CN115029663A - Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell - Google Patents
Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell Download PDFInfo
- Publication number
- CN115029663A CN115029663A CN202210785753.2A CN202210785753A CN115029663A CN 115029663 A CN115029663 A CN 115029663A CN 202210785753 A CN202210785753 A CN 202210785753A CN 115029663 A CN115029663 A CN 115029663A
- Authority
- CN
- China
- Prior art keywords
- layer
- metal
- carbide
- amorphous carbon
- transition layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
-
- 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
- C23C14/06—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/343—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one DLC or an amorphous carbon based layer, the layer being doped or not
-
- 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
- H01M8/0228—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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a metal pole plate composite coating, a metal pole plate, a preparation method of the metal pole plate and a fuel cell. According to the invention, the metal carbide layer with the metal lattice structure and the amorphous carbon lattice structure is arranged between the priming layer and the amorphous carbon layer, so that the compactness of the amorphous carbon layer and the corrosion resistance of the coating are improved, and the service life of a fuel cell prepared by using the amorphous carbon layer as the coating is greatly prolonged; meanwhile, the contact resistance between the metal polar plate composite coating and the carbon paper of the membrane electrode is small, and the output power of the fuel cell is greatly improved.
Description
Technical Field
The invention belongs to the field of fuel cells, and relates to a metal polar plate composite coating, a metal polar plate, a preparation method of the metal polar plate and a fuel cell.
Background
The fuel cell can directly convert chemical energy stored in fuel (such as hydrogen, natural gas and the like) and oxidant (such as air, oxygen) into electric energy through electrochemical reaction, and is a high-efficiency and environment-friendly power generation device. The Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of quick start, low working temperature, no noise, no pollution and the like, and has wide application prospect in automobiles, household residences, small and medium-sized power stations and portable devices.
The structure of the PEMFC mainly includes a Membrane Electrode Assembly (MEA), an electrode plate, a current collector, an end plate, and the like. During the operation of the PEMFC, the polar plate has the functions of supporting MEA, collecting current, conducting heat, distributing gas, and isolating fuel and oxidant; because most of the currently adopted proton exchange membranes are perfluorosulfonic acid membranes, the chain end of a molecular branched chain is a sulfonic acid group with strong oxidizing property; meanwhile, the perfluorosulfonic acid membrane is degraded in the use process of the fuel cell and can release fluoride ions, so that the polar plate can endure sulfonic acid with the pH value of 2-3, hydrofluoric acid with the concentration of about 0.1ppm and the environmental condition of about 80 ℃ in the working environment of the fuel cell, which puts a very high requirement on the corrosion resistance of the polar plate.
The traditional graphite pole plate shows very excellent corrosion resistance and conductivity, for example, in patent CN1553536, graphite powder and resin are mixed, and the graphite pole plate is prepared by a hot press molding method, and the prepared pole plate has good conductivity, but has poor mechanical strength, large volume, more defects, high processing cost and low processing efficiency, and due to the defects, the requirements of smaller volume, higher power density, lower manufacturing cost, higher reliability and convenience for large-scale popularization of the vehicle fuel cell are more and more difficult to meet. In contrast, the polar plate made of metal has the advantages of thin volume, high mechanical strength, high air resistance, good processing technology, high resource recovery rate and the like, but the common metal polar plate generally has the defect of poor corrosion resistance, and the strategy of performing surface treatment on the polar plate or covering a special coating on the surface of the polar plate becomes the mainstream research direction for improving the corrosion resistance of the metal polar plate of the fuel cell.
The existing metal pole plate coating comprises a graphite coating, a nitride coating, a conductive organic matter coating, a noble metal coating and the like. For example, patent CN111525151A discloses that a corrosion-resistant layer is coated on a fuel cell plate, and then a thin layer of noble metal is coated on the surface of the corrosion-resistant layer, which improves the high-potential corrosion resistance of the metal plate, but the noble metal coating has high cost, which is not suitable for large-scale application. Patent CN107195920B discloses a coating material comprising a self-healing layer and a super-corrosion resistant layer, wherein the super-corrosion resistant layer comprises an oxide layer and a nitride layer of tungsten alloy components, which can obtain lower corrosion current density, but the nitride coating or the conductive organic coating is difficult to be applied due to too large resistance. Other common methods are to deposit a low-cost carbon-based coating on the surface of the plate by using a physical vapor deposition method, but the bonding force between the carbon-based coating and the metal substrate is poor, generally a priming layer such as titanium, chromium, tungsten and the like is applied on the metal substrate of the metal plate, and then an amorphous carbon layer is deposited by using physical vapor deposition or plasma chemical vapor deposition, for example, patent CN113445014A, a modified layer of metal such as titanium, nickel or chromium is arranged on the surface of the stainless steel plate, so that the contact resistance and the corrosion current between the stainless steel and the carbon paper are reduced.
In the prior art, the titanium, chromium, tungsten and other metal priming layers are arranged on the surface of the base material of the polar plate, so that the binding force between the carbon-based coating and the metal base material can be effectively improved, and the contact resistance is reduced, but the lattice difference between the metal priming layer and the non-metal carbon-based coating is too large, so that the formed amorphous carbon structure is poor in compactness and easy to corrode. Therefore, it has been a difficult problem how to improve the compactness of the carbon-based coating and improve the corrosion resistance of the coating, thereby improving the service life of the metal plate.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a metal pole plate composite coating, a metal pole plate, a preparation method of the metal pole plate and a fuel cell. According to the invention, the metal carbide layer with the metal lattice structure and the amorphous carbon lattice structure is arranged between the priming layer and the amorphous carbon layer, so that the compactness of the amorphous carbon layer and the corrosion resistance of the coating are improved, and the service life of a fuel cell prepared by using the amorphous carbon layer as the coating is greatly prolonged; meanwhile, the contact resistance between the metal polar plate composite coating and the carbon paper of the membrane electrode is small, and the output power of the fuel cell is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a metal electrode plate composite coating, which comprises a priming layer, a metal carbide layer and an amorphous carbon layer which are sequentially stacked.
