CN110364749A - The preparation method of surface composite coating based on dual polar plates of proton exchange membrane fuel cell - Google Patents
The preparation method of surface composite coating based on dual polar plates of proton exchange membrane fuel cell Download PDFInfo
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- CN110364749A CN110364749A CN201910666614.6A CN201910666614A CN110364749A CN 110364749 A CN110364749 A CN 110364749A CN 201910666614 A CN201910666614 A CN 201910666614A CN 110364749 A CN110364749 A CN 110364749A
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- carbon dust
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- composite coating
- fuel cell
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- 238000000576 coating method Methods 0.000 title claims abstract description 79
- 239000011248 coating agent Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000000446 fuel Substances 0.000 title claims abstract description 31
- 239000012528 membrane Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000009977 dual effect Effects 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 239000000428 dust Substances 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 25
- 239000002322 conducting polymer Substances 0.000 claims abstract description 24
- 238000002848 electrochemical method Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 24
- 239000010935 stainless steel Substances 0.000 claims description 16
- 229910000838 Al alloy Inorganic materials 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 238000001723 curing Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002484 cyclic voltammetry Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007848 Bronsted acid Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 230000005518 electrochemistry Effects 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- 238000004313 potentiometry Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 27
- 230000007797 corrosion Effects 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 229920000128 polypyrrole Polymers 0.000 description 12
- 229920000767 polyaniline Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 7
- 229920000123 polythiophene Polymers 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- -1 noble coatings Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000012803 optimization experiment Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- 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
- H01M8/0221—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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0226—Composites in the form of mixtures
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Energy (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to field of fuel cell technology, and in particular to a kind of preparation method of the surface composite coating based on dual polar plates of proton exchange membrane fuel cell.The conducting polymer Intelligent Composite coating that the present invention is adulterated using electrochemical method in metal surface deposition carbon dust.Dual polar plates of proton exchange membrane fuel cell after the conducting polymer Intelligent Composite of carbon dust doping is coating modified, corrosion electric current density reduce, and prolonged corrosion-resistant effect greatly improves, and has lower surface contacted resistance value.Meanwhile the conducting polymer Intelligent Composite coating of carbon dust doping has stronger adhesive force, chemical stability and conductivity in metal substrate surface.Preparation method of the invention is easy to operate, cheap, and safety and environmental protection, synthesis material are simple and easy to get, is widely used in the protection to dual polar plates of proton exchange membrane fuel cell.
Description
Technical field
The present invention relates to field of fuel cell technology, more particularly to one kind to be based on proton exchange membrane fuel cell metal dual-polarity
The preparation method of the surface composite coating of plate is for one kind to dual polar plates of proton exchange membrane fuel cell corrosion protection
The building and its application of conducting polymer intelligence composite coating.
Background technique
Since environmental pollution is got worse, it is unable to that regenerated resources are increasingly depleted, the sustainable development of the mankind receives sternness
Challenge, exploitation clean and effective, sustainable development new energy technology become very urgent task.Pem fuel
The chemical energy that fuel hydrogen is reacted with oxygen can be converted into electric energy by battery, it is considered to be following most advanced, cleaning, efficient energy
One of source production equipment.Bipolar plates are the important components in Proton Exchange Membrane Fuel Cells, and battery is together in series and constitutes by it
Battery pile, for separating Oxidizing and Reducing Agents, collection conveys electric current, flow out the water energy generated successfully, ensures battery
Uniformity of temperature profile etc..Currently used bipolar plate material has graphite bi-polar plate and metal double polar plates.Graphite bi-polar plate have compared with
Good corrosion resistance and electric conductivity, but due to its structural porous, mechanical strength is low, and processability is poor, reduces fuel cell
Power density, while the high cost of graphite also counteracts its business development.Compared to graphite bi-polar plate, metal double polar plates are due to it
The advantages such as high conductivity, high mechanical strength, low-permeability and low cost are widely used.Metal double polar plates also can be processed
At thin plate, the size and weight of Proton Exchange Membrane Fuel Cells are substantially reduced.But metal double polar plates there is also its deficiency,
Such as etching problem.When metal double polar plates long-term work is in the environment of Proton Exchange Membrane Fuel Cells, metal can occur corrosion and ask
It inscribes, iron, chromium, the nickel plasma dissolved in metal can pollute the catalyst in Proton Exchange Membrane Fuel Cells, pollute membrane electrode.This
Outside, due to corrosion, metal surface can be made to form passivation layer, increase the surface contacted resistance between bipolar plates, cause fuel electric
The power loss in pond shortens the service life of Proton Exchange Membrane Fuel Cells.Therefore we need developing low-cost, low surface contact electricity
The metal double polar plates of the strong anti-corrosion material protection Proton Exchange Membrane Fuel Cells of resistance, electric conductivity.
