CN112993298A - Double-functional coating of fuel cell metal bipolar plate - Google Patents
Double-functional coating of fuel cell metal bipolar plate Download PDFInfo
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Images
Classifications
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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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—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
Abstract
The invention belongs to the field of fuel cells, and particularly relates to a dual-functional coating of a metal bipolar plate of a fuel cell. The coating includes a transition corrosion resistant layer proximate to the metal substrate, and a conductive layer on the transition layer. The corrosion-resistant layer of the bifunctional coating can reduce the surface reaction activity of the substrate, can inhibit the generation of coating pinholes through a self-passivation process, prevents corrosive media from permeating into the substrate, improves the corrosion resistance of the material, has excellent electronic conductivity between a conductive layer on the corrosion-resistant layer and a gas diffusion layer, and effectively reduces the contact resistance.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a dual-functional coating of a metal bipolar plate of a fuel cell.
Background
A fuel cell is a power generation device that electrochemically converts chemical energy stored in a fuel and an oxidant directly into electrical energy. In a different sense from conventionalThe fuel cell of (1) operates more like an engine, theoretically, it can continuously generate electric energy through electrochemical reaction as long as sufficient fuel and oxidant are supplied, so that it has the advantage of uninterrupted operation for a long time; the energy conversion efficiency is as high as 40-60% because the energy conversion process is not carried out and is not limited by Carnot cycle; the fuel cell hardly generates NO during operationx、SOxIso-harmful gas, CO2Also, the amount of emissions is less than that of the conventional power generation apparatus. Because of these outstanding advantages, fuel cell technology is considered as the first choice in the twenty-first century for clean and efficient power generation, and research and development thereof are receiving attention from governments and major companies.
The bipolar plate is one of the key components of the PEMFC, and plays a role in uniformly distributing fuel and oxidant, realizing electrical connection between the single cells in the stack, supporting the stack, collecting and discharging current, blocking reaction gas, and the like. The traditional metal material has good electrical conductivity and thermal conductivity, is excellent in mechanical property, is suitable for mass production, is the first choice of a fuel cell bipolar plate material, but the metal polar plate can be seriously corroded in the working environment of the fuel cell, so that metal ions in the metal polar plate are separated out, the degradation of a proton exchange membrane and the pollution of a catalyst are caused, the service life of the fuel cell is prolonged, and a passive film is easily formed on the metal surface in an acid environment to increase the contact resistance of the polar plate and a gas diffusion layer, so that the output power of the cell is reduced. Therefore, the preparation of the corrosion-resistant and high-conductivity coating on the surface of the metal pole plate is an effective way for improving the performance of the metal pole plate.
Chinese patent CN 102054989A discloses a bipolar plate for proton exchange membrane fuel cell, which comprises a metal substrate, wherein polypyrrole-nano SnO is deposited on the surface of the metal substrate2A composite conductive coating is prepared by mixing nano SnO2The powder is dispersed into the mixed solution of pyrrole and sodium dodecyl benzene sulfonate by ultrasonic wave to prepare nano SnO2Synthesizing solution, and depositing on the surface of the metal substrate by adopting a constant current method. The coating has simple preparation process and low cost, but the polypyrrole-nano SnO2The composite coating may only be provided withBetter corrosion resistance, and the interface conductivity between the gas diffusion layer and the gas diffusion layer is difficult to meet the use requirement of the fuel cell.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the fuel cell metal bipolar plate dual-function coating, which reduces the contact resistance between the metal bipolar plate and the gas diffusion layer and improves the corrosion resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a fuel cell metal bipolar plate uses the dual-functional coating, including the metal substrate, deposit corrosion-resistant layer and conducting layer sequentially on the said metal substrate; the material of the corrosion-resistant layer is any one or more of corresponding oxides of titanium, zirconium, tungsten, niobium, chromium, tantalum, vanadium, molybdenum and hafnium; the conducting layer is made of any one or more of transition metal compounds, amorphous carbon and noble metals.
In the above technical solution, further, the thickness of the corrosion-resistant layer is 10 to 2000nm, and the thickness of the conductive layer is 50 to 3000 nm.
