CN109023282B - Preparation method for preparing CrMoTiN nitride film nano coating on surface of bipolar plate - Google Patents
Preparation method for preparing CrMoTiN nitride film nano coating on surface of bipolar plate Download PDFInfo
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 19
- 239000002103 nanocoating Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 52
- 238000000151 deposition Methods 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000005498 polishing Methods 0.000 claims abstract description 14
- 229910000619 316 stainless steel Inorganic materials 0.000 claims abstract description 11
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 7
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 7
- 239000010432 diamond Substances 0.000 claims abstract description 7
- 238000009501 film coating Methods 0.000 claims abstract description 5
- 239000007888 film coating Substances 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 5
- 238000007733 ion plating Methods 0.000 abstract description 4
- 238000005240 physical vapour deposition Methods 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
- 239000010935 stainless steel Substances 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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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
- 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
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Mechanical Engineering (AREA)
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- Physical Vapour Deposition (AREA)
Abstract
A preparation method for preparing a CrMoTiN nitride film nano coating on the surface of a bipolar plate comprises the following steps: 1) respectively grinding the 316 stainless steel bipolar plate substrate by using SiC sand paper, and then polishing the ground substrate to a mirror surface degree by using diamond polishing paste; 2) before film coating, removing oil stains on the surface to obtain a pretreated substrate; 3) and (3) putting the pretreated substrate into a cavity of a vacuum chamber, and depositing a quaternary nitride film CrMoTiN on the surface of the pretreated substrate by utilizing a non-equilibrium magnetron sputtering ion plating technology to modify the surface of the stainless steel substrate. The invention provides a novel quaternary nitride CrMoTiN coating by adding Ti element on the basis of the bipolar plate with the surface modified by the CrMoN coating by utilizing the physical vapor deposition technology, and further improves the corrosion resistance of the bipolar plate material and ensures the conductivity by doping Mo, Ti and other elements.
Description
Technical Field
The invention relates to a preparation method of a coating on a bipolar plate material of a proton exchange membrane fuel cell, which is to deposit a CrMoTiN quaternary nitride film on the surface of the bipolar plate by a closed field unbalanced magnetron sputtering technology to improve the corrosion resistance and the conductivity of the bipolar plate of the fuel cell, ensure the reliability of the use of the cell and prolong the service life.
Background
The proton exchange membrane fuel cell not only has high energy conversion rate and is environment-friendly, but also can be quickly started at room temperature without electrolytic loss, has long service life and high specific power and specific energy. The power supply is particularly suitable for being used as a movable power source, is one of ideal power sources of electric vehicles and decentralized power stations, and has wide application prospect in the aspect of replacing the traditional fossil energy.
Bipolar plates are one of the important components of a fuel cell, accounting for 80% of the total volume of the stack, 70% of the mass, and 30% of the cost. It has the functions of collecting current, dissipating heat, dispersing reaction medium homogeneously and cooling, and has the requirement of supporting membrane electrode, isolating reaction gas and sealing performance. Therefore, the ideal bipolar plate material should have good electrical conductivity, high air tightness, high mechanical strength, and easy processing. Graphite and its composite have good conductivity and are easy to process, but the material has large brittleness, poor mechanical properties and high processing cost, and is not beneficial to large-scale commercial application. The metal bipolar plate material has high mechanical strength, good conductivity, easy processing and low cost, and can be used in large-scale commercial use. However, in an acidic pem fuel cell environment, the metal bipolar plate material is easily corroded to form a passivation film, which increases the contact resistance between the bipolar plate and the gas diffusion film and also contaminates the membrane electrode and damages the stack. Therefore, surface modification of the stainless steel bipolar plate is required to improve corrosion resistance and electrical conductivity.
