CN116154204A - Carbon film coating process for fuel cell plate - Google Patents
Carbon film coating process for fuel cell plate Download PDFInfo
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- CN116154204A CN116154204A CN202310182400.8A CN202310182400A CN116154204A CN 116154204 A CN116154204 A CN 116154204A CN 202310182400 A CN202310182400 A CN 202310182400A CN 116154204 A CN116154204 A CN 116154204A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 42
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- 230000008569 process Effects 0.000 title claims abstract description 32
- 239000007888 film coating Substances 0.000 title claims abstract description 10
- 238000009501 film coating Methods 0.000 title claims abstract description 10
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
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- 238000010438 heat treatment Methods 0.000 claims abstract description 24
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 71
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- 238000003756 stirring Methods 0.000 claims description 47
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- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
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- 239000002904 solvent Substances 0.000 claims description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229940106681 chloroacetic acid Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- -1 cyclohexanedione octahydrate Chemical compound 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
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- 244000137852 Petrea volubilis Species 0.000 description 3
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- 238000003828 vacuum filtration Methods 0.000 description 3
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- 230000002378 acidificating effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of surface treatment of metal materials, and particularly relates to a carbon film coating process for a fuel cell plate. Pretreating a substrate, placing the pretreated substrate in a carbon-containing solution, and finally performing heat treatment on the substrate to obtain a fuel cell plate with a carbon film on the surface, wherein in the process of preparing the carbon-containing solution, the cyclohexyl-hexaketone octahydrate and 3, 4-diaminophenol are reacted in an ethanol solution to obtain a rigid and nitrogen-rich organic material; then the carboxylated graphene oxide is prepared by reaction; the prepared fuel cell plate has small contact resistance, corrosion current density and good hydrophobicity, and the carbon layer and the base material have good binding force.
Description
Technical Field
The invention belongs to the technical field of surface treatment of metal materials, and particularly relates to a carbon film coating process for a fuel cell plate.
Background
The growth of energy demands of the modern industry has forced us to find and develop new energy sources to replace fossil fuels that are being exploited in large quantities and that lead to a deterioration of the ecological environment. The hydrogen energy is a clean and green renewable energy, and is certainly the key for solving the energy crisis. A fuel cell is a power generation device that directly converts fuel (typically hydrogen) into electric energy by an electrochemical reaction, and has great significance in solving energy crisis and environmental pollution. The main constituent components of the fuel cell are: electrodes, electrolyte separators, current collectors, and the like. The electrode is an electrochemical reaction place where fuel is subjected to oxidation reaction and oxidant is subjected to reduction reaction; the main function of the dielectric separator is to separate the oxidizing agent from the reducing agent and conduct ions; the collector is also called bipolar plate, and has functions of collecting current, separating oxidant from reductant, dredging reactant gas, etc. Bipolar plates, which are one of the key materials in fuel cells, are required to withstand various external loads and to operate in an acidic environment for a long period of time, which puts higher demands on the corrosion resistance of the bipolar plates.
The Chinese patent with application number 201710451190.2 discloses a functional coating of a metal bipolar plate of a fuel cell, which comprises a self-healing layer, a super-corrosion-resistant layer and a selectively deposited super-conductive layer, wherein the self-healing layer can automatically form a filler at a pinhole or mechanical damage part in the use process of the coating, and is easy to react with oxygen due to exposure to the outside, so that an oxidized filler is automatically formed, and the formed oxidized product has better corrosion resistance and better electric conductivity, thereby preventing further occurrence of corrosion reaction.
The Chinese patent with application number 202111055053.X discloses a corrosion-resistant coating of a metal bipolar plate of a fuel cell and a preparation process thereof, wherein the coating comprises a conductive adhesive colloid layer coated on the surface of the metal bipolar plate and a strong corrosion-resistant layer arranged on the outer surface of the conductive adhesive colloid layer, the metal bipolar plate is mechanically polished and cleaned, then the conductive adhesive colloid is coated on the surface of the metal bipolar plate to obtain an uncured pasty conductive adhesive colloid layer, the strong corrosion-resistant layer is cut to a specified shape and attached to the pasty conductive adhesive colloid layer, and pressure is applied, so that the preparation of the corrosion-resistant coating on the metal bipolar plate of the fuel cell is completed after the strong corrosion-resistant layer is fully contacted with the conductive adhesive colloid layer and the pressure is applied, thereby effectively avoiding the contact of the metal bipolar plate with corrosive medium in the environment of the fuel cell.
