CN113737142A - Preparation method of composite gradient carbon-based coating of proton exchange membrane fuel cell titanium bipolar plate - Google Patents
Preparation method of composite gradient carbon-based coating of proton exchange membrane fuel cell titanium bipolar plate Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 66
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 64
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims abstract description 37
- 239000011248 coating agent Substances 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 239000000446 fuel Substances 0.000 title claims abstract description 23
- 239000012528 membrane Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000007704 transition Effects 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 12
- 150000004767 nitrides Chemical class 0.000 claims abstract description 9
- 230000037452 priming Effects 0.000 claims abstract description 6
- 238000000151 deposition Methods 0.000 claims description 42
- 230000008021 deposition Effects 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 18
- 230000001965 increasing effect Effects 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
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- 239000010410 layer Substances 0.000 description 41
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000010287 polarization Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
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Classifications
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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
-
- 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
- C23C14/02—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
- C23C14/0605—Carbon
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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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
- C23C14/06—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0213—Gas-impermeable carbon-containing materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate, which is characterized in that the composite gradient coating is deposited on a titanium plate by utilizing an unbalanced magnetron sputtering technology and sequentially comprises a metal simple substance priming layer, a metal nitride transition layer and a pure carbon working layer from bottom to top. The invention effectively solves the problem of poor conductivity of the corrosion protection coating of the titanium bipolar plate of the proton exchange membrane fuel cell, improves the efficiency of the fuel cell and prolongs the service life, and has important practical significance for promoting the commercialization process of the titanium bipolar plate.
Description
Technical Field
The invention relates to the technical field of fuel cell production, in particular to a preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate.
Background
With the increasing speed of the modern industrialization process, energy and climate problems become one of the essential problems which are inevitable at the present stage. The development of green, environment-friendly and new energy is the main development direction of scientific research and industrial production application in China. The fuel cell is an energy conversion device which converts chemical energy stored in fuel into electric energy through efficient oxidation-reduction reaction, has the advantages of working temperature close to normal temperature, high power density, no pollution, quick start, no noise, long service life and the like, and is considered as one of ideal new energy technologies.
The proton exchange membrane fuel cell mainly comprises a bipolar plate, a membrane electrode assembly, an end plate, a sealing member and the like, wherein the bipolar plate is one of important components of a proton exchange membrane fuel cell stack and accounts for about 70% of the total weight of the stack and 30% of the total cost. The bipolar plates may be classified into graphite bipolar plates, metal bipolar plates, and composite bipolar plates. The graphite has large brittleness, high air permeability and high complex processing cost of the composite plate, and compared with the metal bipolar plate, the metal bipolar plate has better formability, impact resistance and lower air permeability and is suitable for commercial large-scale production. Common metal bipolar plate materials comprise aluminum alloy, titanium alloy and stainless steel, and titanium alloy are widely applied and favored due to excellent corrosion resistance, good conductivity, low specific strength and the like.
In the acidic working environment of the battery, the metal bipolar plate is easy to corrode, metal ions formed in the corrosion process can pollute a proton exchange membrane, so that the poisoning transmission efficiency is reduced, and meanwhile, a passive film formed on the surface of the metal bipolar plate can increase the interface contact resistance, so that the performance of the fuel battery is reduced. At present, the reasonable matching of the conductivity and the corrosion resistance of the metal bipolar plate material is realized, the service life of the whole system is ensured, and one of effective methods is to carry out coating modification on the surface of the metal bipolar plate.
Disclosure of Invention
The invention aims to provide a preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate, which is simple and feasible, can give consideration to surface corrosion resistance and electric conductivity of a metal bipolar plate, improves the efficiency of a fuel cell and prolongs the service life of the fuel cell.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate comprises the following steps:
firstly, pretreatment: polishing and cleaning the titanium plate;
second, unbalanced magnetron sputtering
2.1 plasma cleaning: putting the pretreated titanium plate into a magnetron sputtering cavity, and carrying out plasma cleaning on the titanium plate;
2.2 deposition of the primer layer: depositing a metal bottom layer on the titanium plate, wherein the material of the metal bottom layer is one or more of Ti, Cr and Zr;
2.3 deposition of transition layer: depositing a nitride transition layer on the metal priming layer, wherein the nitride transition layer is made of one of TiN, CrN, ZrN, TiCrN, TiZrN, CrZrN and TiCrZrN;
2.4 deposition of working layer: and depositing a working layer on the nitride transition layer, wherein the working layer is made of amorphous carbon.
The base coat layer is used as a transition layer between the substrate and the coating layer to improve the bonding force of the substrate and the coating layer.
