CN110808384A - 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
CN110808384A
CN110808384A CN201910962146.7A CN201910962146A CN110808384A CN 110808384 A CN110808384 A CN 110808384A CN 201910962146 A CN201910962146 A CN 201910962146A CN 110808384 A CN110808384 A CN 110808384A
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metal substrate
bipolar plate
graphene layer
vacuum chamber
layer
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CN110808384B (en
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上官鹏鹏
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
    • H01M8/0206—Metals or alloys
    • 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
    • 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
    • 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
    • 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
    • C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • 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
    • H01M8/0223—Composites
    • H01M8/0226—Composites in the form of mixtures
    • 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 metal bipolar plate, a preparation method thereof and a fuel cell, and relates to the technical field of fuel cells. The main technical scheme adopted is as follows: the metal bipolar plate comprises a metal substrate, a Cu nano layer, a graphene layer and an amorphous carbon film. Wherein the Cu nanolayer is deposited on the metal substrate; preparing a graphene layer on the Cu nano layer; an amorphous carbon film is deposited on the graphene layer. A fuel cell comprises the metal bipolar plate. The invention is mainly used for improving the corrosion resistance and the electrical conductivity of the metal bipolar plate and improving the binding force between the coating and the metal substrate, thereby prolonging the service life of the metal bipolar plate and the fuel cell.

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
The bipolar plate is one of the most critical components of a PEMFC stack, and its cost accounts for about 35% of the stack cost. The bipolar plate is mainly used for transferring electrons, transferring heat, collecting gas, dividing single cells and the like. Therefore, the development of materials with the characteristics of high electrical and thermal conductivity, low gas permeability, high mechanical strength, high corrosion resistance, easy processing of flow channels and the like is a main target of the current bipolar plate research.
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; at present, the main preparation method of the metal bipolar plate is to deposit a coating on a metal substrate by adopting a physical vapor deposition method. However, the prior art has at least problems as follows:
(1) the bonding force between the coating and the metal substrate is poor, so that the service life of the bipolar plate is short, and the coating often falls off and corrodes inside after hundreds to thousands of hours.
(2) Due to the inherent characteristics of physical vapor deposition, pinholes exist in the coating and on the surface of the coating, and corrosive media enter the film through the pinholes to reach the metal matrix and corrode the matrix. Although the prior art also proposes a repair solution for pinhole defects, the prior repair solution can only seal the pores on the surface of the corrosion-resistant coating and has limited capability of sealing the pores inside the corrosion-resistant coating.
(3) Because the ionization efficiency is low, the film deposition speed is slow, generally the deposition speed is only a few nanometers per minute, and the whole film coating time is long.
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 provide a metal bipolar plate with good corrosion resistance and a coating layer that is not easy to fall off.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a metallic bipolar plate, including:
a metal substrate;
a Cu nanolayer deposited on the metal substrate;
a graphene layer prepared on the Cu nanolayer;
preferably, the graphene layer is grown in situ on the Cu nanolayer.
Preferably, the metal bipolar plate further comprises an amorphous carbon film deposited on the graphene layer.
Preferably, there is a transition portion between the graphene layer and the amorphous carbon film; wherein the transition portion comprises graphene and amorphous carbon.
Preferably, the graphene layer is a biased plasma chemical vapor deposition coating; and/or
The Cu nano layer is a physical vapor deposition coating; preferably, the Cu nanometer layer is a multi-arc ion plating deposition coating; and/or
The amorphous carbon film is a bias plasma chemical vapor deposition coating; and/or
The thickness of the amorphous carbon film is 50nm-10 mu m; and/or
The thickness of the Cu nano layer is 20-2000 nm; and/or
The number of graphene layers is 1-3 (the number of graphene layers refers to the stacking of single carbon atom layers, and the stacking of carbon atom layers within 20 layers in terms of materials can be the graphene layers);
the total thickness of the graphene layer is 0.2-1.0 nm.
