CN116855886A - TiC/(Ti, ta) double-layer coating of metal bipolar plate for fuel cell 3 SnC 2 And a method for preparing the same - Google Patents
TiC/(Ti, ta) double-layer coating of metal bipolar plate for fuel cell 3 SnC 2 And a method for preparing the same Download PDFInfo
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- CN116855886A CN116855886A CN202310451964.7A CN202310451964A CN116855886A CN 116855886 A CN116855886 A CN 116855886A CN 202310451964 A CN202310451964 A CN 202310451964A CN 116855886 A CN116855886 A CN 116855886A
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- 238000000576 coating method Methods 0.000 title claims abstract description 100
- 239000011248 coating agent Substances 0.000 title claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 239000000446 fuel Substances 0.000 title claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000005260 corrosion Methods 0.000 claims abstract description 26
- 230000007797 corrosion Effects 0.000 claims abstract description 22
- 230000007704 transition Effects 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 238000007733 ion plating Methods 0.000 claims abstract description 11
- 238000004544 sputter deposition Methods 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003344 environmental pollutant Substances 0.000 claims description 7
- 238000007731 hot pressing Methods 0.000 claims description 7
- 231100000719 pollutant Toxicity 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- VMQRJIPKBKXPCT-UHFFFAOYSA-N [Ti].[Sn].[C] Chemical compound [Ti].[Sn].[C] VMQRJIPKBKXPCT-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
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- 239000010410 layer Substances 0.000 description 37
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- 238000005530 etching Methods 0.000 description 8
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- 239000000243 solution Substances 0.000 description 6
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- 244000137852 Petrea volubilis Species 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0635—Carbides
-
- 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
-
- 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
-
- 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
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
-
- 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
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- 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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- 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
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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
- C23C14/54—Controlling or regulating the coating process
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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
Abstract
The invention relates to a coating for a metal bipolar plate of a proton exchange membrane fuel cell, wherein the inner layer of the coating is a TiC transition layer, and the outer layer is (Ti, ta) 3 SnC 2 The TiC transition layer of the inner layer is used for reducing the thermal expansion mismatch degree between layers, improving the element compatibility of each layer and increasing the binding force of the coating; said outer layer (Ti, ta) 3 SnC 2 The coating is used for improving the corrosion resistance and the conductivity of the substrate, and a preparation method of the coating is also disclosed. The preparation rate of the integral coating is high, the process is easy to control, and the integral coating can be preparedThe performance of the bipolar plate is greatly improved, the service life of the fuel cell is further prolonged, meanwhile, the preparation method of the coating is easy to control and high-efficiency, the intermediate transition layer is prepared by adopting a high-efficiency arc ion plating technology, the outer coating is prepared by adopting a magnetron sputtering technology capable of obtaining a coating with a compact, flat and uniform composition structure, and the industrial popularization is easy.
Description
Technical Field
The invention relates to a coating for a metal bipolar plate of a proton exchange membrane fuel cell and a preparation method thereof, belonging to the technical field of fuel cells.
Background
The proton exchange membrane fuel cell has the advantages of compact structure, small volume, high energy density, high efficiency, quick start, low-temperature operation and zero emission, and is considered to be an ideal clean power generation energy source at the present stage. The bipolar plate is used as one of the most important component parts of the PEMFC, and single cells are connected in series, parallel or mixed to form a cell stack, so that the bipolar plate has a supporting function, can isolate the reaction gases of a cathode and an anode, and can discharge heat and water generated by the reaction of the cell stack, and is of great importance to the performance of the PEMFC cell stack. Currently, bipolar plates are mainly composed of three types, namely graphite bipolar plates, metal bipolar plates and composite bipolar plates. The metal bipolar plate has high strength, is easy to process, is easy to realize large-scale production, and can improve the specific power of the fuel cell. But there are many corrosive ions in the working environment, such as SO 4 2- 、F - And the like, the metal bipolar plate material is easy to corrode, and a passivation layer is formed, so that the contact resistance between the bipolar plate and the diffusion layer is increased, and the output power and the durability of the fuel cell stack are greatly affected. Therefore, reducing the surface contact resistance of the metal bipolar plate and improving the conductivity and corrosion resistance of the metal bipolar plate are key to the commercial application of the metal bipolar plate through surface coating modification.
