CN113265638A - High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof - Google Patents

High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof Download PDF

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CN113265638A
CN113265638A CN202110821664.4A CN202110821664A CN113265638A CN 113265638 A CN113265638 A CN 113265638A CN 202110821664 A CN202110821664 A CN 202110821664A CN 113265638 A CN113265638 A CN 113265638A
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corrosion
iridium
chromium
composite coating
graphite
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CN113265638B (en
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汪爱英
李�昊
张栋
马冠水
陈仁德
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Ningbo Institute of Material Technology and Engineering of CAS
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—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
    • 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
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating and a preparation method and application thereof. The high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating comprises a chromium-iridium transition layer and a graphite-like amorphous carbon layer which are sequentially formed on the surface of a substrate, wherein the content of iridium element in the chromium-iridium transition layer is 2-10 wt%. Further, the substrate comprises a metallic bipolar plate. The high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating provided by the invention comprises a chromium-iridium transition layer, a corrosion buffer layer is effectively provided by doping iridium element, an iridium oxide conductive path can be formed after the transition layer is corroded, the continuous generation of a chromium oxide layer can be avoided by the conductive path, the contact resistance is prevented from greatly increasing, and the long-acting protection of the metal bipolar plate is realized.

Description

High-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of surface engineering protection, and particularly relates to a high-conductivity corrosion-resistant graphite carbon protection multilayer composite coating, and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are a new type of energy source that can convert hydrogen energy directly into electrical energy. The novel energy-saving power supply has the advantages of quick start, relatively low working temperature, quick response to various environments, no pollution, high energy efficiency and the like, and has good application prospects in the aspects of new energy automobiles, fixed and portable power supplies. One cell unit of a proton exchange membrane fuel cell is generally composed of a bipolar plate (BPP), a Membrane Electrode (MEA), a gasket, and an end plate. In many assemblies, the bipolar plates account for 80% of the total mass, almost the entire volume, and about 18-28% of the manufacturing cost of the fuel cell. Bipolar plates are key functional components in a pem fuel cell stack and serve the primary functions of conducting electrons, distributing chemical fuel, separating individual cells, supporting the membrane electrodes, and facilitating water management within the cells. Therefore, it must satisfy the requirements of easy processing and forming, electrochemical corrosion resistance, low interface resistance, low cost, etc. At present, the traditional fuel cell widely uses graphite bipolar plates, but the volume is large, the strength is low, and the large-scale use is restricted. The metal plate with excellent performances such as high electrical conductivity, high thermal conductivity, high mechanical strength, low stamping cost, low gas permeability and the like is expected to replace graphite to become a main material of the bipolar plate.
The operating environment of the proton exchange membrane fuel cell is usually an acidic (pH = 2-3), warm and humid (65-90 ℃) environment. Under high temperature, the acidic corrosive medium can generate a passivation layer on the surface of the metal bipolar plate, so that the Interface Contact Resistance (ICR) between the metal bipolar plate and Gas Diffusion Layers (GDLs) is increased; on the other hand, the metal bipolar plate is easy to generate serious corrosion, and the output power of the battery is influenced by the two consequences, so that the performance of the battery is rapidly reduced. The deposition of the protective coating on the surface of the metal bipolar plate is an effective means for improving the surface conductivity and the corrosion resistance of the metal bipolar plate. Commonly used protective coatings are noble metal coatings, metal nitride or carbide coatings, conductive polymer coatings, and the like. The amorphous carbon coating is a coating of goldDiamond phase sp3And graphitic phase sp2Hybrid-formed mixed structure coatings have many excellent performances due to the excellent chemical inertness of carbon elements and the special mechanism of amorphous carbon, and have attracted much attention in recent years for the application of amorphous carbon coatings in the surface protective coatings of metal bipolar plates. However, the performance degradation of the plate is particularly serious due to the increase of contact resistance after long-term operation.
Disclosure of Invention
The invention mainly aims to provide a high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating, which comprises a chromium-iridium transition layer and a graphite-like amorphous carbon layer which are sequentially formed on the surface of a substrate; wherein the content of iridium element in the chromium-iridium transition layer is 2-10 wt%; and the corrosion current density of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating is less than 5 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The contact resistance in the deposition state is less than 7m omega cm2And the contact resistance is less than 10m omega cm after 24h of corrosion2And the contact resistance is increased within 5% after 48h of corrosion.