According to the invention, the metal carbide layer with both the metal lattice structure and the amorphous carbon lattice structure is arranged between the priming layer and the amorphous carbon layer, on one hand, the prepared amorphous carbon layer has good compactness and high corrosion resistance of the coating because the metal carbide has both the metal lattice structure of the priming layer and the amorphous carbon lattice structure, thereby greatly prolonging the service life of the fuel cell; meanwhile, the contact resistance between the metal polar plate composite coating and the carbon paper of the membrane electrode is small, so that the output power of the fuel cell is effectively improved; on the other hand, compared with coatings with poor compactness such as graphite, the amorphous carbon in the invention has high compactness, has synergistic effect with the priming layer and the metal carbide layer, does not need to additionally add other metal layers, and further improves the corrosion resistance of the metal polar plate with the composite coating and the output power of the fuel cell when being used for preparing the fuel cell on the metal polar plate.
Preferably, the metal carbide layer includes any one or a combination of at least two of chromium carbide, tungsten carbide, zirconium carbide and dimolybdenum carbide, and may be, for example, a combination of chromium carbide and tungsten carbide, a combination of tungsten carbide and zirconium carbide, a combination of zirconium carbide and dimolybdenum carbide, a combination of chromium carbide, tungsten carbide and dimolybdenum carbide, or a combination of chromium carbide, tungsten carbide, zirconium carbide and dimolybdenum carbide, or the like. The metal carbide is selected as the metal carbide layer, the synergistic effect of the metal carbide layer, the amorphous carbon layer and the priming layer is fully exerted, the compactness of the amorphous carbon layer is further improved, and the corrosion resistance of the metal polar plate with the composite coating, the service life of the fuel cell and the output power of the fuel cell are improved.
Preferably, the primer layer comprises any one or a combination of at least two of titanium, chromium, tungsten, molybdenum and zirconium, and may be, for example, a combination of titanium and chromium, a combination of molybdenum and zirconium, a combination of chromium, tungsten and molybdenum, a combination of titanium, chromium, tungsten, molybdenum and zirconium, or the like.
As a preferable technical scheme of the metal plate composite coating, the thickness of the primer layer is 5-1000 nm, for example, 5nm, 10nm, 20nm, 30nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000 nm; when the thickness of the bottom layer is lower, the binding force between the base material and the metal carbide layer can be reduced, and when the thickness of the bottom layer is higher, the performance is not greatly improved, but the coating time is long, and the coating efficiency can be reduced.
Preferably, the metal carbide layer has a thickness of 5 to 1000nm, and may be, for example, 5nm, 10nm, 20nm, 30nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, or the like. When the thickness of the metal carbide layer is relatively low, the bonding force between the base coat layer and the amorphous carbon layer is reduced, and when the thickness of the metal carbide layer is relatively high, the coating efficiency is reduced.
Preferably, the amorphous carbon layer has a thickness of 5 to 1000nm, and may be, for example, 5nm, 10nm, 20nm, 30nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, or the like. When the thickness of the amorphous carbon layer is low, the durability of the coating is reduced, and when the thickness of the amorphous carbon layer is high, the coating efficiency is reduced and the cost is increased.
According to the invention, the priming layer, the metal carbide layer and the amorphous carbon layer with proper thicknesses are adopted, so that the corrosion resistance of the prepared metal polar plate with the composite coating can be further improved, the contact resistance is reduced, and the service life and the output power of the fuel cell are improved.
As a preferable technical scheme of the metal pole plate composite coating, a first transition layer is further arranged between the priming layer and the metal carbide layer.
Preferably, the first transition layer comprises a transition layer metal and a transition layer metal carbide, the transition layer metal is the same as the metal of the base layer, and the transition layer metal carbide is the same as the metal carbide of the metal carbide layer.
Preferably, the thickness of the first transition layer is 5 to 1000nm, and may be, for example, 5nm, 10nm, 20nm, 30nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, or the like.
Preferably, a second transition layer is further disposed between the metal carbide layer and the amorphous carbon layer.
Preferably, the second transition layer comprises a transition layer metal carbide and amorphous carbon.
Preferably, the thickness of the second transition layer is 5 to 1000nm, and may be, for example, 5nm, 10nm, 20nm, 30nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1000nm, or the like.
The first transition layer containing transition layer metal and transition layer metal carbide is arranged between the priming layer and the metal carbide layer, and the second transition layer containing transition layer metal carbide and amorphous carbon is arranged between the metal carbide layer and the amorphous carbon layer, so that the compactness of the coating can be further improved.
In a second aspect, the invention provides a metal pole plate with a composite coating, the metal pole plate comprises a base material, the metal pole plate composite coating according to the first aspect is arranged on at least one side surface of the base material, and a bottom layer of the metal pole plate composite coating is attached to the base material.
The amorphous carbon layer in the metal polar plate composite coating has high compactness and good corrosion resistance, and the contact resistance between the coating and the carbon paper of the membrane electrode is small.
Preferably, the substrate comprises any one or a combination of at least two of stainless steel, titanium, aluminum, nickel and magnesium, and may be, for example, a combination of stainless steel and titanium, a combination of aluminum and nickel, a combination of nickel and magnesium, a combination of titanium, aluminum, nickel and magnesium, or a combination of stainless steel, titanium, aluminum, nickel and magnesium, or the like.
In a third aspect, the invention provides a method for preparing the metal plate with the composite coating according to the second aspect, wherein the method for preparing the metal plate comprises the following steps:
depositing a base coat on at least one side surface of the substrate, and sequentially depositing metal carbide and amorphous carbon on the surface of the base coat to obtain the metal pole plate with the composite coating.