The existing bipolar plate coating is mainly a carbon-based coating, a noble metal coating, a conductive high polymer coating, a hydrophobic coating, a transition metal ceramic compound and the like. The carbon-based coating has excellent corrosion resistance, excellent electrical conductivity and heat conduction, and low production cost, but low deposition efficiency, and influences large-scale application. Noble metal coatings have excellent corrosion resistance and electrical conductivity, but are too costly. The conductive high polymer coating can play a good role in protecting the bipolar plate, has good corrosion resistance and conductivity, and has more researches on Polyaniline (PANI) and polypyrrole (PPy), but the binding force between the coating and a matrix is weaker. The hydrophobic properties of the hydrophobic coating can greatly affect the corrosion rate of the bipolar plate, but it is difficult to maintain long-term stability. The transition metal ceramic compound has excellent physical, chemical and mechanical properties, has excellent corrosion resistance and stability in the working environment of the bipolar plate, can keep high conductivity, is one of ideal coating materials of the PEMFC bipolar plate, however, large particles in the coating can lead to local accelerated corrosion, columnar crystals of the coating can infiltrate into liquid to lead to the long-term service life not to be ensured, and the preparation rate is high by adopting which material, the process is easy to control, and can stably keep the higher corrosion resistance and conductivity of the coating so as to improve the service life of the fuel cell.
Disclosure of Invention
The invention aims to provide a coating for a metal bipolar plate of a proton exchange membrane fuel cell and a preparation method thereof, wherein an inner layer transition layer is deposited by adopting an arc ion plating technology, an outer layer coating is deposited by adopting a magnetron sputtering technology, and a gradient structure of the double-layer coating is modulated to obtain a coating with uniformity, compactness and high adhesive force, so that the corrosion resistance and the electric conductivity of a stainless steel matrix can be effectively improved. The preparation speed of the integral coating is high, the process is easy to control, the performance of the bipolar plate can be greatly improved, and the service life of the fuel cell is further prolonged.
In order to achieve the above purpose, the present invention provides the following technical solutions: a coating for a metal bipolar plate of a proton exchange membrane fuel cell comprises an inner TiC transition layer and an outer (Ti, ta) layer 3 SnC 2 The TiC transition layer of the inner layer is used for reducing the thermal expansion mismatch degree between layers, improving the element compatibility of each layer and increasing the binding force of the coating; said outer layer (Ti, ta) 3 SnC 2 The coating is used for improving the corrosion resistance and the electrical conductivity of the substrate.
Further, the (Ti, ta) 3 SnC 2 Is a ternary layered ceramic titanium-tin-carbon modified material, and is formed by solid solution doping of element Ta on Ti position of titanium-tin-carbon.
Further, the proportion of the doping element is 0.5 to 30 at%. The corrosion resistance and the conductivity of the doped titanium-tin-carbon are obviously improved, the corrosion current density is reduced by 48-71%, the self-corrosion potential is improved by 0.05-0.13V, and the contact resistance is reduced by 25-72%.
Further, the TiC transition layer has a thickness of 50-150 nm, (Ti, ta) 3 SnC 2 The thickness of the coating is 200-400 nm.
Further, the coating target material of the outer layer is (Ti, ta) 3 SnC 2 The single-phase target material is prepared by sintering Ti powder, ta powder, sn powder and graphite powder in a hot-pressing furnace by adopting a hot-pressing/solid-liquid phase reaction method, wherein the sintering temperature is 1100-1550 ℃, the heat preservation is carried out for 30-90 minutes, the hot-pressing pressure is 30-75 MPa, and flowing argon is used as protective gas.
