CN115020734A - Fuel cell metal bipolar plate composite coating and preparation method thereof - Google Patents
Fuel cell metal bipolar plate composite coating and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000000446 fuel Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 72
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- 238000007733 ion plating Methods 0.000 claims description 18
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Physical Vapour Deposition (AREA)
- Fuel Cell (AREA)
Abstract
The invention relates to a fuel cell metal bipolar plate composite coating and a preparation method thereof. Wherein, the fuel cell metal bipolar plate composite coating comprises: the metal transition layer (2), the metal nitride intermediate gradient layer (3) and the metal passivation surface layer (4) are sequentially formed on the surface of the metal bipolar plate substrate (1) along the deposition direction of the coating. The composite coating of the metal bipolar plate of the fuel cell, which is obtained by the preparation method, can effectively block the continuous growth of pinhole defects in the deposition direction of the coating, can obviously improve the surface integrity of the coating, and obviously improve the corrosion resistance of the coating.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a composite coating of a metal bipolar plate of a fuel cell and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are not limited by the carnot cycle, have high energy conversion efficiency, and have characteristics of high power density, rapid start-up, low temperature operation, and zero emission during operation, and are considered as one of the most promising power sources for automobiles, portable power sources, and future space fuel cell technologies.
The bipolar plate is a core component of the PEMFC, and needs to satisfy requirements of excellent chemical stability, good corrosion resistance, high electrical conductivity, and the like. Compared with graphite bipolar plates, metal plates have better mechanical strength, better electrical conductivity and lower manufacturing cost. However, the metal plate is easily corroded and/or passivated in a weakly acidic environment of the PEMFC to form a passivation film or dissolved, the formation of the passivation film causes an increase in contact resistance, and the dissolved metal contaminates the membrane electrode of the PEMFC and may cause catalyst poisoning.
In order to solve the problems, a physical vapor deposition technology is mostly adopted to prepare a highly conductive coating on the surface of the metal bipolar plate, so that the corrosion resistance of the metal bipolar plate is improved, and the contact resistance is reduced. Chinese patent CN112803033A discloses a method for preparing an oxide-doped nitride coating by selecting an oxide target and a nitride target by adopting a magnetron sputtering technology, wherein the oxide is Al 2 O 3 、TiO 2 、ZrO 2 、SiO 2 One or more than two of the substances are mixed, and the nitride is one of CrN, TiN, NbN and ZrN. Chinese patent CN104617316B discloses a method for preparing a nanocrystalline ZrBN/Zr composite coating suitable for a PEMFC metal bipolar plate, which comprises the steps of sequentially depositing a Zr diffusion layer, a Zr deposition layer and a ZrB layer on the surface of the bipolar plate by adopting a double-cathode plasma sputtering technology, and finally performing ion nitridation to form the ZrBN/Zr composite coating.
However, the surface of the coating prepared by the prior art has defects such as pores and pinholes, and the defects become channels for corrosive media to enter the metal substrate, and the protective effect of the coating is reduced to a certain extent, so that the corrosion of the bipolar plate is aggravated. Therefore, in order to further slow down the performance degradation of the PEMFC and prolong the service life of the PEMFC, a novel surface coating and a preparation process thereof are urgently needed to be developed.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the composite coating of the metal bipolar plate of the fuel cell and the preparation method thereof, which can effectively block the continuous growth of the pinhole defects in the deposition direction of the coating, obviously improve the surface integrity of the coating and obviously improve the corrosion resistance of the coating.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a fuel cell metal bipolar plate composite coating, which comprises: and the metal transition layer, the metal nitride intermediate gradient layer and the metal passivation surface layer are sequentially formed on the surface of the metal bipolar plate substrate along the deposition direction of the coating.
According to one aspect of the invention, the material of the metal bipolar plate substrate is titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum, niobium or stainless steel;
the thickness of the metal bipolar plate substrate is 0.05-2 mm.
According to one aspect of the present invention, the metal material in the metal transition layer is at least one of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum, niobium, and alloys thereof;
the thickness of the metal transition layer is 30-650 nm.
According to one aspect of the invention, the metal material in the metal nitride intermediate gradient layer is at least one of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum and niobium, wherein the metal nitride is MNx, and x is more than or equal to 0 and less than 1.5;
the thickness of the metal nitride intermediate gradient layer is 1-4.2 mu m.