Currently, being mainly coating protection, including metal coating (such as noble coatings, gold for the protection of metal double polar plates
Belong to carbide or nitride coatings and coating of metal oxides etc.) and carbonyl coating (such as equadag coating, diamond-like coating and oneself
Assemble single polymer coating etc.).The corrosion resistance of noble coatings is strong, electric conductivity is high, but the performance degradation rate of coating is fast, with gold
The binding force for belonging to substrate is weak, while the high cost of noble coatings also limits its development；Carbonyl coating is connect due to its surface
Electric shock resistance is larger, is unfavorable for the promotion of proton exchange film fuel battery performance.And electroconductive polymer coating, such as polypyrrole, polyphenyl
Amine and polythiophene etc., environmental stability is good, electric conductivity is adjustable, preparation process is simple, becomes the hot spot of Recent study.It is conductive
The electric conductivity of polymer can be controlled by its unique doping and dedoping mechanism, make its performance conductor and insulator it
Between freely change.In practical applications, dual polar plates of proton exchange membrane fuel cell can also be improved by means such as doping
Corrosion protection.Electroconductive polymer coating can be used as physical barriers and stop corrosive ion, while can also pass through sun
The mode of pole protection plays the role of corrosion protection to bipolar plates.Currently, conducting polymer answering in terms of fuel battery double plates
With receive more and more attention.On the other hand, carbon material also has good electric conductivity, high-specific surface area and chemical stabilization
Property, there is important application in different fields such as battery, capacitor and anticorrosive paints.The present invention uses carbon materials cheap and easy to get
Material --- carbon powder nano particle carries out functional modification to its surface by dopamine, keeps its negatively charged preferably and conductive
Polymer is combined.Carbon material and conducting polymer it is compound, not only reduce the porosity of electroconductive polymer coating, improve
The corrosion resistance and electric conductivity of coating, while also improving the stability and mechanical property of electroconductive polymer coating.
Summary of the invention
That the object of the present invention is to provide a kind of preparation methods is simple, environmental-friendly, can be effectively controlled coating layer thickness based on
The preparation method of the surface composite coating of dual polar plates of proton exchange membrane fuel cell.When the coating of the method preparation has long
Between excellent corrosion resisting property, and surface contacted resistance is low, good with the binding force of metal double polar plates.
The technical solution of the present invention is as follows: the system of the surface composite coating based on dual polar plates of proton exchange membrane fuel cell
Preparation Method, the specific steps are as follows:
(1) pretreatment of metal: using copper wire welding to metal surface as contact conductor；Metal surface is polishing to
Surface is smooth, spare after ultrasonic oil removing, cleaning；
(2) configuration of electropolymerization solution: by conducting polymer monomer, modified carbon powder nano particle and Bronsted acid ultrasound point
It dissipates in deionized water, electropolymerization solution for standby is prepared；
(3) electrochemistry formated of carbon dust doping conducting polymer Intelligent Composite coating: electrochemistry formated uses three electrode bodies
System, using pretreated metal plate in step (1) as working electrode, silver-silver chloride electrode is reference electrode, and platinum electrode is auxiliary
Electrode；Nitrogen is continuously passed through in the electropolymerization solution first configured into step (2)；Then metal plate is placed in the electropolymerization of configuration
In solution, carbon dust doping conducting polymer Intelligent Composite coating is prepared using electrochemical method for synthesizing；It is rinsed with deionized water multiple
Coating surface is closed, and the metal double polar plates for being deposited with carbon dust doping conducting polymer Intelligent Composite coating are put into vacuum oven
In be heating and curing, the coating modified proton exchange membrane fuel cell metal dual-polarity of carbon dust doping conducting polymer Intelligent Composite is made
Plate.
