WO2020019693A1 - 一种用于燃料电池金属双极板的石墨微晶碳涂层及应用 - Google Patents

一种用于燃料电池金属双极板的石墨微晶碳涂层及应用 Download PDF

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WO2020019693A1
WO2020019693A1 PCT/CN2019/072825 CN2019072825W WO2020019693A1 WO 2020019693 A1 WO2020019693 A1 WO 2020019693A1 CN 2019072825 W CN2019072825 W CN 2019072825W WO 2020019693 A1 WO2020019693 A1 WO 2020019693A1
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coating
graphite
carbon coating
bipolar plate
metal
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PCT/CN2019/072825
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English (en)
French (fr)
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彭林法
李骁博
易培云
邱殿凯
来新民
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上海交通大学
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Priority to US16/966,717 priority Critical patent/US11799094B2/en
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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
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3464—Sputtering using more than one target
    • 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
    • C23C14/3485—Sputtering using pulsed power to the target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—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
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3402—Gas-filled discharge tubes operating with cathodic sputtering using supplementary magnetic fields
    • H01J37/3405—Magnetron sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/3426—Material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3464—Operating strategies
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3464—Operating strategies
    • H01J37/3467—Pulsed operation, e.g. HIPIMS
    • 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
    • H01M8/0223—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

Definitions

  • the invention belongs to the technical field of fuel cells, and relates to a graphite microcrystalline carbon coating for a fuel cell metal bipolar plate and application thereof.
  • Fuel cells use hydrogen as an energy source, have the characteristics of high efficiency and cleanliness, and have broad application prospects in many fields.
  • the bipolar plate is one of the important components of a fuel cell, and its performance restricts the commercialization process of the fuel cell.
  • Metal materials have become the main materials of fuel cell bipolar plates because of their advantages such as better mechanical properties, corrosion resistance and low cost.
  • Fuel cell metal bipolar plates generally work in a high-temperature, high-humidity, acidic environment with a pH of 2-5 and a temperature of 70-100 ° C.
  • the surface of metal materials in service in this environment will be passivated to form a dense, poorly conductive layer.
  • the metal oxide film causes the contact resistance between the metal electrode plate and the gas diffusion layer to increase, which in turn leads to an increase in voltage loss due to ohmic polarization of the battery and a decrease in battery output power. Therefore, bipolar plates made of metal materials alone cannot meet the fuel cell's requirements for better corrosion resistance and lower contact resistance.
  • the carbon coating has better conductivity and corrosion resistance, but the actual vehicle operating conditions of the fuel cell vehicle are more complicated. Typical conditions such as low-load idling, cyclic loading, and start-stop will cause the carbon coating performance to deteriorate, and the fuel Battery life also requires better stability and durability of the coating.
  • Chinese patent CN101640276A discloses an amorphous carbon coating for a fuel cell bipolar plate. The coating has good conductivity and corrosion resistance, but the data shows that its contact resistance is greater than 10m ⁇ under the working pressure of the bipolar plate.
  • Chinese patent CN107978770 A discloses a method for preparing a carbon coating on the surface of a metal separator of a fuel cell using a PECVD method, and the coating remains There is a defect that the contact resistance is high under the working pressure of the separator, and the durability of the coating is unknown.
  • the invention will optimize the carbon coating structure by increasing the particle energy in magnetron sputtering, thereby obtaining a highly conductive, corrosion-resistant and stable fuel cell metal bipolar plate carbon coating.
  • the purpose of the present invention is to provide a graphite microcrystalline carbon coating for a fuel cell metal bipolar plate in order to overcome the defects existing in the prior art.
  • a graphite microcrystalline carbon coating for a metal bipolar plate of a fuel cell which is characterized by comprising:
  • Anti-corrosive metal substrate deposited on the surface of the metal bipolar plate to remove the oil and oxide layer on the surface, in order to improve the binding force between the carbon coating and the metal substrate, and further improve the corrosion resistance of the coating in the service environment of fuel cells;
  • Corrosion-resistant metal and carbon coating co-existing transition layer deposited on the surface of the metal base layer to reduce the internal stress of the coating and further improve the coating adhesion and stability;
  • the outermost graphite microcrystalline carbon coating deposited on the surface of the transition layer where the corrosion-resistant metal and carbon coating coexist, to ensure a lower contact resistance between the coating and the gas diffusion layer, and at the same time to ensure better stability and durability of the coating Sex.
