CN110699641B - Composite multilayer corrosion-resistant film and application thereof - Google Patents

Composite multilayer corrosion-resistant film and application thereof Download PDF

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CN110699641B
CN110699641B CN201910921571.1A CN201910921571A CN110699641B CN 110699641 B CN110699641 B CN 110699641B CN 201910921571 A CN201910921571 A CN 201910921571A CN 110699641 B CN110699641 B CN 110699641B
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conductive ceramic
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CN110699641A (en
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李景灵
许泽凌
樊婷
徐雪青
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Foshan University
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    • 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
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    • 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
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    • 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
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    • 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
    • C23C14/0641—Nitrides
    • 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
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    • 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
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    • 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
    • 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
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0215—Glass; Ceramic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a composite multilayer corrosion-resistant film and application thereof. The conductive ceramic chip comprises a metal adhesion layer, a metal corrosion resistant layer, a conductive ceramic amorphous layer, a conductive ceramic crystalline layer and a carbon covering layer from bottom to top; the composition of the metal adhesion layer and the metal resist layer are not identical. The invention introduces two materials of corrosion-resistant metal and conductive ceramic for effectively combining the advantages of good metal conductivity and better corrosion resistance and durability of the conductive ceramic. In order to achieve the composite effect, a metal adhesion layer is introduced to realize the growth of a coating film of corrosion-resistant metal, the crystallinity of a conductive ceramic crystal layer on the conductive ceramic amorphous layer is improved by introducing the conductive ceramic amorphous layer, and the grain boundary gap of polycrystalline ceramic is buried by a carbon covering layer to realize good compactness, so that a multilayer film structure with both conductivity and corrosion resistance is constructed, the application range is wide, and the method has positive promoting significance for the research and development of proton exchange membrane fuel cells.

Description

Composite multilayer corrosion-resistant film and application thereof
Technical Field
The invention relates to the field of metal corrosion resistance, in particular to a composite multilayer corrosion-resistant film and application thereof.
Background
The bipolar plate is one of the important components of the Proton Exchange Membrane Fuel Cell (PEMFC), and the metal material has the advantages of high conductivity, low price, good air tightness, mature preparation process, easy realization of industrial production and the like, so compared with the traditional graphite material, the metal bipolar plate has more commercial competitiveness. However, metal materials are susceptible to corrosion, and metal ions are formed on the surface of the bipolar plate to cause contamination, and the generated oxide film causes an increase in contact resistance. Therefore, a good corrosion resistance effect cannot be achieved by using a metal or alloy material alone. In contrast, the conductive ceramic with the characteristic of strong covalent bond has the characteristics of high melting point, high hardness and good thermal stability, so that the ideal conductive ceramic can ensure the long-term stable operation of the bipolar plate, but under the current technical conditions, the obtained conductive ceramic crystal is in a polycrystalline form and has low density, and the grain boundary is often the place where a corrosion channel is formed and can not fully protect the metal bipolar plate. Therefore, how to design and combine the corrosion-resistant metal and the conductive ceramic corrosion-resistant layer material and optimize the structure of the corrosion-resistant film is a key technology for obtaining the film with good conductivity and excellent corrosion resistance, and is also a key point for applying the metal bipolar plate in a hydrogen fuel cell.
Disclosure of Invention
In view of the above technical problems in the background art, the present patent proposes a multilayer composite structure, which combines the advantages of corrosion-resistant metal and conductive ceramic to form a corrosion-resistant thin film structure with good corrosion resistance and long-term stability, and specifically adopts the following technical scheme:
a composite multilayer corrosion-resistant film comprises a metal adhesion layer, a metal corrosion-resistant layer, a conductive ceramic amorphous layer, a conductive ceramic crystalline layer and a carbon covering layer from bottom to top; the metal adhesion layer and the metal resist layer are different in composition. The film can be applied to metal substrates such as metal bipolar plates, the metal substrates are in direct contact with the metal adhesion layer, and the metal substrates can be at least stainless steel, copper and aluminum.
Preferably, the metal adhesion layer is one or more of titanium, chromium, copper and nickel.
Preferably, the metal corrosion resistant layer is one or more alloys of niobium, tantalum, chromium, nickel and molybdenum.
