CN110797545A - Metal bipolar plate, preparation method thereof and fuel cell - Google Patents

Metal bipolar plate, preparation method thereof and fuel cell Download PDF

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Publication number
CN110797545A
CN110797545A CN201910962149.0A CN201910962149A CN110797545A CN 110797545 A CN110797545 A CN 110797545A CN 201910962149 A CN201910962149 A CN 201910962149A CN 110797545 A CN110797545 A CN 110797545A
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metal substrate
carbon film
carbon
vacuum chamber
deposited
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CN110797545B (en
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上官鹏鹏
金伟特
王海峰
王利生
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Fengyuan New Technology (beijing) Co Ltd
Zhejiang Fengyuan Hydrogen Energy Technology Co Ltd
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Fengyuan New Technology (beijing) Co Ltd
Zhejiang Fengyuan Hydrogen Energy Technology Co Ltd
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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
    • 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
    • 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
    • C23C14/0605—Carbon
    • 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
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • 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
    • H01M8/0206—Metals or alloys
    • H01M8/0208—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

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Abstract

The invention relates to a metal bipolar plate, a preparation method thereof and a fuel cell. The main technical scheme adopted is as follows: the metal bipolar plate comprises a metal substrate and a carbon-based coating; wherein the carbon-based coating is deposited on the metal substrate, and the carbon-based coating comprises at least two carbon films which are sequentially deposited; wherein each carbon film is any one of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film; the carbon-based coating comprises at least two of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film. The invention is mainly used for improving the corrosion resistance, the coating bonding force and the conductivity of the metal bipolar plate.

Description

Metal bipolar plate, preparation method thereof and fuel cell
Technical Field
The invention relates to the technical field of fuel cells, in particular to a metal bipolar plate, a preparation method thereof and a fuel cell.
Background
Compared with a carbon-based bipolar plate fuel cell, the metal bipolar plate fuel cell has the advantages of high power density and the like. However, because of the harsh working environment of the fuel cell itself, the existing metal materials (including common materials such as stainless steel, titanium, aluminum alloy, etc.) cannot meet the requirement of long-term operation of the metal bipolar plate fuel cell; in particular, iron ions dissolved out from the stainless steel material have a serious influence on the performance of the stack.
In order to improve the stability of the metal bipolar plate fuel cell, the prior art modifies the surface of the metal bipolar plate; the method for modifying the metal bipolar plate mainly comprises the step of depositing a surface modified coating on a metal substrate, such as a noble metal (gold, silver and platinum) coating, a corrosion-resistant ceramic material (titanium nitride, titanium carbide, chromium nitride and chromium nitride) coating, an organic polymer film, a carbon-based coating and the like.
Among the existing modified coatings, the carbon-based coating is the most preferable. Compared with noble metal coatings and corrosion-resistant ceramic material coatings, the carbon-based coating has the advantages of high conductivity, good corrosion resistance, low price, simple preparation method and the like.
In the prior art, when depositing a carbon-based coating on a metallic bipolar plate, only one type of carbon film is deposited by one deposition method (e.g., a multi-arc ion plating carbon film is deposited on a metallic substrate by a multi-arc ion plating deposition method). However, the deposition method has defects, which cause the deposition of the carbon-based coating on the metal bipolar plate to have at least one of the following problems: (1) poor bonding between the carbon-based coating and other coatings; (2) the pinhole rate in the carbon-based coating is high, so that the corrosion resistance of the carbon-based coating is poor; (3) carbon films are not pure and can reduce the conductivity of the carbon-based coating. The above problems may reduce the coating adhesion, corrosion resistance and electrical conductivity of the metallic bipolar plate.
Disclosure of Invention
In view of the above, the present invention provides a metal bipolar plate, a method for manufacturing the same, and a fuel cell, and mainly aims to improve the coating adhesion, corrosion resistance, and electrical conductivity of the metal bipolar plate.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide a metallic bipolar plate, wherein the metallic bipolar plate includes:
a metal substrate;
a carbon-based coating deposited on the metal substrate, the carbon-based coating comprising at least two layers of carbon films deposited in sequence;
wherein each layer of the carbon film is any one of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film;
the carbon-based coating comprises at least two carbon films of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film.
Preferably, the metallic bipolar plate further comprises: a corrosion-resistant coating deposited on the metal substrate and positioned between the metal substrate and the carbon-based coating; preferably, the corrosion-resistant coating comprises one or more of titanium nitride, chromium titanium nitride, chromium carbide, tungsten, nickel, aluminum and copper; preferably, the thickness of the corrosion-resistant coating is 20 nm-5 um.
Preferably, the composition of each layer of the carbon film is any one of graphene, graphite, and amorphous carbon film.
Preferably, the thickness of the carbon-based coating is 100nm-5 μm; and/or the thickness of each of the carbon films in the carbon-based coating layer is 5nm to 1 μm.
Preferably, the coating bonding force of the metal bipolar plate is 48-55N; and/or the contact resistance of the metal bipolar plate is 0.7-2.2m omega cm2(ii) a And/or the corrosion potential of the metallic bipolar plate is 305-365 mV; and/or the corrosion current of the metal bipolar plate is 5.0 x 10-8-2.3×10-7A/cm2。
On the other hand, an embodiment of the present invention provides a method for manufacturing the metal bipolar plate, which is characterized by comprising the following steps:
pretreatment: pretreating a metal substrate;
depositing a carbon-based coating: sequentially depositing at least two layers of carbon films on the metal substrate by adopting at least two deposition methods of a laser pulse deposition method, a molecular beam epitaxy deposition method, a magnetron sputtering deposition method, a multi-arc ion plating deposition method and a chemical vapor deposition method;
preferably, the step of pre-treating comprises:
a first pretreatment step: sequentially carrying out oil removal treatment, polishing treatment, cleaning treatment and drying treatment on the metal substrate;
a second pretreatment step: carrying out surface ion sputtering and etching activation treatment on the metal substrate;
preferably, bias magnetic control multi-arc ion plating equipment is adopted to carry out surface ion sputtering and etching activation treatment on the metal substrate;
preferably, the second pretreatment step specifically includes: after the metal substrate was transferred into a vacuum chamber, the vacuum degree of the vacuum chamber was evacuated to 1X 10-3～5×10-3Pa; heating a metal substrate to 150-300 ℃; introducing inert gas into the vacuum chamber to maintain the pressure of the vacuum chamber at 0.05-1 Pa; and carrying out surface ion sputtering and etching activation treatment on the metal substrate for 3-15min under the bias voltage of-200V to-1000V.