Various methods are used in the prior art to modify the corrosion resistance of a bipolar plate of a fuel cell, but the degree of bonding of the modifying layer to the bipolar plate substrate and the effect on the conductivity of the bipolar plate after introduction are not fully considered.
Disclosure of Invention
In order to solve the problems, the invention provides a carbon film coating process for a fuel cell plate, which is characterized in that a substrate is pretreated, the pretreated substrate is placed in a carbon-containing solution, and finally the pretreated substrate is subjected to heat treatment to obtain the fuel cell plate with the carbon film on the surface, wherein the prepared fuel cell plate has small contact resistance, corrosion current density and good hydrophobicity, and a carbon layer and the substrate have good bonding force.
The technical scheme provided by the invention for achieving the purpose is as follows:
a carbon film coating process for a fuel cell plate, comprising the following steps:
s1, pretreatment of a base material: stainless steel is selected as a base material to be mechanically polished, and an organic solvent is adopted to carry out ultrasonic vibration cleaning; when mechanical polishing is carried out, sand paper is adopted for polishing, and 600-mesh sand paper is preferably adopted for polishing the base material; the organic solvent is acetone or absolute ethanol, preferably acetone;
s2, preparing a carbon-containing solution:
1) Adding the cyclohexanecarbon octahydrate and 3, 4-diaminophenol into acetic acid, uniformly mixing, and then introducing inert gas into the mixture, wherein the inert gas is nitrogen or argon, and preferably nitrogen; raising the temperature to 105-125 ℃ under inert atmosphere, preferably raising the temperature to 115 ℃, refluxing at the temperature for 36-48h, preferably refluxing at the temperature for 42h, continuously stirring, and obtaining a mixed solution after the reaction is finished;
2) Adding graphite powder into concentrated sulfuric acid cooled to 0 ℃ and continuously stirring, adding potassium permanganate into the mixture in batches, keeping the temperature of the system at not higher than 20 ℃ in the whole operation process, putting the mixture into an ice water bath for continuously stirring for 20-40min, preferably 30min, raising the temperature to 30-35 ℃ and raising the temperature to 35 ℃, stopping stirring after keeping the temperature for 2-4h, preferably 4h, adding distilled water into the mixture, reducing the temperature to 50-60 ℃, preferably 50 ℃, adding distilled water and hydrogen peroxide into the mixture until the mixture turns from black brown to bright yellow, filtering the mixture while the mixture is hot, washing the mixture with dilute hydrochloric acid, washing the mixture with distilled water until the pH of the solution is 7, obtaining a graphite oxide solution, and stripping the graphite oxide solution by ultrasound to obtain a graphene oxide solution; adding chloroacetic acid and sodium hydroxide into the obtained graphene oxide solution, then placing the graphene oxide solution into a water bath, performing ultrasonic treatment for 1-2 hours, stirring for 18-24 hours, preferably ultrasonic treatment for 2 hours, stirring for 24 hours, performing vacuum filtration on the mixed solution, washing the mixed solution with a large amount of deionized water for multiple times, and drying to obtain carboxylated graphene oxide;
3) Adding the prepared mixed solution and carboxylated graphene oxide into N, N-dimethylformamide serving as a solvent, uniformly mixing, and then adding p-toluenesulfonic acid, thionyl chloride and phosphorus trichloride into the mixture, wherein the thionyl chloride and the phosphorus trichloride serving as accelerators can effectively promote the reaction, stirring and raising the temperature to 110-125 ℃, reacting for 4-6 hours, preferably raising the temperature to 120 ℃, reacting for 5 hours, and obtaining a carbon-containing solution after the reaction is finished;
s3, heat treatment, namely placing the substrate treated in the step S1 into the carbon-containing solution obtained in the step S2, then placing the substrate into an oven for heat treatment, wherein the heat treatment temperature is 120-140 ℃, the treatment time is 20-40min, preferably 130 ℃, the treatment time is 30min, and then placing the substrate into a tube furnace filled with inert gas for sectional heat treatment, so as to finally obtain the fuel cell plate with the carbon film on the surface; wherein the inert gas is high-purity argon; wherein the conditions of the sectional heat treatment are as follows: treating at 400-500 deg.C for 60-80min, and then treating at 800-900 deg.C for 1-2h, preferably under the condition of sectional heat treatment: treatment was carried out at 500℃for 60min, followed by treatment at 900℃for 2h.