The embodiment of the invention also provides a preparation method of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating, which comprises the following steps:
providing a metal bipolar plate as a substrate;
depositing a chromium-iridium transition layer (also marked as a conductive buffer layer) on the surface of the substrate by adopting a high-power pulse magnetron sputtering technology and taking a chromium-iridium composite target as a target material, wherein the content of iridium element in the chromium-iridium composite target is 2-10 wt%;
and depositing a graphite-like amorphous carbon layer on the surface of the chromium-iridium transition layer by adopting a direct-current magnetron sputtering technology and taking a graphite target as a target material, thereby obtaining the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
The embodiment of the invention also provides application of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating in preparing a bipolar plate for a proton exchange membrane fuel cell or a proton exchange membrane fuel cell.
The embodiment of the invention also provides a bipolar plate for a proton exchange membrane fuel cell, which comprises a metal bipolar plate, wherein the metal bipolar plate is coated with the high-conductivity corrosion-resistant graphite carbon protection multilayer composite coating.
The embodiment of the invention also provides a proton exchange membrane fuel cell which comprises the bipolar plate for the proton exchange membrane fuel cell.
Compared with the prior art, the invention has the beneficial effects that:
(1) the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating provided by the invention contains the chromium-iridium transition layer, so that the prepared protective multilayer composite coating has excellent conductivity corrosion resistance, and meanwhile, the protective multilayer composite coating has stable performance in an acidic high-temperature environment and keeps lower contact resistance for a long time;
(2) the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating provided by the invention comprises a chromium-iridium transition layer, a corrosion buffer layer is effectively provided by doping iridium element, an iridium oxide conductive path can be formed after the transition layer (buffer layer) is corroded, the continuous generation of a chromium oxide layer can be avoided through the conductive path, the contact resistance is further prevented from greatly rising, and thus the long-acting protection of the metal bipolar plate is realized;
(3) the invention adopts high-power pulse magnetron sputtering technology to obtain the chromium-iridium transition layer with smooth surface and compact internal structure, can effectively improve the bonding strength of the film substrate, and ensures that the surface of the graphite-like amorphous carbon layer growing on the surface is smooth and compact.
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 description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a corrosion schematic of a highly conductive corrosion resistant graphitic carbon barrier multilayer composite coating according to an exemplary embodiment of the present invention;
FIG. 2 is a graph showing the results of corrosion performance tests of the coatings prepared in example 1 of the present invention and comparative examples 1 to 2;
FIG. 3 is a graph showing the results of contact resistance performance tests of the coatings prepared in example 1 of the present invention and comparative examples 1 to 2;
FIGS. 4 a-4 b are surface topography maps of coatings prepared in example 1 of the present invention and comparative example 3, respectively;
fig. 5 a-5 b are graphs of the bond force scratch profiles of the coatings prepared in example 1 and comparative example 3, respectively, of the present invention.
Detailed Description
In view of the defects of the prior art, the inventors of the present invention have made extensive studies and practice to provide a technical solution of the present invention, which mainly aims at the problem that the application of the existing protective coating on the surface of a metal bipolar plate has insufficient comprehensive performance, and provides a method for preparing a buffer transition layer on the surface of a metal bipolar plate.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiment of the invention provides a high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating, which comprises a chromium-iridium transition layer and a graphite-like amorphous carbon layer which are sequentially formed on the surface of a substrate; wherein the content of iridium element in the chromium-iridium transition layer is 2-10 wt%; and the corrosion current density of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating is less than 5 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The contact resistance in the deposition state is less than 7m omega cm2Contact resistance after 24h of etchingLess than 10m omega cm2And the contact resistance is increased within 5% after 48h of corrosion.
The corrosion schematic diagram of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating is shown in fig. 1, and the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating comprises a chromium-iridium transition layer, wherein a corrosion buffer layer is effectively provided by doping iridium element, and an iridium oxide conductive path can be formed after the transition layer (buffer layer) is corroded, so that the continuous generation of a chromium oxide layer can be avoided through the conductive path, the contact resistance is further prevented from greatly rising, and the long-acting protection on a metal bipolar plate is realized.
In some specific embodiments, the thickness of the chromium-iridium transition layer is 100 to 200 nm.