Preferably, the coating bonding force of the metal bipolar plate is 40-50N; and/or
The contact resistance of the metal bipolar plate is 0.8-1.1m omega cm2(ii) a And/or
The corrosion potential of the metal bipolar plate is 305-345 mV; and/or
The corrosion current of the metal bipolar plate is 1.0 multiplied by 10-9-1.0×10-8A/cm2。
In another aspect, an embodiment of the present invention provides a method for manufacturing a metal bipolar plate, including the steps of:
preprocessing, namely preprocessing the metal substrate;
depositing a Cu nano layer, and depositing the Cu nano layer on the metal substrate;
annealing treatment, namely heating the metal substrate deposited with the Cu nano layer to a set temperature, keeping the temperature for a set time, and then annealing and cooling; preferably, the set temperature is 850-;
preparing a graphene layer, and preparing the graphene layer on the Cu nano layer;
preferably, the pretreatment comprises the following steps:
first pretreatment: sequentially carrying out oil removal treatment, polishing treatment, cleaning treatment and drying treatment on the metal substrate;
and (3) second pretreatment: 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 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 or nitrogen into the vacuum chamber, and maintaining 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, a physical vapor deposition method is adopted to deposit a Cu nano layer on the metal substrate; preferably, a bias multi-arc ion plating deposition method is adopted to deposit a Cu nano layer on the metal substrate; preferably, the step of depositing a Cu nanolayer includes: placing a metal substrate in a vacuum chamber; the vacuum degree in the vacuum chamber is pumped to 3X 10-3～5×10-3Pa; introducing 50-500sccm nitrogen or inert gas to maintain the pressure of the vacuum chamber at 0.05-1 Pa; opening the copper multi-arc target, and depositing a Cu nano layer on the metal substrate; preferably, the current of the copper multi-arc target is 50-600A, and the bias voltage is-100 to-1000V; preferably, the temperature of the metal substrate is 150-500 ℃; preferably, the deposition time is 90s to 10 min.
Preferably, a graphene layer is grown in situ on the Cu nano layer by a bias plasma chemical vapor deposition method; preferably, the step of preparing the graphene layer includes: placing the metal substrate in a vacuum chamber, and evacuating the vacuum chamber to 3 × 10-3～5×10-3Pa; introducing diluent gas, and maintaining the air pressure in the vacuum chamber at 0.8-1.0 KPa; starting a plasma power supply to glow the diluent gas and ionize to generate plasma; introducing carbon source gas, adjusting the air pressure in the vacuum chamber to 3-5KPa, and depositing a graphene layer on the Cu nano layer; preferably, the diluent gas is hydrogen; the introduction amount of the diluent gas is 450-; preferably, the carbon source gas is methane and/or acetylene; the introduction amount of the carbon source gas is 5-10 sccm; preferably, in the preparation of graphiteIn the step of the alkene layer, the deposition time is 3-20 min; preferably, in the step of preparing the graphene layer, the temperature of the metal substrate is 450-750 ℃.
Preferably, the method for preparing the metallic bipolar plate further comprises the following steps: depositing an amorphous carbon film, and depositing the amorphous carbon film on the graphene layer; preferably, an amorphous carbon film is deposited on the graphene layer by using a bias plasma chemical vapor deposition method; preferably, in the step of depositing an amorphous carbon film: the temperature of the metal substrate is 180-300 ℃; the introduction amount of the carbon source gas is 50-100sccm, and the air pressure in the vacuum chamber is maintained at 7.5-10 KPa; the bias voltage is 700-; the deposition time is 20min-1 h.
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:
the embodiment of the invention provides a metal bipolar plate and a preparation method thereof, wherein a Cu nano layer is directly deposited on the surface of a metal substrate, so that on one hand, the Cu nano layer plays a transition role, and the binding force between the metal substrate and a coating is improved; on the other hand, the existence of the Cu nano layer can catalyze and prepare the graphene layer, and the graphene is usually only a few nanometers and has the advantages of good compactness, no pin holes, good corrosion resistance, electric conduction, heat conduction and the like. Therefore, the metal bipolar plate provided and prepared by the embodiment of the invention has excellent coating binding force, corrosion resistance and conductivity.
Furthermore, according to the metal bipolar plate and the preparation method thereof provided by the embodiment of the invention, the graphene layer on the Cu nano layer is deposited by a bias plasma chemical vapor deposition method, so that a graphene film can be generated by taking Cu as a substrate, and the compactness of a coating and the binding force between coatings are further improved; and the coating speed of the metal bipolar plate can be improved.
Furthermore, according to the metal bipolar plate and the preparation method thereof provided by the embodiment of the invention, the amorphous carbon film is deposited on the graphene layer, so that the graphene can be prevented from being oxidized when the metal bipolar plate is used, and the service life of the metal bipolar plate is prolonged.