Disclosure of Invention
In order to overcome the defects of lower corrosion resistance and poorer conductivity of the existing bipolar plate material, the invention provides a preparation method for preparing a CrMoTiN nitride film nano coating on the surface of a bipolar plate, Ti element is added on the basis of the bipolar plate modified by the CrMoN coating surface by utilizing the physical vapor deposition technology, a novel quaternary nitride CrMoTiN coating is provided, and the corrosion resistance of the bipolar plate material is further improved and the conductivity is ensured by doping elements such as Mo, Ti and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method for preparing a CrMoTiN nitride film nano coating on the surface of a bipolar plate comprises the following steps:
1) grinding a 316 stainless steel bipolar plate substrate by using SiC sand paper, and then polishing the ground substrate to a mirror surface degree by using diamond polishing paste;
2) before film coating, removing oil stains on the surface to obtain a pretreated substrate;
3) putting the pretreated substrate into a cavity of a vacuum chamber, closing a door of the vacuum chamber, vacuumizing to a preset threshold, wherein two high-purity Cr targets, a high-purity Mo target and a high-purity Ti target which are symmetrically arranged are arranged in the cavity, and argon is used as protective gas to run a coating program;
under the condition that bias voltage of-520V to-480V and all target currents are set to be 0.2 to 0.4A, the surface of the base body is pretreated for 25 to 35min through ion sputtering bombardment;
the current of the Cr target is increased to 3-5A, the current of the Mo target and the current of the Ti target are correspondingly and slightly increased to 0.4-0.6A, and a Cr transition layer is obtained by depositing for 3-8 min to increase the film-substrate binding force;
introducing nitrogen as a reaction gas to deposit on the surface of the Cr layer for 10-20 min to obtain a CrN film;
adjusting the Mo target current to 3-5A, and depositing for 10-20 min to obtain a CrMoN film;
and finally, depositing the CrMoTiN film, wherein the current range of the Ti target is 0.3A-6A, and the deposition time is 40-80 min, so as to obtain the CrMoTiN coating containing Ti.
Further, in the step 3), the preset threshold is 2.5 × 10-5torr; under the condition that bias voltage of-500V and all target currents are set to be 0.3A, ion sputtering bombards the surface of the substrate for 30min, the Cr target current is increased to 4A, the Mo target and the Ti target current are correspondingly and slightly increased to 0.5A, a Cr transition layer is obtained after 5min of deposition, nitrogen is introduced as reaction gas to deposit on the surface of the Cr layer for 15min, and a CrN film is obtained; regulating the Mo target current to 4A, and depositing for 15min to obtain a CrMoN film; and finally, depositing the CrMoTiN film, wherein the current range of the Ti target is 0.3A-6A, and the deposition time is 60min, so as to obtain the CrMoTiN coating containing Ti.
Further, in the step 1), the 316 stainless steel bar is wire-cut, processed to a set size to obtain a bipolar plate substrate, the substrate is respectively ground by using SiC sand paper with the granularity of 400#, 800#, 1200#, 1500#, 2000#, and then the ground substrate is polished to a mirror surface degree by using diamond polishing paste with the granularity of 0.1 μm.
Furthermore, in the step 2), the polishing substrate is respectively placed into acetone, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15-25 min by using ultrasonic equipment.
In the invention, the coating prepared by the physical vapor deposition technology has high purity, good compactness, high bonding force between the coating and the substrate, and the performance of the coating is not influenced by the substrate material, so the method is an ideal bipolar plate surface modification technology, and the preparation of nitride coatings is more. However, the physical vapor deposition technique produces a single nitride coating that has defects that can form galvanic cells, resulting in localized corrosion. This problem can be effectively avoided by depositing the composite film and adding additional elements. The closed field unbalanced magnetron sputtering ion plating equipment combines the advantages of the magnetron sputtering technology and the ion plating technology, has uniform film thickness, higher binding force between the coating and the substrate, and high flexibility, and can be used for preparing a gradient film coating and depositing a plurality of layers of coatings on the same substrate.
The invention has the following beneficial effects: the electrochemical test including dynamic polarization test, steady state polarization test and electrochemical impedance spectrum is carried out on the composite material by a three-electrode system, the use environment of the PEMFCs is simulated, and the test result shows that: the new quaternary nitride CrMoTiN coating surface modified bipolar plate greatly improves the corrosion potential relative to 316 stainless steel basal body, and reduces the corrosion current density by two orders of magnitude; compared with CrTiN coating, the corrosion resistance is improved by more than one time. The membrane-based bonding force was about 46N.