The invention has the following beneficial effects:
firstly, pretreating a substrate in a mechanical polishing and organic solvent cleaning mode; then preparing a carbon-containing solution; and finally, placing the pretreated substrate into a carbon-containing solution, and performing heat treatment to obtain the fuel cell plate with the carbon film on the surface. In the process of preparing the carbon-containing solution, firstly, utilizing the reaction of the cyclohexanecarbon octahydrate and 3, 4-diaminophenol in ethanol solution to obtain the rigid nitrogen-rich organic material; then the carboxylated graphene oxide is prepared by reaction; hydroxyl contained in the organic material with rigidity and nitrogen enrichment and carboxyl contained in the carboxylated graphene oxide react to form a nitrogen enrichment and reticular structure; on one hand, the dispersion of carboxylated graphene oxide is effectively promoted, the carboxylated graphene oxide is prevented from agglomerating, and on the other hand, a large amount of nitrogen elements contained in the carboxylated graphene oxide can form chemical bonds between stainless steel substrates in the heat treatment process, so that the binding force between a carbon layer and the substrates is effectively enhanced, and the carboxylated graphene oxide is prevented from flaking.
Drawings
FIG. 1 is a schematic diagram of the process of preparing a carbonaceous solution according to the present invention.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Cyclohexanectone octahydrate CAS:7255-28-9;3, 4-diaminophenol CAS:615-72-5, potassium permanganate CAS:7722-64-7; hydrogen peroxide CAS:7722-84-1; chloroacetic acid CAS:79-11-8; sodium hydroxide CAS:1310-73-2; n, N-dimethylformamide CAS:68-12-2; p-toluenesulfonic acid CAS:104-15-4; the reagents used in the invention are all commonly and commercially available.
Example 1
A carbon film coating process for a fuel cell plate, comprising the following steps:
s1, pretreatment of a base material: selecting stainless steel as a base material, mechanically polishing the base material by using 600-mesh sand paper, and ultrasonically vibrating and cleaning by using acetone;
s2, preparing a carbon-containing solution:
1) Adding 18 parts by weight of cyclohexanedione octahydrate and 20 parts by weight of 3, 4-diaminophenol into 25 parts by weight of acetic acid, uniformly mixing, introducing nitrogen into the mixture, raising the temperature to 115 ℃ under inert atmosphere, refluxing for 42 hours at the temperature, continuously stirring, and obtaining a mixed solution after the reaction is finished;
2) Adding 12 parts by weight of graphite powder into concentrated sulfuric acid cooled to 0 ℃ and continuously stirring, adding 3 parts by weight of potassium permanganate into the mixture in batches, averagely dividing the potassium permanganate into 3 parts, adding one part each time, keeping the temperature of the system at not higher than 20 ℃, putting the system into an ice water bath for continuously stirring for 30min after the addition is completed, raising the temperature to 35 ℃, keeping the temperature for stirring for 4h, stopping stirring, adding 100 parts by weight of distilled water into the mixture, raising the temperature of the solution, when the temperature is lowered to 50 ℃, adding distilled water and hydrogen peroxide into the mixture until the mixture turns from black brown to bright yellow, filtering the mixture while the mixture is hot, washing the mixture for 2 times by using dilute hydrochloric acid, wherein the mass fraction of the dilute hydrochloric acid is 5%, washing the mixture by using distilled water until the pH of the solution is 7, obtaining a graphite oxide solution, and stripping the graphite oxide solution by ultrasonic waves to obtain a graphene oxide solution; adding 3 parts by weight of chloroacetic acid and 3.5 parts by weight of sodium hydroxide into the obtained graphene oxide solution, putting into a water bath, performing ultrasonic treatment for 2 hours, stirring for 24 hours, performing vacuum suction filtration, washing with a large amount of deionized water for many times, and drying to obtain carboxylated graphene oxide;