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, as shown in fig. 1, an embodiment of the present invention provides a metallic bipolar plate, wherein the metallic bipolar plate includes: metal substrate 1, Cu nanolayer 2, graphene layer 3. Wherein, the Cu nanolayer 2 is deposited on the metal substrate 1; the graphene layer 3 is prepared on the Cu nanolayer 2 (the graphene layer 3 is grown in situ on the Cu nanolayer 2). Preferably, the metal bipolar plate of the present embodiment includes an amorphous carbon film 4, and the amorphous carbon film 4 is deposited on the graphene layer 3.
Preferably, there is a transition portion between the graphene layer 3 and the amorphous carbon film 4; wherein the transition part comprises graphene and amorphous carbon.
Preferably, the graphene layer 3 is a biased plasma chemical vapor deposition coating.
Preferably, the Cu nanolayer 2 is a physical vapor deposition coating; preferably, the Cu nanolayer 2 is a multi-arc ion plating deposited coating.
Preferably, the amorphous carbon film 4 is a biased plasma chemical vapor deposition coating.
Preferably, the thickness of the amorphous carbon film is 50nm-10 μm.
Preferably, the thickness of the Cu nano-layer is 20 to 2000 nm.
In the above-described metal bipolar plate structure of the present invention:
(1) the Cu nanometer layer plays a role of a transition layer on one hand, and the binding force between the matrix and other layers is improved. On the other hand, the existence of the Cu nano layer can be used for preparing the graphene layer in a catalytic mode (PECVD (plasma enhanced chemical vapor deposition). The graphene is usually only a few nanometers, and has the advantages of good compactness, no pin holes, good corrosion resistance, electric conduction, heat conduction and the like.
(2) The method for growing the graphene by taking the copper as the substrate utilizes the extremely low solubility of the copper-loaded carbon, and the copper has a certain catalytic action on the cracking of hydrocarbon gas, and the growth mechanism is different from that of nickel. Because the solubility of copper is low, cracked active carbon atoms can only be attached to the surface of copper, and are continuously diffused and combined with adjacent carbon atoms to form a graphene film and are continuously expanded, so that the carbon atoms are arranged on the surface of the copper in a single layer to form a single-layer film. Therefore, the graphene prepared by taking copper as the substrate has the characteristics of thin film and large growth area.
(3) Coated metallic materials are commonly used as metallic bipolar plates in fuel cells. In an actual working environment of the fuel cell, the bipolar plate can work intermittently at a high potential to cause graphene oxidation, and in order to prolong the service life of the bipolar plate, the amorphous carbon film is deposited on the surface of the bipolar plate to prolong the service life of the bipolar plate.
Here, the mechanism of graphene growth on the surface of the copper nano-layer is "self-limiting growth". The growth process of the graphene and the thickness and deposition time of the copper substrate have little influence on the number of layers of the graphene. Therefore, the single-layer graphene with higher quality can be prepared on the copper nano layer, the production area is larger, and the defects are fewer. The number of the layers of the graphene growing on the copper nano layer is 1-5, so that the substrate can be completely covered, the permeation of hydrogen ions and fluorine ions in the solution to the substrate of the bipolar plate can be effectively prevented, and the corrosion resistance of the bipolar plate is improved. The number of graphene layers prepared by catalysis of the copper nanolayers is 1-3, so that the thickness of the graphene layer is thinner and is only 0.2-1 nm. Due to the fact that the copper nano layer is completely covered by the single-layer graphene, the copper nano particles are prevented from further catalyzing to form other amorphous carbon films, and therefore only the graphene layer can be formed on the surfaces of the copper nano particles.
In addition, the metal substrate of the metal bipolar plate of the invention is selected from stainless steel plates (such as 316L stainless steel), titanium sheets, aluminum alloy plates and the like.
On the other hand, the embodiment of the invention also provides a preparation method of the metal bipolar plate, which 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, 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, polishing the substrate by using brightening agent such as alumina polishing paste or diamond polishing paste, on one hand, taking out oxide scale on the surface, on the other hand, reducing texture and defects on the surface through polishing treatment, and improving the flatness of the material. And after polishing, cleaning with pure water, 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 magnetic control multi-arc ion plating device is adopted to install a clamp provided with a metal substrate into the metal substrateVacuum chamber, vacuumizing to 1 × 10-3Pa～5×10-3Pa, preferably 2.0X 10-3Pa, heating the metal substrate to 150-300 ℃, introducing 500sccm inert gas or nitrogen, controlling the vacuum degree at 0.05-1Pa, setting the bias voltage at-200V to-1000V, and performing surface ion sputtering and etching activation for 3min to 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. Depositing a Cu nano layer: the method comprises the following steps: and introducing nitrogen into the vacuum chamber, opening the copper multi-arc target, and controlling the target current to deposit. Preferably, the deposition step is performed in a biased magnetron multi-arc ion plating apparatus.