Further, the TiC transition layer is deposited on the metal bipolar plate by utilizing an arc ion plating device with high-efficiency deposition rate, and is used for improving the binding force of the outer coating and increasing the compatibility of the coating and a matrix, (Ti, ta) 3 SnC 2 The coating is deposited by utilizing a magnetron sputtering device, two sputtering power supplies are arranged in a cavity, a sample is hung on a sample rack of the equipment when the coating is deposited, a stand column suspending the sample rotates, and the rotating stand column revolves along with a rotary table at the same time, so that uniform coating is obtained.
Further, the operation steps of the arc ion plating are as follows: before coating preparation, the vacuum chamber was pre-evacuated to 4X 10 -3 After Pa, applying 500V negative pulse bias to the substrate to perform back splash cleaning on the substrate for 5-15 min, removing pollutants and oxide layers on the surface of the substrate, then opening an Ar flow valve, wherein Ar flow is 50ml/min, controlling working air pressure in a vacuum chamber by adjusting pumping speed of a molecular pump to maintain the working air pressure at 0.4Pa, heating a chamber at 100-200 ℃, opening a TiC target direct current power supply, arc current at 40-80A, bias voltage at-200 to-400V, and sputtering time at 2-10 min.
Further, the magnetron sputtering deposition (Ti, ta) 3 SnC 2 The coating comprises the following operation steps: first, the temperature of the chamber is adjusted to 200 to the upper limitPreserving heat at 300deg.C for 15min, and then opening (Ti, ta) 3 SnC 2 And (3) a target direct current power supply, wherein the sputtering power is 0.1-1.5 kw, the sputtering time is 20-50 min, cooling to room temperature at the speed of 10 ℃/min under the original vacuum condition after deposition is finished, and then stopping vacuumizing and pressure removing.
Further, the metal bipolar plate is required to be pretreated, firstly, the metal bipolar plate is polished, then the polished metal bipolar plate is respectively ultrasonically cleaned for 10-20 min through acetone, alcohol and deionized water, and then the metal bipolar plate is dried in air for standby.
Compared with the prior art, the invention has the beneficial effects that: tiC/(Ti, ta) is deposited on the metallic bipolar plate by two sputtering methods 3 SnC 2 The TiC transition layer designed by combining the characteristics of the matrix and the outer coating system can reduce the thermal expansion mismatch degree between the matrix and the coating, improve the element compatibility of each layer and increase the binding force of the coating; (Ti, ta) 3 SnC 2 The coating is made of modified titanium tin carbon material, and can obviously improve the corrosion resistance and conductivity of the coating. The result shows that the addition of the transition layer TiC can reduce the etching current density by 26-58%, the self-etching potential by 0.01-0.09V and the contact resistance by 31-75%. At Ti 3 SnC 2 The Ti position solid solution doped with Ta element can reduce the corrosion current density by 48-71%, the self-corrosion potential by 0.05-0.13V and the contact resistance by 25-72%. The performance of the bipolar plate is greatly improved, and the service life of the fuel cell is further prolonged. Meanwhile, the preparation method of the coating is easy to control and high in efficiency, the intermediate transition layer is prepared by adopting a high-efficiency arc ion plating technology, the outer coating is prepared by adopting a magnetron sputtering technology capable of obtaining a coating with a compact, flat and uniform component structure, and the industrial popularization is easy.