Surface-brightening is polishing to metal surface described in step (1) in above-mentioned preparation method, in order to remove
The oxidation film of metal surface, activated metal surface, makes polymer coating preferably be incorporated in surface.
The modification of carbon powder nano particle modified in step (2) is bibliography Chemical in above-mentioned preparation method
Engineering Journal 335 (2018) 255-266 and International Journal of Hydrogen
The preparation of method described in Energy 39 (2014) 16740-16749 Literature.
It is preferred that above-mentioned conducting polymer monomer is pyrroles, aniline or thiophene monomer；Bronsted acid is hydrochloric acid, sulfuric acid, oxalic acid
Or acetic acid.It is preferred that above-mentioned metal is stainless steel, copper or aluminium alloy.
It is preferred that the concentration of Bronsted acid is 0.1~0.5mol L in the electropolymerization solution-1；Conducting polymer monomer it is dense
Degree is 0.05~0.5mol L-1；The concentration of modified carbon powder nano particle is 0.1~1g L-1。
It is preferred that the electrochemical method for synthesizing is galvanostatic method, potentiostatic method or cyclic voltammetry；Wherein galvanostatic method
Sedimentary condition are as follows: current density be 0.1~5mA cm-2, sedimentation time is 10~20min；The sedimentary condition of potentiostatic method are as follows:
Voltage is 0.75~1.15V, and sedimentation time is 10~20min；The sedimentary condition of cyclic voltammetry are as follows: voltage range be -0.2~
1.2V, sweep speed are 20~50mV/s, and scanning circle number is 20~30 circles；
It is preferred that the temperature being heating and curing in vacuum oven is 60~80 DEG C, the time being heating and curing is 4~6h.
The purpose for being passed through nitrogen in above-mentioned preparation method described in step (3) into electropolymerization solution is removal electropolymerization
Influence of the dissolved oxygen to electrochemistry formated process in solution.
The utility model has the advantages that
(1) present invention is used for by the conducting polymer Intelligent Composite coating that electrochemical means prepare carbon dust doping to proton
Exchange the protection of the battery metal bi-polar plate of membrane fuel.The corrosion electric current density of metal double polar plates has dropped 1~2 after modified
The order of magnitude.
(2) the metal bipolar plate surface contact after the conducting polymer Intelligent Composite of carbon dust of the invention doping is coating modified
Resistance is decreased obviously compared to non-modified bipolar plate of stainless steel, surface contacted resistance.
(3) the conducting polymer Intelligent Composite coating of the carbon dust doping of electrochemical method preparation has good self-repairability
Can, and there is preferable adhesive force between coating and bipolar plates, bipolar plates high mechanical strength can extend pem fuel electricity
The service life of pond metal double polar plates.
(4) synthesis material of the present invention is simple and easy to get, and preparation method is simple, cheap, safety and environmental protection, to the performance of battery
It does not influence, there is important practical significance to promoting metal double polar plates to be commercialized process.The present invention is widely applicable for low temperature
The surface of fuel battery metal double polar plate is modified, has broad application prospects.
Specific embodiment
The modification of carbon powder nano particle is bibliography Chemical Engineering in following case study on implementation
Journal 335 (2018) 255-266 and International Journal of Hydrogen Energy 39 (2014)
Method described in 16740-16749 Literature is all made of following methods and is made, includes the following steps:
(1) it is burnt to round bottom and 50mL concentrated nitric acid is added in flask, magnetic agitation 30min under condition of ice bath, and it is slowly added to 5g
Carbon dust；After carbon dust is uniformly dispersed, 1h is reacted at room temperature, then solution is transferred in beaker, is diluted with deionized water, continue
Stirring to solution is uniformly mixed.The mixed solution of 100mL sulfonitric is added, 1h is stirred under 0 DEG C of condition of ice bath, in room temperature
Lower standing 1h, to solution layered filtration, by the carbon powder nano particle after the isolated oxidation of carbon dust.