Specifically, in this step, the degree of vacuum was maintained at 3X 10 in the state of plating-3Pa～5×10-3Pa, introducing argon gas in an amount of 50-500sccm, maintaining the partial pressure at 0.05-1Pa, keeping the multi-arc target current at 50-600A, keeping a workpiece bias power supply in a working state, controlling the bias equipment at-100 to-1000V, and controlling the temperature of the metal substrate at 150-500 ℃; the deposition time is 90 s-10 min.
3. Annealing treatment: after the Cu nano layer is prepared, starting a heating function to heat up, at 850-950 ℃, preferably 900 ℃, preserving heat for 30-120min, and then annealing and naturally cooling. Here, annealing the Cu nanolayer can eliminate stress inside the coating, and increase the size of crystal ions to facilitate growth of graphene.
4. Preparing a graphene layer: preparing a graphene layer on the Cu nanolayer.
Preferably, the step of preparing the graphene layer is performed in a biased plasma chemical vapor deposition (PECVD) apparatus. The method specifically 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 at 500sccm, adjusting the gas pressure in the reaction chamber to 0.8-1.0KPa, opening and the likeAnd the plasma power supply is used for igniting the hydrogen and ionizing to generate plasma, and simultaneously, the power and the pressure are gradually increased. The temperature of the metal substrate is raised to 450-750 ℃, carbon source gases such as methane, acetylene and the like with the flow rate of 5-10sccm are introduced, the gas pressure in the vacuum chamber is adjusted to be about 3-5KPa, the graphene layer grows on the film in situ, and the deposition time is 3-20 min.
5. Deposition of an amorphous carbon film: and depositing an amorphous carbon film on the surface of the graphene layer.
Preferably, the step of depositing the amorphous carbon film is performed in a biased plasma chemical vapor deposition (PECVD) apparatus. The method specifically comprises the following steps: adjusting the temperature of a substrate (the substrate refers to a metal substrate deposited with a Cu nanometer layer and a graphene layer) to 180-300 ℃, adjusting the flow of carbon source gases such as methane, acetylene and the like to be 50-100sccm, adjusting the pressure of gas in a vacuum chamber to be about 7.5-10KPa, starting a bias power supply, adjusting the bias to be 700-1000V, and depositing an amorphous carbon film on the surface of the graphene layer; the deposition time is 20min-1 h.
The invention is further illustrated by the following specific experimental examples:
example 1
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 by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using a brightening agent such as diamond polishing paste, on one hand, the oxide skin on the surface is taken out, on the other hand, the texture and the defects on the surface are reduced through polishing treatment, and the flatness of the material is improved. And after polishing, cleaning 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 to 5 multiplied by 10-3Pa, andheating the metal substrate to 180 ℃, introducing nitrogen gas with about 1Pa, and setting the bias voltage to-220V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
3) Starting the substrate rotating stand, and maintaining the vacuum degree at 3 × 10 under the state of film coating-3Pa, wherein the introducing amount of argon is 300sccm, so that the air pressure in the vacuum chamber is maintained at 0.3Pa, a copper multi-arc target power supply is started, the current is regulated to 100A, the workpiece bias power supply is kept in a working state, the bias equipment is-150V, and the temperature of the metal substrate is controlled to be 200 ℃; the deposition time was 3 min.
4) Heating the metal substrate to 900 ℃, preserving the temperature for 30min, and then annealing and naturally cooling.
5) Transferring the sample of step 4 into a bias plasma chemical vapor deposition (PECVD) furnace, and vacuumizing to 3 x 10 in a vacuum chamber-3Introducing diluent gas hydrogen with the flow rate set 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 metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and growing a graphene layer on the film (Cu nano layer) in situ for 5 min.
6) Adjusting the temperature of a substrate (namely, a metal substrate) to 180 ℃, adjusting the flow of methane to 50sccm, adjusting the pressure of gas in a vacuum chamber to be about 8KPa, starting a bias power supply, adjusting the bias to be 700V, and depositing an amorphous carbon film on the surface of the graphene layer. Wherein the deposition time is 20 min. And after the deposition is finished, closing the equipment, naturally cooling, and taking out the metal bipolar plate sample for testing.
