CN109755592B - Metal bipolar plate, preparation method thereof and fuel cell - Google Patents
Metal bipolar plate, preparation method thereof and fuel cell Download PDFInfo
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- CN109755592B CN109755592B CN201811600340.2A CN201811600340A CN109755592B CN 109755592 B CN109755592 B CN 109755592B CN 201811600340 A CN201811600340 A CN 201811600340A CN 109755592 B CN109755592 B CN 109755592B
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- 239000002184 metal Substances 0.000 title claims abstract description 264
- 239000000446 fuel Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 182
- 238000000576 coating method Methods 0.000 claims abstract description 182
- 239000000758 substrate Substances 0.000 claims abstract description 140
- 230000007797 corrosion Effects 0.000 claims abstract description 107
- 238000005260 corrosion Methods 0.000 claims abstract description 107
- 238000005121 nitriding Methods 0.000 claims abstract description 42
- 238000000151 deposition Methods 0.000 claims description 58
- 230000002209 hydrophobic effect Effects 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 150000002500 ions Chemical class 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 238000004544 sputter deposition Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
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- 239000010937 tungsten Substances 0.000 claims description 7
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- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 230000008439 repair process Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a metal bipolar plate, a preparation method thereof and a fuel cell, and relates to the technical field of fuel cells. The technical scheme mainly adopted is as follows: the metal bipolar plate comprises a metal substrate, a corrosion-resistant coating and a conductive coating. Wherein, the metal substrate comprises a first surface subjected to nitriding treatment; a corrosion-resistant coating deposited on the first side of the metal substrate; a conductive coating is deposited over the corrosion-resistant coating. A preparation method of the metal bipolar plate comprises the steps of pretreatment, high-temperature nitridation treatment, corrosion-resistant coating deposition on the first surface of the metal substrate subjected to nitridation treatment and conductive coating deposition on the corrosion-resistant coating. A fuel cell comprising the metallic bipolar plate described above. The invention is mainly used for improving the corrosion resistance and the electrical conductivity of the metal bipolar plate, improving the binding force between the coating and the metal substrate and prolonging the service lives of the metal bipolar plate and the fuel cell.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a metal bipolar plate, a preparation method thereof and a fuel cell.
Background
For the PEM electrolytically produced hydrogen and PEMFC fuel cell industry, the cost of bipolar plate materials accounts for 25-35% of the total fuel cell cost. The main material of the bipolar plate is graphite plate, however, graphite has the disadvantages of high price, poor machining performance and the like. Therefore, the prior art adopts a metal plate with large market usage amount, low price, good mechanical processing, toughness and strength to replace the graphite plate. However, the surface of the metal plate may form an oxide layer having poor conductivity, and may be easily corroded in the operating environment of the stack. In addition, after metal ions generated by metal corrosion are diffused, the conductivity of the proton exchange membrane is reduced after the metal ions enter the membrane electrode, and even the catalyst is poisoned, so that the battery performance is adversely affected.
Therefore, in order to overcome the above problems of the metal plate, the prior art mainly adopts a physical vapor deposition method to deposit a corrosion-resistant coating on the surface of the metal plate, so that the performance requirement of the bipolar plate can be met. The initial performance test of the metal plate after being repaired by the corrosion-resistant coating basically meets the requirements of the bipolar plate.
However, the technology of depositing the corrosion-resistant coating on the surface of the metal plate by adopting the physical vapor deposition method has at least the following technical problems:
(1) The binding force between the corrosion-resistant coating and the metal plate is poor (particularly iron-based stainless steel material), so that the service life of the bipolar plate is relatively short, and the coating can often fall off and corrode after hundreds to thousands of hours.
(2) The inherent defect of physical vapor deposition causes the phenomenon of pinholes in the plating layer, and corrosive medium enters the film layer through the pinholes to reach the metal substrate and corrode the substrate. The corroded ions such as iron ions, chromium ions and nickel ions can react with the membrane battery, so that the performance of the fuel battery is greatly reduced.
