CN111082089A - Metal bipolar plate with heterogeneous coatings on surfaces of runner grooves and ridges and preparation method thereof - Google Patents
Metal bipolar plate with heterogeneous coatings on surfaces of runner grooves and ridges and preparation method thereof Download PDFInfo
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- CN111082089A CN111082089A CN201911406310.2A CN201911406310A CN111082089A CN 111082089 A CN111082089 A CN 111082089A CN 201911406310 A CN201911406310 A CN 201911406310A CN 111082089 A CN111082089 A CN 111082089A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
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- 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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- 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
Abstract
The invention relates to a metal bipolar plate with heterogeneous coatings on the surfaces of a runner groove and a ridge, in particular to a metal bipolar plate for a proton exchange membrane fuel cell, wherein the inner surface of the runner groove is provided with a hydrophilic coating, the surface of the ridge is provided with a noble metal coating, the coating on the inner surface of the runner groove of the metal bipolar plate can obviously improve the spontaneous diffusion capability of generated water on the inner surface of the runner in the working process of the fuel cell, so that the runner is effectively prevented from being blocked by liquid drops, and the noble metal coating on the contact part of the ridge and carbon paper can play double effects of reducing the contact resistance of the bipolar plate and a membrane electrode and improving the corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of fuel cell stacks, and particularly relates to a metal bipolar plate with heterogeneous coatings on surfaces of runner grooves and ridges and a preparation method thereof.
Background
Bipolar plates are a key component of a fuel cell stack and their mass, volume and cost determine to a large extent the total mass, volume and cost of the stack. The bipolar plate plays important roles in guiding current in the fuel cell stack, uniformly distributing fuel and oxidant in each unit cell, separating each unit cell, and promoting water management of unit cells.
To accomplish these functions, a wide variety of materials have been used to form bipolar plates. The non-porous graphite plate is used as the material of the bipolar plate in the early period, because the graphite has high conductivity and good chemical stability under the special condition of the fuel cell, but the graphite has the defects of frangibility, lack of mechanical strength and high processing cost of the flow channel, and the large-scale manufacturing of the graphite bipolar plate is also limited. The use of a mixture of polymer and graphite powder as an alternative to pure graphite can be used to make composite bipolar plates, and injection molding using industrially formed thermoplastics or BMC using thermosets can be made on a large scale. The composite bipolar plate with graphite matrix may be prepared with polypropylene, vulcanized polyphenylene, phenolic resin and vinyl ester resin as dopant. The doping of the polymer ensures that the bipolar plate has certain flexibility, enhances the mechanical strength of the bipolar plate and has no serious influence on the chemical stability of the bipolar plate.
However, since the polymer is an insulator, its doping increases the resistance of the bipolar plate to some extent. Therefore, there is a need to design composite bipolar plates that ensure mechanical properties without sacrificing electrical conductivity. Although composite bipolar plates have the advantages of low weight, high yield and stable chemical properties, the disadvantages of lower mechanical strength and poor electrical conductivity of composite bipolar plates are particularly evident in terms of overall performance compared to metallic bipolar plates. In view of the application of fuel cells to vehicles, the metallic bipolar plates have better stability in this respect, since shocks and vibrations may cause fuel cell rupture and reactant leakage. Some research data indicates that the metallic bipolar plate has an electrical conductivity that is many thousands times that of the composite bipolar plate, and in addition, the lower processing cost makes the metallic bipolar plate more competitive in the fuel cell market. However, under the acidic and humid conditions of PEM fuel cells, the surface of the metal bipolar plate is easily corroded, thereby reducing the performance of the bipolar plate, which is a great obstacle to the popularization of the metal bipolar plate. The working temperature of the fuel cell is about 80 ℃, the pH value is 2-4, the metal surface can be decomposed under the condition, the dissolved ions can poison the membrane electrode to reduce the output power of the fuel cell, and the surface passivation of the bipolar plate reduces the conductivity of the bipolar plate. Thus, the formation of surface oxides increases the contact resistance of the bipolar plate, still adversely affecting the conversion efficiency of the fuel cell.
The above problems can be overcome or properly reduced by coating the surface of the metal bipolar plate. Furthermore, most types of fuel cells require a specific relative humidity. During operation of the fuel cell, moisture may enter the anode flow channels and the cathode flow channels due to the reactant gases being humidified or due to water generated at the cathode. As the water droplet size increases, the flow channels are closed and the reactant gas is diverted to other flow channels because the channels flow in a generally parallel direction between the common inlet and outlet manifolds, because the reactant gas may not flow through channels that are blocked by water and therefore cannot push water out of the channels. As more and more flow channels become clogged with water, the power generated by the fuel cell decreases. Because the fuel cells are electrically connected in series, if one fuel cell stops operating, the entire fuel cell stack may also stop operating. The accumulated water in the flow channels can typically be purged by periodically forcing the reactant gas through the flow channels at a higher flow rate. However, this increases the parasitic efficiency of the air compressor, thereby reducing the overall system efficiency.
