CN115000444B - Multilayer composite carbon coating, preparation method and application thereof, fuel cell bipolar plate and fuel cell - Google Patents
Multilayer composite carbon coating, preparation method and application thereof, fuel cell bipolar plate and fuel cell Download PDFInfo
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- CN115000444B CN115000444B CN202210723124.7A CN202210723124A CN115000444B CN 115000444 B CN115000444 B CN 115000444B CN 202210723124 A CN202210723124 A CN 202210723124A CN 115000444 B CN115000444 B CN 115000444B
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- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000000446 fuel Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 113
- 239000002346 layers by function Substances 0.000 claims abstract description 27
- 230000007704 transition Effects 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000004767 nitrides Chemical class 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 22
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000013077 target material Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 argon ions Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010963 304 stainless steel Substances 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- H01M8/0226—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a multilayer composite carbon coating, a preparation method and application thereof, a fuel cell bipolar plate and a fuel cell. The multilayer composite carbon coating of the present invention comprises: the bottom layer, the transition layer and the conductive functional layer; the transition layer comprises a mixed layer and a supporting layer, and the mixed layer and the supporting layer are alternately arranged; the mixed layer comprises an A phase and a B phase, wherein the A phase is a simple substance of an element A, and the B phase is one of a simple substance of an element B, a carbide BC of the element B and a nitride BN of the element B; the support layer is carbide BC of element B or nitride BN of element B; the element a and the element B are each selected from one of Cr, ti, W, ni, ta, zr and Si, and the element a and the element B are different. The multi-layer composite carbon coating has better binding force, higher corrosion resistance and low deposition temperature; the thickness of the coating can be effectively reduced, the raw materials are cheap and easy to obtain, and the cost is reduced.
Description
Technical Field
The invention particularly relates to a multilayer composite carbon coating, a preparation method and application thereof, a fuel cell bipolar plate and a fuel cell.
Background
With the increasing prominence of the problems of massive consumption of traditional fossil energy and environmental pollution, there is an urgent need to find a new energy source to replace fossil energy to reduce the consumption of fossil energy, even completely replace fossil energy. With the continuous and deep research on new energy, people find that the hydrogen energy resource is rich, the heat value is high, and the reactant is only water without other pollution, so that the method is more advantageous. The hydrogen fuel cell is a device for converting chemical energy generated by the reaction of hydrogen and oxygen (air) into electric energy, and is characterized by high efficiency and zero emission. The proton exchange membrane fuel cell has small volume, high starting speed and low operating temperature, and is hopefully applied to new energy automobiles. Its disadvantages such as poor stability, poor durability and high cost have also prevented its large-scale commercial application. A key component of a hydrogen fuel cell is the bipolar plate, which accounts for 80% of the weight and 45% of the cost. During operation of the cell, it serves to conduct and distribute reactant gases, collect and transport current, remove water produced by the reaction, and support the membrane electrode. When the application of the fuel cell to automobiles is discussed, the metal light plate is gradually becoming a mainstream bipolar plate material because of the characteristics of good electric and heat conductivity, small size, easy processing, low manufacturing cost and the like. However, for successful application, it is necessary to solve the problems of poor corrosion resistance and poor electrical conductivity of metal surfaces in acidic environments. Therefore, the metal light plate needs to be subjected to surface treatment, so that the metal light plate can resist corrosion and conduct electricity.
At present, a layer of coating is added on the surface of a metal light plate, and the coating is required to have the characteristics of stable performance, corrosion resistance, good electric conduction, low cost, simple process and the like. Amorphous carbon coatings are becoming a focus of attention because of their good corrosion resistance and electrical conductivity. There are three structures of common carbon coatings: amorphous carbon serving as a supporting skeleton and densification, and flake graphite serving as electric conduction (SP) 2 Hybrid) and diamond or diamond-like particles (SP) acting as high potential corrosion inhibitors 3 And (5) hybridization). Under the acidic environment with high potential, the layers of the coating are not tightly combined, and the coating material is loose, so that the corrosion solution easily penetrates through the coating, and the corrosion resistance and durability of the common carbon coating can be reduced. The prior art also has the effect of improving corrosion resistance by adding a transition layer, but the prior art does not have the effect ofAttention is paid to the corresponding binding force, and thus durability cannot be truly improved. There are also transition layers (CN 108598497 a) obtained by doping noble metals in carbon coatings or co-deposition with noble and non-noble metals, which undoubtedly increase the cost of the material and make mass production difficult.