Preferably, after the step of pretreating and before the step of depositing the carbon-based coating, the method further comprises the following steps: depositing a corrosion-resistant coating: depositing a corrosion-resistant coating on a metal substrate;
preferably, the step of depositing a corrosion-resistant coating comprises:
placing the pretreated metal substrate in a vacuum chamber, and pumping the vacuum chamber to 1.5 × 10-3～3×10-3Pa；
Heating the metal substrate to 150-700 ℃;
introducing inert gas or nitrogen into the vacuum chamber;
opening the metal target, and carrying out ion sputtering on the metal substrate under the bias voltage of-100 to-600V to deposit the corrosion-resistant coating on the metal substrate.
Preferably, the steps of depositing the carbon-based coating are all performed in a vacuum chamber; wherein, in the step of depositing the carbon-based coating:
if the carbon film is deposited by adopting a laser pulse deposition method: the vacuum degree of the vacuum chamber is pumped to 5X 10-4～3×10- 3Pa, heating the temperature in the vacuum chamber to 300-500 ℃, and starting a laser to perform laser pulse deposition; preferably, the distance between the target bases is 5-8 cm; preferably, the laser wavelength is 230-300nm, the power is 180-220mJ, and the frequency is 10-30 Hz; preferably, the deposition time is 15-60 min.
If the magnetron sputtering deposition method is adopted to deposit the carbon film: firstly, the vacuum degree of the vacuum chamber is pumped to 1.5 multiplied by 10-3～3×10-3After Pa, introducing 300-650sccm inert gas or nitrogen gas for magnetron sputtering deposition of carbon film(ii) a Preferably, the sputtering current is 3-20A, and the sputtering bias is-100 to-600V; preferably, the temperature of the metal substrate is 80-500 ℃; preferably, the deposition time is 15min-3 h;
if the multi-arc ion plating deposition method is adopted to deposit the carbon film: firstly, the vacuum degree in the vacuum chamber is pumped to 2 multiplied by 10-3～9×10-3Pa, then introducing 50-500sccm inert gas or nitrogen to perform multi-arc ion plating and deposition of a carbon film; preferably, the sputtering current is 10-200A, and the sputtering bias is-80 to-600V; preferably, the temperature of the metal substrate is 80-450 ℃; preferably, the deposition time is 60s-45 min.
Preferably, when the carbon film is deposited by a chemical vapor deposition method, the method comprises the following steps:
the vacuum degree of the vacuum chamber is pumped to 3X 10-3～5×10-3Pa；
Introducing diluent gas hydrogen with the flow rate set to 400-;
adjusting the air pressure in the vacuum chamber to 0.8-1.0 KPa;
starting a plasma power supply to glow hydrogen and ionize to generate plasma;
introducing a carbon source gas of 5-10sccm, adjusting the air pressure in the vacuum chamber to 3-5KPa, and depositing a carbon film;
preferably, the deposition time of the chemical vapor deposition method is 3-20 min;
preferably, when the carbon film is deposited by chemical vapor deposition, the temperature of the metal substrate is 450-750 ℃.
In still another aspect, an embodiment of the present invention further provides a fuel cell, where the fuel cell includes the metal bipolar plate described in any one of the above.
Compared with the prior art, the metal bipolar plate, the preparation method thereof and the fuel cell have the following beneficial effects:
when the carbon-based coating is deposited on the metal substrate, the carbon-based coating comprises at least two layers of carbon films which are sequentially deposited, wherein each layer of carbon film is any one of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film, and the carbon-based coating comprises at least two of the laser pulse deposited carbon film, the magnetron sputtering deposited carbon film, the multi-arc ion plating deposited carbon film and the chemical vapor deposition carbon film; thus, the deposition methods of at least two carbon films can generate synergistic action, and the at least two carbon films can generate synergistic action, so that the defects of each deposition method or each carbon film can be effectively overcome, and the bonding force of the carbon-based coating and the corrosion resistance and the electrical conductivity of the carbon-based coating are improved; thereby improving the coating binding force, corrosion resistance, conductivity and other properties of the metal bipolar plate.
Furthermore, the metal bipolar plate and the preparation method thereof provided by the embodiment of the invention can further improve the corrosion resistance and the electrical conductivity of the metal bipolar plate by depositing the corrosion-resistant coating on the metal substrate and then depositing the carbon-based coating on the corrosion-resistant coating.
In addition, the fuel cell provided by the embodiment of the invention comprises the metal bipolar plate, and the metal bipolar plate has excellent performances such as bonding force, corrosion resistance and conductivity, so that the fuel cell provided by the embodiment of the invention has good stability.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a schematic structural diagram of a metal bipolar plate according to an embodiment of the present invention.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In one aspect, embodiments of the present invention provide a metallic bipolar plate, as shown in fig. 1, including: metal substrate 1, carbon base coating 3. Wherein the carbon-based coating 3 is deposited on the metal substrate 1, and the carbon-based coating 3 includes at least two carbon films deposited in sequence. Here, each carbon film is any one of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film; and the carbon-based coating comprises at least two carbon films of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film. Preferably, the metallic bipolar plate further comprises a corrosion-resistant coating 2, the corrosion-resistant coating 2 being deposited on the metallic substrate 1 and being located between said metallic substrate 1 and the carbon-based coating 3.