It is therefore important to apply to the surface of the bipolar plate a coating which is advantageous for increasing the corrosion resistance of the bipolar plate and for draining water, for example: one, in publication No. CN 101792899A, discloses a fuel cell component having a durable conductor and a hydrophilic coating, the component having thereon a binary and ternary nitride and oxynitride coating comprising elements of groups IVb and vb of the periodic Table of elements, the coating comprising TiZrN, NbTiN and TaZrN and an oxynitride comprising NbTiOxNy, TiZrOxNy and TaZrOxNy, wherein 0.001 ≦ x ≦ 1 and 0.1 ≦ y ≦ 2; second, in patent publication No. CN 101375442a, there is disclosed a fuel cell bipolar plate having a hydrophilic coating, the coating including nanoparticles (SiO2, HfO2, ZrO2, Al2O3, SnO2, Ta2O5, Nb2O5, MoO2, IrO2, RuO2), the coating further including hydrophilic side chains (amino, sulfonate, sulfate, sulfite, sulfonamide, sulfoxide, carboxylate, polyol, polyether, phosphate), the coating further including a conductive material (Au, Ag, Ru, Rh, Pb, Re, Os, Ir, Pt, polymeric carbon, or graphite); a fuel cell bipolar plate with variable surface properties is disclosed in publication No. CN 101499533 a, wherein one embodiment comprises a first fuel cell element (bipolar plate) comprising a first face, a first hydrophilic coating disposed over at least a first portion (gas flow channels) of the first face, and a non-hydrophilic coating disposed over at least a second portion (plate platform) of the first face. The hydrophilic coating is a metal oxide (SiO2, HfO2, ZrO2, Al2O3, SnO2, Ta2O5, Nb2O5, MoO2, IrO2 and RuO2) coating, and the non-hydrophilic coating is mainly PTFE. The technical scheme can reduce the accumulation of water in the bipolar plate flow channel, but has the defect of complicated preparation process.
Disclosure of Invention
The invention aims to provide a metal bipolar plate with heterogeneous coatings on the surfaces of a runner groove and a ridge, in particular to a metal bipolar plate for a proton exchange membrane fuel cell, wherein the inner surface of the runner groove is a hydrophilic coating, the surface of the ridge is a noble metal coating, the coating on the inner surface of the runner groove of the metal bipolar plate can obviously improve the spontaneous diffusion capability of generated water on the inner surface of the runner in the working process of the fuel cell, so that the runner is effectively prevented from being blocked by liquid drops, and the noble metal coating on the contact part of the ridge and carbon paper can play double effects of reducing the contact resistance of the bipolar plate and a membrane electrode and improving the corrosion resistance of the bipolar plate.
The purpose of the invention is realized by the following technical scheme:
a metal bipolar plate with heterogeneous coatings on the surfaces of runner grooves and ridges is characterized in that the inner surface of a runner of the metal bipolar plate is provided with a polydopamine hydrophilic coating, and the surfaces of the ridges are provided with precious metal coatings.
As a more excellent technical scheme of the invention, the thickness of the polydopamine hydrophilic coating is 5nm-5000nm, and the thickness of the noble metal coating is 5nm-5000 nm.
As a more preferable technical scheme of the invention, the surface of the hydrophilic coating has a contact angle of less than 60 degrees.
As a more preferable technical scheme of the invention, the noble metal is platinum or gold.
The invention also provides a preparation method of the metal bipolar plate with the surfaces of the runner grooves and the ridges being the heterogeneous coatings, which comprises the following steps:
step one, putting the punched and cleaned stainless steel bipolar plate into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, keeping the temperature of the furnace chamber at 20-200 ℃, and then introducing argon into the furnace chamber at the speed of 50-500 ml/min to keep the vacuum degree in the furnace chamber at 0.1-2 Pa; the ion source voltage is loaded to 100V-1000V, the duty ratio is 10% -100%, the substrate bias voltage is loaded to-1000V to-100V, and the duty ratio is 10% -100%; the bombardment time of the high-energy argon ions is 1min-60 min; the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished;
step two, placing the treated stainless steel bipolar plate into a dopamine solution with the pH value of 8-10.5, treating for 2-48h at 20-30 ℃, then taking out the stainless steel bipolar plate, leaching with deionized water, and drying for 0.5-3h at 80-100 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface;
thirdly, dispensing silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the upper surface of the silica gel in the flow channel is 0.05mm-0.2mm lower than the surface of the ridge, standing for 2-24 hours at room temperature, and curing the silica gel in the flow channel;
putting the stainless steel bipolar plate into a chloroauric acid or chloroplatinic acid aqueous solution with the concentration of 1% -10%, ultrasonically mixing for 1-12h, reducing noble metal ions in the chloroauric acid or the chloroplatinic acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the noble metal ions on the surface of the stainless steel bipolar plate ridge, taking out the stainless steel bipolar plate and leaching the stainless steel bipolar plate with deionized water for 1-10min to obtain the bipolar plate with the noble metal particle layer on the surface of the ridge; and taking down the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the inner surface of the flow channel groove being provided with the polydopamine coating and the ridge surface being provided with the noble metal coating.
