CN116140613B - Corrosion-resistant conductive coating material for metal bipolar plate and preparation method thereof - Google Patents
Corrosion-resistant conductive coating material for metal bipolar plate and preparation method thereof Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 73
- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 238000005260 corrosion Methods 0.000 title claims abstract description 44
- 230000007797 corrosion Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 84
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 44
- 239000004917 carbon fiber Substances 0.000 claims abstract description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 36
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 43
- 239000011812 mixed powder Substances 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 33
- 238000005507 spraying Methods 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000010288 cold spraying Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 244000137852 Petrea volubilis Species 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007781 pre-processing Methods 0.000 claims description 4
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015202 MoCr Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/12—Metallic powder containing non-metallic particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/08—Iron group metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- 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
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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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Abstract
The invention relates to the technical field of fuel cells, and particularly discloses a corrosion-resistant conductive coating material for a metal bipolar plate and a preparation method thereof, wherein the corrosion-resistant conductive coating material comprises NiMoCr system powder and Ti 3 SiC 2 Powder, carbon fiber and carbon nanotube; wherein the carbon fiber exists in the form of nickel-coated carbon fiber composite powder, and the carbon nanotube exists in the form of nickel-coated carbon nanotube. The invention can meet the performance requirement of the metal bipolar plate under the complex working condition of the galvanic pile.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a corrosion-resistant conductive coating material for a metal bipolar plate and a preparation method thereof.
Background
The fuel cell uses hydrogen as energy, has the advantages of high efficiency, environmental protection, high specific energy and specific power, quick start and the like, and has wide application prospect in various fields. The bipolar plate is used as one of the key components of the fuel cell, has the key functions of supporting the cell structure, distributing the reaction gas, collecting the current, connecting the cells in series and the like, so that the performance of the bipolar plate restricts the commercialization process of the fuel cell.
The materials commonly used for the bipolar plates at present are graphite or metal, and the metal bipolar plates have become the main materials of the bipolar plates of the fuel cells because of the advantages of good mechanical property, easy processing, no gas permeation, low cost and the like. The metal bipolar plate of the fuel cell generally works in a high-temperature high-humidity acidic environment with the pH value of 2-5 and the temperature of 70-100 ℃, and the surface of the metal bipolar plate serving in the environment is usually passivated to form a layer of compact metal oxide film with poor conductivity, so that the contact resistance between the metal plate and a gas diffusion layer is increased, further the voltage loss of the cell due to ohmic polarization is increased, the output power of the cell is reduced, and meanwhile, metal ions in the bipolar plate are released due to corrosion and react with a catalyst and a membrane electrode to influence the reactivity and mass transfer of the cell, and further influence the performance of the cell. Thus, the use of metal bipolar plates alone is not satisfactory for fuel cells. In addition, with the rapid development of industries such as energy, environmental protection, metallurgy and the like, more realistic functional demands are put forward on novel coating materials, and the single-component or single-function coating hardly meets the performance demands of the metal bipolar plate under the complex working condition of a galvanic pile.
Disclosure of Invention
The invention mainly aims to provide a corrosion-resistant conductive coating material for a metal bipolar plate and a preparation method thereof, and aims to meet the performance requirements of the metal bipolar plate under the complex working condition of a galvanic pile.
To achieve the aim, the invention provides a corrosion-resistant conductive coating material for a metal bipolar plate, which comprises NiMoCr system powder and Ti 3 SiC 2 Powder, carbon fiber and carbon nanotube; wherein the carbon fiber exists in the form of nickel-coated carbon fiber composite powder, and the carbon nanotube exists in the form of nickel-coated carbon nanotube.
Optionally, the NiMoCr system powder comprises 13-17 wt% of Cr, 14-18 wt% of Mo and 65-73 wt% of Ni; the Ti is 3 SiC 2 The powder addition amount is 5-10wt% of NiMoCr system powder; the content of the carbon fiber is 0.5-0.8 wt% of the NiMoCr system powder, and the mass ratio of the carbon fiber to the carbon nano tube is 1:3.