Preferably, the conductive ceramic amorphous layer and the conductive ceramic crystalline layer are respectively formed by an amorphous layer and a crystalline layer which are made of the same material, the material is selected from ternary conductive ceramics or binary conductive ceramics, the ternary conductive ceramics comprise MAX, MNX and MXY, the binary conductive ceramics are MX, M and N are respectively one of scandium, titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium and tantalum, and M and N are different; a is one of aluminum, silicon, phosphorus, sulfur, gallium, germanium, arsenic, cadmium, indium, tin, thallium and lead; x and Y are carbon or nitrogen respectively, and X and Y are different.
Preferably, the thickness of the metal adhesion layer is 50 nm-1 μm, and the thickness of the metal corrosion resistant layer is 100 nm-1 μm; the thickness of the conductive ceramic amorphous layer is 10 nm-100 nm; the thickness of the conductive ceramic crystal layer is 500 nm-10 mu m; the thickness of the carbon covering layer is 100 nm-1 mu m.
The thin film can be respectively coated by one of the preparation methods of multi-arc ion plating, electron beam evaporation, magnetron sputtering and thermal evaporation layer by layer from bottom to top. In the preparation process, the growth temperature of the metal adhesion layer is 25-500 ℃; the growth temperature of the metal corrosion resistant layer is 25-500 ℃; the growth temperature of the conductive ceramic amorphous layer is 25-100 ℃; the growth temperature of the conductive ceramic crystal layer is 300-1000 ℃; the growth temperature of the carbon covering layer is 25-500 ℃.
In the technical scheme of the invention, each layer has a specific function or effect. Firstly, in order to realize the plating film growth of the metal corrosion-resistant layer, the plating film of a metal adhesion layer (also called a metal buffer layer) is needed to be firstly carried out, and the corrosion-resistant metal is plated on the clean metal adhesion layer, so that the adhesion and the growth of the corrosion-resistant metal or the alloy material thereof on the metal adhesion layer can be improved, and the binding force between the film and the substrate is improved; secondly, a conductive ceramic crystal layer grows on the metal corrosion-resistant layer, and in order to obtain the conductive ceramic crystal layer with higher quality and stress release, a buffer layer (namely a conductive ceramic amorphous layer) which has the same components but is amorphous in structure needs to be introduced before the conductive ceramic crystal layer grows. The function of the conductive ceramic amorphous layer is that a physical environment for stress release can be provided for the growth of the conductive ceramic crystalline layer, crystal dislocation and defect are reduced, and the crystalline quality is improved, so that the conductive ceramic amorphous layer and the conductive ceramic crystalline layer have independent characteristics and functions; finally, in order to passivate the defects of grain boundaries, pinholes and the like of the conductive ceramic crystal layer, the invention realizes the burying of grain boundary gaps and defects of the conductive ceramic crystal layer through the carbon covering layer, prevents point corrosion and improves the corrosion resistance of ceramic crystals. Thus, a multi-layer corrosion-resistant film structure comprising a metal adhesion layer, a metal corrosion-resistant layer, a conductive ceramic amorphous layer, a conductive ceramic crystalline layer and a carbon coating layer is formed from bottom to top.
The invention has the beneficial effects that: the invention introduces two materials of corrosion-resistant metal and conductive ceramic for effectively combining the advantages of good metal conductivity and better corrosion resistance and durability of the conductive ceramic. In order to achieve the composite effect, a metal adhesion layer is introduced to realize the growth of a coating film of corrosion-resistant metal, the crystallinity of a conductive ceramic crystal layer on the conductive ceramic amorphous layer is improved by introducing the conductive ceramic amorphous layer, and the grain boundary gap of polycrystalline ceramic is buried by a carbon covering layer to realize good compactness, so that a multilayer film structure with both conductivity and corrosion resistance is constructed, the application range is wide, and the method has positive promoting significance for the research and development of proton exchange membrane fuel cells.