3) 50 parts by weight of N, N-dimethylformamide is taken as a solvent, 15 parts by weight of the prepared mixed solution and 5 parts by weight of carboxylated graphene oxide are added into the solvent, 3 parts by weight of p-toluenesulfonic acid, thionyl chloride and phosphorus trichloride are added into the mixture after the mixture is uniformly mixed, the mixture is stirred and the temperature is increased to 120 ℃, the reaction is carried out for 5 hours, and a carbon-containing solution is obtained after the reaction is finished;
s3, heat treatment, namely placing the substrate treated in the step S1 into the carbon-containing solution obtained in the step S2, then placing the substrate into an oven for heat treatment at 130 ℃ for 30min, and then placing the substrate into a tube furnace filled with inert gas for sectional heat treatment to finally obtain the fuel cell plate with the carbon film on the surface; wherein the inert gas is high-purity argon; wherein the conditions of the sectional heat treatment are as follows: treatment was carried out at 500℃for 60min, followed by treatment at 900℃for 2h.
Example 2
This example is different from example 1 in specific process parameters during the preparation process, and the remainder refers to example 1.
In step S2, 1), the temperature is raised to 105 ℃ under an inert atmosphere, and reflux is carried out at this temperature for 36h; 2) After finishing potassium permanganate, putting the potassium permanganate into an ice water bath, continuously stirring for 20min, then raising the temperature to 30 ℃, keeping the temperature for stirring for 2h, stopping stirring, adding distilled water into the potassium permanganate, and then adding distilled water and hydrogen peroxide into the potassium permanganate when the temperature is reduced to 60 ℃; adding chloroacetic acid and sodium hydroxide into the obtained graphene oxide solution, then putting into a water bath, performing ultrasonic treatment for 1h, stirring for 18h, performing vacuum filtration on the mixed solution, washing with a large amount of deionized water for many times, and drying; 3) After adding p-toluenesulfonic acid, stirring and raising the temperature to 110 ℃ for 4 hours.
In the step S3, placing the mixture into an oven for heat treatment at 120 ℃ for 20min; the conditions for the stage heat treatment were 400℃for 60min, followed by 800℃for 1h.
Example 3
This example is different from example 1 in specific process parameters during the preparation process, and the remainder refers to example 1.
In step S2, 1), the temperature is raised to 125 ℃ under an inert atmosphere, and reflux is carried out at this temperature for 48h; 2) After finishing potassium permanganate, putting the potassium permanganate into an ice water bath, continuously stirring for 40min, then raising the temperature to 35 ℃, keeping the temperature for stirring for 4h, stopping stirring, adding distilled water into the potassium permanganate, and then adding distilled water and hydrogen peroxide into the potassium permanganate when the temperature is reduced to 50 ℃; adding chloroacetic acid and sodium hydroxide into the obtained graphene oxide solution, then putting the graphene oxide solution into a water bath, performing ultrasonic treatment for 2 hours, stirring for 24 hours, performing vacuum filtration on the mixed solution, washing the mixed solution with a large amount of deionized water for many times, and then drying; 3) After adding p-toluenesulfonic acid, stirring and raising the temperature to 125 ℃ for reaction for 6h.
In the step S3, placing the mixture into an oven for heat treatment at the temperature of 140 ℃ for 40min; the conditions for the stage heat treatment were 450℃for 60min, followed by 900℃for 1h.
Comparative example 1
This comparative example uses the prepared mixed solution as a carbon-containing solution as compared with example 1, and the rest of the procedure is referred to in example 1.
