CN115663224B - Metal composite coating of bipolar plate of proton exchange membrane fuel cell and preparation method thereof - Google Patents
Metal composite coating of bipolar plate of proton exchange membrane fuel cell and preparation method thereof Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract 8
- 238000000576 coating method Methods 0.000 title claims abstract 8
- 239000000446 fuel Substances 0.000 title claims abstract 8
- 239000012528 membrane Substances 0.000 title claims abstract 8
- 239000002905 metal composite material Substances 0.000 title claims abstract 8
- 238000002360 preparation method Methods 0.000 title claims abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 54
- 239000002184 metal Substances 0.000 claims abstract 51
- 239000002131 composite material Substances 0.000 claims abstract 14
- 238000005260 corrosion Methods 0.000 claims abstract 10
- 230000007797 corrosion Effects 0.000 claims abstract 10
- 230000003197 catalytic effect Effects 0.000 claims abstract 8
- 239000000758 substrate Substances 0.000 claims abstract 8
- 238000004140 cleaning Methods 0.000 claims abstract 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract 2
- 239000004917 carbon fiber Substances 0.000 claims abstract 2
- 239000003575 carbonaceous material Substances 0.000 claims abstract 2
- 229910021389 graphene Inorganic materials 0.000 claims abstract 2
- 229910002804 graphite Inorganic materials 0.000 claims abstract 2
- 239000010439 graphite Substances 0.000 claims abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims 32
- 238000000151 deposition Methods 0.000 claims 6
- 239000000126 substance Substances 0.000 claims 5
- 230000003647 oxidation Effects 0.000 claims 3
- 238000007254 oxidation reaction Methods 0.000 claims 3
- 239000000956 alloy Substances 0.000 claims 2
- 229910045601 alloy Inorganic materials 0.000 claims 2
- 238000007733 ion plating Methods 0.000 claims 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 2
- 150000004706 metal oxides Chemical class 0.000 claims 2
- 238000005240 physical vapour deposition Methods 0.000 claims 2
- 238000007750 plasma spraying Methods 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 239000002356 single layer Substances 0.000 claims 2
- 238000004544 sputter deposition Methods 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052777 Praseodymium Inorganic materials 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 238000009713 electroplating Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 238000001755 magnetron sputter deposition Methods 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 claims 1
- 229910052701 rubidium Inorganic materials 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 239000011135 tin Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a bipolar plate metal composite coating of a proton exchange membrane fuel cell and a preparation method thereof, wherein the surface of a metal polar plate substrate sequentially comprises a composite metal layer and a nano conductive layer covered on the surface of the composite metal layer from inside to outside, the thickness of the composite metal layer is 5-3000 nm, and the composite metal layer sequentially comprises a metal corrosion-resistant layer, a metal self-healing layer and a metal catalytic layer from inside to outside; the thickness of the nano conductive layer is 5-500 nm, and the nano conductive layer is one or more selected from carbon-based material graphite, amorphous carbon, graphene, carbon fiber and carbide. After plasma cleaning is carried out on a metal substrate, a metal corrosion-resistant layer is deposited on the surface of the metal substrate, then a metal self-healing layer and a metal catalytic layer are alternately deposited on the surface of the metal corrosion-resistant layer in a multi-layer mode, and a nano conductive layer is deposited on the surface of the obtained composite metal layer. The metal composite coating provided by the invention can weaken the corrosion effect on the metal polar plate substrate in the service process of the battery, and prolong the durable service life of the proton exchange membrane fuel battery.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a bipolar plate metal composite coating of a proton exchange membrane fuel cell and a preparation method thereof.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) uses hydrogen as fuel to generate electricity, the product is water without pollution, the PEMFC is very friendly to the environment, the application range of the PEMFC comprises automobiles, unmanned aerial vehicle, fixed power stations and the like, the bipolar plate plays a vital role in a plurality of parts of the PEMFC, the PEMFC mainly plays roles in gas distribution, heat conduction, electric quantity transmission and certain structural support, the metal polar plate also becomes a main stream material for bipolar plate processing by virtue of excellent electric conductivity, heat conductivity and shock resistance, the corrosion performance of the metal polar plate determines the durable service life of the whole fuel cell stack, and the complex working conditions such as temperature/humidity, acidity, anions/cations and electric potential in the fuel cell operation environment provide more challenges for the surface modification of the metal polar plate.