According to one aspect of the invention, the intermediate gradient layer of the metal nitride is of a gradient structure, the metal component in the coating is gradually reduced from 95 wt% to 15-30 wt% along the deposition direction of the coating, and the metal nitride component is gradually increased from 5 wt% to 70-85 wt%.
According to one aspect of the invention, the metal material in the surface layer of the metal passivation is at least one of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum and niobium, wherein the metal passivation is MOy, and 0 < y < 4.
The invention also provides a preparation method of the fuel cell metal bipolar plate composite coating, which comprises the following steps:
s1, carrying out oil removal, ultrasonic cleaning and drying treatment on a base of a metal bipolar plate;
s2, placing the processed metal bipolar plate substrate into an arc ion plating equipment cavity, and etching the metal bipolar plate substrate by utilizing ionized argon ions;
s3, depositing a metal transition layer on the surface of the metal bipolar plate substrate by utilizing an arc ion plating technology;
s4, depositing a metal nitride intermediate gradient layer on the metal transition layer by using an arc ion plating technology;
and S5, preparing a metal passivation surface layer on the metal nitride intermediate gradient layer.
According to another aspect of the present invention, the step S2 includes: setting the temperature of a metal bipolar plate substrate to be 50-350 ℃, setting the vacuum degree to be 9 x 10 < -4 > Pa-7 x 10 < -3 > Pa, introducing argon gas flow to be 5-250 sccm, setting the ion source voltage to be 500-3000V, and etching the metal bipolar plate substrate by utilizing ionized argon ions for 10-50 min.
According to another aspect of the present invention, the step S3 includes: setting the target base distance to be 10-45 cm, setting the substrate temperature of the metal bipolar plate to be 50-350 ℃, introducing argon gas flow to be 5-180 sccm, setting the working air pressure to be 0.1-2.0 Pa, setting the substrate bias voltage of the metal bipolar plate to be-50-200V, setting the target arc flow to be 30-150A, and depositing for 2-50 min.
According to another aspect of the present invention, the step S4 includes: setting the substrate temperature of the metal bipolar plate to be 50-350 ℃, introducing nitrogen flow to be 5-200 sccm, setting the substrate bias voltage of the metal bipolar plate to be-30-200V, setting the arc flow of the electric arc target to be 30-150A, and depositing for 5-110 min.
According to another aspect of the present invention, the step S5 includes: 5-50 sccm of argon and 1-35 sccm of oxygen are introduced into the vacuum chamber, the substrate temperature of the metal bipolar plate is set to be 50-350 ℃, the bias voltage is set to be-250-950V, and oxygen plasma sputtering is carried out for 1-15 min.
Compared with the prior art, the invention has the following advantages:
according to the scheme of the invention, the metal nitride-based composite coating on the surface of the metal bipolar plate has a conductive corrosion-resistant function, and sequentially consists of a metal (M) transition layer, a metal nitride intermediate gradient layer and a metal passivation conductive corrosion-resistant surface layer in the deposition direction, wherein the metal nitride intermediate gradient layer with gradient components can optimize the internal structure of the coating and effectively block the continuous growth of pinhole defects in the deposition direction of the coating. The metal nitride-based composite coating is deposited with a metal passivation layer on the outermost surface layer, so that the surface integrity of the coating can be obviously improved, and the corrosion resistance of the coating is obviously improved. The composite coating has small difference of thermal expansion coefficients between different coatings, small internal stress between the coating and a substrate, can greatly improve the bonding strength between film substrates, and obviously reduces the contact resistance of the coating.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic diagram of a composite coating of a fuel cell metal bipolar plate according to an embodiment of the present invention;
fig. 2 schematically shows a flow chart of a method for preparing a fuel cell metal bipolar plate composite coating according to an embodiment of the invention.
Reference numerals:
1-a metal bipolar plate substrate; 2-a metal transition layer; 3-a metal nitride intermediate gradient layer; 4-metal passivation surface layer.
Detailed Description
The description of the embodiments of this specification is intended to be taken in conjunction with the accompanying drawings, which are to be considered part of the complete specification. In the drawings, the shape or thickness of the embodiments may be exaggerated and simplified or conveniently indicated. Further, the components of the structures in the drawings are described separately, and it should be noted that the components not shown or described in the drawings are well known to those skilled in the art.
Any reference to directions and orientations to the description of the embodiments herein is merely for convenience of description and should not be construed as limiting the scope of the invention in any way. The following description of the preferred embodiments refers to combinations of features which may be present independently or in combination, and the present invention is not particularly limited to the preferred embodiments. The scope of the invention is defined by the claims.