On one hand, when the carbon-based coating is deposited, the metal bipolar plate provided by the embodiment of the invention comprises at least two carbon films which are sequentially deposited, wherein each carbon film is any one of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film, and the carbon-based coating comprises at least two carbon films of the laser pulse deposited carbon film, the magnetron sputtering deposited carbon film, the multi-arc ion plating deposited carbon film and the chemical vapor deposition carbon film; the arrangement can lead the deposition methods of at least two carbon films to generate synergistic action and the at least two carbon films to generate synergistic action, and improve the coating binding force of the carbon-based coating and the corrosion-resistant coating, and the corrosion resistance and the electrical conductivity of the carbon-based coating; on the other hand, the corrosion resistance, the coating bonding force and the conductivity of the metal bipolar plate can be further improved by depositing the corrosion-resistant coating on the metal substrate and then depositing the carbon-based coating on the corrosion-resistant coating.
Preferably, the composition of each carbon film layer is any one of graphene, graphite and amorphous carbon film. Herein, carbon in the amorphous carbon film is sp2And sp3Hybrid mixtures in which chemical elements such as hydrogen, oxygen, etc. may be present; the graphene is a single-layer or multi-layer six-circle carbon ring; graphite is sp2A large number of six-circle carbon rings are hybridized in a disordered stack.
Preferably, the corrosion-resistant coating comprises a composition comprising one or more of titanium nitride, chromium titanium nitride, chromium carbide, tungsten, nickel, aluminum, copper.
Preferably, the metal substrate is selected from stainless steel (e.g., 316L stainless steel), titanium sheet, aluminum alloy plate, etc.
On the other hand, the preparation method of the metal bipolar plate comprises the following steps:
1) pretreatment: the metal substrate is pretreated, so that the cleanliness and the surface roughness of the metal substrate are improved. The method specifically comprises the following steps:
11) the first step of pretreatment: and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate. Specifically, a first degreasing treatment is performed on a selected metal substrate with a 1M sodium hydroxide solution at a high temperature (e.g., 80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using brightening agents such as alumina polishing paste or diamond polishing paste; the purpose of this treatment is: on one hand, the oxide skin on the surface is taken out, on the other hand, the texture and the defects of the surface are reduced through polishing treatment, and the flatness of the material is improved. And finally, cleaning the metal substrate by using pure water after polishing is finished, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
The step is to improve the cleanness and the roughness of the metal substrate and increase the specific surface area of the metal substrate, so that the bonding force between the metal substrate and the coating is enhanced.
12) The second step of pretreatment: in a vacuum state, ion sputtering is performed on a metal substrate.
Specifically, a bias magnetron multi-arc ion plating apparatus was used, a jig with a metal substrate was set in a vacuum chamber, and the vacuum degree of the vacuum chamber was evacuated to 1X 10-3Pa～5×10-3Pa, preferably 2.0X 10-3Pa, heating the metal substrate to 150-300 ℃, introducing 500sccm inert gas, controlling the air pressure in the vacuum chamber to be 0.05-1Pa, and then carrying out surface ion sputtering and etching activation on the metal substrate under the bias voltage of-200V to-1000V for 3-15 min.
Here, the purpose of the pretreatment operation by ion sputtering is to: in order to further remove the oxide on the surface of the metal substrate; meanwhile, the roughness of the surface of the metal substrate can be further improved through ion sputtering and etching activation, the specific surface area is increased, and the binding force between the metal substrate and the coating is enhanced.
2) And (3) depositing a corrosion-resistant coating: and depositing a corrosion-resistant coating on the pretreated metal substrate.
The method comprises the following steps: the vacuum degree of the vacuum chamber is pumped to 1.5X 10-3Pa～3×10-3Pa, introducing inert gas, setting negative bias to be-100 to-600V, turning on a metal target power supply, carrying out ion sputtering on the metal substrate, and depositing a corrosion-resistant layer on the metal substrate; preferably, the corrosion-resistant layer comprises one or more of titanium nitride, chromium titanium nitride, chromium carbide, tungsten, nickel, aluminum and copper;
preferably, in the step of depositing the corrosion-resistant coating, the temperature of the metal substrate is 150-700 ℃.
3) Depositing a carbon-based coating: and sequentially depositing at least two layers of carbon films on the corrosion-resistant coating by adopting at least two deposition methods of a laser pulse deposition method, a molecular beam epitaxy deposition method, a magnetron sputtering deposition method, a multi-arc ion plating deposition method and a chemical vapor deposition method.
The laser pulse deposition method specifically comprises the following steps: in the vacuum chamber, the cooling water is turned on and the vacuum is pumped to 5X 10-4Pa～3×10-3Pa, heating the temperature in the vacuum chamber to 300-450 ℃; the distance between the target bases is 5-8 cm; the laser wavelength is 230-300nm, the power is 180-220mJ, and the frequency is 10-30Hz, preferably 20 Hz; the deposition time is 15min-60 min.
The magnetron sputtering deposition method comprises the following steps: in a vacuum chamber, vacuum is pumped to 1.5X 10-3Pa～3×10-3Pa, introducing 300-650sccm inert gas or nitrogen gas for magnetron sputtering deposition; wherein the sputtering current is 3-20A, the sputtering bias is-100 to-600V, the temperature of the metal substrate is 80-500 ℃, and the deposition time is 15min-3 h.
The multi-arc ion deposition method comprises the following specific steps: under vacuumIn a chamber, vacuum-pumping to 2X 10-3Pa～9×10-3Pa, introducing 50-500sccm inert gas or nitrogen gas to carry out multi-arc ion deposition; wherein the sputtering current is 10-200A, the sputtering bias is-80 to-600V, the temperature of the metal substrate is 80-450 ℃, and the deposition time is 60s-45 min.
