CN112111721A - Preparation method of CrCuC gradient CrCu composite carbon film bipolar plate - Google Patents
Preparation method of CrCuC gradient CrCu composite carbon film bipolar plate Download PDFInfo
- Publication number
- CN112111721A CN112111721A CN202011021448.3A CN202011021448A CN112111721A CN 112111721 A CN112111721 A CN 112111721A CN 202011021448 A CN202011021448 A CN 202011021448A CN 112111721 A CN112111721 A CN 112111721A
- Authority
- CN
- China
- Prior art keywords
- crcu
- crcuc
- gradient
- carbon film
- bipolar plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
- H01M8/021—Alloys based on iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a preparation method of a CrCuC gradient CrCu composite carbon film bipolar plate, which adopts a vacuum high-power micro-pulse magnetron sputtering technology, uses a CrCu target as a sputtering target material, firstly deposits a pure CrCu metal transition layer on the surface of stainless steel, then provides a carbon source by methane gas, and sputters and deposits a CrCuC gradient CrCu composite carbon film on the CrCu metal transition layer. The CrCuC gradient CrCu composite carbon film prepared by vacuum magnetron sputtering has good binding force, greatly improves the hydrophobicity of a substrate, and is beneficial to the water management in a fuel cell; the average corrosion current density of the bipolar plate used as the PEMFC is 0.65-0.71 mu A/cm2(constant potential polarization of 0.6V) and interface contact resistance of 2.84-7.34 m omega cm2(at a pressure of 1.4 MPa) and has both high conductivity and high corrosion resistance.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a preparation method of a CrCuC gradient CrCu composite carbon film bipolar plate.
Background
Fuel cells are considered one of the most promising clean energy sources in the world. Fuel cells are mainly classified into five types according to the operating environment of the cell, electrolytes, and fuels: compared with other four fuel cells, the Alkaline Fuel Cell (AFC), the phosphate fuel cell (PAFC), the alkali metal Molten Carbonate Fuel Cell (MCFC), the oxygen ion ceramic fuel cell (SOFC), and the Proton Exchange Membrane Fuel Cell (PEMFC) start late, but develop rapidly, and are regarded by researchers and automobile enterprises in various countries, but the PEMFC still has the problems of high cost, difficult commercialization, and the like.
The bipolar plate is one of the core components of the PEMFC, the mass of the bipolar plate accounts for about 60-80% of the mass of a cell stack, the cost accounts for about 30-35%, and the bipolar plate almost occupies the whole volume of the fuel cell stack. The PEMFC bipolar plate is mainly classified into a graphite bipolar plate, a metal bipolar plate and a composite bipolar plate according to the difference of the PEMFC bipolar plate materials. The material of the fuel cell bipolar plate mainly focuses on graphite, metal and polymer composite materials, wherein the traditional graphite bipolar plate has the disadvantages of brittle texture, high cost and large volume of an electric pile. Although the polymer composite bipolar plate has low cost, the conductivity is poor, and the energy flow density of a galvanic pile is influenced. Compared with the former two, the metal bipolar plate has the advantages of conductivity, low cost, easy processing and the like, and has wide commercial application prospect. However, the surface of the pure metal bipolar plate is easy to corrode and passivate in an acid environment, so that the service performance of the pure metal bipolar plate is influenced. Therefore, developing a bipolar plate material for a fuel cell is one of the most effective ways to improve the operating efficiency of PEMFCs.
The carbon film coating has excellent corrosion resistance, and is prepared by adopting a graphite target material through a vacuum magnetron sputtering method in most of the current scientific research works, such as patent ZL 2011102350877 (high sp for a bipolar plate of a proton exchange membrane fuel cell)2Hybrid compact carbon coating and preparation method thereof), ZL 200810086374 (a bipolar plate for a fuel cell and preparation method of carbon chromium film on surface of the bipolar plate), and ZL 2011100270990 (a bipolar plate for a fuel cell and preparation method of carbon titanium nano composite film on surface of the bipolar plate). However, the above method still has limitations, and a new carbon-based bipolar plate film needs to be developed to further improve the electrical conductivity and corrosion resistance.
Disclosure of Invention
The invention aims to solve the problem that a PEMFC metal bipolar plate is easy to corrode and passivate, and provides a preparation method of a CrCuC gradient CrCu composite carbon film bipolar plate.