Optionally, the particle size of Ni, cr and Mo powder in the NiMoCr system powder is 19-40 mu m; the Ti is 3 SiC 2 The grain diameter of the powder is 4-10 mu m; the particle size of the nickel-coated carbon fiber composite powder is 50-80 mu m, and the particle size of the nickel-coated carbon nano tube composite powder is 30-50 mu m.
Optionally, the nickel-carbon ratio of the nickel-coated carbon fiber composite powder and the nickel-coated carbon nanotube composite powder is 80:20.
in order to achieve the above purpose, the invention also provides a preparation method of the corrosion-resistant conductive coating of the metal bipolar plate, which comprises the following steps: cleaning and preprocessing a metal substrate; configuring coating powder, wherein the coating powder comprises the corrosion-resistant conductive coating material of the metal bipolar plate; ball milling the coating powder to form a first mixed powder; preheating the first mixed powder to form second mixed powder; and cold spraying the second mixed powder on the surface of the metal substrate to form a corrosion-resistant conductive coating.
Optionally, in the step of performing the cleaning pretreatment on the metal substrate, the method includes the steps of: polishing the surface of the metal substrate by adopting SiC sand paper; carrying out oil removal cleaning treatment on the metal substrate by adopting acetone in an ultrasonic cleaner; wherein the oil removal cleaning treatment time is 20min.
Optionally, in the step of ball milling the coated powder to form a first mixed powder, the method comprises the steps of: placing the coating powder in a planetary ball mill for ball milling treatment to form the first mixed powder; wherein the ball mill adopts argon protection, the ball-material ratio is 5:1, the ball milling rotating speed is 200-250 r/min, and the ball milling time is 3-4 h.
Optionally, in the step of performing the preheating treatment on the first mixed powder to form the second mixed powder, the method includes the steps of: placing the first mixed powder into a resistance furnace, preserving heat for 30min at 200 ℃, taking out, and continuously preserving heat for 30min in a room temperature environment; and (3) placing the first mixed powder into a resistance furnace, preserving heat for 30min at 200 ℃, taking out, and continuing to preserve heat for 30min in a room temperature environment for 3 times to obtain the second mixed powder.
Optionally, in the step of cold spraying the second mixed powder to the surface of the metal substrate to form a corrosion-resistant conductive coating, the method includes the steps of: and (3) using a cold spraying process to enable the second mixed powder to impact the surface of the metal substrate at a high speed so as to enable the second mixed powder to be mechanically combined and locally metallurgically combined with the metal substrate, thereby depositing the corrosion-resistant conductive coating on the surface of the metal substrate.
Optionally, the cold spraying process adopts nitrogen medium spraying, the spraying pressure is 5-6.5 MPa, the spraying temperature is 650-850 ℃, the spraying distance is 10-13 mm, and the powder feeding rate is 6-8 r/s.
Compared with the prior art, the invention has the beneficial effects that: the invention prepares the corrosion-resistant conductive coating on the surface of the metal substrate by a cold spraying process, optimizes the coating material composition, wherein the ceramic material Ti 3 SiC 2 The bonding strength of the coating and the metal substrate is effectively improved; the carbon fiber (Cf) and the Carbon Nanotubes (CNTs) have good electric conduction, heat conduction and corrosion resistance, and the advantages of the carbon fiber and the carbon nanotubes are effectively combined through the form of nickel-coated (carbon fiber and carbon nanotube) composite powder, so that the electric conduction and corrosion resistance of the coating are greatly improved. The synergistic effect of the ceramic phase and the carbon material not only improves the conductive and corrosion-resistant performance, but also improves the bonding strength of the coating, thereby improving the durability of the coating in the fuel cell environment and meeting the use requirement of the metal bipolar plate of the fuel cell.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of one embodiment of a method for preparing a corrosion-resistant conductive coating for a metallic bipolar plate according to the present invention.