The chemical vapor deposition method comprises the following steps: in a vacuum chamber, vacuum is pumped to 3 × 10-3Pa～5×10-3Pa (preferably 3X 10)-3Pa), introducing diluent gas hydrogen, setting the flow rate to be 500sccm, adjusting the gas pressure in the reaction chamber to be 0.8-1.0KPa, starting a plasma power supply, starting the hydrogen to glow, ionizing to generate plasma, and simultaneously gradually increasing the power and the pressure. And after the temperature is raised, introducing carbon source gas such as methane, acetylene and the like of 5-10sccm, adjusting the gas pressure in the vacuum chamber to be about 3-5KPa, and depositing the carbon film. The deposition time is 3-20min, and the temperature of the metal substrate is 450-750 ℃.
The inventors of the present invention found that the above deposition methods have the following advantages and disadvantages, respectively, and proposed:
the laser pulse deposition method can evaporate high-melting-point graphite, and has the advantages of high evaporation speed, less pollution to a deposition cavity, accurate control of the thickness of a coating by controlling pulses, low substrate deposition temperature, easy acquisition of a lamellar grown film and the like. However, the laser pulse deposition method has disadvantages that the formed plasma contains large liquid drops due to high laser energy density, the prepared film usually has micron-sized small particles, which affects the uniformity of the film, and the film with a larger area is difficult to prepare due to the directional effect of the plume. Meanwhile, the bonding force between the carbon film deposited by the laser pulse method and the substrate is not high.
The carbon film prepared by the magnetron sputtering deposition method has smaller particles, good coating compactness and excellent corrosion resistance and conductivity. The "glow" that is generally uniform across the surface of the carbon target allows the carbon target to have a longer life. But the magnetron sputtering method has very low ionization efficiency and high energy consumption. Whether direct current sputtering or radio frequency sputtering, the preparation time is usually more than several hours to obtain a better carbon film.
The multi-arc ion plating deposition method has the characteristic of high ionization efficiency, the ionization efficiency can reach more than ten times of the magnetron sputtering efficiency, the deposition speed of the coating is very high, and meanwhile, the coating and the substrate also have very good binding force. However, the fatal defect of multi-arc ion plating is that large particles are generated in the deposition process, so that the defects of high roughness of a film layer, high pinhole rate and the like are caused.
The most obvious advantages of the chemical vapor deposition method are that: the film can be uniformly deposited on the surface of a workpiece with a complex shape, the winding and plating performance is good, the defects of the film are few, and the bonding force between the film and a base material is good. In addition, the chemical vapor deposition can be used for depositing films under low vacuum and even normal pressure, so that the equipment is relatively simple.
The main drawbacks of chemical vapor deposition are: (1) the deposition rate is not too high, is not as good as evaporation and ion plating, and is even lower than sputtering coating; (2) the deposition temperature is very high, even if a plasma generating device and other new technologies are adopted, the deposition temperature is still higher than that of PVD (physical vapor deposition) coating, particularly for stainless steel substrates, the higher temperature usually causes damage to the substrates; (3) the chemical vapor deposition reaction source and the residual gas after the reaction are inflammable, explosive or toxic, environmental protection measures are needed, the cost is high, and certain pollution is caused to coating equipment.
Therefore, the preparation method of the metal bipolar plate provided by the embodiment of the invention can effectively overcome the defects of each deposition method by adopting a plurality of deposition methods to cooperatively deposit the carbon-based coating, enables different carbon films to generate a synergistic effect, and improves the bonding force, the corrosion resistance, the conductivity and the service life of the carbon films.
The following is further illustrated in detail by specific experimental examples:
example 1
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
1) and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate.
Specifically, a first degreasing treatment is carried out on a selected metal substrate by using 1M sodium hydroxide solution at 80 ℃; after cleaning, the oil is removed for the second time by alcohol. Then, polishing the base body by using brightening agent such as alumina polishing paste or diamond polishing paste, cleaning the metal substrate by using pure water after polishing, storing the cleaned metal substrate in the pure water, and blowing clean by using clean nitrogen before use.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree of the vacuum chamber to 5 x 10-3Pa, heating the metal substrate to 180 ℃, introducing 500sccm of argon, controlling the pressure in the vacuum chamber to be 1Pa, and carrying out surface ion sputtering, etching and activating on the metal substrate under the bias of-800V for 5 min.
3) And (2) starting a substrate rotating stand, introducing 100sccm nitrogen into the vacuum chamber in a coating state, maintaining the air pressure in the vacuum chamber at 0.3Pa, starting a multi-arc titanium target power supply, adjusting the current to 150A, keeping the workpiece bias power supply in a working state, controlling the temperature of the metal substrate at 200 ℃ under the bias of-180V, and depositing the corrosion-resistant coating on the metal substrate for 3 min.
4) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, introducing argon gas of 300sccm into the vacuum chamber, maintaining the air pressure in the vacuum chamber at 0.2Pa, starting a magnetic control graphite target power supply, adjusting the current to 20A, keeping a workpiece bias power supply in a working state, setting the bias voltage to-380V, controlling the temperature of the metal substrate at 200 ℃, and depositing a first carbon film on the substrate by adopting a magnetron sputtering deposition method for 20 min.
5) Transferring the sample in the step 4) into a bias plasma CVD furnace, and pumping the vacuum degree of the vacuum chamber to 3 x 10 in the vacuum chamber-3Pa, introducing diluent gas hydrogen, setting the flow rate to be 500sccm, adjusting the gas pressure in the reaction chamber to be 0.8Kpa, starting a plasma power supply to glow the hydrogen, ionizing to generate plasma, and gradually increasing the power and the pressure; heating the temperature of the metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to about 3KPa, and depositing a first carbon film on the first carbon film by chemical vapor depositionAnd depositing a second carbon film for 5min to obtain the metal bipolar plate.
Example 2
316L stainless steel is selected as the metal substrate of the embodiment. The steps of depositing a coating on the metal substrate to prepare the metal bipolar plate are as follows:
1) and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate.