In the invention, a multi-gradient coating idea is adopted to form a gradient transition layer which shows no interface continuous change from a substrate to the surface, thereby reducing the residual stress and the initiation of cracks, enhancing the interface bonding strength between film layers, improving the conductivity, the corrosion performance and the like.
The titanium plate of the invention is commercially pure titanium TA1 with the specification of 100 mm multiplied by 2 mm, and is sequentially ground and polished by #120#400#1000#1500#2000 sandpaper. Cleaning with analytically pure acetone and ethanol for 15min and 30min respectively.
When plasma cleaning is carried out, the temperature in the magnetron sputtering cavity is controlled at 100 ℃, the temperature is gradually increased in the magnetron sputtering process until the magnetron sputtering is finished, and the temperature in the magnetron sputtering cavity is lower than 200 ℃.
The plasma cleaning selects 99.9% high-purity Ar plasma beam for sputtering cleaning for 30-35 min. The plasma cleaning is intended to remove the scale on the surface of the titanium plate substrate and to improve the binding ability with the plating layer.
The parameters for depositing the bottom layer are set as follows: the metal target current is gradually increased from 0.3A to 2A within 2min and maintained, the bias voltage is adjusted from-500V to-60V and the deposition time is 15-18 min.
The parameters for depositing the transition layer are set as follows: the metal target current is gradually increased from 2A to 4A within 3min and maintained, the bias voltage is maintained at-60V, 99.9% high-purity nitrogen is introduced, the flow rate is controlled by using an OEM value and is set as 75 +/-2%, and the deposition time is 30-35 min.
The parameters for depositing the working layer are set as follows: the C target current is gradually increased from 0.3A to 5A within 3min and maintained, the bias voltage is maintained at-60V, and the deposition time is 85-95 min. The parameters of the working layer are set as described above in order to generate a graphite phase having good conductivity.
In the non-equilibrium magnetron sputtering process, the vacuum degree in the magnetron sputtering cavity is controlled to be lower than 3.0 multiplied by 10-5Pa。
In the unbalanced magnetron sputtering process, the flow of the protective gas Ar is always kept at 20 +/-5 sccm.
In the non-equilibrium magnetron sputtering process, the titanium plate rotates at 2.5-3 r/s.
Preferably, the metal used for the nitride transition layer is the same as the metal used for the metal underlying layer. For example: the Cr priming layer corresponds to a CrN transition layer, and the TiZr priming layer corresponds to a TiZrN transition layer. Thus, gradient change of the same composition is formed, and the bonding force between the substrate and the substrate is further improved.
The invention has the beneficial effects that:
(1) the composite gradient carbon-based coating prepared by the method can effectively solve the problem of poor electrical conductivity of the titanium bipolar plate corrosion protection coating of the proton exchange membrane fuel cell. As a stable protection modified coating, the modified coating not only can provide excellent corrosion protection performance, but also can greatly reduce the surface contact resistance between the bipolar plate and the membrane electrode, thereby improving the efficiency of the fuel cell and prolonging the service life.
(2) The composite gradient carbon-based composite material prepared by the method has the advantages of thin thickness, low manufacturing cost, excellent and stable performance, safety and environmental protection, and has important practical significance for promoting the commercialization process of the titanium bipolar plate.
Drawings
Fig. 1 is a schematic structural diagram of a composite gradient carbon-based coating of a titanium bipolar plate according to the present invention.
Fig. 2 is a cross-sectional scan of a composite gradient carbon-based coating of a titanium bipolar plate prepared according to an embodiment of the present invention.
FIG. 3 is a zeta potential polarization curve diagram of the composite gradient carbon-based coating of the titanium bipolar plate prepared in the embodiment of the present invention, wherein the scanning rate is 1 mV/s, and the scanning potential interval is-0.3V-1.2V (vs. SCE).
FIG. 4 is a constant potential polarization curve diagram of the composite gradient carbon-based coating of the titanium bipolar plate prepared by the embodiment of the invention, the cathode potential is set to + 0.6V (vs. SCE), and the polarization time is 120 min.
Fig. 5 is a surface contact resistance curve of the composite gradient carbon-based coating of the titanium bipolar plate prepared by the embodiment of the invention.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
In the embodiment of the invention, the unbalanced magnetron sputtering equipment is manufactured by TEER coating company in UK and has model DXP 650/4.
Example 1
A preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate comprises the following steps:
(1) commercial industrial pure titanium TA1 was selected as the titanium plate, which had a gauge of 100 mm X2 mm, and was sequentially sanded and polished with #120#400#1000#1500#2000 sandpaper. Then, analytically pure acetone and ethanol are selected for ultrasonic cleaning for 15min and 30min respectively.