(2) carbon powder nano particle and 0.1mg mL obtained in 1g step (1) are weighed-1Dopamine is added jointly to 500mL
Hydroxylamine hydrochloride solution (10mM, pH=8.5), ultrasonic disperse 1h, magnetic agitation makes the dispersion of carbon powder nano particle equal for 24 hours at room temperature
Separation carbon dust is filtered after even.It is finally washed repeatedly with deionized water and ethyl alcohol to neutrality, is placed in drying in 80 DEG C of vacuum ovens,
It is spare that modified carbon powder nano particle is made.
Carbon dust adulterates the specific implementation step of conducting polymer modified dual polar plates of proton exchange membrane fuel cell such as
Under:
Embodiment 1: in 0.05mol L-1Pyrroles, 0.1mol L-1Hydrochloric acid and 1g L-1Not in the electropolymerization solution of carbon dust
Steel surface of becoming rusty prepares carbon dust Doped polypyrrole Intelligent Composite coating, the scanning voltage range of cyclic voltammetry with cyclic voltammetry
For -0.5~0.9V, sweep speed is 20mV s-1, scan circle number 30 and enclose, gained coating is put into 60 DEG C of vacuum ovens and is added
Carbon dust Doped polypyrrole Intelligent Composite coating is prepared in heat cure 4h.Compared to blank Corrosion of Stainless Steel current density 7.07
×10-5A cm-2, Corrosion of Stainless Steel current density 9.25 × 10 after carbon dust Doped polypyrrole Intelligent Composite is coating modified-7A
cm-2.Compared to blank stainless steel surface contact resistance 351m Ω cm-2, after carbon dust Doped polypyrrole Intelligent Composite is coating modified
Stainless steel surface contact resistance is reduced to 54m Ω cm-2。
Embodiment 2: in 0.1mol L-1Pyrroles, 0.3mol L-1Oxalic acid and 0.5g L-1In aluminium in the electropolymerization solution of carbon dust
Alloy surface prepares carbon dust Doped polypyrrole Intelligent Composite coating with potentiostatic method, and the application voltage of potentiostatic method is 1V, deposition
Time is 10min, and gained coating is put into 70 DEG C of vacuum ovens the 4h that is heating and curing, carbon dust Doped polypyrrole intelligence is prepared
It can composite coating.Compared to blank corrosion of aluminium alloy current density 1.22 × 10-4A cm-2, carbon dust Doped polypyrrole Intelligent Composite
Corrosion of aluminium alloy current density 3.89 × 10 after coating modified-5A cm-2.Compared to blank aluminum alloy surface contact resistance
128mΩcm-2, the aluminum alloy surface contact resistance after carbon dust Doped polypyrrole Intelligent Composite is coating modified is reduced to 51m Ω cm-2。
Embodiment 3: in 0.5mol L-1Pyrroles, 0.5mol L-1Hydrochloric acid and 0.1g L-1In copper in the electropolymerization solution of carbon dust
Surface cyclic voltammetry deposits carbon dust doped polyaniline Intelligent Composite coating, and the scanning voltage range of cyclic voltammetry is -0.5
~1.2V, sweep speed are 50mV s-1, scan circle number 30 and enclose, gained coating is put into 80 DEG C of vacuum ovens and is heating and curing
Carbon dust Doped polypyrrole Intelligent Composite coating is prepared in 6h.Compared to blank copper corrosion current density 1.76 × 10-5A cm-2, copper corrosion current density 2.80 × 10 after carbon dust Doped polypyrrole Intelligent Composite is coating modified-7A cm-2.Compared to blank
Copper surface contacted resistance 163m Ω cm-2, copper surface contacted resistance after carbon dust Doped polypyrrole Intelligent Composite is coating modified reduces
To 28m Ω cm-2。
Embodiment 4: in 0.05mol L-1Aniline, 0.1mol L-1Sulfuric acid and 0.1g L-1In the electropolymerization solution of carbon dust
Stainless steel surface deposits carbon dust doped polyaniline Intelligent Composite coating, the scanning voltage range of cyclic voltammetry with cyclic voltammetry
For -0.2~1.2V, sweep speed is 50mV s-1, scan circle number 20 and enclose, gained coating is put into 60 DEG C of vacuum ovens and is added