Specifically, the selected metal substrate is subjected to first degreasing treatment at high temperature (80 ℃) by using 1M sodium hydroxide solution; after cleaning, the oil is removed for the second time by alcohol. Then, the substrate is polished with a brightening agent such as alumina polishing paste or diamond polishing paste. And after polishing, cleaning the metal substrate with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree of the vacuum chamber to 5 x 10-3Pa, heating the metal substrate to 180 ℃, introducing 500sccm of argon, controlling the pressure in the vacuum chamber to be 1Pa, and carrying out surface ion sputtering, etching and activating on the metal substrate under the bias of-800V for 5 min.
3) Opening a substrate rotating stand, introducing 100sccm nitrogen into a vacuum chamber under a film coating state, maintaining the air pressure in the vacuum chamber at 0.3Pa, opening a multi-arc titanium target power supply, adjusting the current to 150A, keeping a workpiece bias power supply in a working state, controlling the temperature of a metal substrate at 200 ℃ under a bias of-180V, and depositing a corrosion-resistant coating on the metal substrate for 3 min.
4) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, introducing 300sccm argon, maintaining the air pressure in the vacuum chamber at 0.2Pa, starting a multi-arc graphite target power supply, adjusting the sputtering current to 150A, keeping a workpiece bias power supply in a working state, controlling the sputtering bias voltage to-380V, and controlling the temperature of the metal substrate at 200 ℃; and depositing a first carbon film layer on the corrosion-resistant coating by adopting a multi-arc ion plating deposition method, wherein the deposition time is 3 min.
5) The vacuum degree of the vacuum chamber is pumped to 2.5X 10-3Pa, introducing 500sccm argon gas, maintaining the air pressure in the vacuum chamber at 0.2Pa, starting a magnetron graphite target power supply, adjusting the sputtering current to 5A, keeping a workpiece bias power supply in a working state, controlling the sputtering bias voltage to-380V, and controlling the metal substrate at 200 ℃; and depositing a second carbon film layer on the first carbon film layer by adopting a magnetron sputtering deposition method, wherein the deposition time is 60min, and obtaining the metal bipolar plate.
Example 3
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
1) and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate.
Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, the substrate is polished with a brightening agent such as alumina polishing paste or diamond polishing paste. And after polishing, cleaning the metal substrate with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree of the vacuum chamber to 5 x 10-3Pa, heating the metal substrate to 180 ℃, introducing 500sccm of argon, controlling the pressure of the vacuum chamber to be 1Pa, and carrying out surface ion sputtering, etching and activating on the metal substrate under the bias of-800V for 5 min.
3) Opening a substrate rotating stand, introducing 100sccm nitrogen into a vacuum chamber under a film coating state, maintaining the air pressure of the vacuum chamber at 0.3Pa, opening a multi-arc titanium target power supply, adjusting the current to 150A, keeping a workpiece bias power supply in a working state, controlling the temperature of a metal substrate at 200 ℃ under a bias of-180V, and depositing a corrosion-resistant coating on the metal substrate for 3 min.
4) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, then introducing 300sccm of argon gas to maintain the vacuum chamberThe air pressure of the sputtering target is 0.2Pa, a multi-arc graphite target power supply is started, the sputtering current is adjusted to 150A, a workpiece bias power supply is kept in a working state, the sputtering bias voltage is-380V, and the temperature of the metal substrate is controlled at 200 ℃; and depositing a first carbon film layer on the corrosion-resistant coating by adopting a multi-arc ion plating deposition method, wherein the deposition time is 3 min.
5) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, regulating the distance between the target substrate and the target substrate to be 5cm, then heating the temperature in the vacuum chamber to 500 ℃, starting and preheating the laser, wherein the preheating time is 10min, the laser wavelength is regulated to be 250nm, the power is 210mJ, and the frequency is 20Hz, depositing a second carbon film on the first carbon film by adopting a laser pulse deposition method, the deposition time is 15min, closing the laser after the deposition is finished, and cooling to the room temperature to obtain the metal bipolar plate.
Example 4
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
1) and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate.
Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, the substrate is polished with a brightening agent such as alumina polishing paste or diamond polishing paste. And after polishing, cleaning the metal substrate with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree of the vacuum chamber to 5 x 10-3Pa, heating the metal substrate to 180 ℃, introducing 500sccm of argon, controlling the pressure of the vacuum chamber to be 1Pa, and carrying out surface ion sputtering, etching and activating on the metal substrate under the bias of-800V for 5 min.
3) Opening a substrate rotating stand, introducing 100sccm nitrogen into a vacuum chamber under a film coating state, maintaining the air pressure of the vacuum chamber at 0.3Pa, opening a multi-arc titanium target power supply, adjusting the current to 150A, keeping a workpiece bias power supply in a working state, controlling the temperature of a metal substrate at 200 ℃ under a bias of-180V, and depositing a corrosion-resistant coating on the metal substrate for 3 min.
4) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, regulating the distance of the target substrate to be 5cm, then heating the temperature in the vacuum chamber to 500 ℃, starting and preheating the laser, wherein the preheating time is 10min, the laser wavelength is regulated to be 250nm, the power is 210mJ, and the frequency is 20Hz, depositing a first carbon film layer on the corrosion-resistant coating by adopting a laser pulse deposition method, the deposition time is 15min, closing the laser after the deposition is finished, and cooling to the room temperature.
5) Transferring the sample in the step 4) into a bias plasma CVD furnace, and pumping the vacuum degree of the vacuum chamber to 3 x 10 in the vacuum chamber-3Pa, introducing diluent gas hydrogen, setting the flow rate to be 500sccm, adjusting the gas pressure in the reaction chamber to be 0.8Kpa, starting a plasma power supply to glow the hydrogen, ionizing to generate plasma, and gradually increasing the power and the pressure; and (3) heating the temperature of the metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and depositing a second carbon film on the first carbon film by adopting a chemical vapor deposition method for 5min to obtain the metal bipolar plate.