The most commonly used surface modification method of the metal polar plate at present is to deposit one or more layers of conductive corrosion-resistant coating on the surface of the metal polar plate, for example, patent application CN110137525A discloses a conductive corrosion-resistant coating of a metal bipolar plate, which comprises a composite material consisting of a composite transition layer consisting of three elements of titanium, carbon and nitrogen and a graphite-like surface layer; patent application CN113737142a discloses a composite gradient carbon-based coating, which comprises a metal simple substance primer layer, a metal nitride transition layer and a pure carbon working layer from bottom to top in sequence. However, the single metal corrosion-resistant transition layer cannot be completely compact and defect-free to prevent corrosion of the corrosion solution on the metal polar plate substrate, particularly in the metal polar plate precoating process, the substrate coated with the conductive corrosion-resistant coating is severely cracked due to insufficient toughness of the coating after stamping forming, and the cracks become channels of the corrosion solution to exacerbate corrosion on the metal polar plate. Therefore, the protection degree of the coating on the metal polar plate is limited, meanwhile, along with the extension of the operation time of the fuel cell, the concentration of anions (such as chloride ions and fluoride ions) and cations (such as iron ions) in the environment can be rapidly increased, the surface of the metal polar plate is etched, and meanwhile, a large amount of free radicals can be generated in the etching solution to damage the metal polar plate, so that the performance of the fuel cell is rapidly attenuated, and the durability life is reduced. Therefore, designing a modified coating that can inhibit the corrosion solution of the fuel cell from eroding the metal plate substrate for a long period of time is of great importance in improving the durable life of the fuel cell.
Disclosure of Invention
Based on the above, the main purpose of the invention is to provide a metal composite coating of a bipolar plate of a proton exchange membrane fuel cell, which solves the problems that the corrosion factors in the environment erode the metal plate substrate in the long-term operation process of the proton exchange membrane fuel cell to cause rapid decay of the cell performance and influence the durability life of the proton exchange membrane fuel cell.
The invention also aims to provide a preparation method of the bipolar plate metal composite coating of the proton exchange membrane fuel cell.
The above object of the present invention can be achieved by the following technical solutions:
the invention provides a bipolar plate metal composite coating of a proton exchange membrane fuel cell, wherein the surface of a metal polar plate substrate sequentially comprises a composite metal layer covered on the surface of the metal polar plate substrate and a nano conductive layer covered on the surface of the composite metal layer from inside to outside; the thickness of the composite metal layer is 5-3000 nm, and the composite metal layer sequentially comprises a metal corrosion-resistant layer, a metal self-healing layer and a metal catalytic layer from inside to outside; the thickness of the nano conductive layer is 5-500 nm, and the nano conductive layer is one or more selected from carbon-based material graphite, amorphous carbon, graphene, carbon fiber and carbide.
Preferably, the thickness of the composite metal layer is 100-1000 nm, the thickness of the nano conductive layer is 20-200 nm, the coating is too thin to exert a good protection effect, and the too thick coating can lead to the reduction of the preparation efficiency and the increase of the preparation cost.
Preferably, the metal self-healing layer and the metal catalytic layer are of a multilayer alternating structure and cover the surface of the metal corrosion-resistant layer, and the single-layer thickness of the multilayer alternating structure is 1-500 nm.
More preferably, the thickness of the multilayer alternating structure single layer formed by the metal self-healing layer and the metal catalytic layer is 10-100 nm, and the surface layer of the composite metal layer is arranged as the metal catalytic layer.
Preferably, the thickness of the metal corrosion-resistant layer is 5-1000 nm, wherein the metal element is one or more selected from transition metal elements of titanium, tantalum, niobium, zirconium and chromium, and exists in a metal simple substance or alloy form.
More preferably, the thickness of the metal corrosion-resistant layer is 50-200 nm.
Preferably, the metal element in the metal self-healing layer is selected from one or more of gold, silver, platinum, copper and tin, and exists in a metal simple substance or alloy form.