The specific process is as follows:
s2, preparing a carbon-containing solution: adding 18 parts by weight of cyclohexanecarbon octahydrate and 20 parts by weight of 3, 4-diaminophenol into 25 parts by weight of acetic acid, uniformly mixing, introducing nitrogen into the mixture, raising the temperature to 115 ℃ under inert atmosphere, refluxing for 42 hours at the temperature, continuously stirring, and obtaining a mixed solution after the reaction is finished, namely the carbon-containing solution.
The remainder of the procedure is as in example 1.
Comparative example 2
This comparative example is different from example 1 in the preparation process of the carbonaceous solution, and the rest of the process is referred to example 1.
The specific process is as follows:
s2, preparing a carbon-containing solution:
1) Adding 18 parts by weight of cyclohexanedione octahydrate and 20 parts by weight of 3, 4-diaminophenol into 25 parts by weight of acetic acid, uniformly mixing, introducing nitrogen into the mixture, raising the temperature to 115 ℃ under inert atmosphere, refluxing for 42 hours at the temperature, continuously stirring, and obtaining a mixed solution after the reaction is finished;
2) Adding 12 parts by weight of graphite powder into concentrated sulfuric acid cooled to 0 ℃ and continuously stirring, adding 3 parts by weight of potassium permanganate into the mixture in batches, averagely dividing the potassium permanganate into 3 parts, adding one part each time, keeping the temperature of the system at not higher than 20 ℃, putting the mixture into an ice water bath for continuously stirring for 30min after the addition is completed, raising the temperature to 35 ℃, keeping the temperature for stirring for 4h, stopping stirring, adding 100 parts by weight of distilled water into the mixture, raising the temperature of the solution, when the temperature is lowered to 50 ℃, adding distilled water and hydrogen peroxide into the mixture until the mixture turns from black brown to bright yellow, filtering the mixture while the mixture is hot, washing the mixture for 2 times with dilute hydrochloric acid, wherein the mass fraction of the dilute hydrochloric acid is 5%, washing the mixture with distilled water until the pH of the solution is 7, obtaining a graphene oxide solution, peeling the graphene oxide solution by ultrasonic wave, and carrying out vacuum suction filtration and drying to obtain graphene oxide;
3) 50 parts by weight of N, N-dimethylformamide is taken as a solvent, 15 parts by weight of the prepared mixed solution and 5 parts by weight of graphene oxide are added into the solvent, and the mixture is stirred and mixed uniformly to obtain a carbon-containing solution.
The remainder of the procedure is as in example 1.
Comparative example 3
This comparative example uses carboxylated graphene oxide as a carbon-containing solution compared to example 1, and the rest of the procedure is referred to in example 1.
The specific process is as follows:
s2, preparing a carbon-containing solution: adding 12 parts by weight of graphite powder into concentrated sulfuric acid cooled to 0 ℃ and continuously stirring, adding 3 parts by weight of potassium permanganate into the mixture in batches, averagely dividing the potassium permanganate into 3 parts, adding one part each time, keeping the temperature of the system at not higher than 20 ℃, putting the system into an ice water bath for continuously stirring for 30min after the addition is completed, raising the temperature to 35 ℃, keeping the temperature for stirring for 4h, stopping stirring, adding 100 parts by weight of distilled water into the mixture, raising the temperature of the solution, when the temperature is lowered to 50 ℃, adding distilled water and hydrogen peroxide into the mixture until the mixture turns from black brown to bright yellow, filtering the mixture while the mixture is hot, washing the mixture for 2 times by using dilute hydrochloric acid, wherein the mass fraction of the dilute hydrochloric acid is 5%, washing the mixture by using distilled water until the pH of the solution is 7, obtaining a graphite oxide solution, and stripping the graphite oxide solution by ultrasonic waves to obtain a graphene oxide solution; adding 3 parts by weight of chloroacetic acid and 3.5 parts by weight of sodium hydroxide into the obtained graphene oxide solution, putting into a water bath, performing ultrasonic treatment for 2 hours, stirring for 24 hours, performing vacuum suction filtration, washing with a large amount of deionized water for many times, and drying to obtain carboxylated graphene oxide; 50 parts by weight of N, N-dimethylformamide is taken as a solvent, 5 parts by weight of the prepared carboxylated graphene oxide is added into the solvent, and the mixture is uniformly mixed to obtain a carbon-containing solution.