As a more excellent technical scheme of the invention, the silica gel is a commercially available two-component room temperature vulcanized silicone mold silica gel.
The invention has the following beneficial effects:
the corrosion-resistant hydrophilic coating is coated on the inner surface of the bipolar plate flow channel, so that water generated by reaction can spontaneously diffuse on the inner surface of the flow channel and exists in a film form, the flow channel is effectively prevented from being blocked by liquid drops, and the noble metal coating on the contact part of the ridge and the carbon paper simultaneously plays double roles of reducing the contact resistance of the bipolar plate and the membrane electrode and improving the corrosion resistance of the bipolar plate.
The hydrophilic coating is polydopamine, and catechol groups and amino groups exist in dopamine molecules, so that the dopamine is easily oxidized into a quinoid structure, can be combined with the surface of a metal matrix, and can construct a hydrophilic biocompatible surface and a corrosion-resistant surface on the metal surface. Meanwhile, the nitrogen and phenol groups in the molecular structure of the poly-dopamine can be reduced in situ to obtain the poly-dopamine functionalized metal nanoparticles under the condition of no reducing agent or stabilizing agent under the adsorption effect on metal ions. Therefore, the precious metal can be reduced in situ by the polydopamine coated on the surface of the ridge of the metal bipolar plate, and then the precious metal coating is formed on the surface of the ridge.
Drawings
FIG. 1 is a schematic view of the surface of a metallic bipolar plate coated with a poly-dopamine coating according to the present invention;
fig. 2 is a schematic view of silica gel filled in the flow channel when the precious metal coating is formed on the ridge surface (the filling of silica gel prevents the poly-dopamine coating on the inner surface of the channel groove of the flow channel from being reduced);
FIG. 3 is a schematic view of a bipolar plate with a polydopamine coating on the inner surface of the flow channel and a noble metal coating on the surface of the ridge according to the present invention;
wherein 1 is an anode plate, 2 is a cathode plate, 3 is a noble metal coating, 4 is a polydopamine coating, 5 is a cooling water flow passage, and 6 is silica gel.
Detailed Description
The following is a detailed description of the embodiments of the present invention, which is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
As shown in fig. 1-3, the present invention provides a metal bipolar plate with heterogeneous coating on the surfaces of the flow channel grooves and the ridges, wherein the inner surface of the flow channel of the metal bipolar plate is provided with a polydopamine hydrophilic coating, and the surfaces of the ridges are provided with noble metal coatings. The thickness of the polydopamine hydrophilic coating is 5nm-5000nm, and the thickness of the noble metal coating is 5nm-5000 nm. The hydrophilic coating surface has a contact angle of less than 60 °.
Example 1
The embodiment is realized by the following steps:
firstly, putting the stainless steel bipolar plate which is punched and formed and cleaned into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, the temperature in the furnace chamber is room temperature, and then argon is introduced into the furnace chamber at a rate of 70ml/min to maintain the vacuum degree in the furnace chamber at 0.5 Pa. The ion source voltage is loaded to 500V, the duty ratio is 50%, the matrix bias voltage is loaded to-600V, and the duty ratio is 50%. The bombardment time of the high-energy argon ions is 10 min. And then the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished.
And secondly, putting the treated stainless steel bipolar plate into a dopamine solution with the pH value of 8.5, completely immersing the stainless steel bipolar plate, treating the stainless steel bipolar plate for 3 hours at the temperature of 20 ℃, taking out the stainless steel bipolar plate, leaching the stainless steel bipolar plate with deionized water, and drying the stainless steel bipolar plate for 0.5 hour at the temperature of 80 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface.