In the above technical solution, further, the oxide is doped with a metal or nonmetal element, the metal element is one or more of titanium, zirconium, tungsten, niobium, chromium, tantalum, vanadium, molybdenum, and hafnium, and the nonmetal element is any one or more of boron, carbon, nitrogen, silicon, and fluorine.
In the above technical solution, the transition metal compound further includes one or more of carbides, nitrides, borides, and silicides of titanium, zirconium, tungsten, niobium, chromium, tantalum, vanadium, molybdenum, and hafnium.
In the above technical solution, further, the preparation method of the coating is vapor deposition, electrodeposition, spray coating or spin coating.
The invention has the beneficial effects that: the double-function coating consists of an inner corrosion-resistant layer and an outer conductive layer. The corrosion-resistant layer close to the metal substrate reduces the reaction activity of the surface of the substrate, a compact film can be formed in a self-passivation mode, generation of coating pinholes is inhibited, a corrosion medium is prevented from permeating into the metal substrate, the corrosion resistance of the substrate is enhanced, the outer conductive layer has excellent electronic conductivity, and the contact resistance between the substrate and the carbon paper is effectively reduced.
Drawings
FIG. 1 is a schematic structural diagram of a bipolar plate according to the present invention, in which 1, a metal plate substrate, 2, a corrosion-resistant layer, 3, and a conductive layer;
FIG. 2 is a graph showing the variation of contact resistance between the bipolar plate and the carbon paper according to the embodiments with pressure;
fig. 3 is a graph of accelerated corrosion testing of bipolar plates prepared in accordance with various examples under simulated fuel cell cathode conditions.
Detailed Description
The invention is further illustrated but is not in any way limited by the following specific examples.
Example 1
Taking 316L stainless steel as a substrate, and ultrasonically cleaning and drying in deionized water, ethanol and acetone in sequence; mounting the substrate on a workpiece frame of a magnetron sputtering ion composite coating machine, and vacuumizing to 3 x 10-3Pa below; introducing argon of 200sccm into the vacuum chamber to keep the pressure at 0.5 Pa; introducing oxygen of 10sccm, using titanium as a sputtering source, controlling the sputtering current to be 1A, and depositing the titanium dioxide corrosion-resistant layer for 10 min; closing the titanium sputtering source, stopping introducing oxygen, introducing 18sccm of acetylene gas into a vacuum chamber, controlling the target current to be 100A by taking the niobium target as an evaporation source, biasing the substrate to be-150V, and depositing a niobium carbide and amorphous carbon codeposition layer for 30 min; and cooling and taking out to obtain the metal plate with the modified surface coating, wherein the thickness of the coating is about 650 nm.
As shown in the figure, the contact resistance between the bipolar plate and the carbon paper is 9.1m omega cm under 1.5MPa2At 80 ℃ 0.5M H2SO4+5ppm F-After the material is corroded for 10 hours at a constant potential of 0.6V (vs. SCE) under the condition of air introduction, the corrosion current is 0.21 mu A/cm2Compared with 316L stainless steel as a substrate, the conductivity and the corrosion resistance are both obviously improved.
Example 2
Using 316L stainless steel as a substrate, sequentially carrying out ultrasonic cleaning in deionized water, ethanol and acetone, and drying(ii) a Mounting the substrate on a workpiece frame of a magnetron sputtering ion composite coating machine, and vacuumizing to 3 x 10-3Pa below; introducing argon of 200sccm into the vacuum chamber to keep the pressure at 0.5 Pa; introducing oxygen of 10sccm, using titanium as a sputtering source, controlling the sputtering current to be 1A, and depositing the titanium dioxide corrosion-resistant layer for 10 min; closing the titanium sputtering source, stopping introducing oxygen, introducing 18sccm of acetylene gas into a vacuum chamber, controlling the target current to be 100A by taking the niobium target as an evaporation source, biasing the substrate to be-200V, and depositing a niobium carbide and amorphous carbon codeposition layer for 30 min; and cooling and taking out to obtain the metal plate with the modified surface coating, wherein the thickness of the coating is about 650 nm.