Disclosure of Invention
The invention solves the technical problems of low corrosion resistance and low binding force of an amorphous carbon coating in the prior art, which cause poor durability, high material cost caused by doping noble metal and difficulty in large-scale production and commercial application, and provides a multilayer composite carbon coating, a preparation method and application thereof, a fuel cell bipolar plate and a fuel cell. The multi-layer composite carbon coating has better corrosion resistance and higher binding force between layers and between the multi-layer composite carbon coating and a base material, so that the multi-layer composite carbon coating has better durability, does not contain noble metal, can reduce the cost of raw materials, and is beneficial to large-scale production and commercial application.
The invention solves the technical problems by the following technical proposal:
the invention provides a multilayer composite carbon coating, which comprises the following components: the bottom layer, the transition layer and the conductive functional layer; the transition layer comprises a mixed layer and a supporting layer, at least one layer is alternately arranged on the mixed layer and the supporting layer, the mixed layer is adjacent to the bottom layer, and the supporting layer is adjacent to the conductive functional layer;
the mixed layer comprises an A phase and a B phase, wherein the A phase is a simple substance of an element A, and the B phase is one of a simple substance of an element B, a carbide BC of the element B and a nitride BN of the element B; the support layer is carbide BC of element B or nitride BN of element B;
the element a and the element B are each selected from one of Cr, ti, W, ni, ta, zr and Si, and the element a and the element B are different.
The mixed layer creatively adopts different elements to form a multi-crystalline mixed phase, and simple substances or compounds in different crystalline states can compensate each other, so that the corrosion resistance of the mixed layer is improved.
In the present invention, in the mixed layer, the a phase and the B phase are generally present in the form of simple substance crystals or compound crystals.
In the present invention, the mass ratio of the A phase to the B phase is preferably 1 (0.5-2), more preferably 1:1.
In the present invention, the element A is preferably selected from Cr or Ti.
In the present invention, the element B is preferably W.
In the present invention, the material of the underlayer may be conventional in the art, preferably the simple substance of element a.
In the present invention, the conductive functional layer may be a conductive layer for a bipolar plate of a fuel cell, which is conventional in the art, preferably an amorphous carbon coating.
In the present invention, the conductive functional layer generally includes carbon, and preferably further includes one or more elements of nitrogen, hydrogen, and fluorine.
The conductive functional layer of the invention adopts SP 2 The carbon structure is mainly in the form of 0.5-4 mu m in thickness, certain corrosion resistance and conductivity are considered, the binding force of the coating reaches 1-2 levels, and the coating performance has better durability.
In the present invention, the thickness of the underlayer may be conventional in the art, preferably 0.05 to 0.5 μm, more preferably 0.08 μm.
In the present invention, the thickness of the mixed layer may be conventional in the art, preferably 0.1 to 1 μm, more preferably 0.5 μm.
In the present invention, the thickness of the support layer may be conventional in the art, preferably 0.1 to 1 μm, more preferably 0.3 μm.
In the present invention, the thickness of the conductive functional layer may be conventional in the art, preferably 0.5 to 4 μm, more preferably 4 μm.
In the present invention, the total thickness of the underlayer and the transition layer may be conventional in the art, preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.
In the present invention, the nano-hardness of the primer layer may be conventional in the art, preferably 500-1500Hv.
In the present invention, the nano hardness of the mixed layer may be conventional in the art, preferably 1000 to 2000Hv.
In the present invention, the nano-hardness of the support layer may be conventional in the art, preferably 2000-3000Hv.
In the present invention, the nano-hardness of the conductive functional layer may be conventional in the art, preferably 1500 to 2000Hv.
The nano hardness of the composite carbon coating is creatively designed into a gentler gradient, so that the combination of the multiple layers of coatings is tighter, and the durability of the coatings in application is ensured by the better combination force. Meanwhile, different crystal boundaries are arranged between layers of the multi-layer composite carbon coating, so that a penetrating mode from top to bottom is broken, further development of corrosion from top to bottom is prevented, and a better corrosion-resistant effect is generated on the whole.
In the present invention, preferably, the multi-layered composite carbon coating layer does not include a noble metal. It will be generally understood by those skilled in the art that the noble metal will generally be one or more of gold, silver, ruthenium, rhodium, palladium, osmium, iridium and platinum.
The invention also provides a preparation method of the multilayer composite carbon coating, which comprises the following steps: the layers of the multilayer composite carbon coating as described above are deposited sequentially.
In the present invention, the deposition method of the underlayer, the mixed layer and the supporting layer is preferably unbalanced magnetron sputtering.
Wherein, the unbalanced magnetron sputtering can be performed by adopting a method conventional in the field, and generally comprises the following steps: and under the protection of inert atmosphere, applying a bias negative voltage on the base material, and sequentially starting targets of all layers of the multilayer composite carbon coating for deposition.
In the unbalanced magnetron sputtering, the bias negative voltage may be conventional in the art, preferably 1000 to 2000V.
The pressure in the chamber of the unbalanced magnetron sputtering may be conventional in the art, preferably 0.1 to 1Pa.
The inert atmosphere may be conventional in the art, preferably argon.
In the present invention, the deposition method of the conductive functional layer preferably includes bombarding the carbon target in a mixed gas, wherein the mixed gas includes C element, and the mixed gas further includes one or more of H, N, ar and F element.
Wherein the mixed gas generally comprises a carbon-containing gas, preferably CH 4 、C 2 H 2 And CF (compact F) 4 One or more of the following.
Wherein the mixed gas preferably further comprises one or more of nitrogen, argon and hydrogen.
In certain preferred embodiments of the present invention, the mixed gas comprises a volume ratio of (1-10): acetylene and nitrogen of 1.
In certain preferred embodiments of the present invention, the mixed gas comprises a volume ratio of (1-10): acetylene and argon of 1.
The method for bombarding the carbon target can be conventional in the art, preferably unbalanced magnetron sputtering or bombarding with an electric arc, a laser pulse or an electron beam, and more preferably unbalanced magnetron sputtering.
In the deposition of the conductive functional layer, the bias negative voltage of the unbalanced magnetron sputtering is preferably 50 to 150V, more preferably 80V.
The bias negative voltage in the lower conductive functional layer deposition adopted by the invention can reduce the deposition temperature of the conductive functional layer, thereby reducing the internal stress in the coating and increasing the bonding strength of the substrate.
In the deposition of the conductive functional layer, the pressure in the cavity of the unbalanced magnetron sputtering may be conventional in the art, and is preferably 0.1 to 1Pa.
The invention also provides a multilayer composite carbon coating obtained by the preparation method.
The invention also provides an application of the multilayer composite carbon coating in a fuel cell bipolar plate.
The invention also provides a fuel cell bipolar plate comprising a substrate and the multilayer composite carbon coating, the bottom layer in the multilayer composite carbon coating being adjacent to the substrate.
In the present invention, the substrate may be a fuel cell bipolar plate substrate conventional in the art, preferably a corrosion-resistant metal or a corrosion-resistant non-metal material.
Wherein the corrosion resistant metal may be conventional in the art, preferably stainless steel, titanium plate, cemented carbide, high speed steel or bearing steel. The stainless steel is preferably 304 stainless steel or 306 stainless steel.
Wherein the corrosion-resistant nonmetallic material is conventional in the art, preferably graphite.
In the present invention, the preparation method of the fuel cell bipolar plate may be conventional in the art, and generally, the multilayer composite carbon coating layer may be deposited on the substrate.
Wherein, preferably, the substrate is further cleaned, baked and etched prior to depositing the multilayer composite carbon coating.
The washing may be performed by a method conventional in the art, preferably by ultrasonic vibration washing in an alkaline solution and filtered pure water in sequence.
Preferably, the method further comprises drying after cleaning and before baking. The drying is preferably performed in a drying box.
The baking may be carried out by methods conventional in the art, preferably heating under vacuum.
The pressure of the vacuum environment is preferably below 10 -2 Pa。
The baking temperature may be conventional in the art, preferably from 0 to 300 ℃, more preferably from 150 to 250 ℃.
Wherein the etching may be performed by methods conventional in the art, preferably plasma etching in a vacuum environment with the substrate biased at a negative voltage.
The pressure of the vacuum environment is preferably lower than 3×10 during the etching process -3 Pa。
In the etching process, the plasma etching is performed by adopting argon ions.
The argon ions may be prepared by methods conventional in the art, typically by ionizing argon. The ionization voltage may be conventional in the art, preferably 1000-1500V.
During the etching, the bias negative voltage is preferably 1000 to 2000V.
The etching time may be conventional in the art, and is preferably 30 to 60 minutes.
The invention also provides a fuel cell comprising a fuel cell bipolar plate as described above.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
(1) The invention effectively reduces the huge drop of hardness between the base material and the conductive functional layer of the outermost layer, so that the layers are better and more tightly connected, the binding force is better, and the coating performance is longer.
(2) The multilayer composite carbon coating contains various grain boundaries, prevents corrosion channels from being generated or further expands to a lower layer, and has higher corrosion resistance.
(3) The deposition temperature of the coating can be lower than 300 ℃, and the energy consumption and the difficulty of equipment manufacturing (whole high temperature resistance and local water cooling and temperature reduction) are greatly reduced.
(4) The invention can effectively reduce the thickness of the multi-layer composite carbon coating, the sum of the thicknesses of the bottom layer and the transition layer can be 0.2-2 mu m, and the thickness of the conductive functional layer can be 0.5-4 mu m, so that the requirements can be met, the consumption of raw materials is reduced, the preparation time is greatly shortened, the efficiency is improved, and the potential equipment hidden trouble caused by long-time deposition of the coating is further avoided.
(5) The invention does not need noble metal elements, has cheap and easily obtained raw materials and reduces the cost.
Drawings
Fig. 1 is a schematic structural view of a bipolar plate of a fuel cell according to the present invention.
Reference numerals
1-a substrate; 2-a bottom layer; 3-a transition layer; 31-a mixed layer; 32-a support layer; 4-conductive functional layer.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
S1: pretreatment of
Placing the metal bipolar plate substrate into vacuum equipment, and vacuumizing until the pressure is lower than 10 -2 Pa; the heater in the equipment is turned on to bake the polar plate and the cavity, so that the temperature is raised to 150-250 ℃. Continuously vacuumizing until the pressure is lower than 3 multiplied by 10 -3 Pa, introducing argon, starting an anode ion beam power supply, starting a bias power supply connected with the bipolar plate at 1000-1500V, wherein the bias negative voltage is 1000-2000V, and the process pressure in the cavity is 0.1-1Pa for 30-60min, so as to clean the surface of the bipolar plate.
S2: depositing an underlayer and a transition layer
Argon is introduced, the process pressure is kept at 0.1-1Pa, an unbalanced magnetron sputtering target is started, the target material is Cr, the bipolar plate base material is deposited, and the deposition thickness is 0.08 mu m, so that a bottom layer is formed. Argon is kept to be introduced, the process pressure is 0.1-1Pa, an unbalanced magnetron sputtering target is started, the targets are Cr and WC (mass ratio is 1:1), the deposition thickness is 0.5 mu m, and a mixed layer is deposited on the surface of the bottom layer. Argon is introduced, the process pressure is kept at 0.1-1Pa, an unbalanced magnetron sputtering target is started, the target material is WC, the deposition thickness is 0.3 mu m, and a supporting layer is deposited on the surface of the mixed layer. The sum of the thicknesses of the base layer, the mixed layer and the support layer was 0.88. Mu.m.
S3: depositing a conductive functional layer
Closing argon, and introducing mixed gas of acetylene and nitrogen in a ratio of 2:1, starting an unbalanced magnetron sputtering carbon target, starting a bias power supply connected with a bipolar plate, wherein the bias negative voltage is 80v, the process pressure in a cavity is 0.1-1Pa, depositing on the supporting layer to form an amorphous conductive carbon coating, and the thickness is 3 mu m, namely a conductive functional layerA fuel cell bipolar plate is obtained. The conductive functional layer of the invention adopts SP 2 The carbon structure is mainly in the form of a certain corrosion resistance and conductivity. Ensures that the final coating binding force reaches 1-2 levels, and the coating performance has better durability.
Example 2
S1 is the same as that of the embodiment 1, the target material of the bottom layer in S2 is a Ti target, the target material of the mixed layer is Ti and WC, the mixed gas in S3 is acetylene and argon, and the ratio is 2:1, the same procedure as in example 1 was repeated to obtain a fuel cell bipolar plate.
Example 3
S1 is the same as that of the embodiment 1, the target material of the bottom layer in S2 is a Ti target, and the target material of the mixed layer is Ti and WC; the mixed gas in S3 is CF 4 And H 2 The proportion is 2:1, the same procedure as in example 1 was repeated to obtain a fuel cell bipolar plate.
Effect examples
Referring to fig. 1, the multi-layer composite carbon coating of the present invention includes a base layer 2, a transition layer 3 and a conductive functional layer 4 in this order, the transition layer 3 including a mixed layer 31 and a support layer 32, the mixed layer 31 and the support layer 32 being alternately arranged one layer each. The fuel cell bipolar plate of the present invention comprises a substrate 1 and the above-described multilayer composite carbon coating layer attached to the substrate 1.
Claims (21)
1. A multilayer composite carbon coating, comprising: the bottom layer, the transition layer and the conductive functional layer; the transition layer comprises a mixed layer and a supporting layer, at least one layer is alternately arranged on the mixed layer and the supporting layer, the mixed layer is adjacent to the bottom layer, and the supporting layer is adjacent to the conductive functional layer;
the mixed layer comprises an A phase and a B phase, wherein the A phase is a simple substance of an element A, and the B phase is one of a simple substance of an element B, a carbide BC of the element B and a nitride BN of the element B; the support layer is carbide BC of element B or nitride BN of element B;
the element a and the element B are each selected from one of Cr, ti, W, ni, ta, zr and Si, and the element a and the element B are different;
the thickness of the bottom layer is 0.05-0.5 mu m;
the thickness of the mixed layer is 0.1-1 mu m;
the thickness of the supporting layer is 0.1-1 mu m;
the thickness of the conductive functional layer is 0.5-4 mu m;
the total thickness of the bottom layer and the transition layer is 0.2-3 mu m.
2. The multilayer composite carbon coating according to claim 1, wherein the mass ratio of the a phase to the B phase is 1 (0.5-2);
and/or, the element A is Cr or Ti;
and/or, the element B is W;
and/or, the bottom layer is a simple substance of the element A;
and/or, the conductive functional layer is an amorphous carbon coating;
and/or the conductive functional layer comprises one or more elements of nitrogen, hydrogen and fluorine.
3. The multilayer composite carbon coating of claim 2, wherein the mass ratio of the a phase to the B phase is 1:1.
4. The multilayer composite carbon coating of claim 1, wherein the underlayer has a thickness of 0.08 μm;
and/or the thickness of the mixed layer is 0.5 μm;
and/or the thickness of the supporting layer is 0.3 μm;
and/or the thickness of the conductive functional layer is 4 μm;
and/or the total thickness of the bottom layer and the transition layer is 0.2-2 mu m.
5. The multilayer composite carbon coating of claim 4, wherein the total thickness of the underlayer and the transition layer is 0.88 μm.
6. The multilayer composite carbon coating of claim 1, wherein the nanohardness of the underlayer is 500 to 1500Hv;
and/or the nano hardness of the mixed layer is 1000-2000Hv;
and/or the nano hardness of the supporting layer is 2000-3000Hv;
and/or the nano hardness of the conductive functional layer is 1500-2000 Hv.
7. The preparation method of the multilayer composite carbon coating is characterized by comprising the following steps of: depositing the layers of the multilayer composite carbon coating according to any one of claims 1-6 in sequence.
8. The method of preparing a multilayer composite carbon coating according to claim 7, wherein the deposition method of the underlayer, the mixed layer and the support layer is unbalanced magnetron sputtering;
and/or the deposition method of the conductive functional layer comprises bombarding a carbon target in a mixed gas, wherein the mixed gas comprises C element, and the mixed gas further comprises one or more of H, N, ar and F element.
9. The method for preparing the multilayer composite carbon coating according to claim 8, wherein the unbalanced magnetron sputtering comprises the following steps: and under the protection of inert atmosphere, applying a bias negative voltage on the base material, and sequentially starting targets of all layers of the multilayer composite carbon coating for deposition.
10. The method for preparing a multi-layer composite carbon coating according to claim 9, wherein the bias negative voltage is 1000-2000 v.
11. The method for preparing a multilayer composite carbon coating according to claim 9, wherein the chamber pressure of the unbalanced magnetron sputtering is 0.1-1 pa.
12. The multi-layered composite carbon coating of claim 8The preparation method is characterized in that the mixed gas comprises CH 4 、C 2 H 2 And CF (compact F) 4 One or more of the following.
13. The method of producing a multilayer composite carbon coating of claim 8, wherein the mixed gas further comprises one or more of nitrogen, argon and hydrogen.
14. The method of claim 8, wherein the method of bombarding the carbon target is unbalanced magnetron sputtering or is performed using an arc, laser pulse or electron beam.
15. The method for preparing a multi-layer composite carbon coating according to claim 14, wherein the bias negative voltage of the unbalanced magnetron sputtering is 50-150 v.
16. The method of claim 15, wherein the bias negative voltage of the unbalanced magnetron sputtering is 80V.
17. The method for preparing a multilayer composite carbon coating according to claim 14, wherein the pressure in the chamber of the unbalanced magnetron sputtering is 0.1-1 pa.
18. A multilayer composite carbon coating produced by the production method of any one of claims 7 to 17.
19. Use of a multilayer composite carbon coating according to any one of claims 1 to 6 and 18 in a fuel cell bipolar plate.
20. A fuel cell bipolar plate comprising a substrate and the multilayer composite carbon coating of any one of claims 1-6 and 18, the underlayer in the multilayer composite carbon coating being adjacent to the substrate.
21. A fuel cell comprising the fuel cell bipolar plate of claim 20.
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