The metal carbide layer is deposited between the priming layer and the amorphous carbon layer, and the prepared amorphous carbon layer has good compactness and high corrosion resistance of the coating, greatly prolongs the service life of the fuel cell, has small contact resistance and greatly improves the output power of the fuel cell because the lattice structure of the metal carbide has the lattice structure of both the metal priming layer and the amorphous carbon.
Preferably, the metal carbide includes any one or a combination of at least two of chromium carbide, tungsten carbide, zirconium carbide and dimolybdenum carbide, and may be, for example, a combination of chromium carbide and tungsten carbide, a combination of tungsten carbide and zirconium carbide, a combination of zirconium carbide and dimolybdenum carbide, a combination of chromium carbide, tungsten carbide and dimolybdenum carbide, or a combination of chromium carbide, tungsten carbide, zirconium carbide and dimolybdenum carbide, or the like.
Preferably, in the step of depositing the primer layer on at least one side surface of the substrate, the deposition mode is physical vapor deposition.
Preferably, in the step of depositing the metal carbide on the surface of the base layer, the deposition mode is physical vapor deposition.
Preferably, in the step of depositing the amorphous carbon on the surface of the underlayer, the deposition mode is physical vapor deposition or/and plasma chemical vapor deposition.
The invention adopts physical vapor deposition and/or plasma chemical vapor deposition to deposit the priming layer, the metal carbide layer and the amorphous carbon layer, and compared with chemical plating and electroplating, the invention can improve the preparation efficiency of the coating and reduce the environmental pollution.
As a preferred technical scheme of the preparation method, the method further comprises the step of depositing transition layer metal and transition layer metal carbide after the bottom layer is deposited and before the metal carbide is deposited.
Preferably, in the step of depositing the transition layer metal and the transition layer metal carbide, the deposition mode is physical vapor deposition.
Preferably, the method further comprises the step of depositing a transition layer of metal carbide and amorphous carbon after depositing the metal carbide and before depositing the amorphous carbon.
Preferably, in the step of depositing the transition layer of metal carbide and amorphous carbon, the deposition mode is physical vapor deposition.
In some embodiments, the physical vapor deposition is by magnetron sputtering.
In a fourth aspect, the invention provides a fuel cell comprising a metal plate with a composite coating according to the second aspect.
The fuel cell of the invention has the advantages of smaller contact resistance, lower corrosion current density, good corrosion resistance, longer service life and higher output power.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the metal carbide layer with both the metal lattice structure and the amorphous carbon lattice structure is arranged between the priming layer and the amorphous carbon layer, on one hand, the prepared amorphous carbon layer has good compactness and high corrosion resistance of the coating because the metal carbide has both the metal lattice structure of the priming layer and the amorphous carbon lattice structure, thereby greatly prolonging the service life of the fuel cell; meanwhile, the contact resistance between the metal polar plate composite coating and the carbon paper of the membrane electrode is smaller, so that the output power of the fuel cell is effectively improved; on the other hand, compared with coatings with poor compactness such as graphite, the amorphous carbon in the invention has high compactness, has synergistic effect with the priming layer and the metal carbide layer, does not need to additionally add other metal layers, and further improves the corrosion resistance of the metal polar plate with the composite coating and the output power of the fuel cell when being used for preparing the fuel cell on the metal polar plate.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a take composite coating's metal polar plate, take composite coating's metal polar plate includes the substrate and sets up the metal polar plate composite coating on substrate one side surface, and metal polar plate composite coating is including the priming layer, first transition layer, metal carbide layer, second transition layer and the amorphous carbon layer that stack gradually the setting, and priming layer and substrate are laminated mutually.
Wherein the base material is stainless steel, and the thickness is 0.1 mm; the bottom layer is made of titanium and has the thickness of 5 nm; the first transition layer is made of titanium and chromium carbide in a mass ratio of 1:9 and has a thickness of 50 nm; the metal carbide layer is made of chromium carbide and has the thickness of 80 nm; the second transition layer is made of chromium carbide and amorphous carbon, the mass ratio is 6:4, and the thickness is 180 nm; the thickness of the amorphous carbon layer was 1000 nm.
The embodiment also provides a preparation method of the metal plate with the composite coating, which comprises the following steps:
(1) placing the stainless steel substrate on a sample holder, feeding the sample holder into a coating deposition equipment cavity, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, the temperature is 100 ℃, argon is introduced to maintain the air pressure at 0.1Pa, a 300V bias voltage is applied to the sample holder for cleaning, and impurities, oil stains and oxidation films on the surface of the stainless steel base material are removed;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, opening a magnetron sputtering titanium target with sputtering power of 6kW and sputtering time of 1 minute, and forming a titanium priming layer with the thickness of 5 nm;
(3) simultaneously opening a magnetron sputtering chromium carbide target and a titanium target, sputtering power is 6kW, and sputtering time is 4 minutes to form a first transition layer of titanium and chromium carbide with the thickness of 50 nm;
(4) closing the titanium target, continuing to perform magnetron sputtering on the chromium carbide target, wherein the sputtering power is 6kW, and the sputtering time is 5 minutes, so as to form a metal carbide layer which is 80nm thick and is made of chromium carbide;
(5) simultaneously opening a magnetron sputtering graphite target and a chromium carbide target, sputtering with the power of 5kW for 10 minutes to form a second transition layer of chromium carbide and amorphous carbon with the thickness of 180 nm;
(6) and closing the chromium carbide target, continuing to open the magnetron sputtering graphite target, and forming an amorphous carbon layer with the thickness of 1000nm at the sputtering power of 3kW for 60 minutes.