Preferably, the metal element in the metal self-healing layer exists in a metal simple substance or alloy form and comprises a main metal element selected from one or more of gold, silver, platinum, copper and tin and a doped metal element selected from one or more of gold, silver, platinum, copper and tin, wherein the main metal element accounts for 50% -90% of the total atomic ratio of the metal in the metal self-healing layer.
Preferably, the metal element in the metal catalytic layer exists in the form of metal simple substance or alloy and metal oxide, and comprises a main metal element selected from one or more of rare earth elements lanthanum, cerium, praseodymium, rubidium or metals with catalytic action, and a doped metal element selected from one or more of gold, silver, platinum, copper and tin; the main metal element accounts for 10% -50% of the total atomic ratio of metal in the metal catalytic layer, wherein the atomic ratio of metal existing in a metal oxide form is more than 5%, the doped metal element exists in a metal simple substance form, and the metal exists in a metal oxide form in the fuel cell environment in a more stable structure and has better catalytic decomposition performance.
In the metal composite coating of the bipolar plate of the proton exchange membrane fuel cell, the metal corrosion-resistant layer not only has a compact coating structure, has better corrosion resistance in the high-temperature high-humidity acidic environment of the fuel cell, but also has very strong combination property with a metal substrate, and ensures that the coating can not be peeled off in the service process; the metal self-healing layer has excellent extensibility and flowability, and can well fill and repair defects when holes and cracks are generated in the preparation or service process of the coating, so that corrosive solution is prevented from directly contacting with a metal polar plate substrate through the defects; the metal catalytic layer has a certain catalytic decomposition effect on corrosion factors in a corrosion environment, can effectively inhibit the increase of corrosion factor concentration in a long-time corrosion process, and avoids the accelerated corrosion of a fuel cell metal substrate. The nano conductive layer is one or more selected from carbon-based material graphite, amorphous carbon, graphene, carbon fiber and carbide, has excellent conductive performance, and can ensure the stability of surface resistance in the service process of the coating.
Preferably, the preparation method of the bipolar plate metal composite coating of the proton exchange membrane fuel cell comprises the following steps:
(1) Plasma cleaning is carried out on the metal substrate;
(2) Depositing the metal corrosion-resistant layer on the surface of the cleaned metal substrate;
(3) Alternately depositing the metal self-healing layer and the metal catalytic layer on the surface of the metal corrosion-resistant layer in multiple layers to obtain the composite metal layer;
(4) And depositing a nano conductive layer on the surface of the composite metal layer.
Preferably, in the step (1), the plasma cleaning method is selected from one of ion source cleaning, self-bias cleaning, radio frequency cleaning or flat panel discharge cleaning.
Preferably, in the step (2) and the step (3), the metal simple substance deposition method in the composite metal layer is selected from one of electroplating, ion plating, plasma spraying, physical vapor deposition and magnetic control sputtering, and the metal oxide deposition method is selected from one of reactive magnetic control sputtering, plasma spraying or plasma oxidation, photocatalytic oxidation and thermal oxidation after depositing the metal simple substance.
Preferably, in the step (4), the deposition method of the nano conductive layer is selected from one of ion plating, physical vapor deposition, chemical vapor deposition and magnetron sputtering.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the metal corrosion-resistant layer, the metal self-healing layer and the metal catalytic layer are combined together through the superposition of the multilayer structure in a mode of a multi-element metal composite coating, the corrosion resistance of the metal polar plate substrate is improved through the metal corrosion-resistant layer by the compact structure, the metal self-healing layer prevents the corrosive solution in the environment of the fuel cell from penetrating into the metal polar plate substrate through the filling and repairing function, the metal catalytic layer inhibits the increase of the concentration of the corrosive factor in the corrosive solution in the long-time operation process of the cell through the catalytic decomposition function, the corrosion action of the whole multi-element metal composite coating on the metal polar plate substrate in the service process of the cell can be weakened, the conductive corrosion resistance of the metal polar plate substrate of the fuel cell can be improved, the corrosion action of the corrosive solution on the metal substrate can be weakened through the filling and self-repairing function, and the durable service life of the fuel cell is prolonged, and the multi-element metal composite coating has important significance in promoting the commercialization of the metal polar plate of the fuel cell.