  • the metal substrate is deposited by a magnetron sputtering method, and the thickness of the coating layer is 1-100 nm;
  • the corrosion-resistant metal in the metal base layer includes one or more of Ti, Cr, W, Zr, Nb, or Ta.
  • the coexisting transition layer of the corrosion-resistant metal and the carbon coating is deposited by means of co-sputtering of the corrosion-resistant metal target and the graphite target, and the coating thickness is 1-100 nm;
  • the energy of the deposited particles can be promoted to promote the chemical bonding of the corrosion-resistant metal and carbon to form a metal compound, thereby further improving the coating.
  • Layer corrosion resistance
  • the energy of the deposited particles is 1-100eV
  • the manner of increasing the energy of the deposited particles includes using a pulsed power source for deposition, increasing the temperature during the deposition process, and changing the intensity of the sputtering magnetic field.
  • the outermost graphite microcrystalline carbon coating is prepared by a magnetron sputtering method, and the coating thickness is 1-500 nm, including sp2 hybrid bonds and sp3 hybrid bonds.
  • the coating contains more sp2 hybrid bonds to ensure better electrical conductivity of the coating, while also containing a certain amount of sp3 hybrid bonds to ensure better mechanical properties of the coating.
  • the outermost graphite microcrystalline carbon coating contains a certain proportion of graphite microcrystals, and the proportion of graphite microcrystals in the carbon coating is 10-50%.
  • the existence of graphite microcrystals ensures that the coating is better. Electrical conductivity and corrosion resistance, graphite microcrystals have a suitable size, the size is 1-2000nm, too small grain size results in increased graphite structure defects, too large results in a loose coating structure, so the grain size is too large or too large A small amount will cause the corrosion resistance and conductivity of the coating to decrease.
  • the carbon coating also needs to have good compactness to prevent the electrolyte from penetrating into the coating through the pores to cause galvanic corrosion, which in turn will aggravate the failure of the coating.
  • the graphite microcrystalline carbon coating can change the energy of the deposited particles by changing the temperature, the sputtering power of the target, the magnetic field structure and the intensity during the coating deposition process, thereby forming a carbon containing a certain proportion of the graphite microcrystalline. Coating to improve coating conductivity, corrosion resistance and stability.
  • the changing the temperature during the coating deposition process may be performed by a heater during the coating deposition process, and the temperature is 150-600 ° C;
  • the DC sputtering power source can be changed to a DC pulse power source to control the deposited ion energy, the frequency of the DC pulse sputtering power source is 50-350 kHz, and the duty ratio is 10-45%;
  • changing the structure and intensity of the sputtering magnetic field can change the arrangement of the magnetic poles, change the magnetic field distribution, and change the magnetic field intensity at the same time, and the magnetic field intensity is 300-1500 Gs.
  • the total thickness of the coating is 50-1000 nm.
  • the method for preparing the graphite microcrystalline carbon coating for a fuel cell metal bipolar plate includes the following steps:
  • the surface of the metal bipolar plate is plated with a corrosion-resistant metal substrate
  • the particle energy is changed by changing the sputtering power source, the sputtering magnetic field, the deposition temperature, etc., thereby controlling the graphite crystal ratio, graphite grain size, crystal defects, and coating compactness in the carbon coating to optimize the carbon coating. Electrical conductivity and corrosion resistance, while improving the stability and durability of the carbon coating.
  • the present invention has the following advantages:
  • the carbon structure is optimized by changing the particle energy method.
  • the obtained carbon coating has better conductivity and corrosion resistance.
  • the coating is used in the service environment of fuel cells. Slow performance decay, better stability and durability;
  • the present invention is of great significance for improving the durability of fuel cell metal bipolar plates and advancing the industrialization process of fuel cells.
  • FIG. 1 is a schematic diagram of the overall structure of the coatings prepared in Examples 2, 3, and 4;
  • Example 2 is a Raman spectrum (Raman) analysis chart of the coating prepared in Example 2;
  • Example 3 is a cross-sectional morphology (SEM) image of the coating prepared in Example 2;
  • Example 5 is a cross-sectional morphology (SEM) image of the coating prepared in Example 3.
  • FIG. 6 is a test result chart of the contact resistance of the coatings prepared in the embodiments.
