds hydrogen) in, the stainless corrosion potential pact-320mV of matrix, coating can make corrosion potential bring up to more than the 60mV.Be higher than Proton Exchange Membrane Fuel Cells anode working current potential-240mV under polarization do not cause the destruction and the corrosion of metal of coating in 4 hours.In above-mentioned medium, coating still can keep good protective after long period of soaking.
Claims (7)
1, a kind of proton exchange membrane fuel cell stainless steel bipolar plate, it is characterized in that: surface coverage one deck polypyrrole/polyaniline of described bipolar plate of stainless steel is anti-corrosion, the conduction composite coating, coating layer thickness 10～25 μ m., the polyaniline coating thickness of bottom polypyrrole coating and top layer is than between 1:1～1:4.
2, according to the described proton exchange membrane fuel cell stainless steel bipolar plate of claim 1, it is characterized in that: composite coating thickness 15 ± 1 μ m.
3, according to claim 1 or 2 described proton exchange membrane fuel cell stainless steel bipolar plates, it is characterized in that: bottom polypyrrole coating compares at 1:3 with the polyaniline coating thickness of top layer.
4, according to the preparation of the described proton exchange membrane fuel cell stainless steel bipolar plate of claim 1, it is characterized in that: described coating adopts electrochemical method synthetic, and the polypyrrole coating of bottom is at 0.1～0.4mol/dm
3Pyrroles+0.05～0.3mol/dm
3Synthetic in the aqueous solution of lauryl sodium sulfate, underlayer thickness is by regulating the control of generated time and current density; Synthesizing of the polyaniline coating of top layer at 0.1～1mol/dm
3Aniline+0.1～1mol/dm
3Carry out in the aqueous solution of sulfuric acid, coating layer thickness is by regulating synthetic cycle-index; Top layer and bottom synthesize in camera bellows to avoid illumination, and temperature remains on 0～5 ℃.
5, according to the preparation of the described proton exchange membrane fuel cell stainless steel bipolar plate of claim 4, it is characterized in that: the polypyrrole coating of bottom is at 0.4mol/dm
3Pyrroles+0.15mol/dm
3Synthetic in the aqueous solution of lauryl sodium sulfate, resultant current is constant in 0.5～10mA/cm
-2, the electric potential scanning interval is-0.2～1V, sweep speed is 30mV/s; Synthesizing of the polyaniline coating of top layer at 0.5mol/dm
3Aniline+1mol/dm
3Carry out in the aqueous solution of sulfuric acid, cycle-index is 2～6 circulations.
6, according to the preparation of claim 4 or 5 described proton exchange membrane fuel cell stainless steel bipolar plates, it is characterized in that: use the method for ice-water bath that synthesis temperature is remained on about 0～5 ℃.
7, according to the processing method on the described proton exchange membrane fuel cell stainless steel bipolar plate of claim 4 surface, it is characterized in that: what preparation bottom polypyrrole coating adopted is the bipolar electrode system, be auxiliary electrode with platinized platinum or stainless steel substrates promptly, stainless steel is a work electrode; What preparation top layer polyaniline coating adopted is three-electrode system, promptly is reference electrode with the saturated calomel electrode, and platinized platinum or stainless steel substrates are auxiliary electrode, and stainless steel/polypyrrole is a work electrode.
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| CN105552399A (en) * | 2015-12-15 | 2016-05-04 | 湖北大学 | Graphene-doping conductive polymer modified metal bipolar plate of proton exchange membrane fuel cell and preparation method of metal bipolar plate |
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| CN106935881A (en) * | 2017-03-21 | 2017-07-07 | 海安南京大学高新技术研究院 | Electrode, Proton Exchange Membrane Fuel Cells and coating production |
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| CN117543038A (en) * | 2024-01-10 | 2024-02-09 | 武汉科技大学 | Modification preparation process of bipolar plate of proton exchange membrane fuel cell |
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