Drawings
FIG. 1 is a schematic view of the metal composite coating layer of bipolar plate of PEMFC in example 1;
FIG. 2 is a schematic view of the metal composite coating layer of the bipolar plate of the PEMFC in example 2;
FIG. 3 is a graph of corrosion current density for a bipolar plate metal composite coating of a PEMFC and a comparative example;
FIG. 4 shows the results of iron ion precipitation from the substrate after electrochemical corrosion of the bipolar plate metal composite coating of the PEMFC and the comparative example;
the reference numerals are as follows: 1 a metal substrate; 2, a composite metal layer; a 21 metal corrosion resistant layer; 22 metal self-healing layers; 23 a metal catalytic layer; a 3 nanometer conductive layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention are clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
Fig. 1 exemplarily illustrates a bipolar plate metal composite coating of a proton exchange membrane fuel cell, which sequentially comprises, from the surface of a metal substrate 1: the composite metal layer 2 is covered on the surface of the metal substrate 1, and the nano conductive layer 3 is covered on the surface of the composite metal layer 2, wherein the composite metal layer 2 sequentially comprises a metal corrosion-resistant layer 21, a metal self-healing layer 22 and a metal catalytic layer 23 from the metal substrate 1.
Fig. 2 exemplarily illustrates a bipolar plate metal composite coating of a proton exchange membrane fuel cell, which sequentially comprises, from the surface of the metal substrate 1: the metal self-healing layer 22 and the metal catalytic layer 23 are of a multilayer alternating structure and cover on the surface of the metal corrosion-resistant layer 21, and the single-layer thickness is 1-500 nm.
Example 1
The bipolar plate metal composite coating of the proton exchange membrane fuel cell is prepared in the embodiment, as shown in fig. 1, and the following steps are adopted:
(1) Under vacuum condition, carrying out radio frequency plasma cleaning on the metal substrate on the sample rack to remove impurities and oxides on the surface of the metal substrate;
(2) Depositing a metal corrosion-resistant layer on the surface of the cleaned metal substrate by adopting a magnetron sputtering method, wherein the sputtering target is metal titanium, and the thickness of the metal corrosion-resistant layer is 100 nm;
(3) Depositing a metal self-healing layer on the metal corrosion-resistant layer by adopting a magnetron sputtering method, wherein the sputtering target is metal silver, and the thickness of the metal self-healing layer is 50 nm;
(4) Depositing a metal catalytic layer on the surface of the metal self-healing layer by adopting a reaction magnetron sputtering method, wherein the sputtering target material is lanthanum metal, the reaction gas is oxygen, the thickness of the metal catalytic layer is 50 nm, and the atomic ratio of lanthanum metal in lanthanum oxide is 20%;
(5) And depositing a layer of amorphous carbon of the nano conductive layer on the surface of the metal catalytic layer by adopting a magnetron sputtering method, wherein a sputtering target material is a graphite target, and the thickness of the nano conductive layer is 100 nm.
Example 2
The bipolar plate metal composite coating of the proton exchange membrane fuel cell is prepared in the embodiment, as shown in fig. 2, and the following steps are adopted:
(1) Under vacuum condition, carrying out radio frequency plasma cleaning on the metal substrate on the sample rack to remove impurities and oxides on the surface of the metal substrate;
(2) Depositing a metal corrosion-resistant layer on the surface of the cleaned metal substrate by adopting a magnetron sputtering method, wherein the sputtering target is metal niobium, and the thickness of the metal corrosion-resistant layer is 300 nm;
(3) Depositing a metal self-healing layer on the metal corrosion-resistant layer by adopting a magnetron sputtering method, wherein the sputtering target is metal tin, and the thickness of the metal self-healing layer is 20 nm;
(4) Depositing a metal catalytic layer on the surface of the metal self-healing layer by adopting a reaction magnetron sputtering method, wherein the sputtering target material is metal cerium, the reaction gas is oxygen, the thickness of the metal catalytic layer is 20 nm, and the atomic ratio of metal cerium in cerium oxide is 50%;
(5) Repeating the step (3) to the step (4) for 5 times to finish the deposition of the multilayer coating of the metal self-healing layer and the metal catalytic layer;
(6) And depositing a layer of amorphous carbon of the nano conductive layer on the surface of the metal catalytic layer by adopting a magnetron sputtering method, wherein a sputtering target material is a graphite target, and the thickness of the nano conductive layer is 100 nm.