Fig. 2 is an SEM image (left image) of a nickel-coated carbon nanotube and an SEM image (right image) of a nickel-coated carbon fiber in an embodiment of a method for preparing a corrosion-resistant conductive coating of a metal bipolar plate according to the present invention.
Detailed Description
The following description of the present invention will be made more fully hereinafter with reference to the accompanying drawings, in which it is shown, however, some, but not all embodiments of the invention are shown. 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 invention discloses a preparation method of a corrosion-resistant conductive coating of a metal bipolar plate, which comprises the following steps with reference to figure 1.
Step S10: and cleaning and preprocessing the metal substrate.
In the step, siC sand paper is adopted to polish the surface of the metal substrate; then, adopting acetone to carry out oil removal cleaning treatment on the metal substrate in an ultrasonic cleaner; wherein the oil removal cleaning treatment time is 20min. Through the steps, the stains on the surface of the metal substrate are cleaned, so that the surface of the metal substrate is ensured to be clean, and the subsequent preparation of the coating is facilitated.
Step S20: and (5) configuring coating powder.
In the above step, the coating powder comprises NiMoCr system powder, ti 3 SiC 2 Powder, carbon fiber and carbon nanotube; wherein the carbon fiber exists in the form of nickel-coated carbon fiber composite powder, and the carbon nanotube exists in the form of nickel-coated carbon nanotube. Specifically, the NiMoCr system powder comprises 13-17wt% of Cr, 14-18wt% of Mo and 65-73wt% of Ni; the Ti is 3 SiC 2 The powder addition amount is 5-10wt% of NiMoCr system powder; the content of the carbon fiber is 0.5-0.8 wt% of the NiMoCr system powder, and the mass ratio of the carbon fiber to the carbon nano tube is 1:3. Further, the particle size of Ni, cr and Mo powder in the NiMoCr system powder is 19-40 mu m; the Ti is 3 SiC 2 The grain diameter of the powder is 4-10 mu m; the particle size of the nickel-coated carbon fiber composite powder is 50-80 mu m, and the nickel-coated carbon nano tubeThe grain diameter of the composite powder is 30-50 mu m; the nickel-coated carbon fiber composite powder and the nickel-carbon ratio in the nickel-coated carbon nanotube composite powder are both 80:20.
step S30: the coated powder is ball milled to form a first mixed powder.
In the above step, the coating powder is put in a planetary ball mill to be ball-milled to form the first mixed powder; wherein the ball mill adopts argon protection, the ball-material ratio is 5:1, the ball milling rotating speed is 200-250 r/min, and the ball milling time is 3-4 h. The coating powder is sufficiently ground through the steps, so that the subsequent coating forming effect is ensured.
Step S40: the first mixed powder is subjected to a preheating treatment to form a second mixed powder.
In the steps, the first mixed powder is placed in a resistance furnace to be kept at 200 ℃ for 30min, and is taken out to be kept at room temperature for 30min; and (3) placing the first mixed powder into a resistance furnace, preserving heat for 30min at 200 ℃, taking out, and continuing to preserve heat for 30min in a room temperature environment for 3 times to obtain the second mixed powder. The coating powder is fully preheated through the steps, so that the subsequent coating forming effect is ensured.
Step S50: and cold spraying the second mixed powder on the surface of the metal substrate to form a corrosion-resistant conductive coating.
In the above step, the second mixed powder is impacted to the surface of the metal substrate at a high speed by adopting a cold spraying process, so that the second mixed powder and the metal substrate are mechanically combined and locally metallurgically combined, and the corrosion-resistant conductive coating is deposited on the surface of the metal substrate. Specifically, the cold spraying process adopts nitrogen medium spraying, the spraying pressure is 5-6.5 MPa, the spraying temperature is 650-850 ℃, the spraying distance is 10-13 mm, and the powder feeding rate is 6-8 r/s.