As shown in the figure, the contact resistance between the bipolar plate and the carbon paper is 11.2m omega cm under 1.5MPa2At 80 ℃ 0.5M H2SO4+5ppm F-After the material is corroded for 10 hours at a constant potential of 0.6V (vs. SCE) under the condition of air introduction, the corrosion current is 0.25 mu A/cm2Compared with 316L stainless steel as a substrate, the conductivity and the corrosion resistance are both obviously improved.
Example 3
Taking 316L stainless steel as a substrate, and ultrasonically cleaning and drying in deionized water, ethanol and acetone in sequence; mounting the substrate on a workpiece frame of a magnetron sputtering ion composite coating machine, and vacuumizing to 3 x 10-3Pa below; introducing argon of 200sccm into the vacuum chamber to keep the pressure at 0.5 Pa; introducing oxygen of 10sccm, using titanium as a sputtering source, controlling the sputtering current to be 1A, and depositing the titanium dioxide corrosion-resistant layer for 10 min; closing the titanium sputtering source, stopping introducing oxygen, introducing 18sccm of acetylene gas into a vacuum chamber, controlling the target current to be 100A by taking the niobium target as an evaporation source, biasing the substrate to be-250V, and depositing a niobium carbide and amorphous carbon codeposition layer for 30 min; and cooling and taking out to obtain the metal plate with the modified surface coating, wherein the thickness of the coating is about 650 nm.
As shown in the figure, the contact resistance between the bipolar plate and the carbon paper is 8.1m omega cm under 1.5MPa2At 80 ℃ 0.5M H2SO4+5ppm F-After the material is corroded for 10 hours at a constant potential of 0.6V (vs. SCE) under the condition of air introduction, the corrosion current is 0.29 mu A/cm2Compared with 316L stainless steel as a substrate, the conductivity and the corrosion resistance are both obviously improved.
Example 4
Taking 316L stainless steel as a substrate, and ultrasonically cleaning and drying in deionized water, ethanol and acetone in sequence; mounting the substrate on a workpiece frame of a magnetron sputtering ion composite coating machine, and vacuumizing to 3 x 10-3Pa below; introducing argon of 200sccm into the vacuum chamber to keep the pressure at 0.5 Pa; introducing oxygen of 10sccm, using titanium as a sputtering source, controlling the sputtering current to be 1A, and depositing the titanium dioxide corrosion-resistant layer for 10 min; closing the titanium sputtering source, stopping introducing oxygen, regulating the flow of argon gas to 300sccm, and introducing 9sccm acetylene gas into the vacuum chamber to keep the pressure of the vacuum chamber at 0.8 Pa; respectively controlling target currents to be 60A and 90A and substrate bias voltage to be-125V by taking a niobium target and a chromium target as evaporation sources, and depositing a niobium carbide and chromium carbide codeposition layer for 60 min; and cooling and taking out to obtain the metal plate with the modified surface coating, wherein the thickness of the coating is about 500 nm.
As shown in the figure, the contact resistance between the bipolar plate and the carbon paper is 7.7m omega cm under 1.5MPa2At 80 ℃ 0.5M H2SO4+5ppm F-After the material is corroded for 10 hours at a constant potential of 0.6V (vs. SCE) under the condition of air introduction, the corrosion current is 0.34 mu A/cm2Compared with 316L stainless steel as a substrate, the conductivity and the corrosion resistance are both obviously improved.
Example 5
Taking 316L stainless steel as a substrate, and ultrasonically cleaning and drying in deionized water, ethanol and acetone in sequence; mounting the substrate on a workpiece frame of a magnetron sputtering ion composite coating machine, and vacuumizing to 3 x 10-3Pa below; introducing argon of 200sccm into the vacuum chamber to keep the pressure at 0.5 Pa; introducing oxygen of 10sccm, using titanium as a sputtering source, controlling the sputtering current to be 1A, and depositing the titanium dioxide corrosion-resistant layer for 10 min; closing the titanium sputtering source, stopping introducing oxygen, regulating the flow of argon gas to 300sccm, and introducing 9sccm acetylene gas into the vacuum chamber to keep the pressure of the vacuum chamber at 0.8 Pa; respectively controlling target currents to be 60A and 90A and substrate bias voltage to be-150V by taking a niobium target and a chromium target as evaporation sources, and depositing a niobium carbide and chromium carbide codeposition layer for 60 min; and cooling and taking out to obtain the metal plate with the modified surface coating, wherein the thickness of the coating is about 500 nm.