Carbon dust doped polyaniline Intelligent Composite coating is prepared in heat cure 4h.Compared to blank Corrosion of Stainless Steel current density 7.07
×10-5A cm-2, Corrosion of Stainless Steel current density 5.12 × 10 after carbon dust doped polyaniline Intelligent Composite is coating modified-6A
cm-2.Compared to blank stainless steel surface contact resistance 351m Ω cm-2, after carbon dust doped polyaniline Intelligent Composite is coating modified
Stainless steel surface contact resistance is reduced to 85m Ω cm-2。
Embodiment 5: in 0.1mol L-1Aniline, 0.3mol L-1Acetic acid and 0.5g L-1Not in the electropolymerization solution of carbon dust
Steel surface of becoming rusty potentiostatic method deposits carbon dust doped polyaniline Intelligent Composite coating, and the application voltage of potentiostatic method is 0.9V, sinks
The product time is 15min, and gained coating is put into 70 DEG C of vacuum ovens the 6h that is heating and curing, carbon dust doped polyaniline is prepared
Intelligent Composite coating.Compared to blank Corrosion of Stainless Steel current density 7.07 × 10-5A cm-2, carbon dust doped polyaniline intelligence is again
Close it is coating modified after Corrosion of Stainless Steel current density 4.73 × 10-7A cm-2.Compared to blank stainless steel surface contact resistance
351mΩcm-2, the stainless steel surface contact resistance after carbon dust doped polyaniline Intelligent Composite is coating modified is reduced to 73m Ω cm-2。
Embodiment 6: in 0.1mol L-1Thiophene, 0.3mol L-1Oxalic acid and 1g L-1It is closed in the electropolymerization solution of carbon dust in aluminium
Gold surface galvanostatic method deposits carbon dust doped polyaniline Intelligent Composite coating, and the current density that galvanostatic method applies is 5mA
cm-2, gained coating is put into 60 DEG C of vacuum ovens the 6h that is heating and curing by sedimentation time 20min, and carbon dust doping is prepared
Polythiophene Intelligent Composite coating.Compared to blank corrosion of aluminium alloy current density 1.22 × 10-4A cm-2, carbon dust doping polythiophene
Corrosion of aluminium alloy current density 3.48 × 10 after Intelligent Composite is coating modified-5A cm-2.It is connect compared to blank aluminum alloy surface
Electric shock resistance 128m Ω cm-2, carbon dust doping polythiophene Intelligent Composite it is coating modified after aluminum alloy surface contact resistance be reduced to 34m
Ωcm-2。
Embodiment 7: in 0.1mol L-1Thiophene, 0.3mol L-1Oxalic acid and 0.5g L-1In aluminium in the electropolymerization solution of carbon dust
Alloy surface galvanostatic method deposits carbon dust doped polyaniline Intelligent Composite coating, and the current density that galvanostatic method applies is 3mA
cm-2, gained coating is put into 60 DEG C of vacuum ovens the 6h that is heating and curing by sedimentation time 10min, and carbon dust doping is prepared
Polythiophene Intelligent Composite coating.Compared to blank corrosion of aluminium alloy current density 1.22 × 10-4A cm-2, carbon dust doping polythiophene
Corrosion of aluminium alloy current density 4.01 × 10 after Intelligent Composite is coating modified-5A cm-2.It is connect compared to blank aluminum alloy surface
Electric shock resistance 128m Ω cm-2, carbon dust doping polythiophene Intelligent Composite it is coating modified after aluminum alloy surface contact resistance be reduced to 38m
Ωcm-2。
The above is the further description to above content of the invention, is optimization experiment mode of the invention,
The scope of protection of the invention is not limited only to above-mentioned case study on implementation.Technical solution under all inventions based on this thinking belongs to
Protection scope of the present invention, improvement and modification without departing from the principle of the present invention are regarded as protection model of the invention
It encloses.