Preparation of CrCuC gradient CrCu composite carbon film bipolar plate
The invention discloses a preparation method of a CrCuC gradient CrCu composite carbon film bipolar plate, which adopts a vacuum high-power micro-pulse magnetron sputtering technology, takes a CrCu target as a sputtering target material, and adopts methane (CH)4) Providing a carbon source by gas, and depositing a CrCuC gradient CrCu composite carbon film on the surface of the stainless steel. The specific deposition process is as follows:
(1) polishing a stainless steel (316L stainless steel) substrate, respectively ultrasonically cleaning the substrate for 15-20 min by using acetone cleaning solution and ethanol cleaning solution, removing surface impurities such as oil stains, rust spots and the like and organic pollutants, then drying the substrate by using nitrogen, and placing the substrate in a coating vacuum chamber to prepare coating;
(2) the vacuum system was evacuated to 1.0X 10-3 Pa and below, introducing argon; starting high bias voltage, controlling the argon pressure to be 1.5-2.0 Pa, and controlling the bias voltage to be 800-900V, and etching and cleaning the surface of the target material and the surface of the stainless steel sample; the time is 15-20 min;
(3) adjusting the bias voltage to 100-150V, keeping the argon pressure at 1.4-1.5 Pa, depositing a pure CrCu metal transition layer by magnetron sputtering, wherein the average current is 6.5A, the voltage is 700V, the duty ratio is 20%, and the pulse length is 3000 ms; the deposition time is 25 min, and the thickness of the CrCu metal transition layer is 330-350 nm;
(4) keeping the average current of the target unchanged, adjusting the duty ratio to be 40 percent and the pulse length to be 1200 ms; adjusting the bias voltage to 300-400V and the argon pressure to 1.4-1.5 Pa; introducing methane for 30-40 min, gradually adding the methane to 40-60 sccm, and depositing a CrCuC gradient transition layer with the thickness of about 400-500 nm;
(5) adjusting the bias voltage to 350-450V, the methane flow to 40-60 sccm, adjusting the duty ratio to 20%, the pulse length to 2000 ms, keeping other conditions unchanged, depositing for 40-60 min, and sputtering and depositing the CrCu doped C carbon film. The thickness of the CrCuC gradient carbon film is 1.2-1.5 mu m.
The structure of the CrCuC gradient CrCu composite carbon film bipolar plate obtained by the method is shown in figure 1.
Performance of CrCuC gradient carbon film bipolar plate
Under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ and air introduction), the modified polar plate with the average sputtering rate of 0.65A has excellent corrosion resistance and conductivity, and the corrosion current density is 9.6-11.7 muA/cm2 (0.6 V.SCE potentiodynamic polarization) and the average corrosion current density is 0.65-0.71 mu A/cm2 (constant potential polarization is 0.6V), and the corrosion resistance of the film is improved due to the existence of the chromium carbide crystal, so that the film has better chemical stability. The contact resistance of the modified polar plate interface is 2.84-7.34 m omega-cm2The contact angle of water is 98.04 degrees (under the pressure of 1.4 MPa), the elastic modulus and the hardness are respectively about 122.68 GPa and 13.53 GPa, the indexes meet the application indexes of the bipolar plate in 2020 of the United states department of energy, and the bipolar plate has certain commercial use value.
In conclusion, the CrCuC gradient CrCu composite carbon film prepared by the vacuum high-power micro-pulse magnetron sputtering method has good binding force, and the hydrophobicity of the base of the bipolar plate of the obtained CrCuC gradient CrCu composite carbon film is greatly improved, so that the water management in the fuel cell is facilitated; the bipolar plate as a PEMFC has stable performance, high conductivity and high corrosion resistance.
Drawings
FIG. 1 is a schematic structural diagram of a CrCuC gradient CrCu composite carbon film bipolar plate prepared by the invention.
Detailed Description
The preparation and performance of the CrCuC gradient CrCu composite carbon film bipolar plate of the invention are further explained by the specific examples.