And thirdly, dispensing the silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the dispenser can automatically dispense the silica gel according to the flow channel track input into a computer in advance, the dispensing amount is controllable, the mass repeated operation is facilitated, the upper surface of the silica gel in the flow channel is 0.05mm lower than the surface of the ridge, and the silica gel is placed in a static state for 12 hours at room temperature until the silica gel in the flow channel is cured. Silica gel is added into the flow channel to effectively prevent the poly dopamine layer on the inner surface of the flow channel groove from being reduced into noble metal in the fourth step. The silica gel is commercially available two-component room temperature vulcanized silicone mold silica gel.
And fourthly, putting the stainless steel bipolar plate into 5% chloroauric acid aqueous solution, carrying out ultrasonic mixing for 2 hours, reducing gold ions in the chloroauric acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the gold ions on the surface of the stainless steel bipolar plate ridge, taking out the stainless steel bipolar plate ridge, and leaching the stainless steel bipolar plate ridge for 2 minutes by using deionized water to obtain the bipolar plate with the gold nanoparticle layer on the surface of the ridge. And taking off the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the polydopamine coating and the nanogold coating on the ridge in the flow channel.
Example 2
The embodiment is realized by the following steps:
firstly, putting the stainless steel bipolar plate which is punched and formed and cleaned into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, the temperature in the furnace chamber is kept at 100 ℃, and then argon is introduced into the furnace chamber at the speed of 100ml/min, so that the vacuum degree in the furnace chamber is kept at 0.8 Pa. The ion source voltage is loaded to 800V, the duty ratio is 60%, the substrate bias voltage is loaded to-600V, and the duty ratio is 60%. The bombardment time of high-energy argon ions is 5 min. And then the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished.
And secondly, putting the treated stainless steel bipolar plate into a dopamine solution with the pH value of 9, completely immersing the stainless steel bipolar plate, treating the stainless steel bipolar plate for 12 hours at the temperature of 25 ℃, taking out the stainless steel bipolar plate, leaching the stainless steel bipolar plate with deionized water, and drying the stainless steel bipolar plate for 1 hour at the temperature of 100 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface.
And thirdly, injecting the silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the dispenser can automatically dispense the silica gel according to the flow channel track input into a computer in advance, the dispensing amount is controllable, the mass repeated operation is facilitated, the upper surface of the silica gel in the flow channel is 0.1mm lower than the surface of the ridge, and the silica gel is placed in a static state for 12 hours at room temperature until the silica gel in the flow channel is cured. Silica gel is added into the flow channel to effectively prevent the poly dopamine layer on the inner surface of the flow channel groove from being reduced into noble metal in the fourth step. The silica gel is commercially available two-component room temperature vulcanized silicone mold silica gel.
And fourthly, putting the stainless steel bipolar plate into 7% chloroauric acid aqueous solution, carrying out ultrasonic mixing for 4 hours, reducing gold ions in the chloroauric acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the gold ions on the surface of the stainless steel bipolar plate ridge, taking out the stainless steel bipolar plate ridge, and leaching the stainless steel bipolar plate ridge for 3 minutes by using deionized water to obtain the bipolar plate with the gold nanoparticle layer on the surface of the ridge. And taking off the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the polydopamine coating and the nanogold coating on the ridge in the flow channel.
Example 3
The embodiment is realized by the following steps:
firstly, putting the stainless steel bipolar plate which is punched and formed and cleaned into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, the temperature in the furnace chamber is kept at 150 ℃, and then argon is introduced into the furnace chamber at the speed of 200ml/min, so that the vacuum degree in the furnace chamber is kept at 1 Pa. The ion source voltage is loaded to 800V, the duty ratio is 50%, the matrix bias voltage is loaded to-800V, and the duty ratio is 50%. The bombardment time of the high-energy argon ions is 10 min. And then the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished.
And secondly, putting the treated stainless steel bipolar plate into a dopamine solution with the pH value of 9.5, completely immersing the stainless steel bipolar plate, treating the stainless steel bipolar plate for 24 hours at the temperature of 25 ℃, taking out the stainless steel bipolar plate, leaching the stainless steel bipolar plate with deionized water, and drying the stainless steel bipolar plate for 1 hour at the temperature of 90 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface.
And thirdly, injecting the silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the dispenser can automatically dispense the silica gel according to the flow channel track input into a computer in advance, the dispensing amount is controllable, the mass repeated operation is facilitated, the upper surface of the silica gel in the flow channel is 0.15mm lower than the surface of the ridge, and the silica gel is placed in a static state for 12 hours at room temperature until the silica gel in the flow channel is cured. Silica gel is added into the flow channel to effectively prevent the poly dopamine layer on the inner surface of the flow channel groove from being reduced into noble metal in the fourth step. The silica gel is commercially available two-component room temperature vulcanized silicone mold silica gel.