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 by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing treatment is carried out on the substrate by using brightening agents such as alumina polishing paste, so that the oxide scale on the surface is taken out, and the texture and the defects of the surface are reduced through the polishing treatment, so that the flatness of the material is improved. And after polishing, cleaning 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 to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing nitrogen gas of about 1Pa, and setting the bias voltage to-220V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
3) Starting the substrate rotating stand, and maintaining the vacuum degree at 3 × 10 under the state of film coating-3Pa, wherein the introducing amount of argon is 300sccm, so that the air pressure in the vacuum chamber is maintained at 0.3Pa, a copper multi-arc target power supply is started, the current is adjusted to 80A, a workpiece bias power supply is kept in a working state, the bias equipment is-220V, and the temperature of the substrate is controlled to be 200 ℃; the deposition time was 5 min.
4) Heating the metal substrate to 900 ℃, preserving the temperature for 30min, and then annealing and naturally cooling.
5) Transferring the sample of step 4 into a bias plasma chemical vapor deposition (PECVD) furnace, and vacuumizing to 3 x 10 in a vacuum chamber-3Introducing diluent gas hydrogen with the flow rate set 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 metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and growing a graphene layer on the film (Cu nano layer) in situ for 5 min.
6) Adjusting the temperature of a substrate (namely, a metal substrate) to 180 ℃, adjusting the flow of methane to 50sccm, adjusting the pressure of gas in a vacuum chamber to be about 8KPa, starting a bias power supply, adjusting the bias to be 700V, and depositing an amorphous carbon film on the surface of the graphene layer. Wherein the deposition time is 40 min. And after the deposition is finished, closing the equipment, naturally cooling, and taking out the metal bipolar plate sample for testing.
Example 3
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 by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using a brightening agent such as diamond polishing paste, on one hand, the oxide skin on the surface is taken out, on the other hand, the texture and the defects on the surface are reduced through polishing treatment, and the flatness of the material is improved. And after polishing, cleaning 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 to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing nitrogen gas of about 1Pa, and setting the bias voltage to-220V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
3) Starting the substrate rotating stand, and maintaining the vacuum degree at 3 × 10 under the state of film coating-3Pa, wherein the introducing amount of argon is 300sccm, so that the air pressure in the vacuum chamber is maintained at 0.3Pa, a copper multi-arc target power supply is started, the current is regulated to 100A, the workpiece bias power supply is kept in a working state, the bias equipment is-150V, and the temperature of the metal substrate is controlled to be 200 ℃; the deposition time was 3 min.
4) Heating the metal substrate to 900 ℃, preserving the temperature for 30min, and then annealing and naturally cooling.
5) Transferring the sample of step 4 into a bias plasma chemical vapor deposition (PECVD) furnace, and vacuumizing to 3 x 10 in a vacuum chamber-3Pa, introducing diluent gas hydrogen, setting the flow rate at 500sccm, adjusting the gas pressure in the reaction chamber to 0.8KPa, turning on the plasma power supply to make the hydrogen glow, ionizing to generate plasma, and performing ionization to obtain plasmaThe power and pressure are gradually increased. Heating the metal substrate to 750 ℃, introducing 10sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and growing a graphene layer on the film (Cu nano layer) in situ for 5 min.
6) And adjusting the temperature of the substrate to 180 ℃, adjusting the flow of methane to 50sccm, adjusting the pressure of gas in the vacuum chamber to about 8KPa, starting a bias power supply, adjusting the bias to 700V, and depositing an amorphous carbon film on the surface of the graphene layer. Wherein the deposition time is 20 min. And after the deposition is finished, closing the equipment, naturally cooling, and taking out the metal bipolar plate sample for testing.