Detailed Description
The invention is further described below.
A preparation method for preparing a CrMoTiN nitride film nano coating on the surface of a bipolar plate comprises the following steps:
1) grinding a 316 stainless steel bipolar plate substrate by using SiC sand paper, and then polishing the ground substrate to a mirror surface degree by using diamond polishing paste;
2) before film coating, removing oil stains on the surface to obtain a pretreated substrate;
3) putting the pretreated substrate into a cavity of a vacuum chamber, closing a door of the vacuum chamber, vacuumizing to a preset threshold, wherein two high-purity Cr targets, a high-purity Mo target and a high-purity Ti target which are symmetrically arranged are arranged in the cavity, and argon is used as protective gas to run a coating program;
under the condition that bias voltage of-520V to-480V and all target currents are set to be 0.2 to 0.4A, the surface of the base body is pretreated for 25 to 35min through ion sputtering bombardment;
the current of the Cr target is increased to 3-5A, the current of the Mo target and the current of the Ti target are correspondingly and slightly increased to 0.4-0.6A, and a Cr transition layer is obtained by depositing for 3-8 min to increase the film-substrate binding force;
introducing nitrogen as a reaction gas to deposit on the surface of the Cr layer for 10-20 min to obtain a CrN film;
adjusting the Mo target current to 3-5A, and depositing for 10-20 min to obtain a CrMoN film;
and finally, depositing the CrMoTiN film, wherein the current range of the Ti target is 0.3A-6A, and the deposition time is 40-80 min, so as to obtain the CrMoTiN coating containing Ti.
Further, in the step 3), the preset threshold is 2.5 × 10-5torr; under the condition that bias voltage of-500V and all target currents are set to be 0.3A, ion sputtering bombards the surface of the substrate for 30min, the Cr target current is increased to 4A, the Mo target and the Ti target current are correspondingly and slightly increased to 0.5A, a Cr transition layer is obtained after 5min of deposition, nitrogen is introduced as reaction gas to deposit on the surface of the Cr layer for 15min, and a CrN film is obtained; regulating the Mo target current to 4A, and depositing for 15min to obtain a CrMoN film; and finally, depositing the CrMoTiN film, wherein the current range of the Ti target is 0.3A-6A, and the deposition time is 60min, so as to obtain the CrMoTiN coating containing Ti.
Further, in the step 1), the 316 stainless steel bar is wire-cut, processed to a set size to obtain a bipolar plate substrate, the substrate is respectively ground by using SiC sand paper with the granularity of 400#, 800#, 1200#, 1500#, 2000#, and then the ground substrate is polished to a mirror surface degree by using diamond polishing paste with the granularity of 0.1 μm.
Furthermore, in the step 2), the polishing substrate is respectively placed into acetone, absolute ethyl alcohol and deionized water for ultrasonic treatment for 15-25 min by using ultrasonic equipment.
The invention provides a bipolar plate prepared from 316 stainless steel and a surface modification layer thereof. The surface modification method is characterized in that 316 stainless steel is used as a substrate, a quaternary nitride film CrMoTiN is deposited on the surface of the substrate by utilizing the unbalanced magnetron sputtering ion plating technology to carry out surface modification on the stainless steel substrate, and the corrosion resistance of the surface modified film is represented by a potentiodynamic polarization test. Simulating the use environment of the PEMFCs, and the test result shows that: the new quaternary nitride CrMoTiN coating surface modified bipolar plate greatly improves the corrosion potential relative to 316 stainless steel basal body, and reduces the corrosion current density by two orders of magnitude; compared with CrTiN coating, the corrosion resistance is improved by more than one time. The membrane-based bonding force was about 46N.