Claims (6)
1. the preparation method of the surface composite coating based on dual polar plates of proton exchange membrane fuel cell, the specific steps are as follows:
(1) pretreatment of metal: using copper wire welding to metal surface as contact conductor；Metal surface is carried out to be polishing to surface
It is smooth, it is spare after ultrasonic oil removing, cleaning；
(2) configuration of electropolymerization solution: by conducting polymer monomer, modified carbon powder nano particle and Bronsted acid ultrasonic disperse exist
In deionized water, electropolymerization solution for standby is prepared；
(3) electrochemistry formated of carbon dust doping conducting polymer Intelligent Composite coating: electrochemistry formated uses three-electrode system, with
Pretreated metal plate is working electrode in step (1), and silver-silver chloride electrode is reference electrode, and platinum electrode is auxiliary electrode；
Nitrogen is continuously passed through in the electropolymerization solution first configured into step (2)；Then metal plate is placed in the electropolymerization solution of configuration
In, carbon dust doping conducting polymer Intelligent Composite coating is prepared using electrochemical method for synthesizing；Compound painting is rinsed with deionized water
Layer surface, and the metal double polar plates for being deposited with carbon dust doping conducting polymer Intelligent Composite coating are put into vacuum oven and are added
The coating modified dual polar plates of proton exchange membrane fuel cell of carbon dust doping conducting polymer Intelligent Composite is made in heat cure.
2. preparation method according to claim 1, it is characterised in that the conducting polymer monomer be pyrroles, aniline or
Thiophene monomer；Bronsted acid is hydrochloric acid, sulfuric acid, oxalic acid or acetic acid.
3. preparation method according to claim 1, it is characterised in that the metal is stainless steel, copper or aluminium alloy.
4. preparation method according to claim 1, it is characterised in that the concentration of Bronsted acid is in the electropolymerization solution
0.1~0.5mol L-1；The concentration of conducting polymer monomer is 0.05~0.5mol L-1；Modified carbon powder nano particle
Concentration is 0.1~1g L-1。
5. preparation method according to claim 1, it is characterised in that the electrochemical method for synthesizing is galvanostatic method, perseverance
Potentiometry or cyclic voltammetry；The wherein sedimentary condition of galvanostatic method are as follows: current density is 0.1~5mA cm-2, sedimentation time is
10~20min；The sedimentary condition of potentiostatic method are as follows: voltage is 0.75~1.15V, and sedimentation time is 10~20min；Cyclic voltammetric
The sedimentary condition of method are as follows: voltage range is -0.2~1.2V, and sweep speed is 20~50mV/s, and scanning circle number is 20~30 circles.
6. preparation method according to claim 1, it is characterised in that the temperature being heating and curing in vacuum oven be 60~
80 DEG C, the time being heating and curing is 4~6h.
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| RU2748967C1 (en) * | 2020-09-14 | 2021-06-02 | федеральное государственное бюджетное образовательное учреждение высшего образования "Южно-Российский государственный политехнический университет (НПИ) имени М.И. Платова" | Protective coating of bipolar plates of fuel cells with solid polymer electrolyte |
| CN113796866A (en) * | 2021-08-10 | 2021-12-17 | 中山大学 | Electrode and preparation method and application thereof |
| CN114318455A (en) * | 2022-03-10 | 2022-04-12 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
| CN114318455B (en) * | 2022-03-10 | 2022-06-17 | 季华实验室 | High-conductivity corrosion-resistant polymer composite coating, preparation method thereof and bipolar plate |
| 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 |
| CN117543038B (en) * | 2024-01-10 | 2024-04-12 | 武汉科技大学 | Modification preparation process of bipolar plate of proton exchange membrane fuel cell |
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