  • 1 metal bipolar plate
  • 2 corrosion resistant metal underlayer
  • 3 corrosion resistant metal and carbon coexisting transition layer
  • 4 metal carbide crystal
  • 5 carbon layer
  • 6 graphite microcrystal
  • 7 defective Graphite microcrystals.
  • a method for preparing a highly conductive, corrosion-resistant, and stable carbon coating for a metal bipolar plate includes the following steps:
  • a corrosion-resistant metal and carbon coexisting transition layer 3 is deposited on the surface of the second layer of the corrosion-resistant metal deposited in the second step. At this time, an appropriate flow of Ar is passed in, and the corrosion-resistant metal Cr target and graphite target are started at the same time. The graphite target is co-sputtered to form the corrosion-resistant metal Cr and carbon coexisting transition layer 3, which further improves the film-base adhesion and prevents the coating from falling off due to excessive internal stress.
  • the thickness of the transition layer is 50nm;
  • the furnace cavity is heated by a heating device, the temperature is increased to 500 ° C and held for a period of time to ensure that the internal temperature of the furnace cavity is uniform, and then a graphite target is sputtered to deposit a carbon film.
  • a carbon layer 5 is obtained.
  • the carbon layer 5 further contains graphite microcrystals 6 and graphite microcrystals 7 with defects.
  • the graphite target sputtering power source is a direct current power source, and the thickness of the coating layer is 200 nm.
  • a corrosion-resistant metal and carbon coexisting transition layer 3 is deposited on the surface of the second layer of the corrosion-resistant metal deposited in the second step.
  • an appropriate flow of Ar is passed in and the corrosion-resistant metal Ti target and graphite target are started at the same time.
  • the graphite target is co-sputtered to form a transition layer in which the corrosion-resistant metal Ti and carbon coexist, which further improves the film-base bonding force and prevents the coating from falling off due to excessive internal stress.
  • the temperature of the deposition process is high, which is beneficial to promote the combination of Ti and C.
  • the metal carbide 4 with better corrosion resistance is formed, and the corrosion resistance of the coating can further improve the deposition thickness of the transition layer to 50 nm;
  • the graphite target is sputter-deposited to deposit a carbon film to obtain a carbon layer 5.
  • the graphite target sputtering power source is a direct current power source, and the thickness of the coating layer is 100 nm;
  • a method for preparing a highly conductive, corrosion-resistant, and stable carbon coating for a metal bipolar plate includes the following steps:
  • a corrosion-resistant metal and carbon coexisting transition layer 3 is deposited on the surface of the second layer of the corrosion-resistant metal deposited in the second step.
  • an appropriate flow of Ar is passed in and the corrosion-resistant metal Ti target and graphite target are started at the same time.
  • the graphite target is co-sputtered to form a transition layer in which the corrosion-resistant metal Ti and carbon coexist, which further improves the film-base bonding force and prevents the coating from falling off due to excessive internal stress.
  • the pulse power source for the Ti target and graphite target sputtering power source is used. Pulse power frequency It is 350kHz and the duty ratio is 40%.
  • the particle energy can be increased by pulse power to promote the combination of Ti and C to form metal compound 4, which further increases the corrosion resistance of the coating.
  • the thickness of the transition layer is 50nm;
  • the graphite target is sputtered to deposit a carbon film to obtain a carbon layer 5.
  • the graphite target sputtering power source uses a pulsed sputtering power source, the pulsed power source frequency is 350 kHz, the duty cycle is 40%, and the thickness of the layer coating is 200 nm;
  • a corrosion-resistant metal and carbon coexisting transition layer 3 is deposited on the surface of the second layer of the corrosion-resistant metal deposited in the second step.
  • an appropriate flow of Ar is passed in and the corrosion-resistant metal Ti target and graphite target are started at the same time.
  • the graphite target is co-sputtered to form a transition layer in which the corrosion-resistant metal Ti and carbon coexist, which further improves the film-base bonding force and prevents the coating from falling off due to excessive internal stress.
  • the pulse power source for the Ti target and graphite target sputtering power source is used. Pulse power frequency It is 350kHz and the duty ratio is 40%. At the same time, the temperature is higher during the deposition process. Both higher temperature and pulse power can increase the particle energy to promote the combination of Ti and C to form metal compound 4, further increase the corrosion resistance of the coating, and the transition Layer deposition thickness is 50nm;
  • the furnace cavity is heated by a heating device, the temperature is increased to 200 ° C and held for a period of time to ensure that the temperature inside the furnace cavity is uniform, and then the graphite target is sputtered to deposit a carbon film.