Example 1
(1) Polishing a stainless steel (316L stainless steel) substrate, respectively ultrasonically cleaning the substrate for 15 min by using acetone cleaning solution and ethanol cleaning solution, removing surface impurities and organic pollutants such as oil stains, rust spots and the like, then drying the substrate by using nitrogen, and placing the substrate in a coating vacuum chamber to prepare coating;
(2) the vacuum system was evacuated to 1.0X 10-3 Pa and below, introducing argon; starting high bias voltage, controlling the argon pressure to be 2.0Pa and the bias voltage to be 800V, and etching and cleaning the surface of the target material and the surface of the stainless steel sample; the time is 15 min;
(3) adjusting the bias voltage to 100V, keeping the argon pressure at 1.4-1.5 Pa, depositing a pure CrCu metal transition layer by magnetron sputtering, wherein the average current is 6.5A, the voltage is 700V, the duty ratio is 20%, and the pulse length is 3000 ms; the deposition time is 25 min, and the thickness of the CrCu metal transition layer is 330 nm;
(4) keeping the average current of the target unchanged, adjusting the duty ratio to be 40 percent and the pulse length to be 1200 ms; adjusting the bias voltage to 300-400V and the argon pressure to 1.4-1.5 Pa; introducing methane for 30 min, gradually adding the methane to 40 sccm, and depositing a CrCuC gradient transition layer with the thickness of about 400 nm;
(5) and adjusting the bias voltage to 350V, the flow of methane to 40-60 sccm, adjusting the duty ratio to 20%, the pulse length to 2000 ms, keeping other conditions unchanged, and sputtering and depositing the CrCu-doped C carbon film for 40 min. The thickness of the CrCuC gradient carbon film is 1.2 mu m;
(6) under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ with air), the modified plate with 0.65A on average in sputtering has excellent corrosion resistance and conductivityThe corrosion current density is 11.7 mu A/cm2 (0.6 V.SCE potentiodynamic polarization) and an average corrosion current density of 0.71 muA/cm2 (constant potential polarization is 0.6V), and the corrosion resistance of the film is improved due to the existence of the chromium carbide crystal, so that the film has better chemical stability. The contact resistance of the modified polar plate interface is 7.34 m omega cm2(at a pressure of 1.4 MPa).
Example 2
(1) Polishing a stainless steel (316L stainless steel) substrate, respectively ultrasonically cleaning the substrate for 15 min by using acetone cleaning solution and ethanol cleaning solution, removing surface impurities and organic pollutants such as oil stains, rust spots and the like, then drying the substrate by using nitrogen, and placing the substrate in a coating vacuum chamber to prepare coating;
(2) the vacuum system was evacuated to 1.0X 10-3 Pa and below, introducing argon; starting high bias voltage, controlling the argon pressure to be 1.5 Pa and the bias voltage to be 900V, and etching and cleaning the surface of the target material and the surface of the stainless steel sample; the time is 20 min;
(3) adjusting the bias voltage to 100V, keeping the argon pressure at 1.4-1.5 Pa, depositing a pure CrCu metal transition layer by magnetron sputtering, wherein the average current is 6.5A, the voltage is 700V, the duty ratio is 20%, and the pulse length is 3000 ms; the deposition time is 25 min, and the thickness of the CrCu metal transition layer is 330 nm;
(4) keeping the average current of the target unchanged, adjusting the duty ratio to be 40 percent and the pulse length to be 1200 ms; adjusting the bias voltage to 300V and the argon pressure to 1.4-1.5 Pa; introducing methane for 40 min, gradually adding the methane to 60 sccm, and depositing a CrCuC gradient transition layer with the thickness of about 500 nm;
(5) and regulating the bias voltage to 450V, regulating the flow rate of methane to 60 sccm, regulating the duty ratio to 20%, regulating the pulse length to 2000 ms, keeping other conditions unchanged, and sputtering and depositing the CrCu-doped C carbon film, wherein the deposition time is 60 min. The thickness of the CrCuC gradient CrCu composite carbon film is 1.5 mu m;
(6) under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ and air) and the average sputtering rate of 0.65A, the modified polar plate has excellent corrosion resistance and conductivity and the corrosion current density of 9.6 muA/cm2 (0.6 V.SCE potentiodynamic polarization), average decayThe etching current density is 0.65 muA/cm2 (constant potential polarization is 0.6V), and the corrosion resistance of the film is improved due to the existence of the chromium carbide crystal, so that the film has better chemical stability. The contact resistance of the modified polar plate interface is 6.82 m omega cm2(at a pressure of 1.4 MPa).