The remainder of the procedure is as in example 1.
Comparative example 4
This comparative example was compared to example 1 in that the mixing was directly performed with carboxylated graphene oxide during the preparation of the carbon-containing solution, and the rest of the procedure was referred to example 1.
The specific process is as follows:
s2, preparing a carbon-containing solution:
1) Adding 18 parts by weight of cyclohexanedione octahydrate and 20 parts by weight of 3, 4-diaminophenol into 25 parts by weight of acetic acid, uniformly mixing, introducing nitrogen into the mixture, raising the temperature to 115 ℃ under inert atmosphere, refluxing for 42 hours at the temperature, continuously stirring, and obtaining a mixed solution after the reaction is finished;
2) Adding 12 parts by weight of graphite powder into concentrated sulfuric acid cooled to 0 ℃ and continuously stirring, adding 3 parts by weight of potassium permanganate into the mixture in batches, averagely dividing the potassium permanganate into 3 parts, adding one part each time, keeping the temperature of the system at not higher than 20 ℃, putting the system into an ice water bath for continuously stirring for 30min after the addition is completed, raising the temperature to 35 ℃, keeping the temperature for stirring for 4h, stopping stirring, adding 100 parts by weight of distilled water into the mixture, raising the temperature of the solution, when the temperature is lowered to 50 ℃, adding distilled water and hydrogen peroxide into the mixture until the mixture turns from black brown to bright yellow, filtering the mixture while the mixture is hot, washing the mixture for 2 times by using dilute hydrochloric acid, wherein the mass fraction of the dilute hydrochloric acid is 5%, washing the mixture by using distilled water until the pH of the solution is 7, obtaining a graphite oxide solution, and stripping the graphite oxide solution by ultrasonic waves to obtain a graphene oxide solution; adding 3 parts by weight of chloroacetic acid and 3.5 parts by weight of sodium hydroxide into the obtained graphene oxide solution, putting into a water bath, performing ultrasonic treatment for 2 hours, stirring for 24 hours, performing vacuum suction filtration, washing with a large amount of deionized water for many times, and drying to obtain carboxylated graphene oxide;
3) 50 parts by weight of N, N-dimethylformamide is taken as a solvent, 15 parts by weight of the prepared mixed solution and 5 parts by weight of carboxylated graphene oxide are added into the solvent, and the mixture is uniformly mixed to obtain the carbon-containing solution.
The remainder of the procedure is as in example 1.
Correlation test:
1. conductivity test
Surface contact electric was performed on the fuel cell plates prepared in examples 1 to 3 and comparative examples 1 to 4, respectivelyResistance test, test data were that the contact resistance (mΩ·cm) of the fuel cell plate and the carbon paper was tested under a pressure of 0.6MPa 2 ) The test data obtained are shown in table 1.
2. Corrosion resistance test
The fuel cell plates prepared in examples 1 to 3 and comparative examples 1 to 4 were tested for corrosion current density (A/cm) by linear potential scanning 2 ) The scan rate was 1mV/s, the potential scan range was-0.5V-1.3V, and the corrosion current density (A/cm) at a potential of 0.6V was recorded 2 ). (the corrosion resistance of the panel is based on the corrosion current density of less than 1X 10 when the potential is 0.6V -6 A/cm 2 ) The test data are shown in table 1.
TABLE 1
| Sample of | Contact resistance (mΩ·cm) 2 ) | Corrosion current Density (A/cm) 2 ) |
| Example 1 | 0.95 | 0.56 |
| Example 2 | 1.10 | 0.62 |
| Example 3 | 1.15 | 0.68 |
| Comparative example 1 | 7.52 | 5.48 |
| Comparative example 2 | 3.65 | 2.46 |
| Comparative example 3 | 5.38 | 6.09 |
| Comparative example 4 | 2.47 | 1.53 |
From the test data, it can be seen that the samples prepared in examples 1-3 have a contact resistance less than that of the samples prepared in comparative examples 1-4, and exhibit good conductivity; wherein the conductivity was optimal as in example 1; the greater the corrosion current density, the smaller the charge transfer resistance, and the poorer the corrosion resistance of the material, and as can be seen from the data in table 1, the corrosion resistance of the sample prepared in example 1 is best as demonstrated by the minimum corrosion current density measured in example 1.