  • a carbon layer 5 was obtained.
  • a pulse sputtering power source was used for the graphite target sputtering power source, the pulse power source frequency was 150 kHz, the duty ratio was 40%, and the thickness of the layer was 200 nm;
  • Figure 1 is a schematic diagram of the coating structure. Electrochemical tests were performed on the coating in a simulated fuel cell service environment. Figure 6 shows the coating contact resistance test results before the coating was etched and after 0.84V (vsSHE) corrosion for 200 hours. The test results show that the method prepared by this method The carbon coating has excellent conductivity, corrosion resistance and stability. The test result of the coating contact resistance is shown in Figure 6.
  • the 0.84V (vs SHE) constant-potential polarization corrosion current density in a fuel cell simulated acidic environment is Figure 7 shows.
  • a method for preparing a highly conductive, corrosion-resistant, and stable carbon coating for a metal bipolar plate includes the following steps:
  • a corrosion-resistant metal and carbon coexisting transition layer 3 is deposited on the surface of the second layer of the corrosion-resistant metal deposited in the second step. At this time, an appropriate flow of Ar is passed in and the corrosion-resistant metal Ti target and graphite target are started at the same time.
  • the graphite target is co-sputtered to form a transition layer 3 in which the corrosion-resistant metal Ti and carbon coexist, which further improves the film-base adhesion and prevents the coating from falling off due to excessive internal stress.
  • the thickness of the transition layer is 50 nm;
  • the graphite target is sputtered to deposit a carbon film to obtain a carbon layer 5.
  • the graphite target sputtering power source is a direct current power source, the corresponding sputtering magnetic field is a strong magnetic field, the magnetic field strength is 800 Gs, and the coating thickness of the layer is 200 nm;