Drawings
FIG. 1 is a scanning electron microscope surface view of the coating prepared in example 1;
FIG. 2 is a scanning electron microscope surface view of the coating prepared in example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The metal substrate used in the following examples is a metal bipolar plate. For deposition (Ti, ta) 3 SnC 2 The target material is prepared through sintering in a hot pressing furnace at 1100-1550 deg.c for 30-90 min under 30-75 MPa under flowing argon as protecting gas, and the material includes Ti powder, ta powder, sn powder and graphite powder in certain proportion, and the material has the following material components 1-x Ta x ) 3 SnC 2 In, ti: ta: sn: preparing raw material powder according to the proportion of 3 (1-x) to 3x to 1:2, wet mixing for 24-50 hours on a ball mill by a wet mixing method, taking out, naturally airing, and sieving for later use.
Example 1
First preparing (Ti 0.95 Ta 0.05 ) 3 SnC 2 And preparing a TiC target and a metal bipolar plate. Step-by-step polishing the alloy substrate by using No. 200, no. 400, no. 600, no. 800, no. 1000, no. 1500 and No. 2000 metallographic sand paper, respectively ultrasonically cleaning the polished metal sample for 20min by using acetone, alcohol and deionized water, and drying in air for later use.
Depositing TiC intermediate layer by arc ion plating, and pre-vacuumizing the vacuum chamber until the back vacuum is 4×10 before coating preparation -3 And after Pa, applying 500V negative pulse bias voltage to the substrate to perform back splash cleaning on the substrate for 5min, and removing pollutants and an oxide layer on the surface of the substrate. Then, an Ar flow valve is opened, ar flow is 50ml/min, the pumping speed of a molecular pump is regulated to control the working air pressure in a vacuum chamber, so that the working air pressure is maintained at about 0.4Pa, and the heating temperature of a chamber is 150 ℃. And (3) switching on a TiC target direct current power supply, wherein the arc current is 60A, the bias voltage is-200V, and the sputtering time is 2min.
Then deposit (Ti) by magnetron sputtering method 0.95 Ta 0.05 ) 3 SnC 2 The outer coating layer was first prepared by adjusting the chamber temperature to 200 c, keeping the temperature for 15min, and then opened (Ti 0.95 Ta 0.05 ) 3 SnC 2 And the sputtering power of the target direct current power supply is 0.5kw, and the sputtering time is 30min. And after the deposition is finished, cooling to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then stopping vacuumizing and removing pressure.
After the experiment, the microscopic morphology of the surface and the section of the deposited coating is observed by a scanning electron microscope, the obtained coating is smooth and compact, the coating is well combined with a matrix, and the thickness of the double-layer coating is uniform everywhere, as shown in figure 1. In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing was performed in HF solution at a concentration of 0.5mol/L and 2ppm at 80deg.C, with an etching current density of 0.77. Mu.A/cm 2 [ self-etching potential 0.10V (vs. SCE)]At an assembly force of 150N/cm 2 Under the condition that the contact resistance is 6.89mΩ cm 2 。
Example 2
First preparing (Ti 0.995 Ta 0.005 ) 3 SnC 2 And preparing a TiC target and a metal bipolar plate. And (3) ultrasonically cleaning a SS316L metal sheet with the thickness of 100 mu m for 10min respectively by using acetone, alcohol and deionized water, and drying in air for later use.
Depositing TiC intermediate layer by arc ion plating, and pre-vacuumizing the vacuum chamber until the back vacuum is 4×10 before coating preparation -3 And after Pa, applying 500V negative pulse bias voltage to the substrate, and performing back splash cleaning on the substrate for 10min to remove pollutants and oxide layers on the surface of the substrate. Then, an Ar flow valve is opened, ar flow is 50ml/min, the pumping speed of a molecular pump is regulated to control the working air pressure in a vacuum chamber, so that the working air pressure is maintained at about 0.4Pa, and the heating temperature of a chamber is 100 ℃. And (3) switching on a TiC target direct current power supply, wherein the arc current is 40A, the bias voltage is-300V, and the sputtering time is 5min.