Example 2
The embodiment provides a take composite coating's metal polar plate, take composite coating's metal polar plate includes the substrate and sets up the metal polar plate composite coating on substrate one side surface, and metal polar plate composite coating is including the priming layer, first transition layer, metal carbide layer, second transition layer and the amorphous carbon layer that stack gradually the setting, and priming layer and substrate are laminated mutually.
Wherein the base material is titanium, and the thickness is 0.08 mm; the bottom layer is made of chromium and has the thickness of 1000 nm; the first transition layer is made of chromium and molybdenum carbide in a mass ratio of 3:7 and has a thickness of 80 nm; the metal carbide layer is made of molybdenum carbide and has the thickness of 80 nm; the second transition layer is made of molybdenum carbide and amorphous carbon, the mass ratio is 1:9, and the thickness is 10 nm; the thickness of the amorphous carbon layer was 5 nm.
The embodiment also provides a preparation method of the metal plate with the composite coating, which comprises the following steps:
(1) placing the titanium substrate on a sample holder, placing the sample holder into a coating deposition equipment cavity, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, the temperature is 100 ℃, argon is introduced to maintain the air pressure at 0.1Pa, and a 300V bias voltage is applied to the sample rack for cleaning to remove impurities, oil stains and oxidation films on the surface of the titanium substrate;
(2) in the same cavity, the temperature and the air pressure of the cavity are kept unchanged, the flow of argon is 80sccm, a chromium arc target is opened, the power is 6kW, and the time is 60 minutes, so that a chromium priming coat with the thickness of 1000nm is formed;
(3) simultaneously opening a molybdenum carbide arc target and a chromium arc target, wherein the power is 6kW, and the time is 5 minutes, so that a first transition layer of chromium and molybdenum carbide with the thickness of 80nm is formed;
(4) closing the chromium arc target, and continuing to open the molybdenum carbide arc target, wherein the power is 6kW, and the time is 5 minutes, so that a metal carbide layer which is 80nm thick and made of the molybdenum carbide is formed;
(5) and simultaneously opening the graphite arc target and the dimolybdenum carbide arc target, wherein the power is 3kW, and the time is 1 minute, so that a second transition layer of dimolybdenum carbide and amorphous carbon with the thickness of 10nm is formed.
(6) And closing the dimolybdenum carbide target, and continuing to open the graphite arc target, wherein the power is 3kW, and the time is 1 minute, so that an amorphous carbon layer with the thickness of 5nm is formed.
In the invention, the arc target refers to a multi-arc ion plating target material, and the multi-arc ion plating is one of physical vapor deposition.
Example 3
This embodiment provides a take composite biocoating's metal polar plate, take composite biocoating's metal polar plate includes the substrate and sets up the metal polar plate composite biocoating on substrate one side surface, and metal polar plate composite biocoating is including the prime coat, first transition layer, metal carbide layer, second transition layer and the amorphous carbon layer that stack gradually the setting, and prime coat and substrate laminate mutually.
Wherein the base material is aluminum, and the thickness is 0.06 mm; the bottom layer is made of tungsten and has the thickness of 50 nm; the first transition layer is made of tungsten and tungsten carbide, the mass ratio is 5:5, and the thickness is 15 nm; the metal carbide layer is made of tungsten carbide and has the mass ratio of 9:1 and the thickness of 5 nm; the second transition layer is made of tungsten carbide and amorphous carbon and has the thickness of 150 nm; the thickness of the amorphous carbon layer was 300 nm.
The embodiment also provides a preparation method of the metal plate with the composite coating, which comprises the following steps:
(1) placing the aluminum substrate on a sample holder, placing the sample holder into the coating deposition device chamber, and evacuating to a vacuum 8 x 10 below background vacuum -4 Pa, the temperature is 100 ℃, argon is introduced to maintain the air pressure at 0.1Pa, and a 300V bias voltage is applied to the sample holder for cleaning to remove impurities, oil stains and oxidation films on the surface of the aluminum substrate;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, enabling the flow of argon to be 100sccm, opening a tungsten arc target, enabling the power to be 6kW, and enabling the time to be 4 minutes to form a tungsten bottom layer with the thickness of 50 nm;
(3) simultaneously opening a tungsten carbide arc target and a tungsten arc target, wherein the power is 6kW, and the time is 2 minutes, so that a first transition layer of tungsten and carbide with the thickness of 15nm is formed;
(4) closing the tungsten arc target, and continuing to open the tungsten carbide arc target with the power of 6kW for 1 minute to form a metal carbide layer which is 5nm thick and made of tungsten carbide;
(5) and simultaneously opening the graphite arc target and the tungsten carbide arc target, wherein the power is 3kW, and the time is 10 minutes, so that a second transition layer of tungsten carbide and amorphous carbon with the thickness of 150nm is formed.
(6) And closing the tungsten carbide target, and continuously opening the graphite arc target with the power of 3kW for 20 minutes to form an amorphous carbon layer with the thickness of 300 nm.
Example 4
The embodiment provides a take composite coating's metal polar plate, take composite coating's metal polar plate includes the substrate and sets up the metal polar plate composite coating on substrate one side surface, and metal polar plate composite coating is including the priming layer, first transition layer, metal carbide layer, second transition layer and the amorphous carbon layer that stack gradually the setting, and priming layer and substrate are laminated mutually.
Wherein the base material is nickel, and the thickness is 0.05 mm; the material of the bottom layer is molybdenum, and the thickness of the bottom layer is 50 nm; the first transition layer is made of molybdenum and zirconium carbide in a mass ratio of 7:3 and has a thickness of 200 nm; the material of the metal carbide layer is zirconium carbide, and the thickness of the metal carbide layer is 1000 nm; the second transition layer is made of zirconium carbide and amorphous carbon, the mass ratio is 5:5, and the thickness is 150 nm; the amorphous carbon layer had a thickness of 300 nm.