Disclosure of Invention
In view of the above, the present invention provides a metal bipolar plate, a method for preparing the same, and a fuel cell, and is mainly aimed at providing a metal bipolar plate with good corrosion resistance, less prone to falling of coating, and good conductivity.
In order to achieve the above purpose, the present invention mainly provides the following technical solutions:
in one aspect, embodiments of the present invention provide a metallic bipolar plate, wherein the metallic bipolar plate comprises:
a metal substrate including a first surface subjected to nitriding treatment;
a corrosion-resistant coating deposited on a first side of the metal substrate;
a conductive coating deposited on the corrosion resistant coating.
Preferably, the nitriding treatment is a gas nitriding treatment; and/or the composition of the corrosion-resistant coating comprises a first metal; the first metal comprises one or more of titanium, chromium, tungsten, nickel, aluminum, and copper; preferably, the thickness of the corrosion-resistant coating is 20 nm-5 um; preferably, the corrosion-resistant coating has a plurality of first pinholes; wherein the first pinholes are distributed on the surface and inside of the corrosion-resistant coating; the first pinholes are plugged with an oxide formed from the first metal.
Preferably, the composition of the conductive coating comprises 60-90% of carbon and 10-40% of a second metal in percentage by mass; preferably, the composition of the conductive coating comprises 85-90% of carbon and 10-15% of a second metal in percentage by mass; preferably, the second metal is titanium; preferably, the conductive coating has a plurality of second pinholes, which are plugged with an oxide formed from the second metal.
Preferably, the metallic bipolar plate further comprises a hydrophobic layer; wherein the hydrophobic layer is disposed on the conductive coating; preferably, the composition of the hydrophobic layer comprises PTFE.
In another aspect, an embodiment of the present invention provides a method for preparing a metal bipolar plate, including the steps of:
the first step of pretreatment: carrying out oil removal treatment on the metal substrate;
nitriding: performing high-temperature nitridation treatment on the metal substrate;
depositing a corrosion-resistant coating: depositing a corrosion-resistant coating on the nitrided first side of the metal substrate;
depositing a conductive coating: depositing a conductive coating over the corrosion resistant coating of the metal substrate.
Preferably, the step of the first pretreatment specifically includes: and (3) carrying out first oil removal treatment on the metal substrate by adopting a sodium hydroxide solution, and carrying out second oil removal treatment on the metal substrate by adopting alcohol.
Preferably, the nitriding step includes: performing heat treatment on the metal substrate under nitriding gas; wherein the temperature of the heat treatment is 450-850 ℃, and the time of the heat treatment is 0.5-4 h; preferably, the temperature of the heat treatment is 800-850 ℃, and the time of the heat treatment is 1-2 hours; preferably, the step of nitriding is performed in an atmosphere furnace.
Preferably, the method further comprises a second pretreatment step after the nitriding step and before the depositing step of the corrosion-resistant coatingTo increase the roughness of the first face of the metal substrate; preferably, the step of the second pretreatment includes: heating the metal substrate subjected to nitriding treatment in a vacuum chamber, introducing working gas, setting negative bias, and performing ion sputtering on the first surface of the metal substrate; preferably, the vacuum degree of the vacuum chamber is 3×10 -3 Pa～6×10 -3 Pa; the working gas is inert gas; the pressure of the working gas is 0.5Pa to 1.5Pa; the negative bias voltage is set to be-200 to-3200V; the temperature of the metal substrate is 120-300 ℃; the ion sputtering time is 1-3 min; preferably, the second pretreatment step is performed in a bias magnetic control multi-arc ion plating device.