Example 4
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 by using 1M sodium hydroxide solution at high temperature (80 ℃); after cleaning, the oil is removed for the second time by alcohol. Then, polishing the substrate by using a brightening agent such as diamond polishing paste, on one hand, the oxide skin on the surface is taken out, on the other hand, the texture and the defects on the surface are reduced through polishing treatment, and the flatness of the material is improved. And after polishing, cleaning 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 to 5 multiplied by 10-3Pa, heating the metal substrate to 180 ℃, introducing nitrogen gas of about 1Pa, and setting the bias voltage to-220V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
3) Starting the substrate rotating stand, and maintaining the vacuum degree at 3 × 10 under the state of film coating-3Pa, the introduction amount of argon is 300sccm, the air pressure in the vacuum chamber is maintained at 0.3Pa, the copper multi-arc target power supply is started, the current is regulated to 100A, the workpiece bias power supply is kept in a working state, and the bias equipment is ion-resistant150V, and the temperature of the substrate is controlled to be 200 ℃; the deposition time was 3 min.
4) Heating the metal substrate to 900 ℃, preserving the temperature for 30min, and then annealing and naturally cooling.
5) Transferring the sample of step 4 into a bias plasma chemical vapor deposition (PECVD) furnace, and vacuumizing to 3 x 10 in a vacuum chamber-3Introducing diluent gas hydrogen with the flow rate set 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 metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and growing a graphene layer on the film (Cu nano layer) in situ for 5 min.
6) Adjusting the temperature of a substrate (namely, a metal substrate) to 280 ℃, adjusting the flow rate of methane to 70sccm, adjusting the pressure of gas in a vacuum chamber to about 10KPa, starting a bias power supply, adjusting the bias to 700V, and depositing an amorphous carbon film on the surface of the graphene layer. Wherein the deposition time is 30 min. And after the deposition is finished, closing the equipment, naturally cooling, and taking out the metal bipolar plate sample for testing.
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. Then, polishing the substrate by using a brightening agent such as diamond polishing paste, on one hand, the oxide skin on the surface is taken out, on the other hand, the texture and the defects on the surface are reduced through polishing treatment, and the flatness of the material is improved. And after polishing, cleaning 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 coating equipment to coat the metal substrateFeeding into a vacuum chamber, and vacuumizing to 5 × 10-3Pa, heating the metal substrate to 180 ℃, introducing nitrogen gas of about 1Pa, and setting the bias voltage to-220V; and carrying out surface ion sputtering and etching activation on the metal substrate, wherein the time is controlled to be 5 min.
3) Starting the substrate rotating stand, and maintaining the vacuum degree at 3 × 10 under the state of film coating-3Pa, wherein the introducing amount of argon is 300sccm, so that the air pressure in the vacuum chamber is maintained at 0.3Pa, a copper multi-arc target power supply is started, the current is regulated to 100A, the workpiece bias power supply is kept in a working state, the bias equipment is-150V, and the temperature of the substrate is controlled to be 200 ℃; the deposition time was 3 min.
4) Heating the metal substrate to 900 ℃, preserving the temperature for 30min, and then annealing and naturally cooling.
5) Transferring the sample of step 4 into a bias plasma chemical vapor deposition (PECVD) furnace, and vacuumizing to 3 x 10 in a vacuum chamber-3Introducing diluent gas hydrogen with the flow rate set 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 metal substrate to 650 ℃, introducing 5sccm methane gas, adjusting the gas pressure in the vacuum chamber to be about 3KPa, and growing a graphene layer on the film (Cu nano layer) in situ for 5 min.
6) Adjusting the temperature of a substrate (namely, a metal substrate) to 180 ℃, adjusting the flow rate of methane to 50sccm, adjusting the pressure of gas in a vacuum chamber to be about 8KPa, starting a bias power supply, adjusting the bias to be 700V, and depositing an amorphous carbon film on the surface of the graphene layer. Wherein the deposition time is 20 min. And after the deposition is finished, closing the equipment, naturally cooling, and taking out the metal bipolar plate sample for testing.
The metal bipolar plate samples prepared in examples 1-5 were tested for performance and the results are shown in the table.
Table 1 shows the data of the performance test of the metal bipolar plates prepared in examples 1 to 5
Figure BDA0002229289770000141
As can be seen from the data in table 1, the metal bipolar plate prepared by the embodiment of the present invention has excellent conductivity and corrosion resistance, and the coating bonding force is high.
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 Cu nanolayer deposited on the metal substrate;
a graphene layer prepared on the Cu nanolayer;
preferably, the graphene layer is grown in situ on the Cu nanolayer.
2. The metallic bipolar plate of claim 1, further comprising an amorphous carbon film deposited on said graphene layer.
3. The metallic bipolar plate of claim 2, wherein there is a transition portion between the graphene layer and the amorphous carbon film; wherein the transition portion comprises graphene and amorphous carbon.