And fourthly, putting the stainless steel bipolar plate into a chloroplatinic acid aqueous solution with the concentration of 9%, ultrasonically mixing for 3 hours, reducing platinum ions in the chloroplatinic acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the platinum ions on the surface of the stainless steel bipolar plate ridge, taking out the stainless steel bipolar plate ridge, and leaching for 5 minutes by deionized water to obtain the bipolar plate with the platinum nanoparticle layer on the surface of the ridge. And taking off the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the flow channel groove inner surface being provided with the polydopamine coating and the ridge surface being provided with the nano platinum coating.
Example 4
The embodiment is realized by the following steps:
firstly, putting the stainless steel bipolar plate which is punched and formed and cleaned into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, the temperature in the furnace chamber is kept at 150 ℃, and then argon is introduced into the furnace chamber at the speed of 300ml/min, so that the vacuum degree in the furnace chamber is kept at 1.5 Pa. The ion source voltage is loaded to 900V, the duty ratio is 50%, the matrix bias voltage is loaded to-900V, and the duty ratio is 50%. The bombardment time of high-energy argon ions is 5 min. And then the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished.
And secondly, putting the treated stainless steel bipolar plate into a dopamine solution with the pH value of 8.5, completely immersing the stainless steel bipolar plate, treating the stainless steel bipolar plate for 36 hours at the temperature of 25 ℃, taking out the stainless steel bipolar plate, leaching the stainless steel bipolar plate with deionized water, and drying the stainless steel bipolar plate for 0.5 to 3 hours at the temperature of 80 to 100 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface.
And thirdly, injecting the silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the dispenser can automatically dispense the silica gel according to the flow channel track input into a computer in advance, the dispensing amount is controllable, the mass repeated operation is facilitated, the upper surface of the silica gel in the flow channel is 0.05-0.2 mm lower than the surface of the ridge, and the silica gel is placed in a static state for 2-24 hours at room temperature until the silica gel in the flow channel is cured. Silica gel is added into the flow channel to effectively prevent the poly dopamine layer on the inner surface of the flow channel groove from being reduced into noble metal in the fourth step. The silica gel is commercially available two-component room temperature vulcanized silicone mold silica gel.
And fourthly, putting the stainless steel bipolar plate into a chloroplatinic acid aqueous solution with the concentration of 1-10%, ultrasonically mixing for 1-12h, reducing platinum ions in the chloroplatinic acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the platinum ions on the surface of the stainless steel bipolar plate ridge, taking out the stainless steel bipolar plate ridge, and leaching the stainless steel bipolar plate ridge with deionized water for 1-10min to obtain the bipolar plate with the platinum nanoparticle layer on the surface of the ridge. And taking down the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the polydopamine coating and the nano platinum coating on the ridge in the flow channel.
Example 5
The embodiment is realized by the following steps:
firstly, putting the stainless steel bipolar plate which is punched and formed and cleaned into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, the temperature in the furnace chamber is kept at 20 ℃, and then argon is introduced into the furnace chamber at the speed of 500ml/min, so that the vacuum degree in the furnace chamber is kept at 0.1 Pa. The ion source voltage is loaded to 100V, the duty ratio is 10%, the matrix bias voltage is loaded to-1000V, and the duty ratio is 10%. The bombardment time of high-energy argon ions is 5 min. And then the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished.
And secondly, putting the treated stainless steel bipolar plate into a dopamine solution with the pH value of 8, completely immersing the stainless steel bipolar plate, treating the stainless steel bipolar plate for 2 hours at the temperature of 25 ℃, taking out the stainless steel bipolar plate, leaching the stainless steel bipolar plate with deionized water, and drying the stainless steel bipolar plate for 0.5 to 3 hours at the temperature of 80 to 100 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface.
And thirdly, injecting the silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the dispenser can automatically dispense the silica gel according to the flow channel track input into a computer in advance, the dispensing amount is controllable, the mass repeated operation is facilitated, the upper surface of the silica gel in the flow channel is 0.05-0.2 mm lower than the surface of the ridge, and the silica gel is placed in a static state for 2-24 hours at room temperature until the silica gel in the flow channel is cured. Silica gel is added into the flow channel to effectively prevent the poly dopamine layer on the inner surface of the flow channel groove from being reduced into noble metal in the fourth step. The silica gel is commercially available two-component room temperature vulcanized silicone mold silica gel.