In the embodiment, the corrosion-resistant conductive coating is prepared on the surface of the metal substrate by a cold spraying process, and the coating material composition is optimized, wherein the ceramic material Ti 3 SiC 2 Effectively promote the junction between the coating and the metal substrateThe combined strength; the carbon fibers (Gr) and the Carbon Nanotubes (CNTs) have good electric conduction, heat conduction and corrosion resistance, and the advantages of the carbon fibers and the carbon nanotubes are effectively combined through the form of nickel-coated (carbon fibers and carbon nanotubes) composite powder, so that the electric conduction and corrosion resistance of the coating are greatly improved. The synergistic effect of the ceramic phase and the carbon material not only improves the conductive and corrosion-resistant performance, but also improves the bonding strength of the coating, thereby improving the durability of the coating in the fuel cell environment and meeting the use requirement of the metal bipolar plate of the fuel cell.
Examples 1-7 were performed on metal bipolar plates according to the above-described method for preparing a corrosion-resistant conductive coating for metal bipolar plates, and comparative analysis was performed by combining comparative examples 1-4.
Example 1.
Step S100: firstly, polishing the surface of the metal substrate by adopting SiC sand paper; then, adopting acetone to carry out oil removal cleaning treatment on the metal substrate in an ultrasonic cleaner; wherein the oil removal cleaning treatment time is 20min.
Step S200: taking NiMoCr system powder, wherein 13wt% of Cr,14wt% of Mo and 73wt% of Ni are taken, and the sum is 100%; ti (Ti) 3 SiC 2 The powder addition amount is 7wt% of the NiMoCr system, the carbon fiber addition amount is 0.6wt% of the NiMoCr system, and the mass ratio of the carbon fiber to the carbon nano tube is 1:3, namely the carbon nano tube addition amount is 1.8wt% of the NiMoCr system, wherein the carbon fiber exists in the form of nickel-coated carbon fiber composite powder, and the carbon nano tube exists in the form of nickel-coated carbon nano tube; the above powders are mixed to form a coating powder.
Step S300: placing the coating powder in the step S200 in a planetary ball mill for ball milling treatment to form the first mixed powder; wherein the ball mill adopts argon protection, the ball-material ratio is 5:1, the ball milling rotating speed is 200r/min, and the ball milling time is 3.5h.
Step S400: placing the first mixed powder in the step S400 into a resistance furnace, preserving heat for 30min at 200 ℃, taking out, and continuously preserving heat for 30min in a room temperature environment; and then the process is installed for 3 times to obtain the second mixed powder, and the second mixed powder is stored for standby.
Step S500: and (3) processing the second mixed powder in the step S500 into the metal substrate in the step S100 through a cold spraying process, wherein a spraying medium is nitrogen, the spraying pressure is 6.0 MPa, the spraying temperature is 700 ℃, the spraying distance is 10 mm, and the powder feeding rate is 7 r/S.
Example 2: example 2 differs from example 1 only in that: the method comprises the steps of mixing three metal powders of Cr, mo and Ni according to a mass ratio of 17:16:67wt% mixing, preparation method referring to example 1, a metal bipolar plate coating of example 2 was obtained.
Example 3: example 3 differs from example 1 only in that: the method comprises the steps of mixing Cr, mo and Ni metal powder according to a mass ratio of 14:18:68wt% mixing, preparation method referring to example 1, a metallic bipolar plate coating of example 3 was obtained.
Example 4: example 4 differs from example 1 only in that: the method comprises the steps of mixing three metal powders of Cr, mo and Ni according to a mass ratio of 17:18:65wt% mixing, preparation method referring to example 1, a metallic bipolar plate coating of example 4 was obtained.