Example 1
Placing the pretreated substrate in the cavity of vacuum chamber, closing the door of the vacuum chamber, and vacuumizing to 2.5 × 10-5torr. Two high-purity Cr targets, a high-purity Mo target and a high-purity Ti target which are symmetrically arranged are arranged in the cavity. Argon is used as protective gas to run a coating program. Under the condition that the bias voltage of-520V and all target currents are set to be 0.2A, the surface of the substrate is bombarded by ion sputtering for 25min, and the aim of removing the surface oxide film and impurities is achieved.The current of the Cr target is increased to 3A, the current of the Mo target and the current of the Ti target are correspondingly and slightly increased to 0.4A, and a Cr transition layer is obtained by deposition for 3min so as to increase the film-substrate binding force. And introducing nitrogen as a reaction gas to deposit on the surface of the Cr layer for 10min to obtain the CrN film. And regulating the Mo target current to 3A, and depositing for 10min to obtain the CrMoN film. And (4) keeping the current of the Ti target at 0.3A, continuing to deposit for 40min, finishing the coating process, cooling and taking out the sample.
The corrosion current density of the prepared CrMoTiN composite membrane bipolar plate subjected to potentiodynamic polarization test is 2.62 multiplied by 10-7A cm-2At 1.5MPa, the interfacial contact resistance between the coating and the carbon paper is 6.2m omega cm2。
Example 2
Placing the pretreated substrate in the cavity of vacuum chamber, closing the door of the vacuum chamber, and vacuumizing to 2.5 × 10-5torr. Two high-purity Cr targets, a high-purity Mo target and a high-purity Ti target which are symmetrically arranged are arranged in the cavity. Argon is used as protective gas to run a coating program. Under the condition that the bias voltage is 500V and all target currents are set to be 0.3A, the surface of the substrate is bombarded by ion sputtering for 30min, and the aim of removing the surface oxide film and impurities is achieved. The current of the Cr target is increased to 4A, the current of the Mo target and the current of the Ti target are correspondingly and slightly increased to 0.5A, and a Cr transition layer is obtained by deposition for 5min so as to increase the film-substrate binding force. And introducing nitrogen as a reaction gas to deposit for 15min on the surface of the Cr layer to obtain the CrN film. And regulating the Mo target current to 4A, and depositing for 15min to obtain the CrMoN film. And finally, depositing a CrMoTiN film, wherein the Ti target current is increased to 2A, and the deposition time is 60 min.
The corrosion current density of the prepared CrMoTiN composite membrane bipolar plate subjected to potentiodynamic polarization test is 1.170 multiplied by 10-7A cm-2The interfacial contact resistance between the coating and the carbon paper is 5.8m omega cm under the pressure of 1.5MPa2。
Example 3
Placing the pretreated substrate in the cavity of vacuum chamber, closing the door of the vacuum chamber, and vacuumizing to 2.5 × 10-5torr. Two high-purity Cr targets, a high-purity Mo target and a high-purity Ti target which are symmetrically arranged are arranged in the cavity. Argon is used as protective gas to run a coating program. Bias voltage at-480V and all target currents were set to 0.4Under the condition of A, ion sputtering bombards the surface of the substrate for 35min, so that the aim of removing the surface oxide film and impurities is achieved. The current of the Cr target is increased to 5A, the current of the Mo target and the current of the Ti target are correspondingly and slightly increased to 0.6A, and a Cr transition layer is obtained by deposition for 8min so as to increase the film-substrate binding force. And introducing nitrogen as a reaction gas to deposit on the surface of the Cr layer for 20min to obtain the CrN film. And regulating the Mo target current to 5A, and depositing for 20min to obtain the CrMoN film. And finally, depositing a CrMoTiN film, wherein the Ti target current is 6A, and the deposition time is 80 min.