Example 5
In this example, a titanium plate was selected as the metal substrate. The steps of depositing a coating on the metal substrate to prepare the metal bipolar plate are as follows:
1) and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate.
Specifically, the selected metal substrate is subjected to first degreasing treatment by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. And after polishing, cleaning the metal substrate with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into the vacuum chamber and make the vacuum chamber be vacuumThe void degree is pumped to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing 500sccm of argon, controlling the pressure of the vacuum chamber to be 1Pa, and carrying out surface ion sputtering, etching and activating on the metal substrate under the bias of-800V for 5 min.
3) And (2) starting a substrate rotating stand, introducing 100sccm nitrogen into the vacuum chamber in a coating state, maintaining the air pressure in the vacuum chamber at 0.3Pa, starting a multi-arc titanium target power supply, adjusting the current to 150A, keeping the workpiece bias power supply in a working state, controlling the temperature of the metal substrate at 200 ℃ under the bias of-180V, and depositing the corrosion-resistant coating on the metal substrate for 3 min.
4) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, introducing argon gas of 300sccm into the vacuum chamber, maintaining the air pressure of the vacuum chamber at 0.2Pa, starting a magnetic control graphite target power supply, adjusting the current to 20A, keeping a workpiece bias power supply in a working state, setting the bias voltage to-380V, controlling the temperature of a substrate (a metal substrate deposited with the corrosion-resistant coating) at 200 ℃, and depositing a first carbon film on the substrate by adopting a magnetron sputtering deposition method for 20 min.
5) Transferring the sample in the step 4) into a bias plasma CVD furnace, and pumping the vacuum degree of the vacuum chamber to 3 x 10 in the vacuum chamber-3Pa, introducing diluent gas hydrogen, setting the flow rate to be 500sccm, adjusting the gas pressure in the reaction chamber to be 0.8Kpa, starting a plasma power supply to glow the hydrogen, ionizing to generate plasma, and gradually increasing the power and the pressure; and heating the metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and depositing a second carbon film on the first carbon film by a chemical vapor deposition method for 5 min.
6) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, regulating the distance of the target substrate to 5cm, heating the vacuum chamber to 500 deg.C, starting and preheating the laser for 10min, regulating the laser wavelength to 250nm, power to 210mJ, and frequency to 20Hz, depositing a third carbon film on the second carbon film by laser pulse deposition for 15min, and closing after depositionAnd closing the laser, and cooling to room temperature to obtain the metal bipolar plate.
Example 6
An aluminum alloy sheet is selected as the metal substrate of the embodiment. The steps of depositing a coating on the metal substrate to prepare the metal bipolar plate are as follows:
1) and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate.
Specifically, the selected metal substrate is subjected to first degreasing treatment at high temperature (80 ℃) by using 1M sodium hydroxide solution; after cleaning, the oil is removed for the second time by alcohol. Then, the substrate is polished with a brightening agent such as alumina polishing paste or diamond polishing paste. And after polishing, cleaning the metal substrate with pure water, putting the cleaned metal substrate into the pure water for storage, and blowing clean nitrogen gas before use.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree of the vacuum chamber to 5 x 10-3Pa, heating the metal substrate to 180 ℃, introducing 500sccm of argon, controlling the pressure of the vacuum chamber to be 1Pa, and carrying out surface ion sputtering, etching and activating on the metal substrate under the bias of-800V for 5 min.
3) Opening a substrate rotating stand, introducing 100sccm nitrogen into a vacuum chamber under a film coating state, maintaining the air pressure of the vacuum chamber at 0.3Pa, opening a multi-arc titanium target power supply, adjusting the current to 150A, keeping a workpiece bias power supply in a working state, controlling the temperature of a metal substrate at 200 ℃ under a bias of-180V, and depositing a corrosion-resistant coating on the metal substrate for 3 min.
4) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, introducing argon gas of 300sccm into the vacuum chamber, maintaining the air pressure of the vacuum chamber at 0.2Pa, starting a magnetic control graphite target power supply, adjusting the current to 20A, keeping a workpiece bias power supply in a working state, setting the bias voltage to-380V, controlling the temperature of a substrate (a metal substrate deposited with the corrosion-resistant coating) at 200 ℃, and depositing a first carbon film on the substrate by adopting a magnetron sputtering deposition method for 20 min.
5) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, introducing 300sccm argon, maintaining the air pressure of the vacuum chamber at 0.2Pa, starting a multi-arc graphite target power supply, adjusting the sputtering current to 150A, keeping a workpiece bias power supply in a working state, controlling the sputtering bias voltage to-380V, and controlling the temperature of the metal substrate at 200 ℃; and depositing a second carbon film layer on the first carbon film layer by adopting a multi-arc ion plating deposition method, wherein the deposition time is 3 min.
6) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3Pa, regulating the distance between the target substrate and the target substrate to be 5cm, then heating the temperature in the vacuum chamber to 500 ℃, starting and preheating the laser, wherein the preheating time is 10min, the laser wavelength is regulated to be 250nm, the power is 210mJ, and the frequency is 20Hz, depositing a third carbon film on the second carbon film by adopting a laser pulse deposition method, the deposition time is 15min, closing the laser after the deposition is finished, and cooling to the room temperature.
7) Transferring the sample in the step 6) into a bias plasma CVD furnace, and pumping the vacuum degree of the vacuum chamber to 3 x 10 in the vacuum chamber-3Pa, introducing diluent gas hydrogen, setting the flow rate to be 500sccm, adjusting the gas pressure in the reaction chamber to be 0.8Kpa, starting a plasma power supply to glow the hydrogen, ionizing to generate plasma, and gradually increasing the power and the pressure; and (3) heating the metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and depositing a fourth carbon film on the third carbon film by adopting a chemical vapor deposition method for 5min to obtain the metal bipolar plate.