Example 5: example 5 differs from example 1 only in that: the addition amount of the carbon fiber is 0.5wt% of the NiMoCr system, the mass ratio of the carbon fiber to the carbon nano tube is 1:3, namely the addition amount of the carbon nano tube is 1.5wt% of the NiMoCr system, and the Ti is as follows 3 SiC 2 The powder addition was 7wt% of the NiMoCr system and the preparation method was as described in example 1 to give the metal bipolar plate coating of example 5.
Example 6: example 6 differs from example 1 in that: the method comprises the steps of mixing three metal powders of Cr, mo and Ni according to a mass ratio of 15:17:68wt% of the carbon fiber is mixed, the addition amount of the carbon fiber is 0.8wt% of the NiMoCr system, the mass ratio of the carbon fiber to the carbon nano tube is 1:3, namely the addition amount of the carbon nano tube is 2.4wt% of the NiMoCr system, and the Ti is 3 SiC 2 The powder addition was 5wt% of the NiMoCr system and the preparation method was as described in example 1 to give the metal bipolar plate coating of example 6.
Example 7: example 7 differs from example 1 in that: the method comprises the steps of mixing three metal powders of Cr, mo and Ni according to a mass ratio of 17:18:65wt% of the carbon fiber is mixed, the adding amount of the carbon fiber is 0.6wt% of the NiMoCr system, the mass ratio of the carbon fiber to the carbon nano tube is 1:3, namely the adding amount of the carbon nano tube is Ni1.8wt% of MoCr system, ti 3 SiC 2 The powder addition was 10wt% of the NiMoCr system and the preparation method was as described in example 1 to give the metal bipolar plate coating of example 7.
Comparative example 1: comparative example 1 differs from example 1 in that: only three metal powders of Cr, mo and Ni are taken, and the mass ratio is 13:14:73wt% of the mixture was mixed, and the preparation method was referred to example 1, resulting in a metallic bipolar plate of comparative example 1.
Comparative example 2: comparative example 1 differs from example 1 in that: only three metal powders of Cr, mo and Ni are taken, and the mass ratio is 25:30:45wt% of the mixture was mixed, and the preparation method was referred to example 1, resulting in a metallic bipolar plate of comparative example 2.
Comparative example 3: comparative example 3 differs from example 1 in that: the addition amount of the carbon fiber is 1.5wt% of the NiMoCr system, the addition amount of the carbon nano tube is 4.5wt% of the NiMoCr system, and the Ti 3 SiC 2 The powder addition was 13wt% of the NiMoCr system and the preparation method was as described in reference to example 1 to obtain a metallic bipolar plate coating of comparative example 3.
Comparative example 4: comparative example 4 differs from example 1 only in that: does not add Ti 3 SiC 2 Preparation method referring to example 1, a metallic bipolar plate coating of comparative example 4 was obtained.
Among them, the conductivity and corrosion resistance properties of the special layers of the metallic bipolar plates of the examples and comparative examples are shown in the following table.
As can be seen from the table, the corrosion potential of the metal bipolar plate coating obtained by the metal bipolar plate corrosion-resistant conductive coating material and the manufacturing method thereof is higher than that of comparative examples 1-4, and the corrosion resistance of the metal bipolar plate is effectively improved. And the interface contact resistance is lower than that of comparative examples 1-4, so that the conductivity of the metal bipolar plate is effectively improved.
It should be noted that, other contents of the corrosion-resistant conductive coating material for metal bipolar plates and the preparation method thereof disclosed by the invention are the prior art, and are not described herein.
In addition, it should be noted that, if there is a directional indication (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention, the directional indication is merely used to explain the relative positional relationship, movement condition, etc. between the components in a specific posture (as shown in the drawings), and if the specific posture is changed, the directional indication is correspondingly changed.
Furthermore, it should be noted that the description of "first," "second," etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The foregoing is merely an alternative embodiment of the present invention, and is not intended to limit the scope of the present invention, and all applications of the present invention directly/indirectly in other related technical fields are included in the scope of the present invention.
Claims (9)
1. A preparation method of a corrosion-resistant conductive coating of a metal bipolar plate is characterized by comprising the following steps: the method comprises the following steps:
cleaning and preprocessing a metal substrate;
configuring a coating powder, wherein the coating powder comprises NiMoCr system powder, ti 3 SiC 2 Powder, carbon fiber and carbon nanotube; wherein the carbon fiber exists in the form of nickel-coated carbon fiber composite powder, and the carbon nanotube exists in the form of nickel-coated carbon nanotube; ball milling the coating powder to form a first mixed powder;
preheating the first mixed powder to form second mixed powder;
and cold spraying the second mixed powder on the surface of the metal substrate to form a corrosion-resistant conductive coating.
2. The method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 1, wherein the method comprises the following steps: the NiMoCr system powder comprises 13-17 wt% of Cr, 14-18 wt% of Mo and 65-73 wt% of Ni; the Ti is 3 SiC 2 The powder addition amount is 5-10wt% of NiMoCr system powder; the content of the carbon fiber is 0.5-0.8 wt% of the NiMoCr system powder, and the mass ratio of the carbon fiber to the carbon nano tube is 1:3.
3. The method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 1, wherein the method comprises the following steps: the particle size of Ni, cr and Mo powder in the NiMoCr system powder is 19-40 mu m; the Ti is 3 SiC 2 The grain diameter of the powder is 4-10 mu m; the particle size of the nickel-coated carbon fiber composite powder is 50-80 mu m, and the particle size of the nickel-coated carbon nano tube composite powder is 30-50 mu m.
4. The method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 1, wherein the method comprises the following steps: the nickel-coated carbon fiber composite powder and the nickel-carbon ratio in the nickel-coated carbon nanotube composite powder are both 80:20.
5. the method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 1, wherein the method comprises the following steps: the step of cleaning and preprocessing the metal substrate comprises the following steps:
polishing the surface of the metal substrate by adopting SiC sand paper;
carrying out oil removal cleaning treatment on the metal substrate by adopting acetone in an ultrasonic cleaner; wherein the oil removal cleaning treatment time is 20min.
6. The method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 1, wherein the method comprises the following steps: in the step of ball-milling the coated powder to form a first mixed powder, the method comprises the steps of:
placing the coating powder in a planetary ball mill for ball milling treatment to form the first mixed powder; wherein the ball mill adopts argon protection, the ball-material ratio is 5:1, the ball milling rotating speed is 200-250 r/min, and the ball milling time is 3-4 h.
7. The method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 1, wherein the method comprises the following steps: the step of preheating the first mixed powder to form a second mixed powder includes the steps of:
placing the first mixed powder into a resistance furnace, preserving heat for 30min at 200 ℃, taking out, and continuously preserving heat for 30min in a room temperature environment;
and (3) placing the first mixed powder into a resistance furnace, preserving heat for 30min at 200 ℃, taking out, and continuing to preserve heat for 30min in a room temperature environment for 3 times to obtain the second mixed powder.
8. The method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 1, wherein the method comprises the following steps: in the step of cold spraying the second mixed powder onto the surface of the metal substrate to form a corrosion-resistant conductive coating, the method comprises the steps of:
and (3) using a cold spraying process to enable the second mixed powder to impact the surface of the metal substrate at a high speed so as to enable the second mixed powder to be mechanically combined and locally metallurgically combined with the metal substrate, thereby depositing the corrosion-resistant conductive coating on the surface of the metal substrate.
9. The method for preparing the corrosion-resistant conductive coating for the metal bipolar plate according to claim 8, wherein the method comprises the following steps: the cold spraying process adopts nitrogen medium spraying, the spraying pressure is 5-6.5 MPa, the spraying temperature is 650-850 ℃, the spraying distance is 10-13 mm, and the powder feeding rate is 6-8 r/s.
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