Preferably, the step of depositing a corrosion-resistant coating comprises:
depositing a first metal layer: the vacuum degree of the vacuum chamber is pumped to 3 multiplied by 10 -3 Pa～6×10 -3 Pa, introducing inert gas, setting negative bias voltage to-100 to-500V, opening a metal target, performing ion sputtering on the conductive coating, and depositing a first metal layer on the first surface of the metal substrate; preferably, the first metal comprises one or more of titanium, chromium, tungsten, nickel, aluminum, copper;
and (3) performing oxidation hole sealing modification treatment: introducing inert gas and oxygen into the vacuum chamber, setting bias voltage to-100 to-500V, and exciting and ionizing the oxygen to bombard the first metal layer by oxygen ions for 1-15 min to obtain a corrosion-resistant coating sealed by the first metal oxide; wherein the pressure of the inert gas is 0.5-1Pa, and the pressure of the oxygen is 0.1-0.5Pa;
preferably, in the step of depositing the corrosion-resistant coating, the temperature of the metal substrate is 350-500 ℃;
preferably, the step of depositing the corrosion-resistant coating is performed in a bias-voltage magnetron multi-arc ion plating apparatus.
Preferably, the step of depositing the conductive coating includes: in a vacuum chamber, vacuum is pumped to 3X 10 -3 Pa～6×10 -3 Pa, introducing 0.5-1.5 Pa inert gas, setting-100 to-500V bias voltage, and depositing a conductive coating containing carbon and a second metal on the corrosion-resistant coating; excellent (excellent)Optionally, the components of the conductive coating comprise 60-90% of carbon and 10-40% of a second metal in percentage by mass; preferably, the composition of the conductive coating comprises 85-90% carbon and 10-15% of a second metal; preferably, the second metal is titanium; preferably, in the step of depositing the conductive coating, the temperature of the metal substrate is maintained at 80 to 500 ℃; preferably, the step of depositing the conductive coating is performed in a bias-voltage magnetron multi-arc ion plating apparatus.
Preferably, the preparation method of the metal bipolar plate further comprises the following steps: surface hydrophobic treatment, namely arranging a hydrophobic layer on the surface of the conductive coating; preferably, the step of surface hydrophobic treatment specifically comprises: immersing the metal substrate sequentially deposited with the corrosion-resistant coating and the conductive coating into a hydrophobizing agent for surface hydrophobizing treatment, and forming a hydrophobic layer on the surface of the conductive coating; solidifying the hydrophobic layer, and cooling to obtain a metal bipolar plate; preferably, the hydrophobizing agent is PTFE solution with the mass fraction of 0.1-5%; preferably, the surface hydrophobic treatment time is 30 s-5 min; preferably, the thickness of the hydrophobic layer is 2-20 nm; preferably, the step of curing the hydrophobic layer comprises: and heating the metal substrate with the hydrophobic layer formed on the surface to 200-450 ℃ and performing heat treatment for 30 s-10 min.
In yet another aspect, embodiments of the present invention also provide a fuel cell, wherein the fuel cell comprises a metallic bipolar plate; wherein the metallic bipolar plate is any one of the metallic bipolar plates described above; or the metal bipolar plate is prepared by the preparation method of any one of the metal bipolar plates.
Compared with the prior art, the metal bipolar plate, the preparation method thereof and the fuel cell have at least the following beneficial effects:
according to the metal bipolar plate and the preparation method thereof, the first surface of the metal substrate is made to be of the nitriding structure (preferably, the first surface of the metal substrate is subjected to nitriding heat treatment), so that the corrosion resistance and the conductivity of the first surface of the metal substrate and the binding force between the first surface of the metal substrate and the corrosion-resistant coating can be improved. In addition, the embodiment of the invention deposits the conductive coating on the corrosion-resistant coating, so that the corrosion resistance and the conductivity of the metal bipolar plate can be further improved.
Further, the metal bipolar plate and the preparation method thereof provided by the embodiment of the invention have the advantages that the main component of the corrosion-resistant coating is first metal (preferably, the first metal comprises one or more of titanium, chromium, tungsten, nickel, aluminum and copper); the corrosion-resistant coating is provided with first pinholes on the inner part and the surface, and the first pinholes are blocked by oxide formed by the first metal. Here, since the physical vapor deposition method has an inherent defect that the wire-outgoing pinholes in the deposited layer are caused (for the problem of repairing pinholes, the prior art also refers to a treatment method of self-repairing and oxidation hole sealing, but these hole sealing measures mainly aim at the defect of the surface of the corrosion-resistant coating, and have limited hole sealing effect on the pinholes inside the coating). The embodiment of the invention firstly provides that a small amount of oxygen is introduced after the first metal is deposited, and high-speed oxygen ions are adopted to bombard the corrosion-resistant coating; on one hand, the part with poor surface binding force can be removed, and the binding force with the conductive coating deposited later is improved; on the other hand, high-energy oxygen ion particles can penetrate through the corrosion-resistant surface and enter the corrosion-resistant coating to carry out oxidation hole sealing on a small amount of first metal to repair defects, and the conductivity of the corrosion-resistant coating cannot be influenced by a small amount of oxidation.