The embodiment also provides a preparation method of the metal plate with the composite coating, which comprises the following steps:
(1) placing the nickel substrate on a sample holder, placing the sample holder into the cavity of a coating deposition device, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, keeping the temperature to 100 ℃, introducing argon to maintain the air pressure at 0.1Pa, and applying a bias voltage of 300V on a sample rack for cleaning to remove impurities, oil stains and an oxidation film on the surface of the nickel base material;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, enabling the flow of argon to be 80sccm, opening a magnetron sputtering molybdenum target, sputtering power to be 6kW, and sputtering time to be 4 minutes to form a molybdenum priming layer with the thickness of 50 nm;
(3) simultaneously opening a magnetron sputtering zirconium carbide target and a molybdenum target, and forming a first transition layer of molybdenum and zirconium carbide with the thickness of 200nm by sputtering with the sputtering power of 6kW for 10 minutes;
(4) closing the molybdenum target, continuing to open the magnetron sputtering zirconium carbide target, and sputtering for 6kW for 50 minutes to form a metal carbide layer which is 1000nm thick and made of zirconium carbide;
(5) and simultaneously opening the magnetron sputtering graphite target and the zirconium carbide target, and sputtering with the power of 3kW for 10 minutes to form a second transition layer of zirconium carbide and amorphous carbon with the thickness of 150 nm.
(6) And closing the zirconium carbide target, and continuing to open the magnetron sputtering graphite target, wherein the sputtering power is 3kW, and the sputtering time is 20 minutes, so that an amorphous carbon layer with the thickness of 300nm is formed.
Example 5
The embodiment provides a take composite coating's metal polar plate, take composite coating's metal polar plate includes the substrate and sets up the metal polar plate composite coating on substrate one side surface, and metal polar plate composite coating is including the priming layer, first transition layer, metal carbide layer, second transition layer and the amorphous carbon layer that stack gradually the setting, and priming layer and substrate are laminated mutually.
Wherein the base material is magnesium, and the thickness is 0.09 mm; the priming coat is made of zirconium and has the thickness of 50 nm; the first transition layer is made of zirconium and molybdenum carbide in a mass ratio of 9:1 and has a thickness of 60 nm; the material of the metal carbide layer is molybdenum carbide, and the thickness of the metal carbide layer is 60 nm; the second transition layer is made of molybdenum carbide and amorphous carbon, the mass ratio is 4:6, and the thickness is 200 nm; the thickness of the amorphous carbon layer was 200 nm.
The embodiment also provides a preparation method of the metal plate with the composite coating, which comprises the following steps:
(1) placing the magnesium substrate on a sample holder, placing the sample holder into the cavity of a coating deposition device, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, temperature to 1Introducing argon at 00 ℃ to maintain the air pressure at 0.1Pa, and applying a bias voltage of 300V on a sample rack for cleaning to remove impurities, oil stains and an oxidation film on the surface of the magnesium substrate;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, enabling the flow of argon to be 80sccm, opening a magnetron sputtering zirconium target, enabling the sputtering power to be 6kW, and enabling the sputtering time to be 4 minutes to form a zirconium bottom layer with the thickness of 50 nm;
(3) simultaneously opening a dimolybdenum carbide arc target and a zirconium target, and sputtering for 6kW for 3 minutes to form a first transition layer of zirconium and dimolybdenum carbide with the thickness of 60 nm;
(4) closing the zirconium target, continuously opening the molybdenum carbide arc target, and sputtering for 3 minutes at the power of 6kW to form a metal carbide layer which is 60nm thick and is made of molybdenum carbide;
(5) simultaneously introducing acetylene with the flow of 100sccm and the plasma power of 3kW for 20 minutes to form a second transition layer of molybdenum carbide and amorphous carbon with the thickness of 200 nm;
(6) closing the dimolybdenum carbide target, continuing to introduce acetylene with the flow of 100sccm, the plasma power of 3kW and the time of 20 minutes to form an amorphous carbon layer with the thickness of 200 nm.
Example 6
The same procedure as in example 1 was repeated, except that the metal plate with the composite coating layer did not include the first transition layer and the second transition layer, i.e., the steps (3) and (5) were not performed.
Example 7
The same as in example 1 was conducted except that the thickness of the metal carbide layer was 1100 nm.
Example 8
The same as in example 1 was conducted except that the thickness of the metal carbide layer was 3 nm.
Comparative example 1
This comparative example provides a composite coated metal plate, which is the same as example 1 except that it does not contain the first transition layer, the metal carbide layer and the second transition layer.
The preparation method of the metal pole plate with the composite coating comprises the following steps:
(1) placing the stainless steel substrate on a sample holder, feeding the sample holder into a coating deposition equipment cavity, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, the temperature is 100 ℃, argon is introduced to maintain the air pressure at 0.1Pa, a 300V bias voltage is applied to the sample holder for cleaning, and impurities, oil stains and oxidation films on the surface of the stainless steel base material are removed;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, opening a magnetron sputtering titanium target with sputtering power of 6kW and sputtering time of 1 minute, and forming a titanium priming layer with the thickness of 5 nm;
(3) and closing the titanium target, opening the magnetron sputtering graphite target, and sputtering with the sputtering power of 3kW for 60 minutes to form an amorphous carbon layer with the thickness of 1000 nm.
Comparative example 2
The comparative example provides a metal pole plate with a composite coating, the metal pole plate with the composite coating comprises a base material, a priming layer and an amorphous carbon layer which are sequentially stacked, the base material is titanium and the thickness of the base material is 0.08mm, the priming layer is chromium and the thickness of the priming layer is 50nm, and the thickness of the amorphous carbon layer is 5 nm.