Example 3
(1) Polishing a stainless steel (316L stainless steel) substrate, respectively ultrasonically cleaning the substrate for 20min by using acetone cleaning solution and ethanol cleaning solution, removing surface impurities such as oil stains, rust spots and the like and organic pollutants, then blow-drying the substrate by using nitrogen, and placing the substrate in a coating vacuum chamber to prepare coating;
(2) the vacuum system was evacuated to 1.0X 10-3 Pa and below, introducing argon; starting high bias voltage, controlling the argon pressure to be 2.0Pa and the bias voltage to be 900V, and etching and cleaning the surface of the target material and the surface of the stainless steel sample; the time is 15 min;
(3) adjusting the bias voltage to 130V, keeping the argon pressure at 1.4-1.5 Pa, depositing a pure CrCu metal transition layer by magnetron sputtering, wherein the average current is 6.5A, the voltage is 700V, the duty ratio is 20%, and the pulse length is 3000 ms; the deposition time is 25 min, and the thickness of the CrCu metal transition layer is 340 nm;
(4) keeping the average current of the target unchanged, adjusting the duty ratio to be 40 percent and the pulse length to be 1200 ms; adjusting the bias voltage to 300V and the argon pressure to 1.4-1.5 Pa; introducing methane for 40 min, gradually adding the methane to 40 sccm, and depositing a CrCuC gradient transition layer with the thickness of about 400 nm;
(5) and adjusting the bias voltage to 450V, the methane flow to 50 sccm, the duty ratio to be 20%, the pulse length to be 2000 ms, keeping other conditions unchanged, and the deposition time to be 50 min, and sputtering and depositing the CrCu-doped C carbon film. The thickness of the CrCuC gradient CrCu composite carbon film is 1.3 mu m;
(6) under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ and air) and the average sputtering rate of 0.65A, the modified polar plate has excellent corrosion resistance and conductivity and the corrosion current density of 10.1 muA/cm2 (0.6 V.SCE potentiodynamic polarization) and an average corrosion current density of 0.67. mu.A/cm2 (constant potential polarization of 0.6V) due to chromium carbide crystalsThe existence of the body improves the corrosion resistance of the film, so that the film has better chemical stability. The contact resistance of the modified plate interface is 2.84 m omega cm2 (under the pressure of 1.4 MPa).
Example 4
(1) Polishing a stainless steel (316L stainless steel) substrate, respectively ultrasonically cleaning the substrate for 15 min by using acetone cleaning solution and ethanol cleaning solution, removing surface impurities and organic pollutants such as oil stains, rust spots and the like, then drying the substrate by using nitrogen, and placing the substrate in a coating vacuum chamber to prepare coating;
(2) the vacuum system was evacuated to 1.0X 10-3 Pa and below, introducing argon; starting high bias voltage, controlling the argon pressure to be 1.80Pa and the bias voltage to be 850V, and etching and cleaning the surface of the target material and the surface of the stainless steel sample; the time is 20 min;
(3) adjusting bias voltage to 150V, argon pressure to 1.4-1.5 Pa, depositing a pure CrCu metal transition layer by magnetron sputtering, wherein the average current is 6.5A, the voltage is 700V, the duty ratio is 20%, and the pulse length is 3000 ms; the deposition time is 25 min, and the thickness of the CrCu metal transition layer is 350 nm;
(4) keeping the average current of the target unchanged, adjusting the duty ratio to be 40 percent and the pulse length to be 1200 ms; adjusting the bias voltage to 400V, and the argon pressure to 1.4-1.5 Pa; introducing methane for 40 min, gradually adding the methane to 50 sccm, and depositing a CrCuC gradient transition layer with the thickness of about 450 nm;
(5) and adjusting the bias voltage to 400V, the methane flow to be 40-60 sccm, adjusting the duty ratio to be 20%, adjusting the pulse length to be 2000 ms, keeping other conditions unchanged, setting the deposition time to be 50 min, and sputtering and depositing the CrCu doped C carbon film. The thickness of the CrCuC gradient CrCu composite carbon film is 1.4 mu m;
(6) under simulated PEMFC cathode environment (1M H)2SO4+ 5ppm HF, 70 ℃ and air) and the average sputtering rate of 0.65A, the modified polar plate has excellent corrosion resistance and conductivity and the corrosion current density of 10.7 muA/cm2 (0.6 V.SCE potentiodynamic polarization) and an average corrosion current density of 0.68 mu A/cm2 (constant potential polarization is 0.6V), and the corrosion resistance of the film is improved due to the existence of the chromium carbide crystal, so that the film has better chemical stability. After modificationThe contact resistance of the polar plate interface is 5.38 m omega cm2(at a pressure of 1.4 MPa).