And fourthly, putting the stainless steel bipolar plate into a chloroplatinic acid aqueous solution with the concentration of 1%, ultrasonically mixing for 2h, reducing platinum ions in the chloroplatinic acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the platinum ions on the surface of the stainless steel bipolar plate ridge, taking out, and leaching for 1min by deionized water to obtain the bipolar plate with the platinum nanoparticle layer on the surface of the ridge. And taking down the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the polydopamine coating and the nano platinum coating on the ridge in the flow channel.
Example 6
The embodiment is realized by the following steps:
firstly, putting the stainless steel bipolar plate which is punched and formed and cleaned into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, the temperature of the furnace chamber is kept at 200 ℃, and then argon is introduced into the furnace chamber at the speed of 50ml/min, so that the vacuum degree in the furnace chamber is kept at 2 Pa. The ion source voltage is loaded to 1000V, the duty ratio is 100%, the substrate bias voltage is loaded to-100V, and the duty ratio is 100%. The bombardment time of high-energy argon ions is 60 min. And then the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished.
And secondly, putting the treated stainless steel bipolar plate into a dopamine solution with the pH value of 10.5, completely immersing the stainless steel bipolar plate, treating the stainless steel bipolar plate for 48 hours at the temperature of 30 ℃, taking out the stainless steel bipolar plate, leaching the stainless steel bipolar plate with deionized water, and drying the stainless steel bipolar plate for 3 hours at the temperature of 100 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface.
And thirdly, injecting the silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the dispenser can automatically dispense the silica gel according to the flow channel track input into a computer in advance, the dispensing amount is controllable, the mass repeated operation is facilitated, the upper surface of the silica gel in the flow channel is 0.2mm lower than the surface of the ridge, and the silica gel is placed in a static state for 24 hours at room temperature until the silica gel in the flow channel is cured. Silica gel is added into the flow channel to effectively prevent the poly dopamine layer on the inner surface of the flow channel groove from being reduced into noble metal in the fourth step. The silica gel is commercially available two-component room temperature vulcanized silicone mold silica gel.
And fourthly, putting the stainless steel bipolar plate into a chloroplatinic acid aqueous solution with the concentration of 10%, ultrasonically mixing for 12h, reducing platinum ions in the chloroplatinic acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the platinum ions on the surface of the stainless steel bipolar plate ridge, taking out the stainless steel bipolar plate ridge, and leaching for 10min by deionized water to obtain the bipolar plate with the platinum nanoparticle layer on the surface of the ridge. And taking down the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the polydopamine coating and the nano platinum coating on the ridge in the flow channel.
The bipolar plates with the coatings in the embodiments provided by the invention have contact resistance of less than 10m omega cm with carbon paper under the pressure condition of a typical fuel cell2The polydopamine inner surface coating can remarkably improve the spontaneous diffusion capability of water generated in the working process of the fuel cell on the inner surface of the flow channel, and effectively avoids liquid drops from blocking the flow channel.
Claims (5)
1. A kind of runner ditch groove and ridge surface are the metal bipolar plate of the dissimilar coating, characterized by that: the inner surface of the metal bipolar plate flow channel is provided with a polydopamine hydrophilic coating, and the surface of the ridge is provided with a noble metal coating.
2. The metallic bipolar plate having a differentially coated surface of the flow channel grooves and ridges of claim 1, wherein: the thickness of the polydopamine hydrophilic coating is 5nm-5000nm, and the thickness of the noble metal coating is 5nm-5000 nm.
3. The metallic bipolar plate having a differentially coated surface of the flow channel grooves and ridges of claim 1, wherein: the hydrophilic coating surface has a contact angle of less than 60 °.