Further, the metal bipolar plate and the preparation method thereof provided by the embodiment of the invention are characterized in that the components of the conductive coating comprise carbon and a second metal (preferably titanium); carbon is used as a main component of the conductive coating, and mainly improves the conductivity of the metal bipolar plate; the second metal is added for oxidizing the hole sealing, namely, in the presence of oxygen, a second metal oxide is formed to seal pinholes on the conductive coating; thereby further improving the corrosion resistance of the conductive coating.
Further, according to the metal bipolar plate and the preparation method thereof provided by the embodiment of the invention, the hydrophobic layer is arranged on the conductive coating, so that the hydrophobicity of the metal bipolar plate is improved, hydrogen ions are further prevented from penetrating into the matrix through pinholes, and the corrosion resistance of the metal bipolar plate is further improved. In addition, the PTFE has good hydrophobic performance, and the conductivity of the metal bipolar plate is not affected.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a schematic structural view of a metal bipolar plate according to an embodiment of the present invention;
fig. 2 is a schematic structural view of another metal bipolar plate according to an embodiment of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the invention, the following detailed description refers to the specific implementation, structure, characteristics and effects according to the application of the invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
Example 1
The present embodiment provides a metal bipolar plate, as shown in fig. 1 and 2, which includes: a metal substrate 1, a corrosion-resistant coating 2 and a conductive coating 3. Wherein the metal substrate 1 includes a first surface subjected to nitriding treatment (here, the first surface of the metal substrate 1 is subjected to nitriding treatment, and a nitrided layer 11 is formed on the first surface of the metal substrate 1 and a portion in the vicinity thereof); a corrosion-resistant coating 2 is deposited on the first side of the metal substrate 1 and a conductive coating 3 is deposited on the corrosion-resistant coating 1.
The metal bipolar plate provided in this embodiment is configured such that the first surface of the metal substrate is of a nitriding structure (preferably, of a nitriding heat structure), so that corrosion resistance and conductivity of the first surface of the metal substrate and the bonding force between the first surface of the metal substrate and the corrosion-resistant coating can be improved. In addition, the conductive coating is deposited on the corrosion-resistant coating, so that the corrosion resistance and the conductivity of the metal bipolar plate can be further improved.
Preferably, the nitriding treatment in the present embodiment is gas nitriding treatment; specific nitridation steps are shown in example 5.
Example 2
Preferably, the present embodiment provides a metal bipolar plate, and as compared with the previous embodiment, as shown in fig. 1 and 2, the main component of the corrosion-resistant coating 2 includes a first metal (i.e., a first metal element). Here, the first metal includes one or more of titanium, chromium, tungsten, nickel, aluminum, and copper. The thickness of the corrosion-resistant coating 2 is 20 nm-5 um. The corrosion-resistant coating 2 has a plurality of first pinholes; wherein, the first pinholes are distributed on the surface and inside of the corrosion-resistant coating 2; the first pinholes are blocked by the oxide 21 formed from the first metal.
The embodiment of the invention firstly provides that a small amount of oxygen is introduced after the first metal is deposited, and the corrosion-resistant coating is bombarded by high-speed oxygen ions, so that on one hand, the part with poor surface binding force can be removed, the binding force with the subsequently deposited conductive coating is improved, and on the other hand, high-energy oxygen ion particles can penetrate the corrosion-resistant surface to enter the corrosion-resistant coating to oxidize a small amount of the first metal to form oxide 21 so as to block pinholes (oxidized hole sealing) and repair the defects, and the small amount of oxidation can not influence the conductivity of the corrosion-resistant coating.