Example 3
The preparation method of the bipolar plate metal composite coating of the proton exchange membrane fuel cell comprises the following steps:
(1) Under vacuum condition, ion source plasma cleaning is carried out on the metal substrate on the sample rack to remove impurities and oxides on the surface of the metal substrate;
(2) Depositing a metal corrosion-resistant layer on the surface of the cleaned metal substrate by adopting a magnetron sputtering method, wherein the sputtering target is metal niobium and metal titanium, and the thickness of the metal corrosion-resistant layer is 200 nm;
(3) A layer of metal self-healing layer is deposited on the metal corrosion-resistant layer by adopting a magnetron sputtering method, wherein the sputtering target material is metal tin and metal niobium, the atomic ratio of the metal tin is 50 percent, and the thickness of the metal self-healing layer is 50 nm;
(4) Depositing a metal catalytic layer on the surface of the metal self-healing layer by adopting a reaction magnetron sputtering method, wherein a sputtering target material is metal cerium and metal niobium, a reaction gas is oxygen, the atomic ratio of the metal cerium is 50%, the thickness of the metal catalytic layer is 50 nm, and the atomic ratio of the metal cerium in cerium oxide is 20%;
(5) Repeating the step (3) to the step (4) for 2 times to finish the deposition of the multilayer coating of the metal self-healing layer and the metal catalytic layer;
(6) And depositing a layer of nano conductive layer amorphous carbon on the surface of the metal catalytic layer by adopting a plasma-assisted vapor deposition method, wherein the thickness of the nano conductive layer is 50 nm.
Example 4
The preparation method of the bipolar plate metal composite coating of the proton exchange membrane fuel cell comprises the following steps:
(1) Under vacuum condition, carrying out radio frequency plasma cleaning on the metal substrate on the sample rack to remove impurities and oxides on the surface of the metal substrate;
(2) Depositing a metal corrosion-resistant layer on the surface of the cleaned metal substrate by adopting a magnetron sputtering method, wherein the sputtering target is zirconium metal, and the thickness of the metal corrosion-resistant layer is 200 nm;
(3) Depositing a metal self-healing layer on the metal corrosion-resistant layer by adopting a magnetron sputtering method, wherein the sputtering target material is metal gold and metal silver, and the thickness of the metal self-healing layer is 5 nm;
(4) Depositing a metal catalytic layer on the surface of the metal self-healing layer by adopting a magnetron sputtering method, wherein the sputtering target material is lanthanum metal, the thickness of the metal catalytic layer is 20 nm, and then performing plasma oxidation, wherein the atomic ratio of lanthanum metal in lanthanum oxide is 30%;
(5) Repeating the step (3) to the step (4) for 5 times to finish the deposition of the multilayer coating of the metal self-healing layer and the metal catalytic layer;
(6) And depositing a layer of carbon fiber of the nano conductive layer on the surface of the metal catalytic layer by adopting a chemical vapor deposition method, wherein the thickness of the nano conductive layer is 30 nm.
Example 5
The preparation method of the bipolar plate metal composite coating of the proton exchange membrane fuel cell comprises the following steps:
(1) Under vacuum condition, ion source plasma cleaning is carried out on the metal substrate on the sample rack to remove impurities and oxides on the surface of the metal substrate;
(2) Depositing a metal corrosion-resistant layer on the surface of the cleaned metal substrate by adopting a magnetron sputtering method, wherein the sputtering target is metal titanium, and the thickness of the metal corrosion-resistant layer is 200 nm;
(3) A layer of metal self-healing layer is deposited on the metal corrosion-resistant layer by adopting a magnetron sputtering method, wherein the sputtering target material is metal silver and metal titanium, the atomic ratio of the metal silver is 60 percent, and the thickness of the metal self-healing layer is 20 nm;
(4) Depositing a metal catalytic layer on the surface of the metal self-healing layer by adopting a reaction magnetron sputtering method, wherein the sputtering target material is lanthanum oxide, the thickness of the metal catalytic layer is 100 nm, and the atomic ratio of metal lanthanum in the lanthanum oxide is 80%;
(5) And depositing a layer of amorphous carbon of the nano conductive layer on the surface of the metal catalytic layer by adopting a magnetron sputtering method, wherein a sputtering target material is a graphite target, and the thickness of the nano conductive layer is 100 nm.