4. The method for preparing a metal bipolar plate with heterogeneous coating on the surfaces of the flow channel grooves and ridges according to claim 1, comprising the following steps:
step one, putting the punched and cleaned stainless steel bipolar plate into a non-equilibrium magnetron sputtering ion plating furnace chamber, and then vacuumizing until the vacuum degree of the furnace chamber is lower than 3.0 multiplied by 10-3Pa, keeping the temperature of the furnace chamber at 20-200 ℃, and then introducing argon into the furnace chamber at the speed of 50-500 ml/min to keep the vacuum degree in the furnace chamber at 0.1-2 Pa; the ion source voltage is loaded to 100V-1000V, the duty ratio is 10% -100%, the substrate bias voltage is loaded to-1000V to-100V, and the duty ratio is 10% -100%; the bombardment time of the high-energy argon ions is 1min-60 min; the passivation layer on the surface of the stainless steel bipolar plate can be removed, and the stainless steel bipolar plate is taken out after the treatment is finished;
step two, placing the treated stainless steel bipolar plate into a dopamine solution with the pH value of 8-10.5, treating for 2-48h at 20-30 ℃, then taking out the stainless steel bipolar plate, leaching with deionized water, and drying for 0.5-3h at 80-100 ℃ to obtain the stainless steel bipolar plate with the polydopamine coating on the surface;
thirdly, dispensing silica gel into the flow channel of the bipolar plate by using a dispenser, wherein the upper surface of the silica gel in the flow channel is 0.05mm-0.2mm lower than the surface of the ridge, standing for 2-24 hours at room temperature, and curing the silica gel in the flow channel;
putting the stainless steel bipolar plate into a chloroauric acid or chloroplatinic acid aqueous solution with the concentration of 1% -10%, ultrasonically mixing for 1-12h, reducing noble metal ions in the chloroauric acid or the chloroplatinic acid aqueous solution by polydopamine on the surface of the bipolar plate ridge in the process, depositing the noble metal ions on the surface of the stainless steel bipolar plate ridge, taking out the stainless steel bipolar plate and leaching the stainless steel bipolar plate with deionized water for 1-10min to obtain the bipolar plate with the noble metal particle layer on the surface of the ridge; and taking down the cured silica gel in the flow channel of the stainless steel bipolar plate to obtain the bipolar plate with the inner surface of the flow channel groove being provided with the polydopamine coating and the ridge surface being provided with the noble metal coating.
5. The method of claim 1, wherein the surface of the flow channel grooves and ridges is coated with a heterogeneous metal bipolar plate, and the method comprises the following steps: the silica gel is commercially available two-component room temperature vulcanized silicone mold silica gel.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111900429A (en) * | 2020-07-24 | 2020-11-06 | 浙江泓林新能源科技有限公司 | Metal bipolar plate of fuel cell and processing method thereof |
| CN112736263A (en) * | 2020-12-25 | 2021-04-30 | 新源动力股份有限公司 | Preparation method of bipolar plate for optimizing drainage capacity of fuel cell |
| CN114725419A (en) * | 2022-03-25 | 2022-07-08 | 湖南氢捷新能源科技有限公司 | Method for manufacturing bipolar plate |
| CN116682986A (en) * | 2023-08-02 | 2023-09-01 | 山东美燃氢动力有限公司 | Method for preparing hydrophilic bipolar plate, hydrophilic bipolar plate and fuel cell |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060105222A1 (en) * | 2004-11-12 | 2006-05-18 | Abd Elhamid Mahmoud H | Hydrophilic surface modification of bipolar plate |
| US20060134496A1 (en) * | 2004-12-13 | 2006-06-22 | Applied Materials, Inc. | Fuel cell conditioning layer |
| US20070254204A1 (en) * | 2006-04-28 | 2007-11-01 | Samsung Sdi Co., Ltd. | Separator for fuel cell, method of preparing same, and fuel cell system including same |
| US20080038619A1 (en) * | 2006-08-09 | 2008-02-14 | Daido Tokushuko Kabushiki Kaisha | Metallic bipolar plate for fuel cells,and fuel cell comprising the same |
| CN101308934A (en) * | 2007-04-04 | 2008-11-19 | 通用汽车环球科技运作公司 | Removal of non-conductive hydrophilic coatings from lands of fuel cell bipolar plates |
| CN101667647A (en) * | 2009-08-17 | 2010-03-10 | 新源动力股份有限公司 | Bipolar plate for proton exchange membrane fuel cell |
| US20100176001A1 (en) * | 2008-11-28 | 2010-07-15 | National Tsing Hua University (Taiwan) | Electroplating solution for manufacturing nanometer platinum and platinum based alloy particles and method thereof |