(2) And (3) putting the pretreated titanium plate into a magnetron sputtering cavity, and carrying out plasma cleaning on the titanium plate, wherein the plasma cleaning is carried out for 30min by using a high-purity Ar plasma beam with the purity of 99.9%.
(3) Depositing a bottom layer, gradually increasing the Ti target current from 0.3A to 2A within 2min and keeping, adjusting the bias voltage from-500 to-60V and keeping the deposition time for 15 min.
(4) Depositing a transition layer, gradually increasing the Ti target current from 2A to 4A within 3min and keeping, keeping the bias voltage at-60V, introducing 99.9% high-purity nitrogen, controlling the flow by using an OEM value, setting the flow as 75%, and setting the deposition time as 30 min.
(5) And depositing a working layer, wherein the C target current is gradually increased to 5A from 0.3A within 3min and is kept, the bias voltage is kept at-60V, and the deposition time is 90 min.
In the non-equilibrium magnetron sputtering process, the vacuum degree in the magnetron sputtering cavity is controlled to be lower than 3.0 multiplied by 10-5Pa; the flow of the protective gas Ar is always kept at 20 sccm; the titanium plate was rotated at 2.5 r/s.
Example 2
A preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate comprises the following steps:
(1) commercial industrial pure titanium TA1 was selected as the titanium plate, which had a gauge of 100 mm X2 mm, and was sequentially sanded and polished with #120#400#1000#1500#2000 sandpaper. Then, analytically pure acetone and ethanol are selected for ultrasonic cleaning for 15min and 30min respectively.
(2) And (3) putting the pretreated titanium plate into a magnetron sputtering cavity, and carrying out plasma cleaning on the titanium plate, wherein the plasma cleaning is carried out for 30min by using a high-purity Ar plasma beam with the purity of 99.9%.
(3) Depositing a bottom layer, gradually increasing the Cr target current from 0.3A to 2A within 2min and keeping, adjusting the bias voltage from-500 to-60V and keeping the deposition time for 15 min.
(4) Depositing a transition layer, gradually increasing the Cr target current from 2A to 4A within 3min and keeping, keeping the bias voltage at-60V, introducing 99.9% high-purity nitrogen, controlling the flow by using an OEM value, setting the flow to be 75%, and setting the deposition time to be 30 min.
(5) And depositing a working layer, wherein the C target current is gradually increased to 5A from 0.3A within 3min and is kept, the bias voltage is kept at-60V, and the deposition time is 90 min.
In the non-equilibrium magnetron sputtering process, the vacuum degree in the magnetron sputtering cavity is controlled to be lower than 3.0 multiplied by 10-5Pa; the flow of the protective gas Ar is always kept at 20 sccm; the titanium plate was rotated at 2.5 r/s.
Example 3
A preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate comprises the following steps:
(1) commercial industrial pure titanium TA1 was selected as the titanium plate, which had a gauge of 100 mm X2 mm, and was sequentially sanded and polished with #120#400#1000#1500#2000 sandpaper. Then, analytically pure acetone and ethanol are selected for ultrasonic cleaning for 15min and 30min respectively.
(2) And (3) putting the pretreated titanium plate into a magnetron sputtering cavity, and carrying out plasma cleaning on the titanium plate, wherein the plasma cleaning is carried out for 30min by using a high-purity Ar plasma beam with the purity of 99.9%.
(3) And (3) depositing the bottom layer, gradually increasing the Ti and Cr target currents from 0.3A to 2A within 2min and keeping the target currents, adjusting the bias voltage from-500 to-60V and keeping the bias voltage at-60V, wherein the deposition time is 15 min.
(4) And (3) depositing a transition layer, gradually increasing the Ti and Cr target currents from 2A to 4A within 3min, maintaining the bias voltage at-60V, introducing 99.9% high-purity nitrogen, controlling the flow by using an OEM value, setting the flow to be 75%, and depositing for 30 min.
(5) And depositing a working layer, wherein the C target current is gradually increased to 5A from 0.3A within 3min and is kept, the bias voltage is kept at-60V, and the deposition time is 90 min.
In the non-equilibrium magnetron sputtering process, the vacuum degree in the magnetron sputtering cavity is controlled to be lower than 3.0 multiplied by 10-5Pa; the flow of the protective gas Ar is always kept at 20 sccm; the titanium plate was rotated at 2.5 r/s.
The prepared titanium bipolar plate coating is subjected to characterization such as observation of section surface appearance and the like, and surface contact resistance test, electrochemical polarization test and the like are performed in a simulated proton exchange membrane fuel cell operating environment.
Fig. 1 is a schematic structural diagram of the composite gradient carbon-based coating of the titanium bipolar plate of the invention, which comprises a titanium plate substrate, a priming layer, a transition layer and a working layer from bottom to top in sequence.