Comparative example 1
316L stainless steel is selected as the metal substrate of the embodiment. Depositing a coating on the metal substrate to prepare the metal bipolar plate, which comprises the following steps:
1) and sequentially carrying out oil removal, polishing, cleaning and drying treatment on the metal substrate.
Specifically, a first degreasing treatment is carried out on a selected metal substrate by using 1M sodium hydroxide solution at 80 ℃; after cleaning, the oil is removed for the second time by alcohol. Then, polishing the base body by using brightening agent such as alumina polishing paste or diamond polishing paste, cleaning the metal substrate by using pure water after polishing, storing the cleaned metal substrate in the pure water, and blowing clean by using clean nitrogen before use.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and pumping the vacuum degree of the vacuum chamber to 5 x 10-3Pa, heating the metal substrate to 180 ℃, introducing 500sccm of argon, controlling the pressure of the vacuum chamber to be 1Pa, and carrying out surface ion sputtering, etching and activating on the metal substrate under the bias of-800V for 5 min.
3) Starting a substrate rotating stand, introducing 100sccm nitrogen into a vacuum chamber in a film coating state, maintaining the air pressure in the vacuum chamber at 0.3Pa, starting a multi-arc titanium target power supply, adjusting the current to 150A, keeping a workpiece bias power supply in a working state, controlling the temperature of a metal substrate at 200 ℃ under a bias of-180V, and depositing a corrosion-resistant coating on the metal substrate for 3 min.
4) Firstly, the vacuum degree of the vacuum chamber is pumped to 2.5 multiplied by 10-3And Pa, introducing argon gas of 300sccm into the vacuum chamber, maintaining the air pressure of the vacuum chamber at 0.2Pa, starting a magnetic control graphite target power supply, regulating the current to 20A, keeping the workpiece bias power supply in a working state, setting the bias voltage to-380V, controlling the temperature of the metal substrate at 200 ℃, and depositing a layer of carbon film on the substrate by adopting a magnetron sputtering deposition method for 40min to obtain the metal bipolar plate.
The structures of the metal bipolar plates prepared in the above examples and comparative examples are respectively as follows:
the metallic bipolar plate of example 1 includes: the coating comprises a metal substrate, a corrosion-resistant coating, a magnetron sputtering deposition carbon film and a chemical vapor deposition carbon film which are sequentially deposited on the metal substrate.
The metallic bipolar plate of example 2 includes: the coating comprises a metal substrate, a corrosion-resistant coating, a multi-arc ion plating deposited carbon film and a magnetron sputtering deposited carbon film, wherein the corrosion-resistant coating, the multi-arc ion plating deposited carbon film and the magnetron sputtering deposited carbon film are sequentially deposited on the metal substrate.
The metallic bipolar plate of example 3 includes: the metal substrate, the corrosion-resistant coating deposited on the metal substrate in sequence, the multi-arc ion plating deposited carbon film and the laser pulse deposited carbon film.
The metallic bipolar plate of example 4 comprises: the metal substrate, the corrosion-resistant coating deposited on the metal substrate in sequence, the laser pulse deposited carbon film and the chemical vapor deposited carbon film.
The metallic bipolar plate of example 5 comprises: the device comprises a metal substrate, a corrosion-resistant coating, a magnetron sputtering deposition carbon film, a chemical vapor deposition carbon film and a laser pulse deposition carbon film which are sequentially deposited on the metal substrate.
The metallic bipolar plate of example 6 comprises: the device comprises a metal substrate, a corrosion-resistant coating sequentially deposited on the metal substrate, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film, a laser pulse deposited carbon film and a chemical vapor deposited carbon film.
The metallic bipolar plate of comparative example 1 includes: a metal substrate, a corrosion-resistant coating sequentially deposited on the metal substrate, and a magnetron sputtering deposited carbon film (the deposition time of the magnetron sputtering deposited carbon film in comparative example 1 is 2 times that of the magnetron sputtering deposited carbon film in example 1, and then the magnetron sputtering deposited carbon film in comparative example 1 is about 2 times that of the magnetron sputtering deposited carbon film in example 1).
The metal bipolar plates prepared in examples 1 to 6 and comparative example 1 were subjected to performance tests, and the test results are shown in table 1.
Table 1 shows the performance test data of the metal bipolar plates prepared in examples 1-6 and comparative example 1
Figure BDA0002229292420000171
As can be seen from table 1: the metal bipolar plate prepared by the embodiment of the invention has excellent corrosion resistance, conductivity and coating bonding force.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.

Claims (10)

1. A metallic bipolar plate, comprising:
a metal substrate;
a carbon-based coating deposited on the metal substrate, the carbon-based coating comprising at least two layers of carbon films deposited in sequence;
wherein each layer of the carbon film is any one of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film;
the carbon-based coating comprises at least two carbon films of a laser pulse deposited carbon film, a magnetron sputtering deposited carbon film, a multi-arc ion plating deposited carbon film and a chemical vapor deposition carbon film.
2. The metallic bipolar plate of claim 1, further comprising:
a corrosion-resistant coating deposited on the metal substrate and positioned between the metal substrate and the carbon-based coating;
preferably, the corrosion-resistant coating comprises one or more of titanium nitride, chromium titanium nitride, chromium carbide, tungsten, nickel, aluminum and copper;
preferably, the thickness of the corrosion-resistant coating is 20 nm-5 um.
3. The metallic bipolar plate of claim 1, wherein the composition of each layer of the carbon film is any one of graphene, graphite, and amorphous carbon film.
4. Metallic bipolar plate as in claim 1,
the thickness of the carbon-based coating is 100nm-5 mu m; and/or
Each of the carbon films in the carbon-based coating layer has a thickness of 5nm to 1 μm.