Then deposit (Ti) by magnetron sputtering method 0.995 Ta 0.005 ) 3 SnC 2 The outer layer coating is prepared by firstly adjusting the temperature of a chamber to 250 ℃, preserving heat for 15min,then open (Ti) 0.995 Ta 0.005 ) 3 SnC 2 And the sputtering power of the target direct current power supply is 1.0kw, and the sputtering time is 20min. And after the deposition is finished, cooling to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then stopping vacuumizing and removing pressure.
After the experiment, the microscopic morphology of the surface and the section of the deposited coating is observed by a scanning electron microscope, the obtained coating is flat and compact, the coating is well combined with a matrix, and the thickness of the double-layer coating is uniform everywhere, as shown in figure 2. In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing was performed in HF solution at 0.5mol/L and 2ppm at 80deg.C, with corrosion current density of 0.92. Mu.A/cm 2 [ self-etching potential 0.09V (vs. SCE)]At an assembly force of 150N/cm 2 Under the condition that the contact resistance is 9.46mΩ cm 2 。
Example 3
First preparing (Ti 0.8 Ta 0.2 ) 3 SnC 2 And preparing a TiC target and a metal bipolar plate. Step-by-step polishing the alloy substrate by using No. 200, no. 400, no. 600, no. 800, no. 1000, no. 1500 and No. 2000 metallographic sand paper, respectively ultrasonically cleaning the polished metal sample for 10min by using acetone, alcohol and deionized water, and drying in air for later use.
Depositing TiC intermediate layer by arc ion plating, and pre-vacuumizing the vacuum chamber until the back vacuum is 4×10 before coating preparation -3 And after Pa, applying 500V negative pulse bias voltage to the substrate, and performing back splash cleaning on the substrate for 15min to remove pollutants and oxide layers on the surface of the substrate. Then, an Ar flow valve is opened, ar flow is 50ml/min, the pumping speed of a molecular pump is regulated to control the working air pressure in a vacuum chamber, so that the working air pressure is maintained at about 0.4Pa, and the heating temperature of a chamber is 200 ℃. And (3) switching on a TiC target direct current power supply, wherein the arc current is 75A, the bias voltage is-350V, and the sputtering time is 7min.
Then deposit (Ti) by magnetron sputtering method 0.8 Ta 0.2 ) 3 SnC 2 The outer coating layer was first prepared by adjusting the chamber temperature to 300 c, maintaining the temperature for 15min, and then opened (Ti 0.9 Ta 0.1 ) 3 SnC 2 The direct current power supply of the target material,the sputtering power was 1.3kw and the sputtering time was 40min. And after the deposition is finished, cooling to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then stopping vacuumizing and removing pressure.
After the experiment, the microscopic morphology of the surface and the section of the deposited coating is observed by a scanning electron microscope, and the obtained coating is smooth and compact, well combined with a matrix and has uniform thickness at all positions of the double-layer coating. In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing was carried out in HF solution at a concentration of 0.5mol/L and 2ppm at a temperature of 80℃with a corrosion current density of 0.52. Mu.A/cm 2 [ self-etching potential 0.17V (vs. SCE)]At an assembly force of 150N/cm 2 Under the condition that the contact resistance is 3.49mΩ cm 2 。
Comparative example
Comparative example 2 TiC/Ti, metallic bipolar plates respectively 3 SnC 2 Double layer coating and (Ti, ta) 3 SnC 2 A single layer coating.
Comparative example 1
First prepare (Ti 0.95 Ta 0.05 ) 3 SnC 2 A bulk target and a commercial metal bipolar plate were prepared. Step-by-step polishing the alloy substrate by using No. 200, no. 400, no. 600, no. 800, no. 1000, no. 1500 and No. 2000 metallographic sand paper, respectively ultrasonically cleaning the polished metal sample for 20min by using acetone, alcohol and deionized water, and drying in air for later use.