The comparative example also provides a preparation method of the metal plate with the composite coating, which comprises the following steps:
(1) placing the titanium substrate on a sample holder, placing the sample holder into a coating deposition equipment cavity, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, the temperature is 100 ℃, argon is introduced to maintain the air pressure at 0.1Pa, and a 300V bias voltage is applied to the sample rack for cleaning to remove impurities, oil stains and oxidation films on the surface of the titanium substrate;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, enabling the flow of argon to be 80sccm, opening a chromium target, and enabling the power to be 6kW and the time to be 60 minutes to form a chromium priming layer with the thickness of 50 nm;
(3) and closing the chromium arc target, opening the graphite arc target, and forming an amorphous carbon layer with the thickness of 5nm at the power of 3kW for 1 minute.
Comparative example 3
This comparative example provides a composite coated metal plate, which is the same as example 3 except that it does not contain the first transition layer, the metal carbide layer and the second transition layer.
The preparation method of the metal pole plate with the composite coating comprises the following steps:
(1) placing the aluminum substrate on a sample holder, placing the sample holder into the coating deposition equipment chamber, and evacuating to a vacuum 8 x 10 below the background vacuum -4 Pa, keeping the temperature to 100 ℃, introducing argon to maintain the air pressure at 0.1Pa, and applying a bias voltage of 300V on the sample frame for cleaning to remove impurities, oil stains and an oxide film on the surface of the aluminum substrate;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, enabling the flow of argon to be 100sccm, opening a tungsten arc target, and enabling the power to be 6kW and the time to be 4 minutes to form a tungsten primer layer with the thickness of 50 nm;
(3) and closing the tungsten arc target, opening the graphite arc target, and forming an amorphous carbon layer with the thickness of 300nm by using the power of 3kW for 20 minutes.
Comparative example 4
This comparative example provides a composite coated metal plate similar to that of example 4 except that the first transition layer, the metal carbide layer and the second transition layer were not included.
The preparation method of the metal pole plate with the composite coating comprises the following steps:
(1) placing the nickel substrate on a sample holder, placing the sample holder into a coating deposition device cavity, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, keeping the temperature to 100 ℃, introducing argon to maintain the air pressure at 0.1Pa, and applying a bias voltage of 300V on a sample rack for cleaning to remove impurities, oil stains and an oxidation film on the surface of the nickel base material;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, enabling the flow of argon to be 80sccm, opening a magnetron sputtering molybdenum target, sputtering power to be 6kW, and sputtering time to be 4 minutes to form a molybdenum priming layer with the thickness of 50 nm;
(3) and closing the molybdenum target, opening the magnetron sputtering graphite target, and sputtering for 20 minutes at the sputtering power of 3kW to form an amorphous carbon layer with the thickness of 300 nm.
Comparative example 5
This comparative example provides a composite coated metal plate similar to that of example 5 except that the first transition layer, the metal carbide layer and the second transition layer were not included.
The preparation method of the metal pole plate with the composite coating comprises the following steps:
(1) placing the magnesium substrate on a sample holder, placing the sample holder into the cavity of a coating deposition device, and vacuumizing to 8 x 10 below the background vacuum -4 Pa, the temperature is 100 ℃, argon is introduced to maintain the air pressure at 0.1Pa, a bias voltage of 300V is applied to the sample rack for cleaning, and impurities, oil stains and an oxidation film on the surface of the magnesium substrate are removed;
(2) in the same cavity, keeping the temperature and the air pressure of the cavity unchanged, enabling the flow of argon to be 80sccm, opening a magnetron sputtering zirconium target, enabling the sputtering power to be 6kW, and enabling the sputtering time to be 4 minutes to form a zirconium bottom layer with the thickness of 50 nm;
(3) closing the dimolybdenum carbide target, continuing to introduce acetylene with the flow of 100sccm, the plasma power of 3kW and the time of 20 minutes to form an amorphous carbon layer with the thickness of 200 nm.
The metal polar plates with the composite coatings of the embodiments 1 to 8 and the comparative examples 1 to 5 of the invention are tested for contact resistance and corrosion current, and the contact resistance and the corrosion current density are according to the 6 th part of the GB/T20042.6-2011 proton exchange membrane fuel cell: testing method for plate characteristics. The test results are shown in Table 1.
TABLE 1 contact resistance and Current Density of examples and comparative examples
| Contact resistance (m omega cm) 2 ) | Corrosion current density (. mu.A/cm) 2 ) | |
| Example 1 | 3.7 | 0.063 |
| Example 2 | 3.4 | 0.059 |
| Example 3 | 2.9 | 0.037 |
| Example 4 | 2.2 | 0.028 |
| Example 5 | 2.8 | 0.041 |
| Example 6 | 4.5 | 0.091 |
| Example 7 | 3.9 | 0.075 |
| Example 8 | 5.8 | 0.221 |
| Comparative example 1 | 8.2 | 0.652 |
| Comparative example 2 | 7.3 | 0.731 |
| Comparative example 3 | 6.5 | 0.567 |
| Comparative example 4 | 7.8 | 0.458 |
| Comparative example 5 | 6.9 | 0.695 |
To sum up, the embodiments 1 to 8 show that the metal carbide layer having both the metal lattice structure and the amorphous carbon lattice structure is disposed between the priming layer and the amorphous carbon layer, so that the compactness of the amorphous carbon layer and the corrosion resistance of the coating are improved, the corrosion current density is reduced, and the service life of the fuel cell is greatly prolonged; meanwhile, the contact resistance between the coating and the carbon paper of the membrane electrode is reduced, and the output power of the fuel cell is greatly improved.