Drawings
FIG. 1 is a schematic structural diagram of a corrosion resistant film of the present invention, in which 11 is a metal substrate, 12 is a metal adhesion layer, 13 is a metal resist layer, 14 is a conductive ceramic amorphous layer, 15 is a conductive ceramic crystalline layer, and 16 is a carbon capping layer;
FIG. 2 is a graph comparing Tafel curves of 316 stainless steel and 316 stainless steel coated with a resist film of the present invention obtained in example 1.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described in the following embodiments to fully understand the objects, aspects and effects of the present invention. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
Example 1:
a kind of metal substrate covering the corrosion-resistant film of the invention, is prepared by magnetron sputtering technology, wherein, the metal substrate is 316 stainless steel, the concrete process is: sputtering a titanium metal adhesion layer on a stainless steel substrate, wherein the growth temperature is 25 ℃, and the thickness is 50 nm; then sputtering a niobium plating corrosion resistant metal layer on the titanium metal adhesion layer, wherein the growth temperature is 25 ℃, and the thickness is 1 mu m; then sputtering and plating a titanium carbide amorphous layer on the niobium metal layer, wherein the growth temperature is 25 ℃, and the thickness is 10 nm; then continuously sputtering and plating a titanium carbide crystal layer on the amorphous layer, wherein the growth temperature is 1000 ℃, and the thickness is 10 mu m; finally, a carbon coating is sputtered on the titanium carbide crystal layer, the growth temperature is 25 ℃, and the thickness is 1 mu m.
Finally, the corrosion-resistant film of the invention is formed on the metal substrate, and the structure sequentially comprises a stainless steel metal substrate, a titanium metal adhesion layer, a niobium corrosion-resistant metal layer, a titanium carbide amorphous layer, a titanium carbide crystalline layer and a carbon covering layer, which are in one-to-one correspondence with the metal substrate, the metal adhesion layer, the metal corrosion-resistant layer, the conductive ceramic amorphous layer, the conductive ceramic crystalline layer and the carbon covering layer in the figure 1.
Example 2:
the metal substrate covered with the corrosion-resistant film is prepared by two technical methods, namely a magnetron sputtering technology and a thermal evaporation technology, wherein the metal substrate is copper, and the specific process comprises the following steps: sputtering a chromium-plated metal adhesion layer on a copper substrate, wherein the growth temperature is 50 ℃, and the thickness is 100 nm; sputtering a tantalum plating corrosion-resistant metal layer on the chromium metal adhesion layer, wherein the growth temperature is 50 ℃, and the thickness is 500 nm; sputtering chromium nitride amorphous layer on the tantalum metal layer, wherein the growth temperature is 50 ℃, and the thickness is 20 nm; continuously sputtering and plating a chromium nitride crystal layer on the amorphous layer, wherein the growth temperature is 800 ℃, and the thickness is 5 mu m; finally, a carbon covering layer is plated on the chromium nitride crystal layer by utilizing a thermal evaporation technology, the growth temperature is 100 ℃, and the thickness is 800 nm.
Finally, the corrosion-resistant film of the invention is formed on the metal substrate, and the structure sequentially comprises a copper metal substrate, a chromium metal adhesion layer, a tantalum corrosion-resistant metal layer, a chromium nitride amorphous layer, a chromium nitride crystalline layer and a carbon covering layer.
Example 3:
a metal substrate covered with the corrosion-resistant film is prepared by a multi-arc ion plating technical method, wherein the metal substrate is aluminum, and the specific process comprises the following steps: plating a copper metal adhesive layer on the aluminum substrate by ions, wherein the growth temperature is 100 ℃, and the thickness is 200 nm; a chromium plating corrosion-resistant metal layer is plated on the copper metal adhesion layer, the growth temperature is 100 ℃, and the thickness is 200 nm; plating a niobium carbide amorphous layer on the chromium metal layer, wherein the growth temperature is 100 ℃, and the thickness is 50 nm; continuously growing a niobium carbide crystal layer on the amorphous layer, wherein the growth temperature is 500 ℃, and the thickness is 2 microns; finally, plating a carbon covering layer on the niobium carbide crystal layer, wherein the growth temperature is 200 ℃, and the thickness is 500 nm.
Finally, the corrosion-resistant film is formed on the metal substrate, and the structure of the corrosion-resistant film is sequentially an aluminum metal substrate, a copper metal adhesion layer, a chromium corrosion-resistant metal layer, a niobium carbide amorphous layer, a niobium carbide crystalline layer and a carbon covering layer.
Example 4:
a metal substrate covered with the corrosion-resistant film is prepared by two methods, namely an electron beam evaporation technology and a magnetron sputtering technology, wherein the metal substrate is stainless steel, and the specific process comprises the following steps: plating a nickel metal adhesion layer on a stainless steel substrate by using an electron beam evaporation technology, wherein the growth temperature is 200 ℃, and the thickness is 500 nm; plating a molybdenum corrosion-resistant metal layer on the nickel metal adhesion layer by utilizing a magnetron sputtering technology, wherein the growth temperature is 200 ℃, and the thickness is 100 nm; sputtering and plating a tantalum nitride amorphous layer on the molybdenum metal layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm; continuously sputtering and plating a tantalum nitride crystal layer on the amorphous layer, wherein the growth temperature is 300 ℃, and the thickness is 1 mu m; finally, plating a carbon covering layer on the tantalum nitride crystal layer, wherein the growth temperature is 500 ℃, and the thickness is 300 nm.
Finally, the corrosion-resistant film is formed on the metal substrate, and the structure of the corrosion-resistant film is sequentially a stainless steel metal substrate, a nickel metal adhesion layer, a molybdenum corrosion-resistant metal layer, a tantalum nitride amorphous layer, a tantalum nitride crystalline layer and a carbon covering layer.
Example 5:
a kind of metal substrate covering the corrosion-resistant film of the invention, is prepared by magnetron sputtering technology, wherein, the metal substrate is stainless steel, the concrete process is: sputtering a chromium plating metal adhesion layer on a stainless steel substrate, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering tantalum and niobium plating corrosion resistant alloy layer on the chromium metal adhesion layer, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering and plating a titanium carbide amorphous layer on the alloy layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm; continuously sputtering and plating a titanium carbide crystal layer on the amorphous layer, wherein the growth temperature is 500 ℃, and the thickness is 500 nm; finally, plating a carbon covering layer on the titanium nitride crystal layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm.
Finally, the corrosion resistant film of the invention is formed on the metal substrate, and the structure of the corrosion resistant film is sequentially stainless steel metal substrate, chromium metal adhesion layer, tantalum, niobium corrosion resistant alloy layer, titanium carbide amorphous layer, titanium carbide crystal layer and carbon covering layer.
Example 6:
a kind of metal substrate covering the corrosion-resistant film of the invention, is prepared by magnetron sputtering technology, wherein, the metal substrate is stainless steel, the concrete process is: sputtering a chromium plating metal adhesion layer on a stainless steel substrate, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering tantalum and niobium plating corrosion resistant alloy layer on the chromium metal adhesion layer, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering a nitrogen-plated zirconium carbide amorphous layer on the alloy layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm; continuously sputtering a nitrogen-plated zirconium carbide crystal layer on the amorphous layer, wherein the growth temperature is 500 ℃, and the thickness is 500 nm; finally, plating a carbon covering layer on the tantalum nitride crystal layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm.
Finally, the corrosion resistant film of the invention is formed on the metal substrate, and the structure sequentially comprises a stainless steel metal substrate, a chromium metal adhesion layer, tantalum, a niobium corrosion resistant alloy layer, a zirconium carbonitride amorphous layer, a zirconium carbonitride crystalline layer and a carbon covering layer.
Example 7:
a kind of metal substrate covering the corrosion-resistant film of the invention, is prepared by magnetron sputtering technology, wherein, the metal substrate is stainless steel, the concrete process is: sputtering a chromium plating metal adhesion layer on a stainless steel substrate, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering a molybdenum and nickel plating corrosion-resistant alloy layer on the chromium metal adhesion layer, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering a titanium silicon carbon amorphous layer on the alloy layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm; continuously sputtering a titanium silicon carbon crystal layer on the amorphous layer, wherein the growth temperature is 500 ℃, and the thickness is 500 nm; finally, plating a carbon covering layer on the tantalum nitride crystal layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm.
Finally, the corrosion resistant film of the invention is formed on the metal substrate, and the structure of the corrosion resistant film is sequentially stainless steel metal substrate, chromium metal adhesion layer, molybdenum, nickel corrosion resistant alloy layer, titanium silicon carbon amorphous layer, titanium silicon carbon crystal layer and carbon covering layer.
Example 8:
a kind of metal substrate covering the corrosion-resistant film of the invention, is prepared by magnetron sputtering technology, wherein, the metal substrate is stainless steel, the concrete process is: sputtering a chromium plating metal adhesion layer on a stainless steel substrate, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering a molybdenum and nickel plating corrosion-resistant alloy layer on the chromium metal adhesion layer, wherein the growth temperature is 500 ℃, and the thickness is 1 mu m; sputtering and plating a niobium tantalum carbide amorphous layer on the alloy layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm; continuously sputtering and plating a niobium and tantalum carbide crystal layer on the amorphous layer, wherein the growth temperature is 500 ℃, and the thickness is 500 nm; and finally plating a carbon covering layer on the niobium and tantalum carbide crystal layer, wherein the growth temperature is 25 ℃, and the thickness is 100 nm.
Finally, the corrosion resistant film of the invention is formed on the metal substrate, and the structure of the corrosion resistant film is sequentially stainless steel metal substrate, chromium metal adhesion layer, molybdenum, nickel corrosion resistant alloy layer, niobium tantalum carbide amorphous layer, titanium silicon carbon crystal layer and carbon covering layer.
Example 9:
the metal substrate coated with the corrosion-resistant film of the present invention prepared in example 1 and pure 316 stainless steel were subjected to a three-electrode electrochemical test in an acidic aqueous solution under the same conditions, respectively, wherein the acidic aqueous solution was prepared by: adding H into water2SO4Prepared at a concentration of 0.5M H2SO4Further, HF was added to the solution so that the concentration of HF in the solution was 5 ppm. Heating the solution to 80 deg.C, and placing the solution at 0.5026cm area2The stainless steel substrate is soaked in the hot solution for three-electrode electrochemical test, a calomel electrode is taken as a counter electrode, platinum is taken as a reference electrode, and stainless steel is taken as a working electrode. As shown in FIG. 2, it can be seen from FIG. 2 that the corrosion currents of pure stainless steel and stainless steel having a clad multi-layered composite structure according to the results of Tafel curve fitting are 397. mu.A/cm2And 0.18. mu.A/cm2. It can be seen that the corrosion current of the metal substrate covered with the corrosion-resistant film of the present invention is reduced 2200 times effectively, which is far lower than the DOE standard (DOE standard) (< 1 μ A/cm) of the bipolar plate of the fuel cell in 2020, which is proposed by the U.S. department of energy2) The practical value is very obvious. In addition, the effects similar to those of embodiment 1 can be obtained in all of embodiments 2 to 8.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (3)

1. The composite multilayer corrosion-resistant film is characterized by comprising a metal adhesion layer, a metal corrosion-resistant layer, a conductive ceramic amorphous layer, a conductive ceramic crystalline layer and a carbon covering layer from bottom to top; the metal adhesion layer and the metal corrosion resistant layer are different in composition;
the metal adhesion layer is one or more of titanium, copper and nickel; the conductive ceramic amorphous layer and the conductive ceramic crystalline layer are respectively formed by the same material;
the metal corrosion resistant layer is one or more of niobium, tantalum, chromium, nickel and molybdenum;
the conductive ceramic amorphous layer and the conductive ceramic crystalline layer are respectively formed by the same material, the material is selected from ternary conductive ceramic or binary conductive ceramic, the ternary conductive ceramic comprises MAX, MNX and MXY, the binary conductive ceramic is MX, M and N are respectively one of scandium, titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium and tantalum, and M and N are different; a is one of aluminum, silicon, phosphorus, sulfur, gallium, germanium, arsenic, cadmium, indium, tin, thallium and lead; x and Y are carbon or nitrogen respectively, and X and Y are different;
the preparation method of the film is that the film is respectively coated by one of multi-arc ion plating, electron beam evaporation, magnetron sputtering and thermal evaporation from bottom to top layer by layer;
the growth temperature of the metal adhesion layer is 25-500 ℃; the growth temperature of the metal corrosion resistant layer is 25-500 ℃; the growth temperature of the conductive ceramic amorphous layer is 25-100 ℃; the growth temperature of the conductive ceramic crystal layer is 300-1000 ℃; the growth temperature of the carbon covering layer is 25-500 ℃.
2. The film of claim 1, wherein the metal adhesion layer has a thickness of 50nm to 1 μm, and the metal resist layer has a thickness of 100nm to 1 μm; the thickness of the conductive ceramic amorphous layer is 10 nm-100 nm; the thickness of the conductive ceramic crystal layer is 500 nm-10 mu m; the thickness of the carbon covering layer is 100 nm-1 mu m.
3. Use of a membrane according to claim 1 or 2 in the field of metal corrosion resistance and/or in the field of bipolar plates.
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