Example 6
The bipolar plate metal composite coating of the proton exchange membrane fuel cell is prepared by the following steps:
(1) Under vacuum condition, carrying out radio frequency plasma cleaning on the metal substrate on the sample rack to remove impurities and oxides on the surface of the metal substrate;
(2) Depositing a metal corrosion-resistant layer on the surface of the cleaned metal substrate by adopting a plasma spraying method, wherein the sputtering target is metal niobium, and the thickness of the metal corrosion-resistant layer is 500 nm;
(3) Depositing a metal self-healing layer on the metal corrosion-resistant layer by adopting a magnetron sputtering method, wherein the sputtering target material is metal tin and metal silver, and the thickness of the metal self-healing layer is 100 nm;
(4) Depositing a metal catalytic layer on the surface of the metal self-healing layer by adopting a reaction magnetron sputtering method, wherein the sputtering target material is metal cerium, the reaction gas is oxygen, the thickness of the metal catalytic layer is 20 nm, and the atomic ratio of metal cerium in cerium oxide is 50%;
(5) Repeating the step (3) to the step (4) for 5 times to finish the deposition of the multilayer coating of the metal self-healing layer and the metal catalytic layer;
(6) And depositing a layer of amorphous carbon of the nano conductive layer on the surface of the metal catalytic layer by adopting a magnetron sputtering method, wherein a sputtering target material is a graphite target, and the thickness of the nano conductive layer is 100 nm.
Comparative example 1
Comparative example 1 a conductive corrosion resistant coating was prepared on the surface of a metal plate substrate using the following steps:
(1) Under vacuum condition, carrying out radio frequency plasma cleaning on the metal substrate on the sample rack to remove impurities and oxides on the surface of the metal substrate;
(2) Depositing a corrosion-resistant layer on the surface of the cleaned metal substrate by adopting a magnetron sputtering method, wherein the sputtering target material is metallic titanium, and the thickness of the corrosion-resistant layer is 200 nm;
(3) And depositing a layer of amorphous carbon of the conducting layer on the surface of the corrosion-resistant layer by adopting a magnetron sputtering method, wherein the sputtering target is a graphite target, and the thickness of the nano conducting layer is 100 nm.
The metal polar plate base material coated with the multi-element metal composite coating is prepared in examples 1-6, the long-time corrosion conductivity of the metal polar plate base material is tested by adopting an electrochemical method, the test potential is 0.84V, the test time is 200 h, the contact resistance of the coating before and after corrosion, namely the conductivity of the coating is evaluated by a surface contact resistance test, the test pressure is 0.6 MPa, and the test result is shown in table 1.
As can be seen from the contact resistance results of the coatings prepared in examples 1 to 6 and comparative example 1 after long-time corrosion, the coatings prepared in examples 1 to 6 all have excellent initial conductivity, and the contact resistance under 0.6 MPa pressure is 3mΩ cm 2 About, but after long-term electrochemical corrosion, the coating of comparative example 1 had contact resistanceThe contact resistance of the coatings prepared in examples 1-6 is 5mΩ cm 2 The following shows that the multi-metal composite coating of the invention can maintain good stability under long-time corrosion conditions.
The metal electrode plates of the example 1, the example 2 and the comparative example 1 are further punched and formed by adopting a precoating process, then electrochemical corrosion test is carried out, the test potential is 1.6V, the test time is 10 h, the change curve of the corrosion current density with time is shown in fig. 3, the iron ion precipitation result of the substrate is shown in fig. 4, it can be seen that compared with the comparative example 1, the corrosion current density of the coating prepared by the examples 1 and 2 is about half of that of the corrosion current density of the comparative example 1, the iron ion concentration of the solution after corrosion is reduced by one order of magnitude, and the corrosion performance is greatly improved.