| CN103196967A (en) * | 2013-03-21 | 2013-07-10 | 上海师范大学 | Dopamine polymer/noble metal nanoparticle electrochemical sensor as well as preparation method and application thereof |
| US20150140204A1 (en) * | 2012-07-11 | 2015-05-21 | Toyota Shatai Kabushiki Kaisha | Fuel cell separator and method for manufacturing same |
| US20160064755A1 (en) * | 2013-04-30 | 2016-03-03 | Aktiengesellschaft | Self-wetting membrane electrode unit and fuel cell having such a unit |
| CN106129422A (en) * | 2016-08-09 | 2016-11-16 | 上海交通大学 | Improve the fine and close and corrosion resistant method of fuel battery metal double polar plate overlay coating |
| US20170092962A1 (en) * | 2015-09-24 | 2017-03-30 | Nuvera Fuel Cells, LLC | Bipolar plate having a polymeric coating |
| US20180212255A1 (en) * | 2015-07-16 | 2018-07-26 | Luxembourg Institute Of Science And Technology | Electrocatalytically active nanocomposite material and a production method therefor |
| CN109768285A (en) * | 2018-12-18 | 2019-05-17 | 北京化工大学 | A kind of uniform dual polar plates of proton exchange membrane fuel cell of thermal conductivity |
-
2019
- 2019-12-31 CN CN201911406310.2A patent/CN111082089B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101057350A (en) * | 2004-11-12 | 2007-10-17 | 通用汽车公司 | Hydrophilic surface modification of bipolar plate |
| US20060105222A1 (en) * | 2004-11-12 | 2006-05-18 | Abd Elhamid Mahmoud H | Hydrophilic surface modification of bipolar plate |
| US20060134496A1 (en) * | 2004-12-13 | 2006-06-22 | Applied Materials, Inc. | Fuel cell conditioning layer |
| US20070254204A1 (en) * | 2006-04-28 | 2007-11-01 | Samsung Sdi Co., Ltd. | Separator for fuel cell, method of preparing same, and fuel cell system including same |
| US20080038619A1 (en) * | 2006-08-09 | 2008-02-14 | Daido Tokushuko Kabushiki Kaisha | Metallic bipolar plate for fuel cells,and fuel cell comprising the same |
| CN101308934A (en) * | 2007-04-04 | 2008-11-19 | 通用汽车环球科技运作公司 | Removal of non-conductive hydrophilic coatings from lands of fuel cell bipolar plates |
| US20100176001A1 (en) * | 2008-11-28 | 2010-07-15 | National Tsing Hua University (Taiwan) | Electroplating solution for manufacturing nanometer platinum and platinum based alloy particles and method thereof |
| CN101667647A (en) * | 2009-08-17 | 2010-03-10 | 新源动力股份有限公司 | Bipolar plate for proton exchange membrane fuel cell |
| US20150140204A1 (en) * | 2012-07-11 | 2015-05-21 | Toyota Shatai Kabushiki Kaisha | Fuel cell separator and method for manufacturing same |
| CN103196967A (en) * | 2013-03-21 | 2013-07-10 | 上海师范大学 | Dopamine polymer/noble metal nanoparticle electrochemical sensor as well as preparation method and application thereof |
| US20160064755A1 (en) * | 2013-04-30 | 2016-03-03 | Aktiengesellschaft | Self-wetting membrane electrode unit and fuel cell having such a unit |
| US20180212255A1 (en) * | 2015-07-16 | 2018-07-26 | Luxembourg Institute Of Science And Technology | Electrocatalytically active nanocomposite material and a production method therefor |
| US20170092962A1 (en) * | 2015-09-24 | 2017-03-30 | Nuvera Fuel Cells, LLC | Bipolar plate having a polymeric coating |
| CN106129422A (en) * | 2016-08-09 | 2016-11-16 | 上海交通大学 | Improve the fine and close and corrosion resistant method of fuel battery metal double polar plate overlay coating |
| CN109768285A (en) * | 2018-12-18 | 2019-05-17 | 北京化工大学 | A kind of uniform dual polar plates of proton exchange membrane fuel cell of thermal conductivity |
Non-Patent Citations (4)
| Title |
|---|
| 潘红涛等: "质子交换膜燃料电池用不锈钢双极板的腐蚀与表面改性研究进展", 《腐蚀与防护》 * |
| 潘红涛等: "质子交换膜燃料电池用不锈钢双极板的腐蚀与表面改性研究进展", 《腐蚀与防护》, no. 08, 15 August 2011 (2011-08-15), pages 13 - 18 * |
| 陈丽娟等: "聚多巴胺涂层的研究与应用进展", 《高分子通报》 * |
| 陈丽娟等: "聚多巴胺涂层的研究与应用进展", 《高分子通报》, no. 07, 15 July 2018 (2018-07-15), pages 45 - 52 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111900429A (en) * | 2020-07-24 | 2020-11-06 | 浙江泓林新能源科技有限公司 | Metal bipolar plate of fuel cell and processing method thereof |
| CN112736263A (en) * | 2020-12-25 | 2021-04-30 | 新源动力股份有限公司 | Preparation method of bipolar plate for optimizing drainage capacity of fuel cell |
| CN114725419A (en) * | 2022-03-25 | 2022-07-08 | 湖南氢捷新能源科技有限公司 | Method for manufacturing bipolar plate |
| CN116682986A (en) * | 2023-08-02 | 2023-09-01 | 山东美燃氢动力有限公司 | Method for preparing hydrophilic bipolar plate, hydrophilic bipolar plate and fuel cell |
| CN116682986B (en) * | 2023-08-02 | 2023-12-08 | 山东美燃氢动力有限公司 | Method for preparing hydrophilic bipolar plate, hydrophilic bipolar plate and fuel cell |
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