Deposition (Ti) by magnetron sputtering method 0.95 Ta 0.05 ) 3 SnC 2 Coating, pre-vacuumizing the vacuum chamber to 4×10 back vacuum before coating preparation -3 And after Pa, applying 500V negative pulse bias voltage to the substrate to perform back splash cleaning on the substrate for 5min, and removing pollutants and an oxide layer on the surface of the substrate. Then the temperature of the chamber was adjusted to 200℃and kept for 15min, and then opened (Ti 0.95 Ta 0.05 ) 3 SnC 2 And the sputtering power of the target direct current power supply is 0.5kw, and the sputtering time is 30min. And after the deposition is finished, cooling to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then stopping vacuumizing and removing pressure.
After the experiment, the deposited coating is observed by a scanning electron microscopeThe surface and cross-section microtopography was found to give a smooth coating, but with slight skinning at the edges of the sample. In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing was performed in HF solution at 0.5mol/L and 2ppm at 80deg.C, with corrosion current density of 1.25 μA/cm 2 [ self-etching potential 0.08V (vs. SCE)]At an assembly force of 150N/cm 2 Under the condition that the contact resistance is 13.69mΩ cm 2 。
Comparative example 2
First, ti is prepared 3 SnC 2 And preparing a TiC target and a stainless steel metal bipolar plate. Step-by-step polishing the alloy substrate by using No. 200, no. 400, no. 600, no. 800, no. 1000, no. 1500 and No. 2000 metallographic sand paper, respectively ultrasonically cleaning the polished metal sample for 15min by using acetone, alcohol and deionized water, and drying in air for later use.
Depositing TiC intermediate layer by arc ion plating, and pre-vacuumizing the vacuum chamber until the back vacuum is 4×10 before coating preparation -3 And after Pa, applying 500V negative pulse bias voltage to the substrate to perform back splash cleaning on the substrate for 5min, and removing pollutants and an oxide layer on the surface of the substrate. Then, an Ar flow valve is opened, ar flow is 50ml/min, the pumping speed of a molecular pump is regulated to control the working air pressure in a vacuum chamber, so that the working air pressure is maintained at about 0.4Pa, and the heating temperature of a chamber is 150 ℃. And (3) switching on a TiC target direct current power supply, wherein the arc current is 40A, the bias voltage is-300V, and the sputtering time is 5min.
Then adopting a magnetron sputtering method to deposit Ti 3 SnC 2 The outer coating layer is prepared by firstly adjusting the temperature of a chamber to 250 ℃, preserving heat for 15min, and then opening Ti 3 SnC 2 And the sputtering power of the target direct current power supply is 1.2kw, and the sputtering time is 20min. And after the deposition is finished, cooling to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then stopping vacuumizing and removing pressure.
After the experiment, the microscopic morphology of the surface and the section of the deposited coating is observed by a scanning electron microscope, and the obtained coating is smooth and well combined with a matrix. In a fuel cell simulation environment, i.e. H 2 SO 4 Electrokinetic potential testing was performed in a solution of 0.5mol/L and 2ppm HF at 80 ℃The corrosion current density was 1.77. Mu.A/cm 2 [ self-etching potential 0.04V (vs. SCE)]At an assembly force of 150N/cm 2 Under the condition that the contact resistance is 12.6mΩ cm 2 。
From the results of the comparison, it can be seen that: the addition of the transition layer TiC can reduce the corrosion current density by 26-58%, the self-corrosion potential by 0.01-0.09V and the contact resistance by 31-75%. At Ti 3 SnC 2 The Ti position solid solution doped with Ta element can reduce the corrosion current density by 48-71%, the self-corrosion potential by 0.05-0.13V and the contact resistance by 25-72%.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A coating for a metal bipolar plate of a proton exchange membrane fuel cell, characterized by: tiC transition layer and outer layer (Ti, ta) of the coating inner layer 3 SnC 2 The TiC transition layer of the inner layer is used for reducing the thermal expansion mismatch degree between layers, improving the element compatibility of each layer and increasing the binding force of the coating; said outer layer (Ti, ta) 3 SnC 2 The coating is used for improving the corrosion resistance and the electrical conductivity of the substrate.