In summary, the proton exchange membrane fuel cell bipolar plate metal composite coating disclosed by the invention not only can be used for rapidly filling and repairing defect sites in the coating, but also can be used for catalytically decomposing corrosion factors in a corrosion environment, so that the concentration of the corrosion factors is reduced, the corrosion resistance of a metal polar plate substrate and the stability of long-time service are greatly improved, and the proton exchange membrane fuel cell bipolar plate metal composite coating has important significance for application and mass production of the fuel cell polar plate coating.
Claims (5)
1. The surface of the metal polar plate substrate sequentially comprises a composite metal layer covered on the surface of the metal polar plate substrate and a nano conductive layer covered on the surface of the composite metal layer from inside to outside; wherein:
the thickness of the composite metal layer is 5-3000 nm, the composite metal layer sequentially comprises a metal corrosion-resistant layer, a metal self-healing layer and a metal catalytic layer from inside to outside, the metal self-healing layer and the metal catalytic layer are of a multilayer alternating structure and cover the surface of the metal corrosion-resistant layer, and the single-layer thickness of the multilayer alternating structure is 1-500 nm;
the thickness of the metal corrosion-resistant layer is 5-1000 nm, wherein metal elements are one or more of transition metal elements of titanium, tantalum, niobium, zirconium and chromium, and exist in a metal simple substance or alloy form;
the metal elements in the metal self-healing layer exist in a metal simple substance or alloy form and are selected from one or more of gold, silver, platinum, copper and tin;
the metal elements in the metal catalytic layer exist in the form of metal simple substances and metal oxides and are selected from one or more of rare earth elements lanthanum, cerium, praseodymium and rubidium;
the thickness of the nano conductive layer is 5-500 nm, and the nano conductive layer is one or more selected from carbon-based material graphite, amorphous carbon, graphene, carbon fiber and carbide;
the preparation method of the bipolar plate metal composite coating of the proton exchange membrane fuel cell comprises the following steps:
(1) Plasma cleaning is carried out on the metal substrate;
(2) Depositing the metal corrosion-resistant layer on the surface of the cleaned metal substrate;
(3) Alternately depositing the metal self-healing layer and the metal catalytic layer on the surface of the metal corrosion-resistant layer in multiple layers to obtain the composite metal layer;
(4) And depositing a nano conductive layer on the surface of the composite metal layer.
2. The bipolar plate metal composite coating for a proton exchange membrane fuel cell according to claim 1, wherein the thickness of the composite metal layer is 100-1000 nm, and the thickness of the nano conductive layer is 20-200 nm.
3. The bipolar plate metal composite coating for the proton exchange membrane fuel cell according to claim 1, wherein the thickness of a multilayer alternating structure monolayer formed by the metal self-healing layer and the metal catalytic layer is 10-100 nm, and the surface layer of the composite metal layer is arranged as the metal catalytic layer.
4. The bipolar plate metal composite coating for a proton exchange membrane fuel cell according to claim 1, wherein the thickness of the metal corrosion resistant layer is 50-200 nm.
5. The bipolar plate metal composite coating for a proton exchange membrane fuel cell according to claim 1, wherein in step (1), the plasma cleaning method is selected from one of ion source cleaning, self-bias cleaning, radio frequency cleaning, or flat discharge cleaning;
and/or in the step (2) and the step (3), the metal simple substance deposition method in the composite metal layer is selected from one of electroplating, ion plating, plasma spraying, physical vapor deposition and magnetic control sputtering, and the metal oxide deposition method is selected from one of reactive magnetic control sputtering, plasma spraying or plasma oxidation, photocatalytic oxidation and thermal oxidation after the metal simple substance is deposited;
and/or in the step (4), the deposition method of the nano conductive layer is selected from one of ion plating, physical vapor deposition, chemical vapor deposition and magnetron sputtering.
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| CN116791126A (en) * | 2023-06-26 | 2023-09-22 | 阳光氢能科技有限公司 | Proton exchange membrane electrolyzer bipolar plate and preparation method thereof |
| CN119092740A (en) * | 2024-09-02 | 2024-12-06 | 长沙海铱雷克氢能科技有限责任公司 | A corrosion-resistant titanium alloy bipolar plate and a preparation method thereof |
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