Further, the thickness of the graphite-like amorphous carbon layer is 500-800 nm.
The corrosion current density of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating provided by the invention is less than 5 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The contact resistance in the deposition state is less than 7m omega cm2And the contact resistance is less than 10m omega cm after 24h of corrosion2And the contact resistance is increased by no more than 5% after 48h of corrosion.
Another aspect of the embodiments of the present invention further provides a method for manufacturing the highly conductive and corrosion resistant graphite-like carbon protective multilayer composite coating, including:
providing a metal bipolar plate as a substrate;
depositing a chromium-iridium transition layer on the surface of the substrate by adopting a high-power pulse magnetron sputtering technology and taking a chromium-iridium composite target as a target material, wherein the content of iridium element in the chromium-iridium composite target is 2-10 wt%;
and depositing a graphite-like amorphous carbon layer on the surface of the chromium-iridium transition layer by adopting a direct-current magnetron sputtering technology and taking a graphite target as a target material, thereby obtaining the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
In some more specific embodiments, the preparation method comprises: the method comprises the steps of placing a substrate in a reaction cavity by adopting a high-power pulse magnetron sputtering technology, depositing and forming a chromium-iridium transition layer on the surface of the substrate by taking a chromium-iridium composite target as a target material and an inert gas as a working gas, wherein the high-power pulse magnetron sputtering technology adopts the pulse frequency of 400-800 Hz, the pulse width of 50-200 microseconds, the pulse voltage of 800-1000V, the power of 2.0-3.5 KW, the air pressure of the reaction cavity of 1.4-2.1 mTorr, the bias voltage of the substrate of-50V-150V, the introduction amount of the inert gas of 30-70 sccm, the deposition temperature of 40-80 ℃ and the deposition time of 5-15 minutes.
Further, the inert gas includes argon, and is not limited thereto.
In some more specific embodiments, the preparation method comprises: and depositing on the surface of the chromium-iridium transition layer to form a graphite-like amorphous carbon layer by adopting a direct current magnetron sputtering technology, taking a graphite target as a target material and inert gas as working gas, wherein the power of a sputtering source adopted in the direct current magnetron sputtering technology is 0.9-1.2 kW, the air pressure of a reaction cavity is 1.4-2.1 mTorr, the bias voltage of a substrate is-50V-250V, the introduction amount of the inert gas is 30-70 sccm, the deposition temperature is 40-80 ℃, and the deposition time is 30-90 min.
Further, the inert gas includes argon, and is not limited thereto.
In some more specific embodiments, the preparation method comprises: further comprising: before the chromium-iridium transition layer is formed through deposition, the surface of the substrate is etched.
Further, the etching process includes: etching the substrate for 30-60 min at room temperature by adopting an Ar ion etching method; the etching treatment adopts the following process conditions: the gas pressure of the reaction cavity is 2.0 x 10-5The argon flow is 40-100 sccm and the bias voltage is-150 to-450V below Torr, and the Ar ion etching method comprises glow etching and/or ion beam etching.
In some more specific embodiments, the preparation method comprises: the metal bipolar plate includes a stainless steel bipolar plate or a titanium alloy bipolar plate, and is not limited thereto.
The invention adopts high-power pulse magnetron sputtering technology, and has the technical characteristics of improving the ionization rate, refining crystal grains and ensuring that the surface of the prepared protective coating is smooth and the internal structure is compact.
The embodiment of the invention also provides application of the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating in preparing a bipolar plate for a proton exchange membrane fuel cell or a proton exchange membrane fuel cell.
In another aspect, the embodiment of the invention further provides a bipolar plate for a proton exchange membrane fuel cell, which comprises a metal bipolar plate, wherein the metal bipolar plate is coated with the high-conductivity corrosion-resistant graphite carbon protection multilayer composite coating.
In another aspect of the embodiments of the present invention, a proton exchange membrane fuel cell is further provided, which includes the bipolar plate for a proton exchange membrane fuel cell.
In another aspect of the embodiment of the invention, the material comprises a substrate, and the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating is further arranged on the substrate.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
In this embodiment, the preparation method of the metal bipolar plate high-conductivity corrosion-resistant protective coating is as follows:
s1, selecting 316L stainless steel as base, ultrasonic cleaning the stainless steel bipolar plate, drying, placing into a vacuum chamber, fixing on a workpiece bracket, and vacuumizing to 2.0 × 10-5 Turning on an ion source under the conditions that the argon flow is 100sccm and the bias voltage is-450V, adjusting the output voltage to 1200V, and etching the surface of the stainless steel bipolar plate for 60min by using argon plasma;
s2, introducing Ar gas into the cavity (the introduction amount of the Ar gas is 30 sccm), maintaining the air pressure of the cavity to be 1.4mTorr by adopting a high-power pulse magnetron sputtering technology, turning on a high-power pulse power supply connected with the chromium-iridium composite sputtering target (the iridium content is 2 wt%), setting the power supply frequency to be 400Hz, the pulse width to be 50 mus, the pulse voltage to be 1000V, the power to be 3.0KW, the substrate bias voltage to be-50V, the deposition temperature to be 50 ℃, and depositing a chromium-iridium transition layer with the thickness of 150 nm;
and S3, continuously introducing Ar gas into the cavity (the introduction amount of the Ar gas is 70 sccm), adopting a direct-current magnetron sputtering technology, maintaining the air pressure of the cavity to be 2.1mTorr, turning on a direct-current power supply connected with the graphite sputtering target, setting the power to be 0.9KW, the bias voltage to be-100V, the deposition temperature to be 50 ℃, and depositing a graphite-like amorphous carbon layer with the thickness of 500nm, thereby obtaining the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
The corrosion current density is 1.2 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The as-deposited contact resistance is 5.8m omega cm2And the contact resistance is 8.5m omega cm after 24h of corrosion2And the contact resistance is 9.5m omega cm after 48h of corrosion2。
Example 2
In this embodiment, the preparation method of the metal bipolar plate high-conductivity corrosion-resistant protective coating is as follows:
s1, selecting 316L stainless steel as base, ultrasonic cleaning the stainless steel bipolar plate, drying, placing into a vacuum chamber, fixing on a workpiece bracket, and vacuumizing to 2.0 × 10-5 Turning on an ion source under the conditions that the argon flow is 40sccm and the bias voltage is-150V, adjusting the output voltage to 1200V, and etching the surface of the stainless steel bipolar plate for 30min by using argon plasma;
s2, introducing Ar gas into the cavity (the introduction amount of the Ar gas is 60 sccm), maintaining the air pressure of the cavity to be 2.0mTorr by adopting a high-power pulse magnetron sputtering technology, turning on a high-power pulse power supply connected with the chromium-iridium composite sputtering target (the iridium content is 10 wt%), setting the power supply frequency to be 800Hz, the pulse width to be 100 mus, the pulse voltage to be 800V, the power to be 3.5KW, the substrate bias voltage to be-80V, the deposition temperature to be 40 ℃, and depositing a chromium-iridium transition layer with the thickness of 200 nm;
s3, continuously introducing Ar gas into the cavity (the introduction amount of the Ar gas is 30 sccm), adopting a direct-current magnetron sputtering technology, maintaining the air pressure of the cavity to be 1.4mTorr, turning on a direct-current power supply connected with the graphite sputtering target, setting the power to be 1.2KW, the bias voltage to be-250V, the deposition temperature to be 40 ℃, and depositing a graphite-like amorphous carbon layer with the thickness of 800nm, thereby obtaining the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
The corrosion current density is 1.3 multiplied by 10 under the standard working voltage of 0.6V through testing-8A/cm2The as-deposited contact resistance is 5.9m omega cm2And the contact resistance is 8.2m omega cm after 24h of corrosion2And the contact resistance is 9.1m omega cm after 48h of corrosion2。
Example 3
In this embodiment, the preparation method of the metal bipolar plate high-conductivity corrosion-resistant protective coating is as follows:
s1, ultrasonic cleaning the Ti alloy bipolar plate, drying, putting it in vacuum chamber, fixing it on workpiece carrier, vacuumizing to 2.0X 10-5 Turning on an ion source under the conditions that the argon flow is 65sccm and the bias voltage is-250V, adjusting the output voltage to 1200V, and etching the surface of the stainless steel bipolar plate for 60min by using argon plasma;
s2, introducing Ar gas into the cavity (the introduction amount of the Ar gas is 70 sccm), maintaining the air pressure of the cavity to be 2.1mTorr by adopting a high-power pulse magnetron sputtering technology, turning on a high-power pulse power supply connected with the chromium-iridium composite sputtering target (the iridium content is 5 wt%), setting the power supply frequency to be 500Hz, the pulse width to be 200 mus, the pulse voltage to be 1000V, the power to be 2.0KW, the substrate bias voltage to be-150V, the deposition temperature to be 80 ℃, and depositing a chromium-iridium transition layer with the thickness of 100 nm;
s3, continuously introducing Ar gas into the cavity (the introduction amount of the Ar gas is 40 sccm), adopting a direct-current magnetron sputtering technology, maintaining the air pressure of the cavity to be 1.7mTorr, turning on a direct-current power supply connected with the graphite sputtering target, setting the power to be 0.9KW, the bias voltage to be-50V, the deposition temperature to be 80 ℃, and depositing a graphite-like amorphous carbon layer with the thickness of 600nm, thereby obtaining the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
The corrosion current density is 1.1 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The as-deposited contact resistance is 5.7m omega cm2Contact resistance after 24h of etchingIs 8.9m omega cm2And the contact resistance is 9.8m omega cm after 48h of corrosion2。
Example 4
In this embodiment, the preparation method of the metal bipolar plate high-conductivity corrosion-resistant protective coating is as follows:
s1, ultrasonic cleaning the Ti alloy bipolar plate, drying, putting it in vacuum chamber, fixing it on workpiece carrier, vacuumizing to 2.0X 10-5 Turning on an ion source under the conditions that the argon flow is 70sccm and the bias voltage is-300V, adjusting the output voltage to 1200V, and etching the surface of the stainless steel bipolar plate for 45min by using argon plasma;
s2, introducing Ar gas (the introduction amount of the Ar gas is 50 sccm) into the cavity, maintaining the air pressure of the cavity to be 1.7mTorr by adopting a high-power pulse magnetron sputtering technology, turning on a high-power pulse power supply connected with the chromium-iridium composite sputtering target (the iridium content is 6 wt%), setting the power supply frequency to be 600Hz, the pulse width to be 100 mus, the pulse voltage to be 900V, the power to be 3.0KW, the substrate bias voltage to be-60V, the deposition temperature to be 60 ℃, and depositing a chromium-iridium transition layer with the thickness of 150 nm;
and S3, continuously introducing Ar gas into the cavity (the introduction amount of the Ar gas is 50 sccm), adopting a direct-current magnetron sputtering technology, maintaining the air pressure of the cavity to be 1.7mTorr, turning on a direct-current power supply connected with the graphite sputtering target, setting the power to be 1.0KW, the bias voltage to be-150V, the deposition temperature to be 60 ℃, and depositing a graphite-like amorphous carbon layer with the thickness of 600nm so as to obtain the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
The corrosion current density is 1.2 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The as-deposited contact resistance is 5.7m omega cm2And the contact resistance is 8.3m omega cm after 24h of corrosion2And the contact resistance is 9.6m omega cm after 48h of corrosion2。
Example 5
In this embodiment, the preparation method of the metal bipolar plate high-conductivity corrosion-resistant protective coating is as follows:
and S1, selecting titanium alloy as a substrate, ultrasonically cleaning the titanium alloy bipolar plate, drying, placing the titanium alloy bipolar plate into a vacuum chamber, fixing the titanium alloy bipolar plate on a workpiece bracket, and vacuumizing to 2.0×10-5 Turning on an ion source under the conditions that the argon flow is 55sccm and the bias voltage is-200V, adjusting the output voltage to 1200V, and etching the surface of the stainless steel bipolar plate for 45min by using argon plasma;
s2, introducing Ar gas (the introduction amount of the Ar gas is 70 sccm) into the cavity, maintaining the air pressure of the cavity to be 2.1mTorr by adopting a high-power pulse magnetron sputtering technology, turning on a high-power pulse power supply connected with the chromium-iridium composite sputtering target (the iridium content is 3 wt%), setting the power supply frequency to be 700Hz, the pulse width to be 150 mus, the pulse voltage to be 900V, the power to be 3.0KW, the substrate bias voltage to be-100V, the deposition temperature to be 70 ℃, and depositing a chromium-iridium transition layer with the thickness of 150 nm;
and S3, continuously introducing Ar gas into the cavity (the introduction amount of the Ar gas is 35 sccm), adopting a direct-current magnetron sputtering technology, maintaining the air pressure of the cavity at 1.5mTorr, turning on a direct-current power supply connected with the graphite sputtering target, setting the power at 1.0KW, the bias voltage at-150V, the deposition temperature at 70 ℃, and depositing a graphite-like amorphous carbon layer with the thickness of 700nm, thereby obtaining the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
The corrosion current density is 1.1 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The as-deposited contact resistance is 5.6m omega cm2And the contact resistance is 8.6m omega cm after 24h of corrosion2And the contact resistance is 9.7m omega cm after 48h of corrosion2。
Comparative example 1
In this example, which is a comparative example of example 1, steps S1 and S3 are exactly the same as example 1, and in step S2, a chromium sputtering target is used as a sputtering target, and other parameters are the same as example 1.
Comparative example 2
In this example, which is a comparative example of example 1, steps S1 and S3 are exactly the same as example 1, and in step S2, a chromium-iridium composite sputtering target (iridium content: 20%) is used as a sputtering target material, and other parameters are the same as example 1.
And (3) performance test comparison:
the corrosion resistance of the sample is measured by adopting a three-electrode electrochemical testing system, and the solution is 0.5M H2SO4+5ppm HF solution at a temperature ofThe measurement results are shown in FIG. 2 at 80 ℃. As can be seen from fig. 2: example 1 the sample has a corrosion current density of 1.9X 10 at a standard working voltage of 0.6V-8A/cm2Compared with the standard of the United states department of energy (DOE 2020) 1 multiplied by 10-6A/cm2Reduced by about 2 orders of magnitude, and the corrosion current density of the sample of comparative example 1 is 2.9X 10 at the standard working voltage of 0.6V- 7A/cm2Comparative example 2 sample having a corrosion current density of 6.9X 10 at a standard working voltage of 0.6V-6A/cm2The corrosion current density of the examples is significantly reduced compared to the two comparative examples, indicating that the coatings prepared by the examples of the invention have better corrosion resistance.
The contact resistance test was carried out by applying an assembly pre-tightening force of 1.5MPa to the surface of the sample, and the result is shown in FIG. 3, in which the contact resistance in the as-deposited state (i.e., the highly conductive and corrosion resistant graphite-like carbon protective multilayer composite coating) in example 1 was 5.4m Ω. cm2After 24h of corrosion, the contact resistance is slightly increased to 8.3m omega cm2After 48h of corrosion, the contact resistance increased slightly to 9.2m omega cm2Less than 10m omega cm meeting the standard requirement of the United states department of energy2The as-deposited (i.e., coated) contact resistance in comparative example 1 was 8.7m Ω. cm2After 24h of corrosion, the contact resistance is increased to 11.3m omega cm2After 48h of corrosion, the contact resistance is increased to 33.4m omega cm2In comparative example 2, the as-deposited (i.e., coated) contact resistance was 7.9 m.OMEGA.cm2After 24h of corrosion, the contact resistance is increased to 11.8m omega cm2After 48h of corrosion, the contact resistance is increased to 26.7m omega cm2The contact resistance of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating in the example 1 and the contact resistance after 24 hours of corrosion are lower than those of the two comparative examples, and only the contact resistance of the example rises to the minimum extent along with the increase of the corrosion time, and only the example can meet the DOE2020 standard, so that the initial conductivity of the example is proved to be better, and the performance of the example is influenced to a smaller extent by long-time corrosion.
Comparative example 3
This example was a comparative example of example 1, steps S1 and S3 were exactly the same as example 1, and in step S2, the sputtering source was changed to dc magnetron sputtering, and other parameters were the same as example 1.
And (3) performance test comparison:
FIGS. 4 a-4 b are surface topographies of example 1 and comparative example 3, respectively, as determined by scanning electron microscopy analysis: the smooth structure of the surface of the protective multilayer composite coating prepared in example 1 is compact, and the surface of the coating prepared in comparative example 3 is rough and has cracks, and the result shows that the surface of the coating prepared in example 1 by high-power pulse magnetron sputtering is smoother and more compact, and further shows that the coating in example 1 has better protective performance.
Fig. 5a to 5b are scratch patterns of the bonding force of the coatings prepared in example 1 and comparative example 3 of the present invention, respectively, and it can be seen that the coating prepared in example 1 has stronger bonding force.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.

Claims (10)

1. A high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating is characterized by comprising a chromium-iridium transition layer and a graphite-like amorphous carbon layer which are sequentially formed on the surface of a substrate; wherein the content of iridium element in the chromium-iridium transition layer is 2-10 wt%; and the corrosion current density of the high-conductivity corrosion-resistant graphite carbon protective multilayer composite coating is less than 5 multiplied by 10 under the standard working voltage of 0.6V-8A/cm2The contact resistance in the deposition state is less than 7m omega cm2And the contact resistance is less than 10m omega cm after 24h of corrosion2And the contact resistance is increased within 5% after 48h of corrosion.
2. The highly conductive corrosion-resistant graphitic carbon protective multilayer composite coating according to claim 1, characterized in that: the thickness of the chromium-iridium transition layer is 100-200 nm;
the thickness of the graphite-like amorphous carbon layer is 500-800 nm.
3. The highly conductive corrosion-resistant graphitic carbon protective multilayer composite coating according to claim 1, characterized in that: the substrate comprises a metallic bipolar plate.
4. A method for preparing a highly conductive corrosion-resistant graphite-like carbon protective multilayer composite coating according to any one of claims 1 to 3, comprising:
providing a metal bipolar plate as a substrate;
depositing a chromium-iridium transition layer on the surface of the substrate by adopting a high-power pulse magnetron sputtering technology and taking a chromium-iridium composite target as a target material, wherein the content of iridium element in the chromium-iridium composite target is 2-10 wt%;
and depositing a graphite-like amorphous carbon layer on the surface of the chromium-iridium transition layer by adopting a direct-current magnetron sputtering technology and taking a graphite target as a target material, thereby obtaining the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating.
5. The method for preparing the highly conductive corrosion-resistant graphite-like carbon protective multilayer composite coating according to claim 4, characterized by comprising: the method comprises the steps of placing a substrate in a reaction cavity by adopting a high-power pulse magnetron sputtering technology, depositing and forming a chromium-iridium transition layer on the surface of the substrate by taking a chromium-iridium composite target as a target material and an inert gas as a working gas, wherein the high-power pulse magnetron sputtering technology adopts the pulse frequency of 400-800 Hz, the pulse width of 50-200 microseconds, the pulse voltage of 800-1000V, the power of 2.0-3.5 KW, the air pressure of the reaction cavity of 1.4-2.1 mTorr, the bias voltage of the substrate of-50V-150V, the introduction amount of the inert gas of 30-70 sccm, the deposition temperature of 40-80 ℃ and the deposition time of 5-15 minutes.
6. The method for preparing the highly conductive corrosion-resistant graphite-like carbon protective multilayer composite coating according to claim 4, characterized by comprising: and depositing on the surface of the chromium-iridium transition layer to form a graphite-like amorphous carbon layer by adopting a direct-current magnetron sputtering technology and taking a graphite target as a target material and inert gas as working gas, wherein the power of a sputtering source is 0.9-1.2 kW, the air pressure of a reaction cavity is 1.4-2.1 mTorr, the bias voltage of a matrix is-50V-250V, the introduction amount of the inert gas is 30-70 sccm, the deposition temperature is 40-80 ℃, and the deposition time is 30-90 min.
7. The method for preparing the highly conductive corrosion-resistant graphite-like carbon protective multilayer composite coating according to claim 4, further comprising: before the chromium-iridium transition layer is formed, the surface of the substrate is etched.
8. The method for preparing the highly conductive corrosion-resistant graphite-like carbon protective multilayer composite coating according to claim 7, wherein the etching treatment comprises: etching the substrate for 30-60 min at room temperature by adopting an Ar ion etching method; the etching treatment adopts the following process conditions: the gas pressure of the reaction cavity is 2.0 x 10-5The argon flow is 40-100 sccm and the bias voltage is-150 to-450V below Torr, and the Ar ion etching method comprises glow etching and/or ion beam etching.
9. The method for preparing the high-conductivity corrosion-resistant graphite-like carbon protective multilayer composite coating according to claim 4, characterized in that: the metal bipolar plate comprises a stainless steel bipolar plate or a titanium alloy bipolar plate.
10. A bipolar plate for a proton exchange membrane fuel cell, comprising a metallic bipolar plate, characterized in that it is coated with a highly conductive corrosion-resistant graphitic carbon protective multilayer composite coating according to any one of claims 1 to 3.
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