Fig. 2 is a cross-sectional scanning view of the composite gradient carbon-based coating of the titanium bipolar plate in the embodiment of the invention, which shows that the coating in the embodiment has a certain thickness, a compact structure, good bonding between the coating and the substrate, and a clear interface between the coating and the substrate, and is in a columnar structure, and that in the whole coating, the bottom layer is not easy to see, and the transition layer is clearly distinguished from the working layer in depth. The thicknesses of the coatings of example 1, example 2 and example 3 were 721, 827 and 913nm, respectively.
As shown in fig. 3, which is a plot of potentiodynamic polarization of the composite gradient carbon-based coating of the titanium bipolar plate in the embodiment of the present invention, it can be seen that, in the simulated cathode environment, the corrosion potential of the composite gradient carbon-based coating during potentiodynamic polarization is significantly higher than that of the TA1 titanium bipolar plate, and the corrosion current densities of example 1, example 2 and example 3 are 1.12 × 10-6 A/cm2、8.41×10-7A/cm2And 8.09X 10-7A/cm2Less than 2.76X 10 of unmodified TA1 titanium plate-6A/cm2。
As shown in fig. 4, which is a constant potential polarization curve diagram of the composite gradient carbon-based coating of the titanium bipolar plate in the embodiment of the present invention, it can be seen that the corrosion current density is significantly reduced, respectively 1.42 × 10, in the examples 1, 2 and 3, when the coating is polarized at constant potential under the simulated cathode environment-6 A/cm2、9.64×10-7A/cm2And 8.75X 10-7A/cm2Less than 3.21X 10 of unmodified TA1 titanium plate-6A/cm2。
As shown in FIG. 5, which is a surface contact curve diagram of the composite gradient carbon-based coating of the titanium bipolar plate in the embodiment of the present invention, it can be seen that the surface contact resistance of the titanium bipolar plate in the embodiment 1, the embodiment 2 and the embodiment 3 is significantly reduced under the pressing force of 1.4MPa, and is respectively 12.3m omega cm2、5.4mΩ·cm2And 6.5 m.OMEGA.cm2Is less than93.5m omega cm of modified TA1 titanium plate2。
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (9)
1. A preparation method of a composite gradient carbon-based coating of a proton exchange membrane fuel cell titanium bipolar plate is characterized by comprising the following steps:
firstly, pretreatment: polishing and cleaning the titanium plate;
second, unbalanced magnetron sputtering
2.1 plasma cleaning: putting the pretreated titanium plate into a magnetron sputtering cavity, and carrying out plasma cleaning on the titanium plate;
2.2 deposition of the primer layer: depositing a metal bottom layer on the titanium plate, wherein the material of the metal bottom layer is one or more of Ti, Cr and Zr;
2.3 deposition of transition layer: depositing a nitride transition layer on the metal priming layer, wherein the nitride transition layer is made of one of TiN, CrN, ZrN, TiCrN, TiZrN, CrZrN and TiCrZrN;
2.4 deposition of working layer: and depositing a working layer on the nitride transition layer, wherein the working layer is made of amorphous carbon.
2. The method according to claim 1, wherein the plasma cleaning is performed by sputtering with 99.9% high purity Ar plasma for 30-35 min.
3. The method according to claim 1, wherein the parameters for depositing the primer layer are set as follows: the metal target current is gradually increased from 0.3A to 2A within 2min and maintained, the bias voltage is adjusted from-500V to-60V and the deposition time is 15-18 min.
4. The method according to claim 1, wherein the parameters for depositing the transition layer are set as follows: the metal target current is gradually increased from 2A to 4A within 3min and maintained, the bias voltage is maintained at-60V, 99.9% high-purity nitrogen is introduced, the flow rate is controlled by using an OEM value and is set as 75 +/-2%, and the deposition time is 30-35 min.
5. The method according to claim 1, wherein the parameters for depositing the working layer are set as: the C target current is gradually increased from 0.3A to 5A within 3min and maintained, the bias voltage is maintained at-60V, and the deposition time is 85-95 min.
6. The method according to claim 1, wherein the degree of vacuum in the magnetron sputtering chamber is controlled to be less than 3.0 x 10 during the unbalanced magnetron sputtering process-5Pa。
7. The method according to claim 1, wherein the flow rate of Ar protective gas is always maintained at 20 ± 5sccm during the unbalanced magnetron sputtering process.
8. The method according to claim 1, wherein the titanium plate is rotated at 2.5 to 3r/s during the unbalanced magnetron sputtering.
9. The method according to claim 1, wherein the metal selected for the nitride transition layer is the same as the metal of the metal primer layer.
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