Claims (7)
1. A preparation method of a CrCuC gradient CrCu composite carbon film bipolar plate adopts a vacuum high-power micro-pulse magnetron sputtering technology, a CrCu target is used as a sputtering target material, a pure CrCu metal transition layer is firstly deposited on the surface of stainless steel, then methane gas provides a carbon source, and a CrCuC gradient CrCu composite carbon film is sputtered and deposited on the CrCu metal transition layer.
2. The method for preparing a CrCuC gradient CrCu composite carbon film bipolar plate as claimed in claim 1, wherein: the specific deposition process is as follows:
(1) polishing a stainless steel substrate, respectively ultrasonically cleaning the substrate for 15-20 min by using an acetone cleaning solution and an ethanol cleaning solution, removing surface impurities and organic pollutants, then blow-drying the substrate by using nitrogen, and placing the substrate into a film coating vacuum chamber to prepare film coating;
(2) the vacuum system was evacuated to 1.0X 10-3 Pa and below, introducing argon; starting high bias voltage, controlling the argon pressure to be 1.5-2.0 Pa, and controlling the bias voltage to be 800-900V, and etching and cleaning the surface of the target material and the surface of the stainless steel sample; the time is 15-20 min;
(3) adjusting the bias voltage to 100-150V, keeping the argon pressure at 1.4-1.5 Pa, and depositing a pure CrCu transition layer by magnetron sputtering; the average current is 6.5A, the voltage is 700V, the duty ratio is 20%, and the pulse length is 3000 ms;
(4) keeping the average current of the target unchanged, adjusting the duty ratio to be 40 percent and the pulse length to be 1200 ms; adjusting the bias voltage to 300-400V and the argon pressure to 1.4-1.5 Pa; introducing methane for 30-40 min, and depositing a CrCuC gradient transition layer with the thickness of about 400-500 nm;
(5) adjusting the bias voltage to 350-450V, the methane flow to 40-60 sccm, adjusting the duty ratio to 20%, the pulse length to 2000 ms, keeping other conditions unchanged, and sputtering and depositing the CrCu-doped C carbon film.
3. The method for preparing a CrCuC gradient CrCu composite carbon film bipolar plate as claimed in claim 1, wherein: the stainless steel substrate was 316L stainless steel.
4. The method for preparing a CrCuC gradient CrCu composite carbon film bipolar plate as claimed in claim 1, wherein: in the deposition of the pure CrCu metal transition layer, the deposition time is 15-25 min, and the thickness of the CrCu metal transition layer is 330-350 nm.
5. The method for preparing a CrCuC gradient CrCu composite carbon film bipolar plate as claimed in claim 1, wherein: during the deposition of the CrCuC gradient transition layer, the methane is gradually added to 40-60 sccm, and the deposition thickness is 400-500 nm.
6. The method for preparing a CrCuC gradient CrCu composite carbon film bipolar plate as claimed in claim 1, wherein: in the deposition of the CrCu doped C carbon film, a target of CrCu and C with the ratio of 7:3 is used as a sputtering target material.