An embodiment of the present invention provides a fuel cell metal bipolar plate composite coating, as shown in fig. 1, the composite coating includes: a metal (M) transition layer 2, a metal nitride intermediate gradient layer 3 and a metal passivation surface layer 4 which are sequentially formed on the surface of the metal bipolar plate substrate 1 along the coating deposition direction.
The material of the metal bipolar plate substrate 1 is titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum, niobium, stainless steel or the like, and the thickness of the metal bipolar plate substrate 1 is 0.05 to 2mm, preferably 0.1 to 0.15 mm.
The metal material in the metal transition layer 2 is at least one (one or a combination of several) of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum, niobium and an alloy thereof, preferably titanium, chromium, zirconium, niobium, a titanium-chromium alloy, a titanium-niobium alloy and a titanium-chromium-niobium alloy. The thickness of the metal transition layer 2 is 30 to 650nm, preferably 50 to 550 nm.
The metal material in the metal nitride intermediate gradient layer 3 is at least one (one or a combination of several) of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum and niobium, preferably titanium, chromium, zirconium and niobium. The metal nitride is MNx, x is more than or equal to 0 and less than 1.5, the metal nitride comprises nitride formed by one or more of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum and niobium, preferably one or more of TiN, CrN, NbN, ZrN, TiCrN, TiNbN, TiZrN, CrNbN, CrZrN and NbZrN, and the mass fraction of the metal nitride is 70-85%, preferably 75-80%. The thickness of the metal nitride intermediate gradient layer is 1 to 4.2 μm, preferably 1.5 to 3.8 μm.
The metal nitride intermediate gradient layer 3 is of a gradient structure, the metal component in the coating is gradually reduced to 15-30 wt% from 95 wt% along the deposition direction of the coating, and the metal nitride component is gradually increased to 70-85 wt% from 5 wt%. In the present embodiment, the metal nitride intermediate gradient layer 3 is provided with 3 to 7 composition gradients, preferably 5 composition gradients.
Wherein, the metal material in the metal passivation surface layer 4 is at least one (one or a combination of several) of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum and niobium, preferably titanium, chromium, niobium and zirconium. Wherein the metal passivation is oxide MOy, and y is more than 0 and less than 4.
As shown in fig. 2, an embodiment of the present invention further provides a method for preparing the fuel cell metal bipolar plate composite coating, including:
s1, carrying out oil removal, ultrasonic cleaning and drying treatment on a base of a metal bipolar plate;
s2, placing the processed metal bipolar plate substrate into a cavity of arc ion plating equipment, and etching the metal bipolar plate substrate by utilizing ionized argon ions;
s3, depositing a metal transition layer on the surface of the metal bipolar plate substrate by using an arc ion plating technology;
s4, depositing a metal nitride intermediate gradient layer on the metal transition layer by using an arc ion plating technology;
and S5, preparing a metal passivation surface layer on the metal nitride intermediate gradient layer.
Wherein, step S2 includes: setting the base temperature of the metal bipolar plate at 50-350 ℃, preferably 100-300 ℃, and further preferably 150-250 ℃; the vacuum degree was set to 9X 10 -4 Pa～7×10 -3 Pa, preferably 1X 10 -3 Pa～6×10 -3 Pa, more preferably 2X 10 -3 Pa～4×10 -3 Pa; introducing argon gas with the flow rate of 5-250 sccm, preferably 40-200 sccm, and further preferably 80-120 sccm; setting the ion source voltage to be 500-3000V, preferably 1000-2300V, and further preferably 1300-2100V; and etching the metal bipolar plate substrate by using ionized argon ions for 10-50 min, preferably 20-40 min, and further preferably 25-35 min.
Step S3 includes: the cathode target is a metal M target (wherein M is one or a combination of more of titanium, chromium, zirconium, niobium, titanium-chromium alloy, titanium-niobium alloy and titanium-chromium-niobium alloy), and the target base distance is 10-45 cm, preferably 15-30 cm, and further preferably 22-24 cm; setting the temperature of the base of the metal bipolar plate at 50-350 ℃, preferably 80-300 ℃, and further preferably 100-250 ℃; introducing argon gas with the flow rate of 5-180 sccm, preferably 30-150 sccm, and further preferably 80-120 sccm; setting the working air pressure to be 0.1-2.0 Pa, preferably 0.3-1.8 Pa, and further preferably 0.6-1.2 Pa; setting the base bias voltage of the metal bipolar plate to-50 to-250V, preferably-60 to-200V, and further preferably-70 to-130V; setting the target arc flow to be 30-150A, preferably 50-90A, and further preferably 60-80A; depositing for 2-50 min, preferably 3-40 min, and further preferably 5-30 min.
Step S4 includes: setting the temperature of the base of the metal bipolar plate at 50-350 ℃, preferably 80-250 ℃, and further preferably 100-180 ℃; introducing nitrogen gas at a flow rate of 5-200 sccm, preferably 40-180 sccm; further preferably 40 to 160 sccm; setting the base bias voltage of the metal bipolar plate to-30 to-200V, preferably-35 to-150V, and further preferably-40 to-90V; setting the arc flow of the arc target to be 30-150A, preferably 40-100A, and further preferably 60-80A; and depositing for 5-110 min, preferably 10-95 min, and further preferably 15-75 min.
Step S5 includes: introducing argon gas into the vacuum chamber for 5-50 sccm, preferably 15-40 sccm, further preferably 20-30 sccm, and introducing oxygen gas for 1-35 sccm, preferably 2-15 sccm, further preferably 3-8 sccm; setting the temperature of the base of the metal bipolar plate to be 50-350 ℃, preferably 80-250 ℃, and further preferably 150-220 ℃; setting the bias voltage to-250 to-950V, preferably-450 to-850V, and further preferably-550 to-750V; the oxygen plasma sputtering is performed for 1-15 min, preferably 2-10 min, and more preferably 3-6 min. The surface layer of the metal passivation (MOy, wherein y is more than 0 and less than 4) is prepared, and the purpose of sealing pinholes on the surface layer is realized under the condition of lower oxide content which does not influence the contact resistance and corrosion resistance of the metal nitride coating.
Example 1
In the present embodiment, as shown in fig. 1, a metal transition layer 2, a metal nitride intermediate gradient layer 3 and a metal passivation surface layer 4 are sequentially coated on a surface of a metal bipolar plate substrate 1 of a metal bipolar plate. In this embodiment, the metal bipolar plate substrate 1 is a pure titanium bipolar plate for a proton exchange membrane fuel cell, and the preparation method of the composite coating on the substrate surface is as follows:
(1) the metal bipolar plate substrate 1 after being degreased, cleaned by ultrasonic and dried is placed into a cavity of arc ion plating equipment, the temperature of the substrate 1 is heated to 170 ℃, and the vacuum degree reaches 3 multiplied by 10 -3 And after the pressure is lower than Pa, introducing 100sccm of argon gas, setting the voltage of an ion source to be 2000V, and etching the metal bipolar plate substrate 1 for 30min by utilizing ionized argon ions.
(2) And depositing a Ti transition layer 2 on a pure titanium substrate 1 by adopting an arc ion plating technology, wherein a cathode target is an elemental Ti target, the target base distance is set to be 23cm, the arc target current is 70A, the substrate 1 temperature is 150 ℃, the argon flow is 100sccm, the working pressure is 0.8Pa, the substrate 1 bias voltage is-100V, the deposition time is 12min, and the thickness of the Ti transition layer 2 obtained by deposition is about 400 nm.
(3) And depositing a TiCrN gradient intermediate layer 3 on the Ti transition layer 2 by adopting an arc ion plating technology. Wherein the cathode target is an elemental Cr target and an elemental Ti target, the target base distance is 23cm, the electric arc target current is 50A, the temperature of the substrate 1 is 150 ℃, the bias voltage of the substrate 1 is-80V, and if the nitrogen flow is 60sccm, the deposition time is 5 min; if the nitrogen flow is 80sccm, the deposition time is 8 min; if the nitrogen flow is 100sccm, the deposition time is 12 min; if the nitrogen flow is 120sccm, the deposition time is 15 min; if the nitrogen flow is 150sccm, the deposition time is 20 min. The final deposited TiCrN interlayer 3 was about 3.2 μm thick.
(4) A metal passivation surface layer 4 is prepared. Under the lower oxide amount that does not influence metal nitride coating layer contact resistance and corrosion resistance, realize the purpose of top layer pinhole shutoff, include: argon gas of 25sccm and oxygen of 4sccm are introduced into the vacuum chamber, the temperature of the substrate 1 is set to 200 ℃, the bias voltage is set to-650V, and oxygen plasma sputtering is carried out for 5 min.
Example 2
In the present embodiment, as shown in fig. 1, a metal transition layer 2, a metal nitride intermediate gradient layer 3 and a metal passivation surface layer 4 are sequentially coated on the surface of a metal bipolar plate substrate 1. In this embodiment, the substrate 1 is a pure titanium bipolar plate for a proton exchange membrane fuel cell, and the preparation method of the composite coating on the surface of the substrate is as follows:
(1) placing the substrate 1 which is degreased, ultrasonically cleaned and dried into a cavity of arc ion plating equipment, heating the substrate 1 to 170 ℃, introducing 100sccm argon after the vacuum degree reaches below 3 x 10 < -3 > Pa, setting the voltage of an ion source to be 1500V, and etching the metal substrate 1 for 25min by utilizing ionized argon ions.
(2) And depositing a Ti transition layer 2 on a pure titanium substrate 1 by adopting an arc ion plating technology, wherein a cathode target is an elemental Ti target, the target base distance is set to be 23cm, the arc target current is 70A, the substrate 1 temperature is 150 ℃, the argon flow is 100sccm, the working pressure is 0.8Pa, the substrate 1 bias voltage is-80V, the deposition time is 10min, and the thickness of the Ti transition layer 2 obtained by deposition is about 280 nm.
(3) And depositing a TiCrN gradient intermediate layer 3 on the Ti transition layer 2 by adopting an arc ion plating technology. Wherein the cathode target is an elemental Cr target and an elemental Ti target, the target base distance is 23cm, the electric arc target current is 70A, the temperature of the substrate 1 is 150 ℃, the bias voltage of the substrate 1 is-50V, and if the nitrogen flow is 50sccm, the deposition time is 3 min; if the nitrogen flow is 70sccm, the deposition time is 5 min; if the nitrogen flow is 100sccm, the deposition time is 8 min; if the nitrogen flow is 115sccm, the deposition time is 10 min; if the nitrogen flow is changed to 135sccm, the deposition time is 15 min; the final deposited TiCrN interlayer 3 was about 2.4 μm thick.
(4) The preparation of metal passivation object surface layer 4 realizes the purpose of surface layer pinhole blocking under the lower oxide volume that does not influence metal nitride coating layer contact resistance and corrosion resistance, includes: introducing argon gas of 25sccm and oxygen of 4sccm into the vacuum chamber, setting the substrate at the temperature of 1 ℃ of 200 ℃, setting the bias voltage of-650V, and sputtering by using oxygen plasma for 3 min.
Example 3
In the present embodiment, as shown in fig. 1, a metal transition layer 2, a metal nitride intermediate gradient layer 3, and a metal passivation surface layer 4 are sequentially coated on a surface of a metal bipolar plate substrate 1. In this embodiment, the substrate 1 is a pure titanium bipolar plate for a proton exchange membrane fuel cell, and the preparation method of the composite coating on the surface of the substrate is as follows:
(1) placing the substrate 1 after degreasing, ultrasonic cleaning and drying into a cavity of arc ion plating equipment, heating the substrate 1 to 170 ℃, introducing 100sccm argon after the vacuum degree reaches below 3 x 10 < -3 > Pa, setting the ion source voltage to 2000V, and etching the metal substrate 1 for 30min by utilizing ionized argon ions.
(2) And depositing a Ti transition layer 2 on a pure titanium substrate 1 by adopting an arc ion plating technology, wherein a cathode target is an elemental Ti target, the target base distance is set to be 23cm, the arc target current is 70A, the substrate 1 temperature is 150 ℃, the argon flow is 100sccm, the working pressure is 0.8Pa, the substrate 1 bias voltage is-100V, the deposition time is 6min, and the thickness of the Ti transition layer 2 obtained by deposition is about 180 nm.
(3) And depositing a TiN gradient intermediate layer 3 on the Ti transition layer 2 by adopting an arc ion plating technology. Wherein, the cathode target is selected from a single Ti target, the target base distance is set to be 23cm, the electric arc target current is 50A, the temperature of the substrate 1 is 150 ℃, the bias voltage of the substrate 1 is-80V, and if the nitrogen flow is 60sccm, the deposition time is 3 min; if the nitrogen flow is 80sccm, the deposition time is 5 min; if the nitrogen flow is 90sccm, the deposition time is 8 min; if the nitrogen flow is 100sccm, the deposition time is 12 min; if the nitrogen flow is 120sccm, the deposition time is 15 min; the final deposited TiN interlayer 3 was about 1.5 μm thick.
(4) Preparing a metal passivation surface layer. Under the condition of lower oxide content which does not affect the contact resistance and corrosion resistance of the metal nitride coating, the purpose of blocking surface layer pinholes is realized, which comprises the following steps: argon gas of 25sccm and oxygen of 4sccm are introduced into the vacuum chamber, the temperature of the substrate 1 is set to 200 ℃, the bias voltage is set to-650V, and oxygen plasma sputtering is carried out for 5 min.
The sequence numbers of the above steps related to the method of the present invention do not mean the order of execution of the method, and the order of execution of the steps should be determined by their functions and inherent logic, and should not limit the implementation process of the embodiment of the present invention.
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 present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A fuel cell metal bipolar plate composite coating, comprising: the metal transition layer (2), the metal nitride intermediate gradient layer (3) and the metal passivation surface layer (4) are sequentially formed on the surface of the metal bipolar plate substrate (1) along the deposition direction of the coating.
2. The fuel cell metal bipolar plate composite coating according to claim 1, wherein the material of the metal bipolar plate substrate (1) is titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum, niobium, or stainless steel;
the thickness of the metal bipolar plate substrate (1) is 0.05-2 mm.
3. The fuel cell metallic bipolar plate composite coating according to claim 1, wherein the metallic material in the metallic transition layer (2) is at least one of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum, niobium, and alloys thereof;
the thickness of the metal transition layer (2) is 30-650 nm.
4. The fuel cell metal bipolar plate composite coating according to claim 1, wherein the metal material in the metal nitride intermediate gradient layer (3) is at least one of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum and niobium, wherein the metal nitride is MNx, and x is greater than or equal to 0 and less than 1.5;
the thickness of the metal nitride intermediate gradient layer (3) is 1-4.2 mu m.
5. The fuel cell metal bipolar plate composite coating according to claim 1, wherein the metal nitride intermediate gradient layer (3) is a gradient structure, the metal component in the coating gradually decreases from 95 wt% to 15-30 wt% and the metal nitride component gradually increases from 5 wt% to 70-85 wt% along the coating deposition direction.
6. The fuel cell metallic bipolar plate composite coating according to claim 1, wherein the metallic material in the metallic passivation surface layer (4) is at least one of titanium, tungsten, chromium, aluminum, nickel, copper, zirconium, molybdenum, niobium, wherein the metallic passivation is MOy, and 0 < y < 4.
7. A method for preparing the composite coating of the fuel cell metal bipolar plate as claimed in any one of claims 1 to 6, comprising:
s1, carrying out oil removal, ultrasonic cleaning and drying treatment on a base of a metal bipolar plate;
s2, placing the processed metal bipolar plate substrate into an arc ion plating equipment cavity, and etching the metal bipolar plate substrate by utilizing ionized argon ions;
s3, depositing a metal transition layer on the surface of the metal bipolar plate substrate by utilizing an arc ion plating technology;
s4, depositing a metal nitride intermediate gradient layer on the metal transition layer by using an arc ion plating technology;
and S5, preparing a metal passivation surface layer on the metal nitride intermediate gradient layer.
8. The method according to claim 7, wherein the step S2 includes: setting the temperature of the base of the metal bipolar plate to be 50-350 ℃, setting the vacuum degree to be 9 x 10 < -4 > Pa-7 x 10 < -3 > Pa, introducing argon gas flow to be 5-250 sccm, setting the voltage of an ion source to be 500-3000V, and etching the base of the metal bipolar plate for 10-50 min by using ionized argon ions.
9. The method according to claim 7, wherein the step S3 includes: setting the target base distance to be 10-45 cm, setting the substrate temperature of the metal bipolar plate to be 50-350 ℃, introducing argon gas flow to be 5-180 sccm, setting the working air pressure to be 0.1-2.0 Pa, setting the substrate bias voltage of the metal bipolar plate to be-50-200V, setting the target arc flow to be 30-150A, and depositing for 2-50 min.
10. The method according to claim 7, wherein the step S4 includes: setting the substrate temperature of the metal bipolar plate to be 50-350 ℃, introducing nitrogen flow to be 5-200 sccm, setting the substrate bias voltage of the metal bipolar plate to be-30-200V, setting the arc flow of an electric arc target to be 30-150A, and depositing for 5-110 min;
the step S5 includes: 5-50 sccm of argon and 1-35 sccm of oxygen are introduced into the vacuum chamber, the substrate temperature of the metal bipolar plate is set to be 50-350 ℃, the bias voltage is set to be-250-950V, and oxygen plasma sputtering is carried out for 1-15 min.
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