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Abstract

本发明涉及一种用于燃料电池金属双极板的石墨微晶碳涂层及应用，该涂层涂覆在金属双极板表面，所述的石墨微晶碳涂层为类石墨涂层，该涂层中包含石墨微晶5-50wt％，同时具备较好的致密性。该涂层在常规的磁控溅射技术的基础上，通过改变靶材溅射电源、溅射磁场强度、涂层沉积温度等方法改变沉积粒子能量，进而改变碳涂层结构，从而制备高导电、耐腐蚀、稳定的碳涂层。与现有技术相比，本发明在不增加涂层制备成本的前提下，能够降低燃料电池金属双极板与气体扩散层间接触电阻，同时提高碳涂层在燃料电池酸性环境中的耐腐蚀性能及长时间测试后导电性能的稳定性，对推动燃料电池的商业化进程具有重要意义。

Description

一种用于燃料电池金属双极板的石墨微晶碳涂层及应用 技术领域
本发明属于燃料电池技术领域，涉及一种用于燃料电池金属双极板的石墨微晶碳涂层及应用。
背景技术
燃料电池使用氢气作为能源，具有高效清洁的特点，在许多领域具有广泛的应用前景。其中，双极板作为燃料电池的重要组成部分之一，其性能好坏制约着燃料电池的商业化进程。金属材料因其具有较好的机械性能、耐腐蚀性能及低成本等优势，已成为燃料电池双极板的主要材料。
燃料电池金属双极板一般工作在pH值为2-5、温度为70-100℃的高温高湿酸性环境中，该环境下服役的金属材料表面会发生钝化形成一层致密、导电性差的金属氧化膜，导致金属极板与气体扩散层间接触电阻增大，进而导致电池因欧姆极化产生的电压损失增加，电池输出功率下降。因此，仅靠金属材料制备的双极板不能满足燃料电池对其较好耐腐蚀性能、较低接触电阻的性能要求。目前可通过PVD(物理气相沉积)、CVD(化学气相淀积)、离子镀、化学镀、电镀等方式在金属双极板表面镀覆功能性薄膜，以提高其耐腐蚀性并降低接触电阻，其中，制备的非晶碳膜、贵金属薄膜在一定程度上已满足美国能源部对燃料电池极板提出的要求，但贵金属薄膜成本高，制约着其商业化应用。由于碳资源量丰富且无害，考虑资源及环境问题，碳是一种极好的材料，目前国内外多针对非晶碳膜进行改进，以提高其耐腐蚀性，降低接触电阻。
碳涂层具有较好的导电性能及耐腐蚀性，但燃料电池汽车实际车载工况较为复杂，其中低载怠速、循环加载、启动停止等典型工况均会导致碳涂层性能衰减，同时燃料电池使用寿命也要求涂层具有较好的稳定性及耐久性。中国专利CN 101640276 A公开了一种燃料电池双极板无定型碳涂层，该涂层具备较好的导电性及耐腐蚀性，但数据表明其接触电阻在双极板工作压力下大于10mΩ·〖cm〗^2，同时该涂层在长时间电化学测试后导电性能未知；中国专利CN107978770 A公开了一种使用PECVD方法在燃料电池金属隔板表面制备碳涂 层的方法，该涂层依旧存在着在隔板工作压紧力下接触电阻较高的缺陷，同时该涂层耐久性未知。本发明将通过增加磁控溅射中的粒子能量以优化碳涂层结构，从而获取高导电、耐腐蚀且稳定的燃料电池金属双极板碳涂层。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种用于燃料电池金属双极板的石墨微晶碳涂层。
本发明的目的可以通过以下技术方案来实现：一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，包括：
耐蚀金属打底层：沉积于去除表面油污、氧化层的金属双极板表面，用以提高碳涂层与金属基体的结合力，同时进一步提高涂层在燃料电池服役环境中的耐腐蚀性；
耐蚀金属与碳涂层共存过渡层：沉积于金属打底层表面，用以降低涂层内应力，进一步提高涂层结合力及其稳定性；
最外层石墨微晶碳涂层：沉积于耐蚀金属与碳涂层共存过渡层表面，用以保证涂层与气体扩散层较低的接触电阻，同时保证涂层较好的稳定性及耐久性。
优选的，所述的金属打底层，采用磁控溅射的方法进行沉积，涂层厚度为1-100nm；
进一步地，所述的金属打底层中耐蚀金属包括Ti、Cr、W、Zr、Nb或Ta中的一种或更多种。
优选的，所述的耐蚀金属与碳涂层共存过渡层，采用耐蚀金属靶与石墨靶共同溅射的方式进行沉积，涂层厚度为1-100nm；
进一步地，所述的耐蚀金属与碳涂层共存过渡层在制备过程中，可通过增加沉积粒子能量的方式进行促进其进行耐蚀金属与碳化学键合，以形成金属化合物，从而进一步提高涂层耐腐蚀性能。
进一步地，所述的沉积粒子能量为1-100eV；