As can be seen from the comparison between examples 1 to 5 and comparative examples 1 to 5, the composite coatings prepared in examples 1 to 5, in which the metal carbide layer, the first transition layer and the second transition layer are all present between the primer layer and the amorphous carbon layer, have corrosion current densities that are one order of magnitude lower than those without the metal carbide layer (comparative examples 1 to 5), thereby greatly improving the life of the bipolar plate of the fuel cell; and the contact resistance of examples 1 to 5 was 50% or less of that of the case without the metal carbide layer (comparative examples 1 to 5), indicating that the addition of the metal carbide layer significantly improved the output of the fuel cell; it can also be seen from the comparison between example 6 and comparative example 1 that the contact resistance and corrosion current density are significantly higher than those of example 6 when the metal carbide layer is absent in comparative example 1.
Meanwhile, as is clear from a comparison between example 1 and example 6, since the denseness of the coating layer can be further improved by providing the first transition layer containing metal and metal carbide between the undercoat layer and the metal carbide layer and the second transition layer containing metal carbide and amorphous carbon between the metal carbide layer and the amorphous carbon layer, example 1 has lower contact resistance and corrosion current density than example 6.
As can be seen from the comparison of example 1 with examples 7-8, the metal carbide layer can further improve the compactness of the coating, improve the corrosion resistance of the coating and reduce the contact resistance within a proper thickness range; in example 7, the thickness of the metal carbide layer was high, and the performance was not significantly improved as compared with example 1, but the plating time was long and the efficiency was low. The thickness of the metal carbide layer in example 8 was too thin to result in lack of denseness, and the improvement of the contact resistance and the corrosion resistance was insignificant compared to that of comparative example 1, and thus, the low contact resistance and the corrosion resistance of example 1 were more excellent.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The metal pole plate composite coating is characterized by comprising a bottom layer, a metal carbide layer and an amorphous carbon layer which are sequentially stacked.
2. The metal plate composite coating of claim 1, wherein the metal carbide layer comprises any one of chromium carbide, tungsten carbide, zirconium carbide, and dimolybdenum carbide, or a combination of at least two thereof;
preferably, the primer layer comprises any one of titanium, chromium, tungsten, molybdenum and zirconium or a combination of at least two thereof.
3. The metal plate composite coating according to claim 1 or 2, wherein the thickness of the primer layer is 5-1000 nm;
preferably, the thickness of the metal carbide layer is 5-1000 nm;
preferably, the thickness of the amorphous carbon layer is 5 to 1000 nm.
4. The metal plate composite coating according to any one of claims 1 to 3, wherein a first transition layer is further disposed between the primer layer and the metal carbide layer;
preferably, the first transition layer comprises a transition layer metal and a transition layer metal carbide, the transition layer metal is the same as the metal of the base layer, and the transition layer metal carbide is the same as the metal carbide of the metal carbide layer;
preferably, the thickness of the first transition layer is 5-1000 nm;
preferably, a second transition layer is further arranged between the metal carbide layer and the amorphous carbon layer;
preferably, the second transition layer comprises a transition layer metal carbide and amorphous carbon;
preferably, the thickness of the second transition layer is 5-1000 nm.
5. The metal pole plate with the composite coating is characterized by comprising a base material, wherein the surface of at least one side of the base material is provided with the metal pole plate composite coating according to any one of claims 1 to 4, and a bottom layer of the metal pole plate composite coating is attached to the base material.
6. The composite coated metal plate of claim 5, wherein the substrate comprises any one or a combination of at least two of stainless steel, titanium, aluminum, nickel, and magnesium.
7. A method for preparing a metal plate with a composite coating according to claim 5 or 6, characterized in that the method comprises:
and depositing a priming layer on at least one side surface of the base material, and sequentially depositing metal carbide and amorphous carbon on the surface of the priming layer to obtain the metal pole plate with the composite coating.
8. The production method according to claim 7, wherein the metal carbide includes any one of chromium carbide, tungsten carbide, zirconium carbide, and dimolybdenum carbide or a combination of at least two of them;
preferably, in the step of depositing the primer layer on at least one side surface of the substrate, the deposition mode is physical vapor deposition;
preferably, in the step of depositing the metal carbide on the surface of the base layer, the deposition mode is physical vapor deposition;
preferably, in the step of depositing amorphous carbon on the surface of the base layer, the deposition is performed by physical vapor deposition and/or plasma chemical vapor deposition.
9. The method according to claim 7 or 8, wherein the method further comprises a step of depositing a transition layer metal and a transition layer metal carbide after the deposition of the base layer and before the deposition of the metal carbide;
preferably, in the step of depositing the transition layer metal and the transition layer metal carbide, the deposition mode is physical vapor deposition;
preferably, after depositing the metal carbide and before depositing the amorphous carbon, the method further comprises the step of depositing a transition layer of the metal carbide and the amorphous carbon;
preferably, in the step of depositing the transition layer metal carbide and the amorphous carbon, the deposition mode is physical vapor deposition.