3. Water contact angle test
The water contact angle test is an index for describing the hydrophilic and hydrophobic properties of the surface of a material, and is an important parameter for measuring the surface energy of the material. In this test, the surface water contact angle of the prepared panel was measured using an optical contact angle measuring instrument DSA 100, and the detection results are shown in table 2.
4. Binding force test
The bonding force between the carbon film and the substrate directly affects whether the carbon film is easily peeled off or not, which is an important index for measuring the durability of the carbon film, and the bonding force between the carbon film on the surface of the fuel cell plates prepared in examples 1 to 3 and comparative examples 1 to 4 and the substrate was measured by using a An Dongpa (Switzerland CSM) micrometer scratcher, and the detection results are shown in Table 2.
TABLE 2
As can be seen from the data in table 2, examples 1 to 3 and comparative example 1 show hydrophobic properties, while comparative examples 2 to 4 show hydrophilic properties, and the reaction product of the fuel cell is water during operation, and when the prepared carbon film shows good hydrophobicity, the timely discharge of the water generated during the operation of the fuel cell is facilitated. As can be seen from the binding force test data, the binding force of example 1 was the highest among all the samples, i.e., the binding force between the carbon film prepared in example 1 and the substrate was the strongest.
The operating environment of the fuel cell is acidic and the operating temperature is relatively high, so the corrosion resistance of the fuel cell plate is critical. The invention provides a carbon film coating process for a fuel cell plate, which comprises the steps of firstly, pretreating a base material in a mechanical polishing and organic solvent cleaning mode; then preparing a carbon-containing solution; and finally, placing the pretreated substrate into a carbon-containing solution, and performing heat treatment to obtain the fuel cell plate with the carbon film on the surface. The reaction mechanism involved in preparing the carbon-containing solution is shown in fig. 1, and first, cyclohexanedione octahydrate and 3, 4-diaminophenol are mixed in an ethanol solution, and reflux is performed at an elevated temperature under an inert atmosphere to obtain a mixed solution. In the process, the cyclohexanetrione octahydrate reacts with amino groups on 3, 4-diaminophenol to form a ring, so that a rigid and nitrogen-rich organic material is formed; further, adding graphite powder into concentrated sulfuric acid cooled to 0 ℃, adding potassium permanganate into the concentrated sulfuric acid in batches, controlling the temperature to be continuously stirred within a certain range, adding distilled water into the mixture, adding distilled water and hydrogen peroxide into the mixture when the temperature is reduced to about 50 ℃, filtering and washing the mixture when the mixture turns from black brown to bright yellow to obtain graphene oxide, and continuing to obtain the graphene oxideChloroacetic acid and sodium hydroxide are added to react under certain conditions to obtain carboxylated graphene oxide; graphene is a kind of graphene with sp 2 The hybridized and connected carbon atoms are closely stacked to form a single-layer two-dimensional honeycomb lattice structure material, besides a honeycomb layered structure that sigma bonds are connected with other carbon atoms to form a hexagonal ring, pz orbits of each carbon atom perpendicular to a layer plane can form multi-atom large pi bonds penetrating through the whole layer, and the material has excellent electric conductivity, heat conductivity and structural stability, higher strength and good toughness on the surface; in the invention, the obtained graphene is treated to obtain the functionalized graphene, and functional groups such as carboxyl are introduced into the graphene; further taking N, N-dimethylformamide as a solvent, adding the prepared mixed solution and carboxylated graphene oxide into the solvent, taking p-toluenesulfonic acid as a catalyst, adding thionyl chloride and phosphorus trichloride into the catalyst as an accelerator, and reacting hydroxyl contained in the prepared rigid and nitrogen-rich organic material with carboxyl contained in the carboxylated graphene oxide to further form a nitrogen-rich and reticular