5. The method for preparing a metal substrate according to any one of claims 1 to 4, wherein the coating bonding force of the metal bipolar plate is 48 to 55N; and/or
The contact resistance of the metal bipolar plate is 0.7-2.2m omega cm2(ii) a And/or
The corrosion potential of the metal bipolar plate is 305-365 mV; and/or
The corrosion current of the metal bipolar plate is 5.0 multiplied by 10-8-2.3×10-7A/cm2。
6. The method of manufacturing a metallic bipolar plate as set forth in any one of claims 1 to 5, comprising the steps of:
pretreatment: pretreating a metal substrate;
depositing a carbon-based coating: sequentially depositing at least two layers of carbon films on the metal substrate by adopting at least two deposition methods of a laser pulse deposition method, a molecular beam epitaxy deposition method, a magnetron sputtering deposition method, a multi-arc ion plating deposition method and a chemical vapor deposition method;
preferably, the step of pre-treating comprises:
a first pretreatment step: sequentially carrying out oil removal treatment, polishing treatment, cleaning treatment and drying treatment on the metal substrate;
a second pretreatment step: carrying out surface ion sputtering and etching activation treatment on the metal substrate;
preferably, bias magnetic control multi-arc ion plating equipment is adopted to carry out surface ion sputtering and etching activation treatment on the metal substrate;
preferably, the second pretreatment step specifically includes: after the metal substrate was transferred into a vacuum chamber, the vacuum degree of the vacuum chamber was evacuated to 1X 10-3～5×10-3Pa; heating a metal substrate to 150-300 ℃; introducing inert gas into the vacuum chamber to maintain the pressure of the vacuum chamber at 0.05-1 Pa; and carrying out surface ion sputtering and etching activation treatment on the metal substrate for 3-15min under the bias voltage of-200V to-1000V.
7. The method of claim 6, further comprising, after the step of pretreating and before the step of depositing the carbon-based coating:
depositing a corrosion-resistant coating: depositing a corrosion-resistant coating on a metal substrate;
preferably, the step of depositing a corrosion-resistant coating comprises:
placing the pretreated metal substrate in a vacuum chamber, and pumping the vacuum chamber to 1.5 × 10-3～3×10- 3Pa；
Heating the metal substrate to 150-700 ℃;
introducing inert gas or nitrogen into the vacuum chamber;
opening the metal target, and carrying out ion sputtering on the metal substrate under the bias voltage of-100 to-600V to deposit the corrosion-resistant coating on the metal substrate.
8. The method of manufacturing a metallic bipolar plate as claimed in claim 6 or 7, wherein the steps of depositing the carbon-based coating are all performed in a vacuum chamber; wherein, in the step of depositing the carbon-based coating:
if the carbon film is deposited by adopting a laser pulse deposition method: the vacuum degree of the vacuum chamber is pumped to 5X 10-4～3×10-3Pa, heating the temperature in the vacuum chamber to 300-500 ℃, and starting a laser to perform laser pulse deposition; preferably, the distance between the target bases is 5-8 cm; preferably, the laser wavelength is 230-300nm, the power is 180-220mJ, and the frequency is 10-30 Hz; preferably, the deposition time is 15-60 min;
if the magnetron sputtering deposition method is adopted to deposit the carbon film: firstly, the vacuum degree of the vacuum chamber is pumped to 1.5 multiplied by 10-3～3×10-3After Pa, introducing 300-650sccm inert gas or nitrogen gas to perform magnetron sputtering to deposit a carbon film; preferably, the sputtering current is 3-20A, and the sputtering bias is-100 to-600V; preferably, the temperature of the metal substrate is 80-500 ℃; preferably, the deposition time is 15min-3 h;
if the multi-arc ion plating deposition method is adopted to deposit the carbon film: firstly, the vacuum degree in the vacuum chamber is pumped to 2 multiplied by 10-3～9×10- 3Pa, then 50 of gas is introduced-500sccm of an inert gas or nitrogen gas, performing multi-arc ion plating to deposit a carbon film; preferably, the sputtering current is 10-200A, and the sputtering bias is-80 to-600V; preferably, the temperature of the metal substrate is 80-450 ℃; preferably, the deposition time is 60s-45 min.
9. The method of claim 8, wherein the step of depositing the carbon film by chemical vapor deposition comprises the steps of:
the vacuum degree of the vacuum chamber is pumped to 3X 10-3～5×10-3Pa；
Introducing diluent gas, wherein the flow rate is set to 400-;
adjusting the air pressure in the vacuum chamber to 0.8-1.0 KPa;
starting a plasma power supply to glow the diluent gas and ionize to generate plasma;
introducing a carbon source gas of 5-10sccm, adjusting the air pressure in the vacuum chamber to 3-5KPa, and depositing a carbon film;
preferably, the diluent gas is hydrogen;
preferably, the deposition time of the chemical vapor deposition method is 3-20 min;
preferably, when the carbon film is deposited by chemical vapor deposition, the temperature of the metal substrate is 450-750 ℃.
10. A fuel cell comprising the metallic bipolar plate of any one of claims 1 to 5.
CN201910962149.0A 2019-10-11 2019-10-11 Metal bipolar plate, preparation method thereof and fuel cell Active CN110797545B (en)

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CN112909281A (en) * 2021-01-21 2021-06-04 深圳大学 Stainless steel metal bipolar plate, preparation method thereof and fuel cell
CN112886033A (en) * 2021-01-27 2021-06-01 浙江锋源氢能科技有限公司 Polar plate structure, preparation method thereof, bipolar plate with polar plate structure and fuel cell
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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
CN113584441B (en) * 2021-08-02 2023-11-07 杭州兴态环保科技有限公司 Metal bipolar plate coating and preparation method thereof
CN114231897A (en) * 2021-12-20 2022-03-25 深圳市福容科技有限公司 Carbon film current collector produced by vacuum magnetron sputtering and preparation method thereof
CN114824339A (en) * 2022-04-06 2022-07-29 中汽创智科技有限公司 Metal bipolar plate coating and preparation method and application thereof
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CN116314904B (en) * 2023-03-19 2023-09-19 畔星科技(浙江)有限公司 Metal bipolar plate of hydrogen fuel cell, processing equipment and preparation process

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