进一步地，所述的增加沉积粒子能量的方式，包括采用脉冲电源进行沉积、增加沉积过程中温度、改变溅射磁场强度等。
优选的，所述的最外层石墨微晶碳涂层通过磁控溅射的方式制备，涂层厚 度为1-500nm，包含sp2杂化键及sp3杂化键，涂层中包含较多的sp2杂化键以保证涂层较好的导电性，同时还包含一定量的sp3杂化键，以保证涂层较好的机械性能。
进一步地，所述的最外层石墨微晶碳涂层包含一定比例的石墨微晶，石墨微晶在碳涂层中的比例为10-50％，石墨微晶的存在保证涂层较好的导电性及耐腐蚀性，石墨微晶具有合适的尺寸，尺寸为1-2000nm，晶粒尺寸过小导致石墨结构缺陷增多，过大则导致涂层结构较为疏松，因此晶粒尺寸过大或过小均将导致涂层耐腐蚀性能及导电性能下降，同时碳涂层还需要具有较好的致密性，防止电解液通过孔隙渗入涂层内部发生电偶腐蚀，进而加剧涂层失效。
优选的，所述的石墨微晶碳涂层可通过改变涂层沉积过程中温度、靶材溅射电源、磁场结构及强度等方式改变沉积粒子能量，进而形成包含一定比例的石墨微晶的碳涂层，以提高涂层导电性能、耐腐蚀性及稳定性。
进一步的，所述的改变涂层沉积过程中温度，可在涂层沉积过程中通过加热器改变沉积温度，温度为150-600℃；
进一步的，所述的改变靶材溅射电源，可改变直流溅射电源为直流脉冲电源以控制沉积离子能量，直流脉冲溅射电源频率为50-350kHz，占空比为10-45％；
进一步的，所述的改变溅射磁场结构及强度，可改变磁极布置改变磁场分布，同时改变磁场强度，磁场强度为300-1500Gs。
优选的，所述的涂层总厚度为50-1000nm。
上述用于燃料电池金属双极板的石墨微晶碳涂层的制备方法，该方法包括以下步骤：
1)清洗金属双极板以去除其表面的油污及氧化膜；
2)在金属双极板表面镀覆耐蚀金属打底层；
3)在耐蚀金属打底层表面沉积耐蚀金属与碳共存过渡层；
4)在过渡层表面沉积高导电、耐腐蚀且稳定的纯碳涂层。
本发明中，通过改变溅射电源、溅射磁场、沉积温度等方式改变粒子能量，进而控制碳涂层中石墨晶体比例、石墨晶粒大小、晶体缺陷、涂层致密性，从而优化碳涂层导电性及耐腐蚀性，同时提高碳涂层稳定性及耐久性。
与现有技术相比，本发明具有以下优点：
1)在磁控溅射制备碳涂层的基础上通过改变粒子能量的方法对碳结构进行优化，得到的碳涂层具有更优的导电性能及耐腐蚀性，在燃料电池服役环境中涂层性能衰减速度慢，具有更优的稳定性及耐久性；
2)上述改变粒子能量的方法，可方便的在磁控溅射设备实现，且所需成本较低，因此制备该高导电、耐腐蚀且稳定的碳涂层依旧具有较低的成本；
综上，本发明对提高燃料电池金属双极板耐久性、推进燃料电池产业化进程具有重要意义。
附图说明
图1为实施例2、3、4中制备得到的涂层的整体结构示意图；
图2为实施例2中制备得到的涂层拉曼光谱(Raman)分析图；
图3为实施例2中制备得到的涂层截面形貌(SEM)图；
图4为实施例3中制备得到的涂层拉曼光谱(Raman)分析图；
图5为实施例3中制备得到的涂层截面形貌(SEM)图；
图6为各实施例中制备得到的涂层接触电阻测试结果图；
图7为实施例4中制备得到的涂层在pH＝3、80℃的H2SO4(含0.1ppm HF)溶液中0.84V(vs SHE)恒电位极化200h电流密度曲线。
图中标记说明：
1—金属双极板、2—耐蚀金属打底层、3—耐蚀金属与碳共存过渡层、4—金属碳化物晶体、5—碳层、6—石墨微晶、7—带有缺陷的石墨微晶。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例1：
如图1所示，用于金属双极板的高导电、耐腐蚀、稳定的碳涂层的制备方法包括以下步骤：
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1烘干放入炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除极板1表面金属氧化层，提高表面清洁度，进而提高膜基结合力；
2)在第一步处理后的金属双极板1表面预先沉积100nm的耐蚀金属(Cr)打底层2，提高涂层耐腐蚀性，并提高膜基结合力；
3)在第二步沉积的耐蚀金属打底层2表面沉积耐蚀金属与碳共存过渡层3，此时通入合适流量的Ar，同时开始耐蚀金属Cr靶及石墨靶，通过Cr靶与石墨靶共溅射形成耐蚀金属Cr与碳共存过渡层3，进一步提高膜基结合力，防止因内应力过大导致涂层脱落，过渡层沉积厚度为50nm；
4)在第三步过渡层沉积结束后，通过加温装置对炉腔进行加温，将温度升至500℃并保温一段时间以保证炉腔内部温度均匀，随后开启石墨靶溅射沉积碳膜，得到碳层5，该碳层5中还含有石墨微晶6和带有缺陷的石墨微晶7，石墨靶溅射电源采用直流电源，该层涂层沉积厚度为200nm；