As shown in the figure, the contact resistance between the bipolar plate and the carbon paper is 8.5m omega cm under 1.5MPa2At 80 ℃ 0.5M H2SO4+5ppm F-After the material is corroded for 10 hours at a constant potential of 0.6V (vs. SCE) under the condition of air introduction, the corrosion current is 0.24 mu A/cm2Compared with 316L stainless steel as a substrate, the conductivity and the corrosion resistance are both obviously improved.
Example 6
Taking 316L stainless steel as a substrate, and ultrasonically cleaning and drying in deionized water, ethanol and acetone in sequence; mounting the substrate on a workpiece frame of a magnetron sputtering ion composite coating machine, and vacuumizing to 3 x 10-3Pa below; introducing argon of 200sccm into the vacuum chamber to keep the pressure at 0.5 Pa; introducing oxygen of 10sccm, using titanium as a sputtering source, controlling the sputtering current to be 1A, and depositing the titanium dioxide corrosion-resistant layer for 10 min; closing the titanium sputtering source, stopping introducing oxygen, regulating the flow of argon gas to 300sccm, and introducing 12sccm acetylene gas into the vacuum chamber to keep the pressure of the vacuum chamber at 0.8 Pa; taking a niobium target and a chromium target as evaporation sources, respectively controlling the target current to be 60A and 100A, and the substrate bias voltage to be-200V, and depositing a niobium carbide and chromium carbide codeposition layer for 60 min; and cooling and taking out to obtain the metal plate with the modified surface coating, wherein the thickness of the coating is about 500 nm.
As shown in the figure, the contact resistance between the bipolar plate and the carbon paper is 9.5m omega cm under 1.5MPa2At 80 ℃ 0.5M H2SO4+5ppm F-After the material is corroded for 10 hours at a constant potential of 0.6V (vs. SCE) under the condition of air introduction, the corrosion current is 0.27 mu A/cm2Compared with 316L stainless steel as a substrate, the conductivity and the corrosion resistance are both obviously improved.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (5)
1. A fuel cell metal bipolar plate uses the dual-functional coating, including the metal substrate, characterized by that, deposit corrosion-resistant layer and conducting layer sequentially on the said metal substrate; the material of the corrosion-resistant layer is any one or more of corresponding oxides of titanium, zirconium, tungsten, niobium, chromium, tantalum, vanadium, molybdenum and hafnium; the conducting layer is made of any one or more of transition metal compounds, amorphous carbon and noble metals.
2. The bifunctional coating of claim 1, wherein the corrosion resistant layer has a thickness of 10 to 2000nm and the conductive layer has a thickness of 50 to 3000 nm.
3. The dual function coating of claim 1, wherein the oxide is doped with a metallic or non-metallic element, the metallic element is one or more of titanium, zirconium, tungsten, niobium, chromium, tantalum, vanadium, molybdenum, hafnium, and the non-metallic element is one or more of boron, carbon, nitrogen, silicon, and fluorine.
4. The bifunctional coating of claim 1, wherein the transition metal compound comprises one or more of carbides, nitrides, borides, silicides of titanium, zirconium, tungsten, niobium, chromium, tantalum, vanadium, molybdenum, hafnium.
5. The bifunctional coating of claim 1, wherein the coating is prepared by vapor deposition, electrodeposition, spray coating or spin coating.
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| CN113445014A (en) * | 2021-07-02 | 2021-09-28 | 扬州市普锐泰新材料有限公司 | Surface functional coating process for hydrogen fuel cell titanium bipolar plate |
| CN113584441A (en) * | 2021-08-02 | 2021-11-02 | 杭州兴态环保科技有限公司 | Metal bipolar plate coating and preparation method thereof |
| CN113690455A (en) * | 2021-08-16 | 2021-11-23 | 杭州兴态环保科技有限公司 | Long-life anode electrode material and preparation method thereof |
| CN114214658A (en) * | 2021-12-14 | 2022-03-22 | 中国科学院大连化学物理研究所 | Composite coating for water electrolysis metal bipolar plate and preparation method thereof |
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