The corrosion current density of the prepared CrMoTiN composite membrane bipolar plate subjected to potentiodynamic polarization test is 5.884 multiplied by 10-8A cm2The interfacial contact resistance between the coating and the carbon paper is 5.2m omega cm under the pressure of 1.5MPa2。
Claims (4)
1. A preparation method for preparing a CrMoTiN nitride film nano coating on the surface of a bipolar plate is characterized by comprising the following steps:
1) grinding a 316 stainless steel bipolar plate substrate by using SiC sand paper, and then polishing the ground substrate to a mirror surface degree by using diamond polishing paste;
2) before film coating, removing oil stains on the surface to obtain a pretreated substrate;
3) putting the pretreated substrate into a cavity of a vacuum chamber, closing a door of the vacuum chamber, vacuumizing to a preset threshold, wherein two high-purity Cr targets, a high-purity Mo target and a high-purity Ti target which are symmetrically arranged are arranged in the cavity, and argon is used as protective gas to run a coating program;
under the condition that bias voltage of-520V to-480V and all target currents are set to be 0.2 to 0.4A, the surface of the base body is pretreated for 25 to 35min through ion sputtering bombardment;
the current of the Cr target is increased to 3-5A, the current of the Mo target and the current of the Ti target are correspondingly and slightly increased to 0.4-0.6A, and a Cr transition layer is obtained by depositing for 3-8 min to increase the film-substrate binding force;
introducing nitrogen as a reaction gas to deposit on the surface of the Cr layer for 10-20 min to obtain a CrN film;
adjusting the Mo target current to 3-5A, and depositing for 10-20 min to obtain a CrMoN film;
and finally, depositing the CrMoTiN film, wherein the current range of the Ti target is 0.3A-6A, and the deposition time is 40-80 min, so as to obtain the CrMoTiN coating containing Ti.
2. The method for preparing a nano coating of a CrMoTiN nitride film on a surface of a bipolar plate as claimed in claim 1, wherein the predetermined threshold value in the step 3) is 2.5 x 10-5torr; under the condition that bias voltage of-500V and all target currents are set to be 0.3A, ion sputtering bombards the surface of the substrate for 30min, the Cr target current is increased to 4A, the Mo target and the Ti target current are correspondingly and slightly increased to 0.5A, a Cr transition layer is obtained after 5min of deposition, nitrogen is introduced as reaction gas to deposit on the surface of the Cr layer for 15min, and a CrN film is obtained; regulating the Mo target current to 4A, and depositing for 15min to obtain a CrMoN film; and finally, depositing the CrMoTiN film, wherein the current range of the Ti target is 0.3A-6A, and the deposition time is 40min, so as to obtain CrMoTiN coatings with different Ti contents.
3. The method for preparing a nano coating of a CrMoTiN nitride film on a bipolar plate surface according to claim 1 or 2, wherein in the step 1), a 316 stainless steel bar is wire-cut and processed to a set size to obtain a bipolar plate substrate, the substrate is respectively ground by SiC sand paper with the granularity of 400#, 800#, 1200#, 1500#, 2000#, and then the ground substrate is polished to a mirror surface degree by diamond polishing paste with the granularity of 0.1 μm.
4. The method for preparing a CrMoTiN nitride film nano-coating on the surface of a bipolar plate according to claim 1 or 2, wherein in the step 2), the polishing substrate is respectively put into acetone, absolute ethyl alcohol and deionized water by ultrasonic equipment for 15-25 min.
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| CN102723499B (en) * | 2012-06-07 | 2014-08-06 | 上海交通大学 | Metal bipolar plate of fuel cell with surface plating layers and preparation method thereof |
| CN102800871B (en) * | 2012-08-14 | 2015-07-08 | 上海交通大学 | Fuel cell metal bipolar plate carbon chromium gradient coating and preparation method |
| CN103199279B (en) * | 2013-04-03 | 2016-06-08 | 上海交通大学 | The doping type multi-gradient coating of fuel battery metal double polar plate |
| US9618836B2 (en) * | 2014-04-22 | 2017-04-11 | Asahi Glass Company, Limited | Reflective mask blank for EUV lithography, substrate with funtion film for the mask blank, and methods for their production |
| CN104577144B (en) * | 2015-01-27 | 2017-12-22 | 大连理工常州研究院有限公司 | A kind of bipolar plate for fuel cell for nitrogenizing enhancing surface and preparation method thereof |
| CN104862644A (en) * | 2015-05-22 | 2015-08-26 | 浙江工业大学 | Cr-CrN-CrMoAlN gradient nano multi-layered thin film with high-temperature wear resistance and preparation method thereof |
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