4. The metallic bipolar plate of claim 2 wherein said graphene layer is a biased plasma chemical vapor deposition coating; and/or
The Cu nano layer is a physical vapor deposition coating; preferably, the Cu nanometer layer is a multi-arc ion plating deposition coating; and/or
The amorphous carbon film is a bias plasma chemical vapor deposition coating; and/or
The thickness of the amorphous carbon film is 50nm-10 mu m; and/or
The thickness of the Cu nano layer is 20-2000 nm; and/or
The number of the graphene layers is 1-3; and/or
The total thickness of the graphene layer is 0.2-1.0 nm.
5. Metallic bipolar plate as in any of claims 1 to 4,
the coating bonding force of the metal bipolar plate is 45-50N; and/or
The contact resistance of the metal bipolar plate is 0.8-1.1m omega cm2(ii) a And/or
The corrosion potential of the metal bipolar plate is 305-345 mV; and/or
The corrosion current of the metal bipolar plate is 1.0 multiplied by 10-9-1.0×10-8A/cm2。
6. A method of manufacturing a metallic bipolar plate as claimed in any one of claims 1 to 5, comprising the steps of:
preprocessing, namely preprocessing the metal substrate;
depositing a Cu nano layer, and depositing the Cu nano layer on the metal substrate;
annealing treatment, namely heating the metal substrate deposited with the Cu nano layer to a set temperature, keeping the temperature for a set time, and then annealing and cooling; preferably, the set temperature is 850-;
preparing a graphene layer, and preparing the graphene layer on the Cu nano layer;
preferably, the pretreatment comprises the following steps:
first pretreatment: sequentially carrying out oil removal treatment, polishing treatment, cleaning treatment and drying treatment on the metal substrate;
and (3) second pretreatment: 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 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 or nitrogen into the vacuum chamber, and maintaining 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, wherein a Cu nanolayer is deposited on the metal substrate using a physical vapor deposition process;
preferably, a bias multi-arc ion plating deposition method is adopted to deposit a Cu nano layer on the metal substrate;
preferably, the step of depositing a Cu nanolayer includes: placing a metal substrate in a vacuum chamber; the vacuum degree in the vacuum chamber is pumped to 3X 10-3～5×10-3Pa; introducing 50-500sccm nitrogen or inert gas to maintain the pressure of the vacuum chamber at 0.05-1 Pa; opening the copper multi-arc target, and depositing a Cu nano layer on the metal substrate;
preferably, the current of the copper multi-arc target is 50-600A, and the bias voltage is-100 to-1000V;
preferably, the temperature of the metal substrate is 150-500 ℃;
preferably, the deposition time is 90s to 10 min.
8. The method of claim 6, wherein the graphene layer is grown in situ on the Cu nanolayer using a bias plasma chemical vapor deposition method;
preferably, the step of preparing the graphene layer includes:
placing the metal substrate in a vacuum chamber, and evacuating the vacuum chamber to 3 × 10-3～5×10-3Pa；
Introducing diluent gas, and maintaining the air pressure in the vacuum chamber at 0.8-1.0 KPa;
starting a plasma power supply to glow the diluent gas and ionize to generate plasma;
introducing carbon source gas, adjusting the air pressure in the vacuum chamber to 3-5KPa, and depositing a graphene layer on the Cu nano layer;
preferably, the diluent gas is hydrogen; the introduction amount of the diluent gas is 450-;
preferably, the carbon source gas is methane and/or acetylene; the introduction amount of the carbon source gas is 5-10 sccm;
preferably, in the step of preparing the graphene layer, the deposition time is 3-20 min;
preferably, in the step of preparing the graphene layer, the temperature of the metal substrate is 450-750 ℃.
9. The method of manufacturing a metallic bipolar plate as claimed in any one of claims 6 to 8, further comprising the steps of:
depositing an amorphous carbon film: depositing an amorphous carbon film on the graphene layer;
preferably, an amorphous carbon film is deposited on the graphene layer by using a bias plasma chemical vapor deposition method;
preferably, in the step of depositing an amorphous carbon film: the temperature of the metal substrate is 180-300 ℃; the introduction amount of the carbon source gas is 50-100sccm, and the air pressure in the vacuum chamber is maintained at 7.5-10 KPa; the bias voltage is 700-; the deposition time is 20min-1 h.
10. A fuel cell comprising the metallic bipolar plate of any one of claims 1 to 5.
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