5)涂层接触电阻测试结果如图6所示。
实施例2
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1烘干放入炉腔，随后控制炉腔真空度，待真空度达到设定值后开始通过加热装置对炉腔进行升温，待温度升高至400℃后进行保温一段时间，待腔体内温度均匀后开启离子源产生等离子体轰击金属双极板表面，以去除金属双极板1表面金属氧化层，提高表面清洁度，进而提高膜基结合力；
2)在第一步处理后的金属双极板1表面预先沉积50nm的耐蚀金属Ti打底层，提高涂层耐腐蚀性，并提高膜基结合力；
3)在第二步沉积的耐蚀金属打底层2表面沉积耐蚀金属与碳共存过渡层3，此时通入合适流量的Ar，同时开始耐蚀金属Ti靶及石墨靶，通过Ti靶与石墨靶共溅射形成耐蚀金属Ti与碳共存的过渡层，进一步提高膜基结合力，防止因内应力过大导致涂层脱落，同时该沉积过程温度较高，利于促进Ti与C进行化合形成耐腐蚀性更好的金属碳化物4，涂层耐腐蚀性可进一步提高过渡层沉积厚度为50nm；
4)在第三步过渡层沉积结束后，开启石墨靶溅射沉积碳膜得到碳层5，石墨靶溅射电源采用直流电源，该层涂层沉积厚度为100nm；
5)将沉积好的涂层进行性能表征，如图1、2、3所示分别为涂层结构示意图、Raman结构图、截面SEM分析图。相较于常规磁控溅射制备的非晶碳层，本实施例制备的碳涂层存在一定比例的石墨晶体6，石墨晶体缺陷较少、晶粒较大，涂层也具备较好的致密性，因此该涂层具备较优的导电性、耐腐蚀性及耐久性，涂层接触电阻测试结果如图6所示。
实施例3
用于金属双极板高导电、耐腐蚀、稳定的碳涂层的制备方法包括以下步骤：
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1烘干放入炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除极板1表面金属氧化层，提高表面清洁度，进而提高膜基结合力；
2)在第一步处理后的金属双极板1表面预先沉积50nm的耐蚀金属Ti打底层，提高涂层耐腐蚀性，并提高膜基结合力；
3)在第二步沉积的耐蚀金属打底层2表面沉积耐蚀金属与碳共存过渡层3，此时通入合适流量的Ar，同时开始耐蚀金属Ti靶及石墨靶，通过Ti靶与石墨靶共溅射形成耐蚀金属Ti与碳共存的过渡层，进一步提高膜基结合力，防止因内应力过大导致涂层脱落，Ti靶与石墨靶溅射电源选用脉冲电源，脉冲电源频率为350kHz，占空比为40％，可通过脉冲电源增加粒子能量以促进Ti与C化合形成金属化合物4，进一步增加涂层耐腐蚀性，过渡层沉积厚度为50nm；
4)开启石墨靶溅射沉积碳膜得到碳层5，石墨靶溅射电源采用脉冲溅射电源，脉冲电源频率为350kHz，占空比为40％，该层涂层沉积厚度为200nm；
5)将沉积好的涂层进行性能表征，如图1、4、5所示分别为涂层结构示意图、Raman结构图、截面SEM分析图。相较于常规磁控溅射制备的非晶碳层，本实施例制备的碳涂层存在一定比例的石墨晶体6，石墨晶体缺陷较少、晶粒较大，涂层也具备较好的致密性，因此该涂层具备较优的导电性、耐腐蚀性及耐久性，涂层接触电阻测试结果如图6所示。
实施例4
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1烘干放入炉腔，随后控制炉腔真空度，待真空度达到设定值后开始通过加热装置对炉腔进行升温，待温度升高至200℃后进行保温一段时间，待腔体内温度均匀后开启离子源产生等离子体轰击金属双极板1表面，以去除极板1表面金属氧化层，提高表面清洁度，进而提高膜基结合力；
2)在第一步处理后的金属双极板表面预先沉积50nm的耐蚀金属Ti打底层，提高涂层耐腐蚀性，并提高膜基结合力；
3)在第二步沉积的耐蚀金属打底层2表面沉积耐蚀金属与碳共存过渡层3，此时通入合适流量的Ar，同时开始耐蚀金属Ti靶及石墨靶，通过Ti靶与石墨靶共溅射形成耐蚀金属Ti与碳共存的过渡层，进一步提高膜基结合力，防止因内应力过大导致涂层脱落，Ti靶与石墨靶溅射电源选用脉冲电源，脉冲电源频率为350kHz，占空比为40％，同时在沉积过程中温度较高，较高温度与脉冲电源均可增加粒子能量以促进Ti与C化合形成金属化合物4，进一步增加涂层耐腐蚀性，过渡层沉积厚度为50nm；
4)在第三步过渡层沉积结束后，通过加温装置对炉腔进行加温，将温度升至200℃并保温一段时间以保证炉腔内部温度均匀，随后开启石墨靶溅射沉积碳膜得到碳层5，石墨靶溅射电源采用脉冲溅射电源，脉冲电源频率为150kHz，占空比为40％，该层涂层沉积厚度为200nm；