7. The method for preparing a CrCuC gradient CrCu composite carbon film bipolar plate as claimed in claim 1, wherein: in the deposition of the CrCu doped C carbon film, the deposition time is 40-60 min, and the thickness of the CrCuC gradient carbon film is 1.2-1.5 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011021448.3A CN112111721B (en) | 2020-09-25 | 2020-09-25 | Preparation method of CrCuC gradient CrCu composite carbon film bipolar plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011021448.3A CN112111721B (en) | 2020-09-25 | 2020-09-25 | Preparation method of CrCuC gradient CrCu composite carbon film bipolar plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112111721A true CN112111721A (en) | 2020-12-22 |
| CN112111721B CN112111721B (en) | 2021-07-13 |
Family
ID=73796770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011021448.3A Active CN112111721B (en) | 2020-09-25 | 2020-09-25 | Preparation method of CrCuC gradient CrCu composite carbon film bipolar plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112111721B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104778992A (en) * | 2014-01-09 | 2015-07-15 | 吕传盛 | Wear-resisting anti-corrosion coating-free copper wire and manufacturing method thereof |
| CN107146899A (en) * | 2016-03-01 | 2017-09-08 | 中国科学院大连化学物理研究所 | Proton exchange membrane fuel cell stainless steel bipolar plate face coat structure and preparation |
| CN109728307A (en) * | 2017-10-27 | 2019-05-07 | 中国科学院大连化学物理研究所 | A kind of preparation and bipolar plates and application of the metal double polar plates based on carbon film modification |
| CN110684946A (en) * | 2019-11-07 | 2020-01-14 | 中国科学院宁波材料技术与工程研究所 | Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof |
-
2020
- 2020-09-25 CN CN202011021448.3A patent/CN112111721B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104778992A (en) * | 2014-01-09 | 2015-07-15 | 吕传盛 | Wear-resisting anti-corrosion coating-free copper wire and manufacturing method thereof |
| CN107146899A (en) * | 2016-03-01 | 2017-09-08 | 中国科学院大连化学物理研究所 | Proton exchange membrane fuel cell stainless steel bipolar plate face coat structure and preparation |
| CN109728307A (en) * | 2017-10-27 | 2019-05-07 | 中国科学院大连化学物理研究所 | A kind of preparation and bipolar plates and application of the metal double polar plates based on carbon film modification |
| CN110684946A (en) * | 2019-11-07 | 2020-01-14 | 中国科学院宁波材料技术与工程研究所 | Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| J. MUSIL等: "Nanocrystalline and nanocomposite CrCu and CrCu–N films prepared by magnetron sputtering", 《SURFACE AND COATINGS TECHNOLOGY》 * |
| KUNITERU MIHARA等: "Effect of Carbon Addition on Solidification Structure and Strength in Cu-Cr In-situ Composite", 《JOURNAL OF THE JAPAN INSTITUTE OF METALS》 * |
| M.A. BAKER等: "The nanostructure and mechanical properties of PVD CrCu (N) coatings", 《SURFACE AND COATINGS TECHNOLOGY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112111721B (en) | 2021-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110684946B (en) | Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof | |
| CN110284102B (en) | Metal carbide crystal composite coating and preparation method thereof | |
| CN111519157B (en) | Preparation method and application of Cr-Al-C series MAX phase coating | |
| CN113265638B (en) | High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof | |
| CN113991134B (en) | Amorphous carbon coating for fuel cell metal bipolar plate and preparation method thereof | |
| CN110137525A (en) | A kind of fuel battery metal double polar plate coating and technology of preparing | |
| CN113235062B (en) | MAX-phase multilayer composite coating and preparation method and application thereof | |
| CN112803033B (en) | Film for fuel cell metal bipolar plate and preparation method thereof | |
| WO2023284596A1 (en) | High-conductivity, corrosion-resistant and long-lifetime max phase solid solution composite coating, and preparation method therefor and use thereof | |
| CN112993298A (en) | Double-functional coating of fuel cell metal bipolar plate | |
| CN114481048B (en) | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating and preparation method and application thereof | |
| CN113937301B (en) | Transition metal nitride and carbon composite modified film on surface of metal bipolar plate and preparation method thereof | |
| CN112820890B (en) | Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate | |
| CN104051743B (en) | Metal double polar plates and preparation method thereof | |
| CN111477899B (en) | Conductive corrosion-resistant metal bipolar plate for fuel cell and preparation method thereof | |
| CN112111721B (en) | Preparation method of CrCuC gradient CrCu composite carbon film bipolar plate | |
| CN116855900A (en) | Modified carbon-based composite coating, preparation method thereof and bipolar plate | |
| CN112993293A (en) | Metal bipolar plate of fuel cell and preparation method thereof | |
| CN102306804B (en) | High-sp2 hybridization compact carbon coating layer for proton exchange membrane fuel cell bipolar plate and preparation method of high-sp2 hybridization compact carbon coating layer | |
| CN112993300A (en) | Transition layer for fuel cell metal bipolar plate coating | |
| CN115029663A (en) | Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell | |
| CN112993299B (en) | Silicon-doped niobium carbide coating of metal bipolar plate of fuel cell and preparation method thereof | |
| CN206878105U (en) | A kind of fuel battery double plates | |
| CN216389442U (en) | Deposition titanium niobium alloy hydrogen fuel cell bipolar plate based on magnetron sputtering circulation | |
| CN115928017A (en) | High-conductivity corrosion-resistant protective composite coating and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |