CN114540752B - Fuel cell metal polar plate with conductive corrosion-resistant coating and preparation method thereof - Google Patents

Fuel cell metal polar plate with conductive corrosion-resistant coating and preparation method thereof Download PDF

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CN114540752B
CN114540752B CN202210206361.6A CN202210206361A CN114540752B CN 114540752 B CN114540752 B CN 114540752B CN 202210206361 A CN202210206361 A CN 202210206361A CN 114540752 B CN114540752 B CN 114540752B
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titanium nitride
metal
silver
nitride layer
target
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CN114540752A (en
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邵文婷
王瑜
陈建
杨巍
刘曜
何佳华
卢帅丹
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Xian Technological University
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Xian Technological University
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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
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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 fuel cell metal polar plate with a conductive corrosion-resistant coating and a preparation method thereof, and the metal polar plate is subjected to plasma cleaning on a metal matrix under vacuum condition; sequentially depositing a pure titanium layer, a titanium nitride layer and a silver-doped titanium nitride layer on the metal substrate subjected to plasma cleaning by adopting a magnetron sputtering method; the magnetron sputtering method is to periodically perform magnetron sputtering by adopting a direct current power supply or a radio frequency power supply; taking the metal matrix deposited with the pure titanium layer, the titanium nitride layer and the silver-doped titanium nitride layer as a fuel cell metal polar plate; according to the invention, the conductive corrosion-resistant coating with the equiaxial crystal structure is periodically and sequentially deposited on the metal substrate by the magnetron sputtering method, so that corrosive medium in the fuel cell environment can be effectively prevented from contacting with the metal polar plate; the self-escaping path of silver in the silver-doped titanium nitride coating is effectively prolonged, and the self-escaping of silver in the silver-doped titanium nitride coating is restrained; and further, the graphite plate is replaced by the metal polar plate, and the thickness of the PEMFC polar plate is reduced.

Description

Fuel cell metal polar plate with conductive corrosion-resistant coating and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a fuel cell metal polar plate with a conductive corrosion-resistant coating and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are considered as the terminal power of new energy automobiles because of their high conversion efficiency, no pollution, fast start-up, etc. Most of the traditional PEMFC bipolar plates are graphite plates with single plates of which the thickness is 2mm, and the thickness is large, so that the technical updating requirements of the small volume and high energy density of the automobile battery pack are difficult to meet.
The metal polar plate with the thickness of less than 0.5mm is used for replacing the traditional graphite plate with the thickness of 2mm, which is an effective way for realizing the reduction of the scale and the weight of the fuel cell for the vehicle, but the service life of the PEMFC is seriously influenced because the metal polar plate is extremely easy to passivate and corrode.
Disclosure of Invention
The invention aims to provide a fuel cell metal polar plate with a conductive corrosion-resistant coating and a preparation method thereof, which reduce the thickness of a PEMFC polar plate so as to realize the reduction of the scale and the weight of a fuel cell for a vehicle.
The invention adopts the following technical scheme: the preparation method of the fuel cell metal polar plate with the conductive corrosion-resistant coating comprises the following steps:
plasma cleaning is carried out on the metal matrix under the vacuum condition;
sequentially depositing a pure titanium layer, a titanium nitride layer and a silver-doped titanium nitride layer on the metal substrate subjected to plasma cleaning by adopting a magnetron sputtering method; the magnetron sputtering method is to periodically perform magnetron sputtering by adopting a direct current power supply or a radio frequency power supply;
when a pure titanium layer is deposited, a Ti target is used as a sputtering source, and argon is used as a working gas; when depositing the titanium nitride layer, taking a Ti target as a sputtering source and argon and nitrogen as working gases; when depositing the silver-doped titanium nitride layer, taking a Ti target and an Ag target as sputtering sources and taking argon and nitrogen as working gases;
and taking the metal matrix deposited with the pure titanium layer, the titanium nitride layer and the silver-doped titanium nitride layer as a fuel cell metal polar plate.
Further, when depositing a pure titanium layer:
the pressure in the vacuum cavity is 0.5-0.8 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of the Ti target is 100-200W, the bias voltage of the metal matrix is-250-100V, the temperature of the metal matrix is less than or equal to 200 ℃, and T on For 5-15 min, T off 2-5 min, and the total sputtering time is 5-15 min;
wherein T is on For the sputtering time of the target material, T off To stop the sputtering time of the target material, and T on Less than or equal to the total sputtering time, when T on Equal to the total sputtering time T off Is 0.
Further, when depositing the titanium nitride layer:
the pressure in the vacuum cavity is 0.8-1.0 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of Ti target is 100-200W, the bias voltage of the metal matrix is-250 to-100V, the temperature of the metal matrix is less than or equal to 300 ℃, T on 5-20 min, T off 2-10 min, and the total sputtering time is 10-20 min.
Further, when depositing the silver-doped titanium nitride layer:
the pressure in the vacuum cavity is 0.8-1.0 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of Ti target is 100-200W, ag, the power of target is 20-50W, the bias voltage of the metal matrix is-250 to-100V, the temperature of the metal matrix is 300-400 ℃, and T is the same as that of the metal matrix on Is 5 to 60min, T off 2-10 min, and the total sputtering time is 120-300 min;
wherein T is on For the sputtering time of the target material, T off To stop the sputtering time of the target;
the power of the Ag target is gradually increased during the deposition of the silver-doped titanium nitride layer.
Further, plasma cleaning the metal substrate under vacuum conditions includes:
the air pressure in the vacuum cavity is 0.5Pa, the bias voltage of the metal matrix is-400V, the temperature of the metal matrix is 100 ℃, and the cleaning time is 10-30 min.
Further, before the metal substrate is subjected to plasma cleaning under the vacuum condition, the method further comprises the following steps:
putting the metal matrix into a solution containing an oil removing agent, and carrying out ultrasonic oil removing treatment for 5-10 min;
ultrasonically cleaning the deoiled metal matrix in deionized water for 2-3 times, wherein each cleaning time is 3-5 min;
and ultrasonically cleaning the metal matrix subjected to ultrasonic cleaning in absolute ethyl alcohol for 2-3 times, wherein each time of cleaning is 3-5 min.
Further, the distance between the metal matrix and the target material in the pulse magnetron sputtering method is 60-90 mm.
Another technical scheme of the invention is as follows: the fuel cell metal polar plate with the conductive corrosion-resistant coating is manufactured by adopting the manufacturing method, and comprises a metal matrix and the conductive corrosion-resistant coating deposited on the surface of the metal matrix, wherein the conductive corrosion-resistant coating sequentially comprises a pure titanium layer, a titanium nitride layer and a silver-doped titanium nitride layer; the pure titanium layer is connected with the surface of the metal matrix;
wherein, the pure titanium layer, the titanium nitride layer and the silver-doped titanium nitride layer are all equiaxed crystal structures.
Further, the thickness of the metal matrix is less than or equal to 0.5mm, and the thickness of the conductive corrosion-resistant coating is 1-5 mu m.
Further, the nitrogen element content in the titanium nitride layer gradually increases along a first direction, and the first direction points to the silver-doped titanium nitride layer from the metal matrix;
the silver element content in the silver-doped titanium nitride layer gradually increases along the first direction.
The beneficial effects of the invention are as follows: according to the invention, the pure titanium layer, the titanium nitride layer and the silver-doped titanium nitride layer which are in equiaxed crystal structures are periodically deposited on the metal substrate in sequence through the magnetron sputtering method, so that columnar interfaces penetrating through the whole thickness of the conductive corrosion-resistant coating do not exist, the density of the coating is increased, the defect density is reduced, the corrosive medium in the fuel cell environment can be effectively prevented from contacting with the metal polar plate, and the contact resistance of the coating is reduced; the silver in the silver-doped titanium nitride coating is uniformly distributed at the cluster interface of the equiaxed crystal silver-doped titanium nitride coating, so that the path of spontaneous escape of the silver in the silver-doped titanium nitride coating is effectively prolonged, and spontaneous escape of the silver in the silver-doped titanium nitride coating is inhibited; and further, the graphite plate is replaced by the metal polar plate, and the thickness of the PEMFC polar plate is reduced.
Drawings
FIG. 1 is a schematic view of a portion of a fuel cell metal plate having a conductive corrosion resistant coating according to an embodiment of the present invention;
FIG. 2 is an electron micrograph of a conductive corrosion resistant coating of a metal plate of a fuel cell having a conductive corrosion resistant coating according to example 1 of the present invention;
fig. 3 is an electron microscope image of a conductive corrosion-resistant coating of a metal plate of a fuel cell with a conductive corrosion-resistant coating prepared by a conventional magnetron sputtering process.
Wherein: 10. a metal matrix;
20. a conductive corrosion resistant coating; 21. a silver-doped titanium nitride layer; 22. a titanium nitride layer; 23. a pure titanium layer.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
Because the metal polar plate is an effective way for reducing the battery scale and the weight, the problem that the metal polar plate is easy to passivate and corrode needs to be solved. The invention seeks a method for preparing a layer of conductive corrosion-resistant coating on the surface of a metal polar plate, and the problem of passivation and corrosion of the metal polar plate is prevented by the conductive corrosion-resistant coating, so that a new technical path is provided for reducing the scale and the weight of the fuel cell for the vehicle.
Titanium nitride coatings are widely focused on by researchers with excellent conductivity and corrosion resistance, but titanium nitride coatings prepared by a magnetron sputtering method are of a typical columnar crystal structure, and have high defect density, so that contact resistance is high. The incorporation of metallic silver is effective in reducing the contact resistance of titanium nitride coatings, but the spontaneous escape behavior of silver limits the application of this approach to reducing the contact resistance of coatings by silver incorporation.
Therefore, the research on the method for inhibiting the spontaneous escape of silver in the silver-doped titanium nitride coating has important scientific significance and engineering value for the metallization of the fuel cell electrode plate, and provides theoretical basis and experimental support for the subsequent development of the fuel cell metal electrode plate.
The invention discloses a preparation method of a fuel cell metal polar plate with a conductive corrosion-resistant coating, which comprises the following steps: plasma cleaning is carried out on the metal matrix under the vacuum condition; sequentially depositing a pure titanium layer, a titanium nitride layer and a silver-doped titanium nitride layer on the metal substrate subjected to plasma cleaning by adopting a magnetron sputtering method; the magnetron sputtering method is to periodically perform magnetron sputtering by adopting a direct current power supply or a radio frequency power supply; in the method, the distance between the metal matrix and the target material in the pulse magnetron sputtering method is 60-90 mm. When a pure titanium layer is deposited, a Ti target is used as a sputtering source, and argon is used as a working gas; when depositing the titanium nitride layer, taking a Ti target as a sputtering source and argon and nitrogen as working gases; when depositing the silver-doped titanium nitride layer, taking a Ti target and an Ag target as sputtering sources and taking argon and nitrogen as working gases; and taking the metal matrix deposited with the pure titanium layer, the titanium nitride layer and the silver-doped titanium nitride layer as a fuel cell metal polar plate.
According to the invention, through a periodic magnetron sputtering method, a pure titanium layer, a titanium nitride layer and a silver-doped titanium nitride layer with equiaxed crystal structures can be sequentially deposited on a metal substrate, so that the traditional columnar crystal structure coating is changed, a columnar interface penetrating through the whole thickness of the coating does not exist in the conductive corrosion-resistant coating, the density of the coating is increased, the defect density is reduced, a corrosive medium in the fuel cell environment can be effectively prevented from contacting with a metal polar plate, and the contact resistance of the coating is reduced; the silver in the silver-doped titanium nitride coating is uniformly distributed at the cluster interface of the equiaxed crystal silver-doped titanium nitride coating, so that the path of spontaneous escape of the silver in the silver-doped titanium nitride coating is effectively prolonged, and spontaneous escape of the silver in the silver-doped titanium nitride coating is inhibited; and further, the graphite plate is replaced by the metal polar plate, and the thickness of the PEMFC polar plate is reduced.
In one embodiment, the method further comprises, prior to plasma cleaning the metal substrate under vacuum: putting the metal matrix into a solution containing an oil removing agent, and carrying out ultrasonic oil removing treatment for 5-10 min; ultrasonically cleaning the deoiled metal matrix in deionized water for 2-3 times, wherein each cleaning time is 3-5 min; and ultrasonically cleaning the metal matrix subjected to ultrasonic cleaning in absolute ethyl alcohol for 2-3 times, wherein each time of cleaning is 3-5 min.
As a specific implementation, plasma cleaning of a metal substrate under vacuum conditions includes: the air pressure in the vacuum cavity is 0.5Pa, the bias voltage of the metal matrix is-400V, the temperature of the metal matrix is 100 ℃, and the cleaning time is 10-30 min.
In the technical scheme of the invention, when a pure titanium layer is deposited: the pressure in the vacuum cavity is 0.5-0.8 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of the Ti target is 100-200W, the bias voltage of the metal matrix is-250-100V, the temperature of the metal matrix is less than or equal to 200 ℃, and T on 5-15 min, T off 2-5 min, and the total sputtering time is 5-15 min; wherein T is on For the sputtering time of the target material, T off To stop the sputtering time of the target material, and T on Less than or equal to the total sputtering time, when T on Equal to the total sputtering time T off Is 0.
In one embodiment, when depositing the titanium nitride layer: the pressure in the vacuum cavity is 0.8-1.0 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of Ti target is 100-200W, the bias voltage of the metal matrix is-250 to-100V, the temperature of the metal matrix is less than or equal to 300 ℃, T on 5-20 min, T off 2-10 min, and the total sputtering time is 10-20 min.
In one embodiment, when depositing the silver-doped titanium nitride layer: the pressure in the vacuum cavity is 0.8-1.0 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of Ti target is 100-200W, ag, the power of target is 20-50W, the bias voltage of the metal matrix is-250 to-100V, the temperature of the metal matrix is 300-400 ℃, and T is the same as that of the metal matrix on For 5-60 min, T off 2-10 min, and the total sputtering time is 120-300 min; wherein T is on For the sputtering time of the target material, T off To stop the sputtering time of the target; the power of the Ag target is gradually increased during the deposition of the silver-doped titanium nitride layer.
Example 1:
the embodiment is a preparation method of a fuel cell metal polar plate with a conductive corrosion-resistant coating, which adopts a stainless steel substrate (namely a stainless steel polar plate) as a metal substrate, and the thickness is 0.5mm, and the specific preparation method is as follows:
(1) Pretreatment of a metal matrix: placing the stainless steel polar plate into a solution containing an oil removing agent, and carrying out ultrasonic oil removing treatment for 5min; and ultrasonically cleaning the deoiled stainless steel polar plate in deionized water for 2 times, each time for 3min, and then ultrasonically cleaning in absolute ethyl alcohol for 2 times, each time for 3min, and drying for later use.
(2) Coating deposition preparation: and (5) conveying the cleaned stainless steel polar plate into a vacuum cavity filled with a Ti target and an Ag target, wherein the target base distance is 90mm. Vacuumizing to 3×10 -3 After Pa, argon gas of 60sccm was introduced to maintain the pressure in the vacuum chamber at about 0.5Pa, and plasma cleaning was performed at a temperature of 100℃for 10 minutes under a bias of-400V for the stainless steel plate.
(3) Preparing a pure titanium layer: the Ti target power is 100W, the stainless steel polar plate bias voltage is-250V, the temperature is 150 ℃, and the magnetron sputtering time T in each period on A stop time T of magnetron sputtering in each period of 5min off 2min, co-sputtering a pure Ti layer for 5min (namely, magnetron sputtering is only needed for one period, and no stop time exists in the period), continuously introducing argon in the deposition process, ensuring that the air pressure in the vacuum cavity is 0.5Pa, and ensuring that the rotating speed of the workpiece frame is 5r/min in the preparation process.
(3) Preparing a titanium nitride layer: the Ti target power is 100W, the stainless steel polar plate bias voltage is-250V, the temperature is 250 ℃, and the magnetron sputtering time T in each period on A stop time T of magnetron sputtering in each period of 5min off The total sputtering deposition time is 2min, namely the total sputtering deposition time is 10min (namely 2 periods of magnetron sputtering, wherein the magnetron sputtering is carried out for 5min in the first period and then is stopped for 2min, and the magnetron sputtering is carried out for 5min in the second period), so that the titanium nitride layer is obtained, argon and nitrogen are continuously introduced in the deposition process (the flow of the nitrogen is continuously increased in the process), the air pressure in the vacuum chamber is ensured to be 0.8Pa, and the rotating speed of the workpiece frame in the preparation process is 5r/min.
(4) Preparing a silver-doped titanium nitride layer: maintaining the power of the Ti target as 100W, ag target power as 20W (i.e. the power of the Ag target gradually increases from 0W to 20W), the bias voltage of the stainless steel polar plate as-250V, the temperature as 300 ℃, the air pressure in the vacuum cavity as 0.8Pa, the rotating speed of the workpiece frame as 5r/min, and T on 5min, T off For 2min, the total sputtering time is 120min (i.e. each period of magnetron sputtering is 5min, then stopping for 2min, then continuing the next magnetron sputtering period until the total magnetron sputtering time is 120 min), thus obtaining the stainless steel polar plate with the conductive corrosion resistant coating, namely the stainless steel with the conductive corrosion resistant coatingAnd manufacturing a fuel cell metal polar plate by using the steel substrate.
In this example, the conductive corrosion-resistant coating was measured to have a thickness of 1. Mu.m, and the surface contact resistance of the fuel cell metal plate was 5mΩ. Cm 2 Corrosion current density is 9.238 ×10 -8 A.cm -2 . As shown in fig. 2, compared with the electron microscope image of the metal electrode plate of the fuel cell prepared by the embodiment shown in fig. 3 (the electron microscope image of the metal electrode plate of the fuel cell prepared by the traditional method), the Ti layer, the TiN layer and the silver-doped titanium nitride layer of the metal electrode plate of the fuel cell prepared by the embodiment are all in equiaxed crystal structures, no columnar interface penetrating the whole thickness of the coating exists, and silver in the silver-doped titanium nitride coating is uniformly distributed on the cluster interface of the equiaxed crystal titanium nitride coating, so that the spontaneous escape path of silver in the silver-doped titanium nitride coating is effectively prolonged, and further the spontaneous escape of silver in the silver-doped titanium nitride coating can be effectively inhibited.
Example 2:
in this example, the metal substrate is a stainless steel substrate (i.e., stainless steel plate) having a thickness of 0.5mm. The preparation method comprises the following steps:
(1) Sample pretreatment: placing the stainless steel polar plate into a solution containing an oil removing agent, and carrying out ultrasonic oil removing treatment for 10min; and ultrasonically cleaning the deoiled stainless steel polar plate in deionized water for 3 times, wherein the cleaning time is 5min each time, ultrasonically cleaning in absolute ethyl alcohol for 3 times, and drying for later use each time for 5min.
(2) Coating deposition preparation: and (5) conveying the cleaned stainless steel polar plate into a vacuum cavity filled with the Ti target and the Ag target, wherein the target base distance is 60mm. Vacuumizing to 3×10 -3 After Pa, argon gas of 60sccm was introduced to maintain the pressure in the vacuum chamber at about 0.5Pa, and plasma cleaning was performed at a temperature of 100deg.C for 30min under a bias of-400V for the stainless steel plate.
(3) Preparing a pure titanium layer: ti target power of 200W, stainless steel plate bias of-100V, temperature of 200deg.C, T on Is 15min, T off Sputtering a pure Ti layer for 15min under the condition of 5min, continuously introducing argon in the deposition process, ensuring the air pressure in the vacuum cavity to be 0.8Pa, and ensuring the rotating speed of the workpiece frame to be 10r/min in the preparation process.
(3) Preparing a titanium nitride layer: ti target power of 200W, stainless steel plate bias of-100V, temperature 300 deg.C, T on Is 20min, T off And sputtering and depositing for 20min under the condition of 10min, obtaining a TiN coating on the surface of the pure titanium layer, continuously introducing argon and nitrogen in the deposition process (the flow of the nitrogen is continuously increased in the process), and ensuring that the air pressure in the vacuum cavity is 1.0Pa and the rotating speed of the workpiece frame in the preparation process is 10r/min.
(4) Preparing a silver-doped titanium nitride layer: maintaining the power of the Ti target at 200W W, ag target power at 50W (i.e. the power of the Ag target gradually increases from 0W to 50W), the bias voltage of the stainless steel polar plate at-100V, the temperature at 400 ℃, the air pressure in the vacuum cavity at 1.0Pa, the rotating speed of the workpiece frame at 10r/min, and T on Is 60min, T off And the total sputtering time is 300min, and the fuel cell metal polar plate is manufactured by the stainless steel substrate with the conductive corrosion-resistant coating.
The thickness of the conductive corrosion-resistant coating in this example was measured to be 5. Mu.m, and the surface contact resistance of the metal plate of the fuel cell was measured to be 8mΩ. Cm 2 Corrosion current density is 4.396 ×10 -8 A.cm -2 。
Example 3:
in this example, the metal substrate is a stainless steel substrate (i.e., stainless steel plate) having a thickness of 0.5mm. The preparation method comprises the following steps:
(1) Sample pretreatment: placing the stainless steel polar plate into a solution containing an oil removing agent, and carrying out ultrasonic oil removing treatment for 10min; and ultrasonically cleaning the deoiled stainless steel polar plate in deionized water for 2 times, wherein the cleaning time is 5min each time, and then ultrasonically cleaning in absolute ethyl alcohol for 2 times, wherein the cleaning time is 5min each time, and drying for later use.
(2) Coating deposition preparation: and (5) conveying the cleaned stainless steel polar plate into a vacuum cavity filled with the Ti target and the Ag target, wherein the target base distance is 70mm. Vacuumizing to 3×10 -3 After Pa, argon gas of 60sccm was introduced to maintain the pressure in the vacuum chamber at about 0.5Pa, and plasma cleaning was performed at a temperature of 100deg.C for 20min under a bias of-400V for the stainless steel plate.
(3) Preparing a Ti layer: ti target power of 150W and stainless steel plate bias200V, temperature 180 ℃, T on Is 10min, T off Sputtering for 10min of pure Ti layer under the condition of 3min, continuously introducing argon in the deposition process, ensuring the air pressure in the vacuum cavity to be 0.7Pa, and ensuring the rotating speed of the workpiece frame to be 8r/min in the preparation process.
(3) Preparing a TiN layer: ti target power of 150W, stainless steel plate bias of-200V, temperature of 280 deg.C, T on Is 10min, T off And (3) sputtering and depositing the TiN coating for 15min under the condition of 5min (namely, magnetron sputtering is stopped for 10min and is finished after the magnetron sputtering is continued for 5 min), continuously introducing argon and nitrogen in the deposition process (the flow of the nitrogen in the process is gradually increased), ensuring that the air pressure in the vacuum cavity is 0.9Pa, and the rotating speed of the workpiece frame in the preparation process is 8r/min.
(4) Preparing a silver-doped titanium nitride layer: maintaining the Ti target power at 150-W, ag target power at 30W, stainless steel polar plate bias at-200V, temperature at 350deg.C, vacuum chamber internal air pressure at 0.9Pa, workpiece frame rotation speed at 8r/min, T on 30min, T off And the total sputtering time is 240min for 5min, and the fuel cell metal polar plate is manufactured by the stainless steel substrate with the conductive corrosion-resistant coating.
The thickness of the conductive corrosion-resistant coating in this example was measured to be 3. Mu.m, and the surface contact resistance of the metal plate of the fuel cell was measured to be 4mΩ. Cm 2 Corrosion current density is 6.317 ×10 -8 A.cm -2 。
Example 4:
in this example, the metal substrate is a stainless steel substrate (i.e., stainless steel plate) having a thickness of 0.5mm. The preparation method comprises the following steps:
(1) Sample pretreatment: placing the stainless steel polar plate into a solution containing an oil removing agent, and carrying out ultrasonic oil removing treatment for 8min; and ultrasonically cleaning the deoiled stainless steel polar plate in deionized water for 3 times, wherein the cleaning time is 4min each time, ultrasonically cleaning in absolute ethyl alcohol for 3 times, and drying for later use, wherein the cleaning time is 4min each time.
(2) Coating deposition preparation: and (3) conveying the cleaned metal polar plate into a vacuum cavity filled with a Ti target and an Ag target, wherein the base distance of the target is 80mm. Vacuumizing to 3×10 -3 After Pa, argon with the pressure of 60sccm is introduced to maintain the pressure in the vacuum cavity at 0.5PaAbout, the plasma cleaning is carried out for 15min under the conditions that the bias voltage of the stainless steel polar plate is-400V and the temperature is 100 ℃.
(3) Preparing a Ti layer: ti target power of 200W, stainless steel plate bias of-200V, temperature of 200deg.C, T on Is 10min, T off Sputtering a pure Ti layer for 15min under the condition of 2min, continuously introducing argon in the deposition process, ensuring the air pressure in the vacuum cavity to be 0.7Pa, and ensuring the rotating speed of the workpiece frame to be 5r/min in the preparation process.
(3) Preparing a TiN layer: ti target power of 200W, stainless steel plate bias of-200V, temperature 300 deg.C, T on Is 10min, T off And sputtering and depositing a TiN coating for 15min under the condition of 2min, continuously introducing argon and nitrogen in the deposition process (the flow of the nitrogen in the process is gradually increased), and ensuring that the air pressure in the vacuum cavity is 0.9Pa and the rotating speed of the workpiece frame in the preparation process is 5r/min.
(4) Preparing a silver-doped titanium nitride layer: maintaining the Ti target power of 200-W, ag target power of 30W, stainless steel polar plate bias voltage of-200V, temperature of 400 ℃, air pressure in the vacuum cavity of 0.9Pa, workpiece frame rotating speed of 5r/min and T on 10min, T off And the total sputtering time is 120min for 2min, and the fuel cell metal polar plate is manufactured by the stainless steel substrate with the conductive corrosion-resistant coating.
The thickness of the conductive corrosion-resistant coating in this example was measured to be 2. Mu.m, and the surface contact resistance of the metal plate of the fuel cell was measured to be 5mΩ. Cm 2 Corrosion current density is 8.364 ×10 -8 A.cm -2 。
The invention adopts the sputtering method which is periodically carried out to evolve the titanium nitride coating from the traditional columnar crystal structure into an equiaxial crystal structure, thereby avoiding the formation of columnar crystal interfaces penetrating through the whole thickness of the coating, effectively preventing corrosive medium in the fuel cell environment from reaching the surface of the metal polar plate, and reducing the corrosion current density to 10 -8 A·cm -2 Simultaneously, the spontaneous escape of silver in the silver-doped titanium nitride coating can be inhibited, so that nano silver particles are uniformly distributed at the cluster interface of the isometric crystal titanium nitride coating to form a nano silver network structure, and the contact resistance is less than 10mΩ cm under the contact pressure of 1.5MPa -2 . The coating prepared by the method has conductivity and corrosion resistanceThe service life of the metal bipolar plate of the fuel cell can be prolonged, the preparation method is simple, and the conductive corrosion-resistant effect is good.
The invention also discloses a fuel cell metal polar plate with the conductive corrosion-resistant coating, which is prepared by adopting the preparation method, as shown in figure 1, the metal polar plate comprises a metal substrate 10 and a conductive corrosion-resistant coating 20 deposited on the surface of the metal substrate, wherein the conductive corrosion-resistant coating 20 sequentially comprises a pure titanium layer 23, a titanium nitride layer 22 and a silver-doped titanium nitride layer 21; the pure titanium layer 23 is connected with the surface of the metal matrix 10; wherein, the pure titanium layer 23, the titanium nitride layer 22 and the silver-doped titanium nitride layer 21 are all of equiaxed crystal structures. The thickness of the metal substrate 10 is 0.5mm or less, and the thickness of the conductive corrosion-resistant coating 20 is 1 to 5 μm.
In addition, the nitrogen element content in the titanium nitride layer 22 gradually increases along a first direction, which is directed from the metal base 10 to the silver-doped titanium nitride layer 21; the silver element content in the silver-doped titanium nitride layer 21 gradually increases in the first direction.
The conductive corrosion-resistant coating component is changed continuously in gradient from the Ti layer to the surface of the silver-doped titanium nitride layer, and the fuel cell metal polar plate with the conductive corrosion-resistant coating has the characteristics of conductivity and corrosion resistance, low contact resistance, corrosion resistance, good process stability and the like.

Claims (7)

1. The preparation method of the fuel cell metal polar plate with the conductive corrosion-resistant coating is characterized by comprising the following steps:
plasma cleaning is carried out on the metal matrix under the vacuum condition;
sequentially depositing a pure titanium layer, a titanium nitride layer and a silver-doped titanium nitride layer on the metal substrate subjected to plasma cleaning by adopting a magnetron sputtering method; the magnetron sputtering method is to periodically perform magnetron sputtering by adopting a direct current power supply or a radio frequency power supply;
when a pure titanium layer is deposited, a Ti target is used as a sputtering source, and argon is used as a working gas; when depositing the titanium nitride layer, taking a Ti target as a sputtering source and argon and nitrogen as working gases; when depositing the silver-doped titanium nitride layer, taking a Ti target and an Ag target as sputtering sources and taking argon and nitrogen as working gases;
taking the metal matrix deposited with the pure titanium layer, the titanium nitride layer and the silver-doped titanium nitride layer as a fuel cell metal polar plate;
when depositing the pure titanium layer:
the pressure in the vacuum cavity is 0.5-0.8 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of the Ti target is 100-200W, the bias voltage of the metal matrix is-250-100V, the temperature of the metal matrix is less than or equal to 200 ℃, and T on 5-15 min, T off 2-5 min, and the total sputtering time is 5-15 min;
wherein T is on For the sputtering time of the target material, T off To stop the sputtering time of the target material, and T on Less than or equal to the total sputtering time, when T on Equal to the total sputtering time T off Is 0;
when depositing the titanium nitride layer:
the pressure in the vacuum cavity is 0.8-1.0 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of Ti target is 100-200W, the bias voltage of the metal matrix is-250 to-100V, the temperature of the metal matrix is less than or equal to 300 ℃, T on 5-20 min, T off 2-10 min, and the total sputtering time is 10-20 min;
the flow of nitrogen is gradually increased in the process of depositing the titanium nitride layer;
when depositing the silver-doped titanium nitride layer:
the pressure in the vacuum cavity is 0.8-1.0 Pa, the rotating speed of the workpiece frame is 5-10 r/min, the power of Ti target is 100-200W, ag, the power of target is 20-50W, the bias voltage of the metal matrix is-250 to-100V, the temperature of the metal matrix is 300-400 ℃, and T is the same as that of the metal matrix on Is 5 to 60min, T off 2-10 min, and the total sputtering time is 120-300 min;
wherein T is on For the sputtering time of the target material, T off To stop the sputtering time of the target;
the power of the Ag target is gradually increased during the deposition of the silver-doped titanium nitride layer.
2. The method of preparing a metal plate for a fuel cell having a conductive corrosion resistant coating of claim 1, wherein plasma cleaning the metal substrate under vacuum comprises:
the air pressure in the vacuum cavity is 0.5Pa, the bias voltage of the metal matrix is-400V, the temperature of the metal matrix is 100 ℃, and the cleaning time is 10-30 min.
3. The method for preparing a metal plate for a fuel cell having a conductive corrosion resistant coating according to claim 2, further comprising, prior to plasma cleaning the metal substrate under vacuum:
putting the metal matrix into a solution containing an oil removing agent, and carrying out ultrasonic oil removing treatment for 5-10 min;
ultrasonically cleaning the deoiled metal matrix in deionized water for 2-3 times, wherein each cleaning time is 3-5 min;
and ultrasonically cleaning the metal matrix subjected to ultrasonic cleaning in absolute ethyl alcohol for 2-3 times, wherein each time of cleaning is 3-5 min.
4. The method for preparing a metal plate of a fuel cell with a conductive corrosion resistant coating according to claim 3, wherein the distance between the metal substrate and the target in the magnetron sputtering method is 60-90 mm.
5. The fuel cell metal polar plate with the conductive corrosion-resistant coating is characterized in that the fuel cell metal polar plate is manufactured by adopting the manufacturing method of any one of claims 1-4, the metal polar plate comprises a metal substrate (10) and a conductive corrosion-resistant coating (20) deposited on the surface of the metal substrate, and the conductive corrosion-resistant coating (20) sequentially comprises a pure titanium layer (23), a titanium nitride layer (22) and a silver-doped titanium nitride layer (21); the pure titanium layer (23) is connected with the surface of the metal matrix;
wherein, the pure titanium layer (23), the titanium nitride layer (22) and the silver-doped titanium nitride layer (21) are all of equiaxed crystal structures.
6. The fuel cell metal plate with conductive corrosion resistant coating according to claim 5, wherein the thickness of the metal base (10) is 0.5mm or less, and the thickness of the conductive corrosion resistant coating (20) is 1 to 5 μm.
7. The fuel cell metal plate with electrically conductive corrosion resistant coating according to claim 6, wherein the nitrogen element content in the titanium nitride layer (22) increases gradually along a first direction, which is directed from the metal substrate (10) to the silver-doped titanium nitride layer (21);
the silver element content in the silver-doped titanium nitride layer (21) gradually increases along a first direction.
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