10. A fuel cell comprising a composite coated metal plate according to claim 5 or 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210785753.2A CN115029663A (en) | 2022-07-04 | 2022-07-04 | Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210785753.2A CN115029663A (en) | 2022-07-04 | 2022-07-04 | Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115029663A true CN115029663A (en) | 2022-09-09 |
Family
ID=83128665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210785753.2A Pending CN115029663A (en) | 2022-07-04 | 2022-07-04 | Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115029663A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115312798A (en) * | 2022-09-16 | 2022-11-08 | 广东省科学院新材料研究所 | Metal pole plate surface protective coating, preparation method and application thereof, and metal pole plate |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444985A (en) * | 2007-12-19 | 2009-06-03 | 中国人民解放军装甲兵工程学院 | Amorphous carbon coating and preparation method and application thereof |
| CN106374116A (en) * | 2016-12-01 | 2017-02-01 | 上海电机学院 | High-entropy alloy composite coating on metal bipolar plate of fuel cell and process |
| CN108011115A (en) * | 2017-10-20 | 2018-05-08 | 上海交通大学 | It is a kind of for the corrosion resistant alloy embedded type amorphous carbon coating of metal polar plate and its preparation |
| CN110284102A (en) * | 2019-06-13 | 2019-09-27 | 上海治臻新能源装备有限公司 | A kind of metal carbides crystal composite coating and preparation method thereof |
| CN210628419U (en) * | 2019-05-17 | 2020-05-26 | 北京中氢绿能科技有限公司 | Metal bipolar plate coating of fuel cell |
| CN112609165A (en) * | 2020-12-15 | 2021-04-06 | 辽宁科技大学 | Composite coating on surface of bipolar plate of stainless steel-based fuel cell and preparation method thereof |
| CN112760606A (en) * | 2020-12-07 | 2021-05-07 | 上海航天设备制造总厂有限公司 | Amorphous carbon-based space antibacterial wear-resistant solid lubricating composite film and preparation method thereof |
| CN113991134A (en) * | 2021-10-22 | 2022-01-28 | 北京格睿能源科技有限公司 | Amorphous carbon coating for fuel cell metal bipolar plate and preparation method thereof |
| CN114665114A (en) * | 2022-04-11 | 2022-06-24 | 上海电气集团股份有限公司 | Multilayer composite carbon coating and preparation method and application thereof |
-
2022
- 2022-07-04 CN CN202210785753.2A patent/CN115029663A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101444985A (en) * | 2007-12-19 | 2009-06-03 | 中国人民解放军装甲兵工程学院 | Amorphous carbon coating and preparation method and application thereof |
| CN106374116A (en) * | 2016-12-01 | 2017-02-01 | 上海电机学院 | High-entropy alloy composite coating on metal bipolar plate of fuel cell and process |
| CN108011115A (en) * | 2017-10-20 | 2018-05-08 | 上海交通大学 | It is a kind of for the corrosion resistant alloy embedded type amorphous carbon coating of metal polar plate and its preparation |
| CN210628419U (en) * | 2019-05-17 | 2020-05-26 | 北京中氢绿能科技有限公司 | Metal bipolar plate coating of fuel cell |
| CN110284102A (en) * | 2019-06-13 | 2019-09-27 | 上海治臻新能源装备有限公司 | A kind of metal carbides crystal composite coating and preparation method thereof |
| CN112760606A (en) * | 2020-12-07 | 2021-05-07 | 上海航天设备制造总厂有限公司 | Amorphous carbon-based space antibacterial wear-resistant solid lubricating composite film and preparation method thereof |
| CN112609165A (en) * | 2020-12-15 | 2021-04-06 | 辽宁科技大学 | Composite coating on surface of bipolar plate of stainless steel-based fuel cell and preparation method thereof |
| CN113991134A (en) * | 2021-10-22 | 2022-01-28 | 北京格睿能源科技有限公司 | Amorphous carbon coating for fuel cell metal bipolar plate and preparation method thereof |
| CN114665114A (en) * | 2022-04-11 | 2022-06-24 | 上海电气集团股份有限公司 | Multilayer composite carbon coating and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115312798A (en) * | 2022-09-16 | 2022-11-08 | 广东省科学院新材料研究所 | Metal pole plate surface protective coating, preparation method and application thereof, and metal pole plate |
| CN115312798B (en) * | 2022-09-16 | 2023-12-05 | 广东省科学院新材料研究所 | Metal polar plate surface protective coating, preparation method and application thereof, and metal polar plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110684946B (en) | Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof | |
| CN110284102B (en) | Metal carbide crystal composite coating and preparation method thereof | |
| CN101800318B (en) | Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof | |
| CN109560289B (en) | Metal bipolar plate, preparation method thereof and fuel cell | |
| CN101604756B (en) | Bipolar plate and fuel cell | |
| CN113265638B (en) | High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof | |
| WO2023284596A1 (en) | High-conductivity, corrosion-resistant and long-lifetime max phase solid solution composite coating, and preparation method therefor and use thereof | |
| CN112993298A (en) | Double-functional coating of fuel cell metal bipolar plate | |
| CN104577144A (en) | Fuel-cell bipolar plate with nitrified and enhanced surface and preparation method thereof | |
| CN111218656A (en) | High-corrosion-resistance high-conductivity fuel cell metal bipolar plate protective film and preparation method thereof | |
| CN113737142A (en) | Preparation method of composite gradient carbon-based coating of proton exchange membrane fuel cell titanium bipolar plate | |
| CN110061257A (en) | Metal Substrate bipolar plates and preparation method thereof for PEMFC | |
| CN106684394A (en) | Surface modification method of proton-exchange membrane fuel cells' stainless steel bipolar plates | |
| CN114665114A (en) | Multilayer composite carbon coating and preparation method and application thereof | |
| CN114481048B (en) | High-conductivity corrosion-resistant amorphous/nanocrystalline composite coexisting coating and preparation method and application thereof | |
| CN111244493A (en) | Surface modification method of thin titanium bipolar plate of proton exchange membrane fuel cell | |
| CN113937301B (en) | Transition metal nitride and carbon composite modified film on surface of metal bipolar plate and preparation method thereof | |
| CN115029663A (en) | Metal polar plate composite coating, metal polar plate and preparation method thereof, and fuel cell | |
| CN114214658A (en) | Composite coating for water electrolysis metal bipolar plate and preparation method thereof | |
| CN112820890B (en) | Preparation method and structure of anticorrosive conductive coating and fuel cell polar plate | |
| CN104051743B (en) | Metal double polar plates and preparation method thereof | |
| CN113025980A (en) | Corrosion-resistant film layer for fuel cell bipolar plate and preparation method thereof | |
| CN204361172U (en) | A kind of nitrogenize strengthens the bipolar plate for fuel cell on surface | |
| CN201717318U (en) | Metal bipolar plate for proton exchange membrane fuel cell | |
| CN110265668A (en) | Hydrogen fuel battery metal bi-polar plate and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |