CN112909281B - Stainless steel metal bipolar plate, preparation method thereof and fuel cell - Google Patents

Stainless steel metal bipolar plate, preparation method thereof and fuel cell Download PDF

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CN112909281B
CN112909281B CN202110080670.9A CN202110080670A CN112909281B CN 112909281 B CN112909281 B CN 112909281B CN 202110080670 A CN202110080670 A CN 202110080670A CN 112909281 B CN112909281 B CN 112909281B
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bipolar plate
stainless steel
steel metal
metal bipolar
transition layer
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CN112909281A (en
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朱光明
陆境莲
胡仁涛
唐杰
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Shenzhen University
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Shenzhen University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
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    • 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
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • 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
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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
    • C23C14/0635—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
    • C23C14/0641—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
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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
    • C23C14/14—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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—Metals or alloys
    • H01M8/0208—Alloys
    • H01M8/021—Alloys based on iron
    • 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 stainless steel metal bipolar plate, a preparation method thereof and a fuel cell. The stainless steel metal bipolar plate comprises a stainless steel metal bipolar plate substrate, a transition layer and a MAX phase anticorrosive coating, wherein the transition layer is laminated on the surface of the stainless steel metal bipolar plate substrate, and the MAX phase anticorrosive coating is laminated on the surface of the transition layer. The stainless steel metal bipolar plate has excellent conductivity and corrosion resistance, and the MAX phase anticorrosive coating is compact, high in hardness, wear-resistant, high-temperature resistant, flat, smooth, few in microscopic defects, good in hydrophobicity and firm in structure. The preparation method can ensure the stable performance of the prepared stainless steel metal bipolar plate, and has the advantages of easily controlled conditions and high efficiency. The fuel cell containing the stainless steel metal bipolar plate has stable electrochemical performance, high power density and excellent electrochemical performance.

Description

Stainless steel metal bipolar plate, preparation method thereof and fuel cell
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a stainless steel metal bipolar plate, a preparation method thereof and a fuel cell.
Background
Fuel cells are efficient power generation devices that convert chemical energy directly into electrical energy. The proton exchange membrane fuel cell stack mainly comprises a bipolar plate, a gas diffusion layer and a membrane electrode. The bipolar plate has the functions of separating fuel and oxidant, collecting and conducting current, uniformly distributing gas to a reaction layer of an electrode to perform electrochemical electrode reaction, discharging heat, keeping a temperature field of a battery uniform and the like, and is one of important components of a fuel cell. Therefore, the bipolar plate material is required to have high conductivity, gas barrier property, corrosion resistance, wear resistance, impact resistance and vibration resistance, and also required to have the characteristics of light weight, thin thickness, low cost and easy processing.
Materials currently used to manufacture bipolar plates include carbon plates, metal plates, and the like. Among them, carbon plates are widely used as materials for manufacturing bipolar plates because of their excellent conductivity and corrosion resistance. However, the carbon bipolar plate is thick and heavy, and accounts for about 70% of the total volume in the stack, and 80% of the total weight. The volume and the weight of the galvanic pile can be greatly reduced by replacing a thick and heavy carbon plate with the metal sheet, and the power density of the galvanic pile is improved, wherein the volume power density can be improved by 80 percent generally, and the weight power density can be improved by one time, namely 100 percent. However, metallic bipolar plates also have a number of problems. Specifically, although the electrical conductivity and the heat conductivity of the metal bipolar plate are superior to those of a carbon plate, the metal bipolar plate can be light and thin, but the metal has no carbon stability in chemical property, is easy to oxidize and corrode, and forms an oxide layer with low electrical conductivity on the surface, so that the contact resistance is increased. In addition, the corroded metal cations can affect the activity of the Pt catalyst, and the performance of the pile is degraded. Therefore, the metal bipolar plate needs to be subjected to appropriate surface corrosion prevention treatment before it can be used.
The common base materials of the metal bipolar plate at present are aluminum, titanium and stainless steel, and the surface is generally plated with a carbon film, a metal carbide or a nitride film. The plating method generally employs PVD method, CVD method, and carburizing and nitriding method. Compared with aluminum and titanium, stainless steel has the comprehensive advantages of better rigidity, plasticity, corrosion resistance, easy processing and low cost, thus being widely researched. Stainless steel, commonly selected for use as a bipolar plate, is of types 310, 304, 316 and 904, and the films deposited thereon are typically diamond-like films, graphite-like films and metal compound films. Among metal compound films, tiC, tiN, tiCN, crN, etc. are widely used because of their excellent electrical conductivity, corrosion resistance, oxidation resistance and wear resistance. However, the electrical conductivity of metals such as titanium, vanadium, and chromium is still high, and carbon compounds or nitrides thereof have high resistance and are semiconductors.
In the metal carbide compound or nitride, there is a microscopic layered ternary compound called MAX phase, which has both the electrical conductivity of metal and the hardness, corrosion resistance and oxidation resistance of metal carbide or nitride ceramic, i.e. has the advantages of both metal and ceramic, and is an ideal anticorrosive coating material for metal bipolar plates. MAX phase available formula M n+1 AX n Wherein M is a transition metal element, a is a main group IIIA or IVA element, X is C or N, and N =1 to 6. The crystal structure of the MAX phase is M with a rock-salt like structure n+1 X n The hexagonal lattice, which is composed of lamellae and closely packed A-group atom surface lamellae stacked alternately in the c-axis direction, has a P63/mmc space group. According to the general formula M n+1 AX n Where n is different (i.e. MX sheet thickness), the MAX phase is often subdivided into M 2 AX (211) phase, M 3 AX 2 (312) Phase, M 4 AX 3 (413) Phase, M 5 AX 4 (514) Phase, M 6 AX 5 (615) Phase, M 7 AX 6 (716) The structure of the phases is formed by alternately stacking n +1 (n = 1-6) layers MX and one layer A. M-X is bonded with strong covalent bond and ionic bond, M-A is bonded with weak covalent bond and metal bond, and M-M is bonded with metal bond. As the value of n increases, the MX sheet thickens and the properties of the MAX phase get closer to the corresponding M-X binary carbide, which means that the properties of the MAX phase can be tuned by changing the value of n. In addition, under proper conditions, MX layers with different n values and A layers are alternately arranged in a mixed mode, and a stacking fault structure similar to a dense plane in a metal crystal is formed. Found are M5A2X3 (523) phases formed by alternately arranging (211) and (312) and M formed by alternately arranging (312) and (413) 7 A 2 X 5 (725) Phase, can be represented by the general formula M m+2 A 2 X m (m =3,5). However, in the practical application process, the obtained MAX phase coating still has unsatisfactory conductivity, or the existing MAX phase coating has more cracks and micro defects, which result in poor compactness, thereby leading to poor conductivityResulting in poor corrosion resistance of the existing MAX phase coatings. Or the existing MAX phase coating has the defects of unsatisfactory conductivity and poor compactness, so that the requirement of the bipolar plate of the fuel cell cannot be met.
Common methods for preparing MAX phase thin films include Physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), and solid phase reaction. PVD methods include Magnetron Sputtering (MS), cathodic Arc Deposition (CAD), and Pulsed Laser Deposition (PLD). Most PVD methods require a substrate temperature of 800-1000 ℃, CVD methods require a decomposition temperature of 1000 ℃ or above for preparing MAX phase films, and the growth of the films is not easy to control and a single MAX phase is difficult to obtain. Among the solid phase reaction methods, thermal spray coating is most commonly used, and the coating obtained by this method has a loose structure and cannot be used as an anticorrosive coating. The MS method can reduce the deposition temperature to 450 ℃ by adopting a proper magnetic field, and can realize low-temperature deposition of the MAX phase, but the current MS method also has some defects, for example, the MAX phase coating prepared by the current MS method has low conductivity of the coating due to low MAX phase in the coating, or the MAX phase coating meets the formation of the MAX phase in the coating, but the coating has more cracks and micro defects and has poor compactness, so that the prepared MAX phase can not meet the application requirements of the fuel cell bipolar plate.
Just as the current MAX phase coating cannot be both electrically conductive and dense, it is currently used in fuel cells. Therefore, how to develop MAX phase coatings with good electrical conductivity and good compactness and methods for their preparation are technical difficulties that those skilled in the art are trying to solve.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a stainless steel metal bipolar plate containing an MAX phase anticorrosive coating and a preparation method thereof, so as to solve the technical problem that the electrochemical performance of a fuel cell is not ideal due to high resistance or poor corrosion resistance of the conventional coated metal bipolar plate.
Another object of the present invention is to provide a fuel cell, which overcomes the technical problem of non-ideal electrochemical performance of the existing fuel cell.
To achieve the above objects, according to one aspect of the present invention, there is provided a stainless steel metal bipolar plate. The stainless steel metal bipolar plate comprises a stainless steel metal bipolar plate substrate, and further comprises a transition layer and a MAX phase anticorrosive coating, wherein the transition layer is combined on the surface of the stainless steel metal bipolar plate substrate in a laminated mode, and the MAX phase anticorrosive coating is combined on the outer surface of the transition layer in a laminated mode.
In another aspect of the invention, a method for preparing a stainless steel metal bipolar plate is provided. The preparation method of the stainless steel metal bipolar plate comprises the following steps:
providing a stainless steel metal bipolar plate substrate, a transition layer target material and a MAX phase target material, and performing surface pretreatment on the stainless steel metal bipolar plate substrate, the transition layer target material and the MAX phase target material;
depositing the transition layer target subjected to the surface pretreatment on the surface of the stainless steel metal bipolar plate substrate by adopting a magnetron sputtering method, and growing a transition layer on the surface of the stainless steel metal bipolar plate substrate in situ;
depositing the MAX phase target subjected to the surface pretreatment on the surface of the transition layer by adopting a magnetron sputtering method, and growing a MAX phase target coating on the surface of the transition layer in situ;
and carrying out vacuum heat treatment on the MAX phase target coating.
In yet another aspect of the present invention, a fuel cell is provided. The fuel cell comprises a bipolar plate, wherein the bipolar plate is a stainless steel metal bipolar plate or a stainless steel metal bipolar plate prepared by the preparation method.
Compared with the prior art, the MAX phase anticorrosive coating is combined on the surface of the stainless steel metal bipolar plate substrate through the transition layer, so that the MAX phase anticorrosive coating is low in contact resistance and corrosion potential and has excellent conductivity; and the MAX phase anticorrosive coating is compact, flat, smooth, few in microscopic defects and good in hydrophobicity, so that the MAX phase anticorrosive coating has excellent corrosion resistance. Therefore, the MAX phase anti-corrosion coating contained in the stainless steel metal bipolar plate can effectively balance MAX phase and compactness thereof, so that the stainless steel metal bipolar plate has excellent conductivity and corrosion resistance at the same time, and the MAX phase anti-corrosion coating has the advantages of high hardness, wear resistance, high temperature resistance and firm combination with the stainless steel metal bipolar plate substrate.
The preparation method of the stainless steel metal bipolar plate sequentially grows the transition layer and the MAX phase anticorrosive coating on the bottom surface of the stainless steel metal bipolar plate in situ, so that the grown MAX phase anticorrosive coating has excellent conductivity, and the MAX phase anticorrosive coating is compact, flat, smooth, few in microscopic defects, good in hydrophobicity and excellent in corrosion resistance. The MAX phase anticorrosive coating also has the advantages of high hardness, wear resistance, high temperature resistance, firm combination with the stainless steel metal bipolar plate substrate and the like. In addition, the preparation method of the stainless steel metal bipolar plate can ensure that the prepared stainless steel metal bipolar plate has stable performance, easily controlled conditions and high efficiency.
The metal bipolar plate of the fuel cell adopts the stainless steel metal bipolar plate, so that the metal bipolar plate of the fuel cell has good conductivity, corrosion resistance and firm structure, effectively ensures the corrosion resistance of the stainless steel metal bipolar plate substrate, and ensures the activity of a catalyst contained in the fuel cell, thereby endowing the fuel cell with stable electrochemical performance, high power density and excellent electrochemical performance.
Drawings
FIG. 1 is a schematic structural view of a stainless steel metal bipolar plate according to an embodiment of the present invention;
FIG. 2 is a schematic process flow diagram of a method for manufacturing a stainless steel metal bipolar plate according to an embodiment of the present invention;
fig. 3 is an SEM photograph and an XRD spectrum of the stainless steel metal bipolar plate provided in example 1 of the present invention; wherein, fig. 3A is an SEM photograph of the stainless steel metal bipolar plate provided in the embodiment 1 of the present invention, and fig. 3B is an XRD pattern of the stainless steel metal bipolar plate provided in the embodiment 1 of the present invention;
FIG. 4 is an SEM and AFM photograph of a stainless steel metal bipolar plate provided in example 2 of the present invention; fig. 4A is an SEM photograph of the stainless steel metal bipolar plate provided in example 2 of the present invention, and fig. 4B is an atomic force microscope photograph of the stainless steel metal bipolar plate provided in example 2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
In one aspect, embodiments of the present invention provide a stainless steel metal bipolar plate. The structure of the stainless steel metal bipolar plate is shown in FIG. 1, and comprises a stainless steel metal bipolar plate substrate 1, a transition layer 2 and a MAX phase anti-corrosion coating 3. And the transition layer 2 is laminated and combined on the surface of the stainless steel metal bipolar plate substrate 1, and the MAX phase anticorrosive coating 3 is laminated and combined on the outer surface of the transition layer. That is, along the direction from the stainless steel metal bipolar plate substrate 1 to the MAX phase anticorrosive coating 3, the stainless steel metal bipolar plate substrate 1, the transition layer 2 and the MAX phase anticorrosive coating 3 are sequentially laminated and combined.
The stainless steel metal bipolar plate substrate 1 included in the stainless steel metal bipolar plate may be a conventional stainless steel metal material, and specifically may be a stainless steel metal material such as 310, 304, 316, 904, 201, and the like. The thickness of the stainless steel metal bipolar plate substrate 1 can be selected according to the needs of the application.
The transition layer 2 contained in the stainless steel metal bipolar plate can effectively enhance the bonding strength of the MAX phase anticorrosive coating 3, can assist the MAX phase anticorrosive coating 3 to have the advantages of compactness, high hardness, flatness, smoothness, few microscopic defects and the like, and assists the MAX phase in the MAX phase anticorrosive coating 3 to be balanced with the compactness phase, so that the MAX phase has excellent conductivity and corrosion resistance. Therefore, in an embodiment, the material of the transition layer 2 is at least one of Ti, V, cr, zr, W, nb, and Mo. In another aspect, the thickness of the transition layer 2 is controlled to be 50 to 150nm, preferably 80 to 100nm. By selecting and optimizing the material and thickness of the transition layer 2, the function of the transition layer 2 can be further exerted, so that the firmness of the combination of the MAX phase anticorrosive coating 3 is improved, and meanwhile, the corrosion resistance of the stainless steel metal bipolar plate is improved and the resistivity of the stainless steel metal bipolar plate is reduced.
The MAX phase anticorrosive coating 3 contained in the stainless steel metal bipolar plate can be effectively and firmly combined with the stainless steel metal bipolar plate substrate 1 and the transition layer 2 and can be used as a functional surface of the stainless steel metal bipolar plate, so that the stainless steel metal bipolar plate is endowed with excellent corrosion resistance, low resistivity and excellent mechanical properties. In one embodiment, the MAX phase in the MAX phase anticorrosive coating 3 is chemical M n+1 AX n Or formula M m+2 A 2 X m (ii) a Wherein N =1 to 6,m =3 or 5,m is a transition metal element, a is a main group IIIA or IVA element, preferably at least one group element of Al, si, P, S, ga, ge, as, cd, in, sn, tl, pb, and X is C or N. In a specific embodiment, the transition metal element includes any one of Sc, ti, V, cr, zr, nb, mo, hf, ta, W. In another embodiment the thickness of the MAX phase anti-corrosion coating 3 is 300-2000 nm, preferably 400-800 nm. By adjusting and controlling the composition and thickness of the MAX phase anticorrosive coating 3, the corrosion resistance of the MAX phase anticorrosive coating 3 can be further improved and its resistivity reduced and its surface properties improved.
Therefore, the stainless steel metal bipolar plate in each of the above embodiments can enable the MAX-phase anticorrosive coating 3 to have excellent conductivity and excellent corrosion resistance through the synergistic effect between the transition layer 2 and the MAX-phase anticorrosive coating 3, and the MAX phase and the dense phase in the MAX-phase anticorrosive coating 3 are balanced, so that the stainless steel metal bipolar plate has stable electrochemical performance, and thus the stability of the electrochemical performance of the fuel cell can be effectively improved. But also the conductivity and corrosion resistance of the stainless steel metal bipolar plate can be further optimized by optimizing the composition and thickness of the transition layer 2 and the MAX phase corrosion protection coating 3. The MAX phase corrosion protection coating 3 was measured to have a conductivity comparable to metallic iron.
Correspondingly, the embodiment of the invention also provides a preparation method of the stainless steel metal bipolar plate. Referring to fig. 1, the process flow of the method for manufacturing a stainless steel metal bipolar plate is shown in fig. 2, and comprises the following steps:
s01, surface pretreatment is carried out on the stainless steel metal bipolar plate substrate and the target: providing a stainless steel metal bipolar plate substrate 1, a transition layer target and a MAX phase target, and performing surface pretreatment on the stainless steel metal bipolar plate substrate 1, the transition layer target and the MAX phase target;
s02, growing a transition layer on the surface of the stainless steel metal bipolar plate substrate: depositing the transition layer target material subjected to the surface pretreatment on the surface of the stainless steel metal bipolar plate substrate 1 by adopting a magnetron sputtering method, and growing a transition layer 2 in situ on the surface of the stainless steel metal bipolar plate substrate 1;
s03, growing an MAX phase anticorrosive coating on the surface of the transition layer: depositing the MAX phase target subjected to the surface pretreatment on the surface of the transition layer by adopting a magnetron sputtering method, and growing a MAX phase target coating on the surface of the transition layer in situ;
s04, carrying out heat treatment on the MAX phase target coating: and carrying out vacuum heat treatment on the MAX phase target coating.
Wherein, the surface pretreatment of the stainless steel metal bipolar plate substrate 1 in the step S01 comprises the following steps:
and sequentially carrying out polishing treatment, cleaning treatment and argon ion surface etching treatment on the stainless steel metal bipolar plate substrate.
The surface pretreatment of the transition layer target and the MAX phase target comprises the following steps:
and performing argon ion surface etching treatment on the transition layer target and the MAX phase target.
The surface performance of the stainless steel metal bipolar plate substrate 1 is improved by polishing the stainless steel metal bipolar plate substrate 1, on one hand, an oxide layer on the surface of the stainless steel metal bipolar plate substrate 1 is removed, and on the other hand, the flatness of the stainless steel metal bipolar plate substrate 1 is improved. After the polishing treatment, the surface roughness Ra <1 μm or a smoothness rating greater than ^ 10 of the stainless steel metal bipolar plate substrate 1. In addition, the polishing treatment method is preferably selected from magnetic grinding polishing, electrolytic polishing and mechanical grinding polishing.
The cleaning treatment after the polishing treatment of the stainless steel metal bipolar plate substrate 1 may be, but not limited to, the cleaning treatment by placing the polished stainless steel metal bipolar plate substrate 1 in a cleaning solution. Wherein, the cleaning solution is preferably a volatile organic solvent with better fat dissolving capacity, such as acetone, alcohol, isopropanol, ether and the like. The cleaning treatment mode can be soaking or soaking and ultrasonic oscillation. The time of the cleaning treatment should be sufficient, for example, the soaking time is 5 to 60min.
The argon ion surface etching treatment is performed on the stainless steel metal bipolar plate substrate 1, the transition layer target and the MAX phase target to further remove the surfaces of the three, so as to remove the possible oxide layers on the surfaces of the three. The argon ion surface etching treatment on the surface of the stainless steel metal bipolar plate substrate 1 can also improve the surface performance of the stainless steel metal bipolar plate substrate 1, such as obtaining a certain roughness, so as to enhance the bonding strength between the stainless steel metal bipolar plate substrate 1 and the transition layer 2 and the MAX phase anticorrosive coating 3, and improve the firmness of the MAX phase anticorrosive coating 3 to improve the stability of corrosion resistance and low resistivity of the stainless steel metal bipolar plate. Therefore, in one embodiment, the argon ion surface etching process conditions are as follows: the temperature is between room temperature and 730 ℃, and the vacuum degree is lower than 3 multiplied by 10 -3 Pa。
In addition, in a specific embodiment, the transition layer target may be a target capable of forming the above-mentioned transition layer 2 by magnetron sputtering, and may be at least one of metals Ti, V, cr, zr, W, nb, and Mo. Wherein the titanium metal may be a titanium plate having a purity of 99.99%. The MAX phase target may be a MAX phase target capable of forming the above MAX phase anticorrosive coating 3 by magnetron sputtering, and therefore, the MAX phase target may be the MAX phase described above in the MAX phase anticorrosive coating 3, or a mixture in which individual elements M, a, and X are mixed in a stoichiometric ratio (e.g., a molar ratio) of the elements in the MAX phase, or a mixture of X compounds of M and a.
And in the step S02, depositing a transition layer target on the surface of the stainless steel metal bipolar plate substrate 1 by magnetron sputtering to grow a transition layer 2. In one embodiment, the conditions of the magnetron sputtering method for depositing and growing the transition layer 2 by magnetron sputtering are as follows: the power is 1.5-3.5 kW, and 2.5kW is optimized; the pressure of the vacuum chamber is 3 x 10 -3 Pa below, the flow rate of Ar gas is 10-80 sccm, preferably 50sccm; the duty cycle of the direct current pulse is 30 to 80%, preferably 60%, and the sputtering time is 5 to 50min, preferably 15min. The transition layer 2 is deposited under the magnetron sputtering condition, so that the transition layer 2 has the advantages of compact and smooth surface and the like. The thickness of the transition layer 2 can be controlled and adjusted by controlling the time and the like, for example, the thickness of the transition layer 2 is controlled to be 50 to 150nm, preferably 80 to 100nm.
In the step S03, a MAX phase target coating is deposited and grown on the surface of the transition layer 2 by depositing a MAX phase target through magnetron sputtering. In one embodiment, the magnetron sputtering conditions for growing the MAX-phase target coating by magnetron sputtering deposition are as follows: the power is 1.5-5.0 kW, and 3.0kW is preferred; the pressure of the vacuum chamber is 3 multiplied by 10 -3 Pa or less; the flow rate of Ar gas is 10-80 sccm, preferably 30-75 sccm; the bias voltage is-40 to-160V; the duty ratio of the direct current pulse is 30-80%, preferably 60%; the sputtering time is 30-360 min, preferably 60-120 min. The MAX phase target coating is deposited and grown under the magnetron sputtering condition, so that the MAX phase target coating has the advantages of flatness, smoothness, few microscopic defects, good hydrophobicity and the like. The thickness of the MAX phase target coating may be controlled and adjusted by controlling the conditions such as time, for example, the thickness of the MAX phase target coating is controlled to be 300 to 2000nm, preferably 400 to 800nm.
In the step S04, the MAX-phase target coating is subjected to vacuum heat treatment, so that the elements in the MAX-phase target coating are regularly arranged in the heat treatment process, thereby forming the MAX-phase anticorrosive coating 3 as shown in fig. 1, and the MAX-phase anticorrosive coating 3 thus formed has not only low contact resistance and corrosion potential, but also excellent conductivity and corrosion resistance. Moreover, the MAX phase anticorrosive coating is compact, high in hardness, wear-resistant,High temperature resistance, smoothness, few microscopic defects, good hydrophobicity and firm structure. In one embodiment, the vacuum heat treatment is performed by placing the stainless steel bipolar plate substrate 1 with the MAX-phase target coating grown thereon in the step S03 into a vacuum environment for heat treatment. Wherein, the vacuum heat treatment conditions are as follows: vacuum pressure of 3 × 10 -3 Pa or less, the heat treatment temperature is 800-1100 deg.C, and the holding time is sufficient, such as 0.5-3 hours, specifically 1 hour. In addition, the heat treatment temperature is preferably raised to 800 to 1100 ℃ by gradually raising the temperature, for example, to 800 to 1100 ℃ at a temperature raising rate of 10 ℃/min. By controlling the vacuum heat treatment conditions, the MAX phase target coating can effectively form the MAX phase anticorrosive coating 3, so that the film quality and the corrosion resistance of the MAX phase anticorrosive coating 3 are improved, and the MAX phase target coating has low resistivity, such as electric conductivity equivalent to that of metallic iron.
Therefore, in the preparation method of the stainless steel metal bipolar plate, the transition layer and the MAX phase anticorrosive coating 3 are sequentially grown in situ on the surface of the stainless steel metal bipolar plate substrate, and the MAX phase anticorrosive coating 3 is effectively balanced with the MAX phase and the compactness thereof by optimizing the process steps and the corresponding process conditions in the preparation method, so that the MAX phase anticorrosive coating 3 has excellent electrical conductivity and good surface properties (such as compactness, flatness, smoothness, few microscopic defects and good hydrophobicity) and simultaneously has excellent corrosion resistance, and the MAX phase anticorrosive coating 3 has high hardness, wear resistance, high temperature resistance and firm combination with the stainless steel metal bipolar plate substrate 1. In addition, the preparation method of the stainless steel metal bipolar plate can ensure that the prepared stainless steel metal bipolar plate has stable performance, easily controlled conditions and high efficiency.
On the basis of the stainless steel metal bipolar plate and the preparation method thereof, the embodiment of the invention also provides a fuel cell. The fuel cell includes necessary components such as bipolar plates, gas diffusion layers, and membrane electrodes. As a matter of course, the fuel cell may further include other necessary components or auxiliary components, and the like. Wherein the bipolar plate contained in the fuel cell is the stainless steel metal bipolar plate. Therefore, the metal bipolar plate of the fuel cell has good conductivity and corrosion resistance, and the MAX phase anticorrosive coating on the surface layer is compact, high in hardness, wear-resistant, high-temperature-resistant, flat, smooth, few in microscopic defects, good in corrosion resistance, good in hydrophobicity and firm in structure, so that the corrosion resistance of the stainless steel metal bipolar plate substrate is effectively guaranteed, and the activity of a catalyst contained in the fuel cell is guaranteed, so that the fuel cell is endowed with stable electrochemical performance, high in power density and excellent in electrochemical performance.
The present invention will now be described in further detail with reference to specific examples.
1. Stainless steel metal bipolar plate and preparation method embodiment thereof
Example 1
The embodiment provides a stainless steel metal bipolar plate and a preparation method thereof. The structure of the stainless steel metal bipolar plate is shown in fig. 1, and the stainless steel metal bipolar plate comprises a stainless steel metal bipolar plate substrate 1, a transition layer 2 and a MAX phase anticorrosive coating 3, and the stainless steel metal bipolar plate substrate 1, the transition layer 2 and the MAX phase anticorrosive coating 3 are sequentially laminated and combined into a whole along the direction from the stainless steel metal bipolar plate substrate 1 to the MAX phase anticorrosive coating 3. The stainless steel metal bipolar plate substrate 1 is made of SS201 stainless steel bipolar plate substrates with the thickness of 0.1 mm; the transition layer 2 is made of titanium metal with the thickness of 100nm; the MAX phase anticorrosive coating 3 is made of Ti 3 SiC 2 And the thickness thereof is 500nm.
The preparation method of the stainless steel metal bipolar plate comprises the following steps:
s11, pretreatment of the stainless steel bipolar plate and the sputtering target:
preparing a stainless steel bipolar plate, performing surface treatment and cleaning treatment: cutting a 0.1mm thick SS201 stainless steel sheet with a specified area, punching into a fuel cell metal bipolar plate, adopting magnetic grinding and polishing to enable two surfaces to be mirror surfaces (the surface roughness Ra is less than 0.1 mu m), then sequentially immersing into acetone and alcohol, respectively carrying out ultrasonic treatment for 30min, taking out, and drying at the temperature of below 50 ℃;
surface etching of stainless steel bipolar plate and targetAnd (3) processing: installing the dried stainless steel bipolar plate and the dried target material on a sample rack in a vacuum chamber of pulse direct current sputtering equipment, covering all samples by using a cover, then installing a pure titanium target material with the purity of 99.99 percent on the target rack, and closing a door of the vacuum chamber and an exhaust valve; turning on a main power supply, and setting the temperature of the vacuum chamber to be 350 ℃; opening the mechanical pump to vacuumize until the air pressure is less than 3.2Pa, then opening the molecular pump, and continuing to vacuumize until the air pressure is 3 multiplied by 10 -3 Pa or less; introducing argon, wherein the flow rate is set as 35sccm; turning on an ion source power supply, setting the current to be 2.0A and the duty ratio to be 70%; turning on a bias power supply, setting the bias voltage to be 200V and the duty ratio to be 50%; switching on a direct current power supply of the target material, setting a constant current working mode, setting the current to be 6.0A, sputtering for 15min, and cleaning an oxide layer on the surface of the titanium target material by using argon ions; turning off the ion source power supply, bias power supply and target DC power supply, introducing argon gas with flow rate of 35sccm, and adjusting the pressure in the vacuum chamber to 6.8 × 10 -2 Pa; opening a cover on the sample holder, rotating the sample holder at a constant speed of 2rpm, then opening an ion source power supply and a bias power supply, and still setting a constant current working mode, wherein the duty ratio is 70%, but the current is 0.5A; the bias voltage is still set to be 200V, but the duty ratio is changed to be 50%, sputtering is carried out for 15min, so that the oxide film layer on the surface of the stainless steel is removed, certain surface roughness is obtained, and the binding force of the coating and the substrate is increased.
S12, sputtering and depositing a titanium transition layer 2 on the surface of the stainless steel bipolar plate: after the sputtering cleaning in the step S11 is finished, turning off an ion source power supply, adjusting the argon flow to be 50sccm, turning on a titanium target power supply, setting the power to be a constant power mode, setting the power to be 2.5kW, setting the duty ratio to be 60%, starting sputtering a titanium transition layer for 15min, and then turning off the titanium target power supply;
s13, sputtering and depositing a Ti-Si-C composite target layer on the surface of the titanium transition layer 2: after the step S12, the argon flow is adjusted to 75sccm and the bias voltage is adjusted to 100V. Opening of Ti 3 SiC 2 Setting a power supply of the composite target in a constant power working mode, wherein the power is 3.0kW, the duty ratio is 60%, and the sputtering time is 60min to obtain a Ti-Si-C composite target layer of the metal stainless steel bipolar plate;
s14, for the Ti-Si-C composite target materialVacuum heat treatment of the layers: after the step S13, the stainless steel bipolar plate with the finished film layer is transferred to a high vacuum heat treatment furnace and is vacuumized until the air pressure is less than 10 -3 Pa, then heating at the heating rate of 10 ℃/min, setting the heat treatment temperature at 1000 ℃, and keeping the temperature for 1h to promote the diffusion between the Ti-Si-C film layer and the Ti transition layer and the SS304 substrate, so that the Ti-Si-C coating forms MAX phase Ti 3 SiC 2 And (4) an anticorrosive coating.
Ti was measured by Scanning Electron Microscope (SEM) on the stainless steel metal bipolar plate prepared in example 1 3 SiC 2 The thickness of the anti-corrosion coating 3 is 400nm, the thickness of the titanium transition layer 2 is 100nm 3 SiC 2 The thickness of the corrosion-resistant coating 3 and the titanium transition layer 2 is 500nm in total, as shown in FIG. 3A. Heat treated Ti 3 SiC 2 The phases in the corrosion protection coating 3 are mainly MAX phases with only a very small amount of TiC phases, as shown in fig. 3B. The resistivity of the film layer measured by a four-probe method is 2.0 multiplied by 10 -6 Ω · m, corresponding to the resistivity of the aluminum alloy. Corrosion potential-0.4V, corrosion current 1.0X 10 -7 A·cm -2 . With SS201 matrix (-0.4V, 1.0X 10 -3 A·cm -2 ) In contrast, the corrosion potential was unchanged, but the corrosion current decreased by 4 orders of magnitude.
Example 2
The embodiment provides a stainless steel metal bipolar plate and a preparation method thereof. The structure of the stainless steel metal bipolar plate is shown in fig. 1, and the stainless steel metal bipolar plate comprises a stainless steel metal bipolar plate substrate 1, a transition layer 2 and a MAX phase anticorrosive coating 3, and the stainless steel metal bipolar plate substrate 1, the transition layer 2 and the MAX phase anticorrosive coating 3 are sequentially laminated and combined into a whole along the direction from the stainless steel metal bipolar plate substrate 1 to the MAX phase anticorrosive coating 3. The stainless steel metal bipolar plate substrate 1 is made of SS304 stainless steel bipolar plate substrates with the thickness of 0.1 mm; the transition layer 2 is made of titanium metal with the thickness of 100nm; the MAX phase anticorrosive coating 3 is made of Ti 3 AlC 2 And the thickness thereof is 400nm.
The preparation method of the stainless steel metal bipolar plate comprises the following steps:
s11, pretreatment of the stainless steel bipolar plate and the sputtering target:
preparing a stainless steel bipolar plate, performing surface treatment and cleaning treatment: cutting a 0.1mm thick SS304 stainless steel sheet with a specified area, punching into a fuel cell metal bipolar plate, adopting magnetic grinding and polishing to enable two surfaces to be mirror surfaces (the surface roughness Ra is less than 0.1 mu m), then sequentially immersing into acetone and alcohol, respectively carrying out ultrasonic treatment for 30min, taking out, and drying at the temperature of below 50 ℃;
surface etching treatment of the stainless steel bipolar plate and the target material: installing the dried stainless steel bipolar plate and the dried target material on a sample rack in a vacuum chamber of pulse direct-current sputtering equipment, covering all samples by using a cover, then installing a pure titanium target material with the purity of 99.99 percent on the target rack, and closing a door of the vacuum chamber and an exhaust valve; turning on a main power supply, and setting the temperature of the vacuum chamber to be 350 ℃; opening the mechanical pump to vacuumize until the air pressure is less than 3.2Pa, then opening the molecular pump, and continuing to vacuumize until the air pressure is 3 multiplied by 10 -3 Pa or less; introducing argon, wherein the flow rate is set as 35sccm; turning on an ion source power supply, setting the current to be 2.0A and the duty ratio to be 70%; turning on a bias power supply, setting the bias voltage to be 200V and the duty ratio to be 50%; switching on a direct current power supply of the target material, setting a constant current working mode, setting the current to be 6.0A, sputtering for 15min, and cleaning an oxide layer on the surface of the titanium target material by using argon ions; turning off the ion source power supply, the bias power supply and the target DC power supply, continuing to introduce argon gas with the flow rate of 35sccm, and adjusting the pressure in the vacuum chamber to 6.8 × 10 -2 Pa; opening a cover on the sample holder, rotating the sample holder at a constant speed of 2rpm, then opening an ion source power supply and a bias power supply, and still setting a constant current working mode, wherein the duty ratio is 70%, but the current is 0.5A; and (4) setting the bias voltage to be 200V, but changing the duty ratio to be 50%, and sputtering for 15min to remove the oxide film layer on the surface of the stainless steel, obtain certain surface roughness and increase the bonding force of the coating and the substrate.
S12, sputtering and depositing a titanium transition layer 2 on the surface of the stainless steel bipolar plate: after the sputtering cleaning in the step S11 is finished, turning off an ion source power supply, adjusting the argon flow to be 50sccm, turning on a titanium target power supply, setting the power to be a constant power mode, setting the power to be 2.5kW, setting the duty ratio to be 60%, starting sputtering a titanium transition layer for 15min, and then turning off the titanium target power supply;
s13, sputtering and depositing Ti on the surface of the titanium transition layer 2 twice 3 AlC 2 Layer (b):
first sputter depositing Ti 3 AlC 2 Film formation: adjusting the argon flow to 50sccm and the bias voltage to 120V, and opening Ti 3 AlC 2 The power supply of the composite target material carries out sputtering in a constant power mode, the corresponding constant power is 3.0kW, the duty ratio is 60%, the frequency is 40kHz, and the sputtering time is 60min; turning off the power supply, continuously cooling the sample chamber for 1 hour by using circulating water, taking out the sample, transferring the sample into a high vacuum heat treatment furnace, and vacuumizing until the air pressure is less than 10 -3 Pa, then heating at a heating rate of 10 ℃/min, setting the heat treatment temperature to 1000 ℃, and keeping the temperature for 1h to promote the diffusion between the Ti-Al-C film layer, the Ti transition layer and the SS304 substrate and enable the Ti-Al-C coating to form MAX phase Ti 3 AlC 2 ；
Second sputtering of Ti 3 AlC 2 Film formation: taking out the sample after the vacuum heat treatment is cooled, and transferring the sample back to a sample rack in a vacuum chamber of the pulse direct current sputtering equipment; adjusting the argon flow to 50sccm, the bias voltage to 100v, adjusting the Ti target direct current power supply, and setting the current to 1.6A; opening of Ti 3 AlC 2 The direct-current pulse power supply of the composite target material performs sputtering in a constant power mode, the corresponding constant power is 2.5kW, the duty ratio is 60%, and the frequency is 40kHz; the sputtering time is 60min; turning off the power supply, continuously introducing circulating water to cool the sample chamber for 1 hour, taking out the sample, transferring the sample into a high vacuum heat treatment furnace again to perform secondary vacuum heat treatment, wherein the technological conditions and the first sputtering Ti are 3 AlC 2 The procedure for the film is the same.
Testing the stainless steel metal bipolar plate prepared in this example 2 revealed that two magnetron sputtering depositions of Ti were used 3 AlC 2 The film can cover the MAX crystal boundary through multiple times of magnetron sputtering deposition, and the crystal boundary corrosion of the MAX phase is reduced. Two-layer Ti was measured by Scanning Electron Microscope (SEM) 3 AlC 2 The total thickness of the film layer is 400nm, and the thickness of the titanium transition layer is 100nm, as shown in FIG. 4A. Ti after heat treatment 3 AlC 2 The phase in the film being predominantly Ti 3 AlC 2 A phase and a TiC phase, wherein the TiC phase is mainly concentrated in the first sputtered Ti 3 AlC 2 Layer, since the Ti of the transition layer is sputtered towards the Ti of the layer during the vacuum heat treatment 3 AlC 2 The layer diffuses to cause an excess of Ti element in the layer. The elastic modulus of the film is 170 +/-5 GPa, the water contact angle is 101.3 degrees, and the elastic modulus is 140N/cm 2 The contact resistance under the contact pressure is only 3.725m omega cm 2 . After the PEMFC cathode environment is simulated and the constant potential polarization is carried out for 10 hours, ti 3 AlC 2 The contact resistance of the phase film sample remained unchanged. Corrosion potential-0.4V and corrosion current density 8.8X 10 -7 A/cm 2 . The surface roughness Ra measured by atomic force microscope was 2.63nm, as shown in FIG. 4B. These data indicate that Ti was plated experimentally 3 AlC 2 The film has high hardness, corrosion resistance, high conductivity, better hydrophobicity and smooth surface, and is very suitable for the environment of a proton exchange membrane fuel cell.
In addition, the stainless steel metal bipolar plate provided in the above examples 1-2 is assembled with components such as a gas diffusion layer and a membrane electrode to form a fuel cell, and the fuel cell has stable electrochemical performance, high power density and excellent electrochemical performance. Therefore, the stainless steel metal bipolar plate provided by the embodiment of the invention has excellent conductivity and corrosion resistance, and the MAX phase anticorrosive coating is compact, high in hardness, wear-resistant, high-temperature resistant, flat, smooth, few in microscopic defects, good in hydrophobicity and firm in structure. Thereby enabling to impart excellent electrochemical properties to the corresponding fuel cell.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. A preparation method of a stainless steel metal bipolar plate comprises the following steps:
providing a stainless steel metal bipolar plate substrate, a transition layer target material and a MAX phase target material, and performing surface pretreatment on the stainless steel metal bipolar plate substrate, the transition layer target material and the MAX phase target material;
depositing the transition layer target material subjected to the surface pretreatment on the surface of the stainless steel metal bipolar plate substrate by adopting a magnetron sputtering method, and growing a transition layer in situ on the surface of the stainless steel metal bipolar plate substrate;
depositing the MAX phase target subjected to surface pretreatment on the surface of the transition layer by adopting a magnetron sputtering method through twice sputtering, and growing two MAX phase target coatings on the surface of the transition layer in situ;
after each sputtering is finished, carrying out vacuum heat treatment on the sample comprising the MAX phase target coating;
the magnetron sputtering conditions for depositing the transition layer target material subjected to the surface pretreatment on the surface of the stainless steel metal bipolar plate substrate by adopting a magnetron sputtering method are as follows: the power is 1.5-3.5 kW, and the pressure of the vacuum chamber is 3 multiplied by 10 -3 Pa below, ar gas flow rate of 10-80 sccm, DC pulse duty ratio of 30-80%, and sputtering time of 5-50 min; and
depositing the MAX phase target material subjected to the surface pretreatment on the surface of the transition layer by adopting a magnetron sputtering method under the magnetron sputtering conditions that: the power is 1.5-5.0 kW, and the pressure of the vacuum chamber is 3 multiplied by 10 -3 Pa below, the flow rate of Ar gas is 10-80 sccm, the bias voltage is-40 to-160V, the duty ratio of direct current pulse is 30-80 percent, and the sputtering time is 30-360 min;
the transition layer target is a metal Ti target or a metal Zr target; and is provided with
The MAX phase target material is represented by a chemical formula M 3 AX 2 The target material is represented by M is Ti or Zr, A is Al or Ga, and X is C.
2. The method according to claim 1, wherein the vacuum heat treatment is performed under the following conditions: vacuum pressure of 3 × 10 -3 Pa below, heat treatment temperature of 800-1100 deg.c and heat maintaining time of 0.5-3 hr.
3. The method for preparing the metal bipolar plate according to any one of claims 1 to 2, wherein the surface pretreatment of the stainless steel metal bipolar plate substrate, the transition layer target and the MAX phase target comprises the following steps:
sequentially carrying out polishing treatment, cleaning treatment and argon ion surface etching treatment on the stainless steel metal bipolar plate substrate;
the surface pretreatment of the transition layer target and the MAX phase target comprises the following steps:
and performing argon ion surface etching treatment on the transition layer target and the MAX phase target.
4. The production method according to claim 3, characterized in that: after the polishing treatment, the surface roughness Ra of the stainless steel metal bipolar plate substrate<1 μm, or a finish grade of greater than
Figure FDA0003856784590000021
And/or
The argon ion surface etching treatment conditions are as follows: the temperature is between room temperature and 730 ℃, and the vacuum degree is lower than 3 multiplied by 10 -3 Pa。
5. A stainless steel metal bipolar plate made according to the method of claim 1, comprising a stainless steel metal bipolar plate substrate, wherein: the stainless steel metal bipolar plate further comprises a transition layer and a MAX phase anticorrosive coating, wherein the transition layer is laminated on the surface of the stainless steel metal bipolar plate substrate, the MAX phase anticorrosive coating is laminated on the outer surface of the transition layer,
the transition layer is made of metal Ti or Zr, and the MAX phase in the MAX phase anti-corrosion coating is represented by the chemical formula M 3 AX 2 M is Ti or Zr, A is Al or Ga, and X is C.
6. The stainless steel metallic bipolar plate of claim 5, wherein: the thickness of the MAX phase anticorrosive coating is 300-2000 nm; and/or
The thickness of the transition layer is 50-150 nm.
7. A fuel cell comprising a bipolar plate, wherein: the bipolar plate is a stainless steel metal bipolar plate according to any one of claims 5 to 6.
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