5)将沉积好的涂层进行性能表征，如图1所示为涂层结构示意图。模拟燃料电池服役环境对该涂层进行电化学测试，如图6所示为涂层腐蚀前及0.84V(vs SHE)腐蚀200h后涂层接触电阻测试结果，该测试结果表明，该方法制备的碳涂层具有优异的导电性、耐腐蚀性及稳定性，涂层接触电阻测试结果如图6所示，在燃料电池模拟酸性环境中进行0.84V(vs SHE)恒电位极化腐蚀电流密度如图7所示。
实施例5
用于金属双极板高导电、耐腐蚀、稳定的碳涂层的制备方法包括以下步骤：
1)使用清洗剂清洗金属双极板1表面油污、杂质，并将清洗后的金属双极板1烘干放入炉腔，随后控制炉腔真空度，待真空度达到设定值后开启离子源产生等离子体轰击金属双极板1表面，以去除极板1表面金属氧化层，提高表 面清洁度，进而提高膜基结合力；
2)在第一步处理后的金属双极板表面预先沉积50nm的耐蚀金属Ti打底层，提高涂层耐腐蚀性，并提高膜基结合力；
3)在第二步沉积的耐蚀金属打底层2表面沉积耐蚀金属与碳共存过渡层3，此时通入合适流量的Ar，同时开始耐蚀金属Ti靶及石墨靶，通过Ti靶与石墨靶共溅射形成耐蚀金属Ti与碳共存的过渡层3，进一步提高膜基结合力，防止因内应力过大导致涂层脱落，过渡层沉积厚度为50nm；
4)开启石墨靶溅射沉积碳膜得到碳层5，石墨靶溅射电源采用直流电源，对应溅射磁场为强磁场，磁场强度为800Gs，该层涂层厚度为200nm；
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种用于燃料电池金属双极板的石墨微晶碳涂层，该涂层涂覆在金属双极板表面，其特征在于，所述的石墨微晶碳涂层为类石墨涂层，该涂层中包含石墨微晶5-50wt％。
  2. 根据权利要求1所述的一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，所述的石墨微晶碳涂层是由石墨微晶嵌入在碳层中形成的，涂层厚度为1-500nm，石墨微晶占碳层总重量的比例为10-30％
  3. 根据权利要求1所述的一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，所述的石墨微晶的晶粒尺寸为1-2000nm。
  4. 根据权利要求1所述的一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，所述的石墨微晶碳涂层是在沉积石墨粒子的过程中，通过改变沉积粒子的能量制备出高导电、耐腐蚀且稳定的类石墨碳涂层。
  5. 根据权利要求4所述的一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，所述的沉积粒子的能量为1-100eV。
  6. 根据权利要求4所述的一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，所述的改变沉积粒子的能量的方法为改变涂层沉积过程中温度，在涂层沉积过程中通过加热器改变沉积温度，温度为150-600℃；
  7. 根据权利要求4所述的一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，所述的改变沉积粒子的能量的方法为改变靶材溅射电源，改变直流溅射电源为直流脉冲电源以控制沉积离子能量，直流脉冲溅射电源频率为50-350kHz，占空比为10-45％。
  8. 根据权利要求4所述的一种用于燃料电池金属双极板的石墨微晶碳涂层，其特征在于，所述的改变沉积粒子的能量的方法为改变溅射磁场结构及强度，改变磁极布置改变磁场分布，同时改变磁场强度，磁场强度为300-1500Gs。
  9. 一种如权利要求1所述的用于燃料电池金属双极板的石墨微晶碳涂层的 应用，其特征在于，在金属双极板表面向上依次设置的耐蚀金属打底层、耐蚀金属与碳涂层共存过渡层和石墨微晶碳涂层。
  10. 根据权利要求9所述的一种用于燃料电池金属双极板的石墨微晶碳涂层的应用，其特征在于，所述的耐蚀金属打底层采用磁控溅射的方法沉积在金属双极板表面，厚度为1-100nm；所述的耐蚀金属打底层中耐蚀金属包括Ti、Cr、W、Zr、Nb或Ta中的一种或更多种；
    所述的耐蚀金属与碳涂层共存过渡层采用耐蚀金属靶与石墨靶共同溅射的方式沉积在耐蚀金属打底层表面，厚度为1-100nm。
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