2. The coating for a metal bipolar plate of a proton exchange membrane fuel cell as claimed in claim 1, wherein: said (Ti, ta) 3 SnC 2 Is a ternary layered ceramic titanium-tin-carbon modified material, and is formed by solid solution doping of element Ta on Ti position of titanium-tin-carbon.
3. The coating for a proton exchange membrane fuel cell metallic bipolar plate of claim 2, wherein: the proportion of the doping elements is 0.5-30at%.
4. According to claimThe coating for a metal bipolar plate of a proton exchange membrane fuel cell as recited in claim 1, wherein: the thickness of the TiC transition layer is 50-150 nm, (Ti, ta) 3 SnC 2 The thickness of the coating is 200-400 nm.
5. The coating for a metal bipolar plate of a proton exchange membrane fuel cell as claimed in claim 1, wherein: the coating target material of the outer layer is (Ti, ta) 3 SnC 2 The single-phase target material is prepared by sintering Ti powder, ta powder, sn powder and graphite powder in a hot-pressing furnace by adopting a hot-pressing/solid-liquid phase reaction method, wherein the sintering temperature is 1100-1550 ℃, the heat preservation is carried out for 30-90 minutes, the hot-pressing pressure is 30-75 MPa, and flowing argon is used as protective gas.
6. The coating for a metal bipolar plate of a proton exchange membrane fuel cell as claimed in claim 1, wherein: the TiC transition layer is deposited on the metal bipolar plate by utilizing an arc ion plating device with high-efficiency deposition rate and is used for improving the binding force of an outer coating and increasing the compatibility of the coating and a matrix, (Ti, ta) 3 SnC 2 The coating is deposited by utilizing a magnetron sputtering device, two sputtering power supplies are arranged in a cavity, a sample is hung on a sample rack of the equipment when the coating is deposited, a stand column suspending the sample rotates, and the rotating stand column revolves along with a rotary table at the same time, so that uniform coating is obtained.
7. The metal bipolar plate coating for a proton exchange membrane fuel cell as recited in claim 6, wherein: the operation steps of the arc ion plating are as follows: before coating preparation, the vacuum chamber was pre-evacuated to 4X 10 -3 After Pa, applying 500V negative pulse bias to the substrate to perform back splash cleaning on the substrate for 5-15 min, removing pollutants and oxide layers on the substrate surface, then opening an Ar flow valve, ar gas flow rate of 50ml/min, controlling working air pressure in a vacuum chamber by adjusting pumping speed of a molecular pump to maintain the working air pressure in the vacuum chamber at 0.4Pa, heating the chamber at 100-200 ℃, opening TiC target direct current power supply, arc current of 40-80A, bias voltage of-200 to-400V, sputtering time2-10 min.
8. The coating for a metal bipolar plate of a proton exchange membrane fuel cell as recited in claim 6, wherein: the magnetron sputtering deposition (Ti, ta) 3 SnC 2 The coating comprises the following operation steps: firstly, regulating the temperature of a chamber to 200-300 ℃, preserving heat for 15min, and then opening (Ti, ta) 3 SnC 2 And (3) a target direct current power supply, wherein the sputtering power is 0.1-1.5 kW, the sputtering time is 20-50 min, after deposition, the temperature is reduced to room temperature at the speed of 10 ℃/min under the original vacuum condition, and then the vacuumizing and the pressure removing are stopped.
9. The coating for a metal bipolar plate of a proton exchange membrane fuel cell as recited in claim 6, wherein: the metal bipolar plate is subjected to pretreatment, firstly, the metal bipolar plate is polished, then the polished metal bipolar plate is respectively ultrasonically cleaned for 10-20 min through acetone, alcohol and deionized water, and then the metal bipolar plate is dried in air for standby.
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