structure; the formed reticular structure has a plurality of benzene ring-like rigid structures, so that the reticular structure has good stability; in addition, in the reaction process, the carboxylated graphene oxide can be further dispersed, and agglomeration of the carboxylated graphene oxide is prevented, so that the prepared carbon film has good uniformity; the prepared nitrogen-rich and netlike structure contains a large amount of nitrogen elements, and the nitrogen elements can form chemical bonds with metal elements contained in the stainless steel substrate in the heat treatment process, so that the binding force between the carbon layer and the substrate can be effectively enhanced, and the carbon layer is prevented from peeling.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A carbon film coating process for a fuel cell plate, comprising the steps of:
s1, pretreatment of a base material: stainless steel is selected as a base material to be mechanically polished, and an organic solvent is adopted to carry out ultrasonic vibration cleaning;
s2, preparing a carbon-containing solution:
1) Adding cyclohexanedione octahydrate and 3, 4-diaminophenol into acetic acid, uniformly mixing, introducing inert gas into the mixture, raising the temperature to 105-125 ℃ in inert atmosphere, refluxing at the temperature for 36-48h, continuously stirring, and obtaining mixed solution after the reaction is finished;
2) Adding graphite powder into concentrated sulfuric acid cooled to 0 ℃ and continuously stirring, adding potassium permanganate into the mixture in batches, keeping the temperature of the system at not higher than 20 ℃ in the whole operation process, putting the mixture into an ice water bath for continuously stirring for 20-40min after the addition is completed, raising the temperature to 30-35 ℃, keeping the temperature for stirring for 2-4h, stopping stirring, adding distilled water into the mixture, adding distilled water and hydrogen peroxide into the mixture when the temperature is reduced to 50-60 ℃ until the mixture turns from black brown to bright yellow, filtering the mixture while the mixture is hot, washing the mixture with dilute hydrochloric acid, flushing the mixture with distilled water until the pH of the solution is 7, obtaining a graphite oxide solution, and stripping the graphite oxide solution by ultrasound to obtain the graphene oxide solution; adding chloroacetic acid and sodium hydroxide into the obtained graphene oxide solution, then putting the graphene oxide solution into a water bath, performing ultrasonic treatment for 1-2 hours, stirring for 18-24 hours, performing vacuum suction filtration, washing with a large amount of deionized water for multiple times, and drying to obtain carboxylated graphene oxide;
3) Adding the prepared mixed solution and carboxylated graphene oxide into N, N-dimethylformamide serving as a solvent, uniformly mixing, adding p-toluenesulfonic acid, thionyl chloride and phosphorus trichloride into the mixture, stirring and raising the temperature to 110-125 ℃, and reacting for 4-6h to obtain a carbon-containing solution after the reaction is finished;
s3, heat treatment, namely placing the substrate treated in the step S1 into the carbon-containing solution obtained in the step S2, then placing the substrate into an oven for heat treatment at the temperature of 120-140 ℃ for 20-40min, and then placing the substrate into a tube furnace filled with inert gas for sectional heat treatment, thereby finally obtaining the fuel cell plate with the carbon film on the surface.
2. The process of claim 1, wherein the substrate is polished with 600 mesh sandpaper during mechanical polishing.
3. The process of claim 1, wherein the organic solvent is acetone or absolute ethanol.
4. The process of claim 1, wherein the inert gas used in step S2 is nitrogen or argon.
5. The process of claim 1, wherein the inert gas used in step S3 is high purity argon.
6. The carbon film coating process for a fuel cell plate according to claim 1, wherein the conditions of the stage heat treatment in step S3 are: treating at 400-500 deg.C for 60-80min, and then treating at 800-900 deg.C for 1-2 hr.
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Denomination of invention: A Carbon Film Coating Process for Fuel Cell Panels Granted publication date: 20230725 Pledgee: Zhejiang Chongzhou Commercial Bank Co.,Ltd. Pujiang Sub branch Pledgor: ZHEJIANG FITER TECHNOLOGY Co.,Ltd. Registration number: Y2024980000243 |