Of course, the particular pinhole plugging is dependent on the amount of oxygen introduced, where the plugged pinhole is defined as the first pinhole. The first pinholes are not only distributed on the surface of the corrosion-resistant coating but also inside the corrosion-resistant coating.
Example 3
Preferably, compared with the above embodiments, as shown in fig. 1 and 2, the embodiment provides a metal bipolar plate, and specifically designs the conductive coating 2 as follows: the conductive coating 2 comprises, by mass, 60-90% of carbon and 10-40% of a second metal; preferably, the composition of the conductive coating 2 comprises 85 to 90% carbon and 10 to 15% of the second metal in mass percent. Preferably, the second metal is titanium. Preferably, the conductive coating 2 has a plurality of second pinholes, which are plugged by an oxide formed from the second metal.
The metal bipolar plate provided in this embodiment is formed by including carbon and a second metal (preferably titanium) in the composition of the conductive coating; carbon is used as a main component of the conductive coating, and mainly improves the conductivity of the metal bipolar plate; the second metal is added to oxidize the hole sealing, i.e. in the presence of oxygen, to form a second metal oxide to seal pinholes (the sealed pinholes are defined as second pinholes) in the conductive coating; thereby further improving the corrosion resistance of the conductive coating.
Example 4
Preferably, compared with the above embodiment, as shown in fig. 1, the metal bipolar plate of the present embodiment further includes a hydrophobic layer 4; wherein the hydrophobic layer 4 is arranged on the conductive coating 3; further preferably, the composition of the hydrophobic layer 4 comprises PTFE.
According to the metal bipolar plate provided by the embodiment, the hydrophobic layer is arranged on the conductive coating 3, so that the hydrophobicity of the metal bipolar plate is improved, hydrogen ions are further prevented from penetrating into the matrix through pinholes, and the corrosion resistance of the metal bipolar plate is further improved. In addition, the PTFE has good hydrophobic performance, and the conductivity of the metal bipolar plate is not affected.
Preferably, the metal substrate in the above embodiment is made of iron-based stainless steel, titanium alloy, aluminum alloy, nickel, etc.
Example 5
On the other hand, this embodiment provides a method for preparing a metal bipolar plate (the metal bipolar plate is a metal bipolar plate according to any one of the above embodiments), as shown in fig. 1 to 2, specifically including the following steps:
1. the first step of pretreatment: carrying out oil removal treatment on the metal substrate 1;
specifically, the method comprises the following steps: and (3) carrying out first oil removal treatment on the metal substrate by adopting a sodium hydroxide solution, and carrying out second oil removal treatment on the metal substrate by adopting alcohol.
2. Nitriding: performing high-temperature nitriding treatment on the metal substrate 1;
preferably, the step of nitriding comprises: performing heat treatment on the metal substrate under nitriding gas (preferably, the nitriding gas comprises nitrogen, or the nitriding gas is a mixed gas of nitrogen and argon, or the nitriding gas is a mixed gas of nitrogen and hydrogen); wherein the temperature of the heat treatment is 450-850 ℃, and the time of the heat treatment is 0.5-4 h; preferably, the temperature of the heat treatment is 800-850 ℃, and the time of the heat treatment is 1-2 hours; preferably, the step of nitriding is performed in an atmosphere furnace.
3. And step two, pretreatment: in the vacuum chamber, the metal substrate 1 after nitriding treatment is heated, working gas is introduced, negative bias is set, and ion sputtering is carried out on the first surface of the metal substrate, so that the roughness of the first surface of the metal substrate is improved.
Preferably, the vacuum degree of the vacuum chamber is 3×10 -3 Pa～6×10 -3 Pa; the working gas is inert gas; the pressure of the working gas is 0.5Pa to 1.5Pa; the negative bias voltage is set to be-200 to-3200V; the temperature of the metal substrate is 120-300 ℃; the ion sputtering time is 1-3 min;
preferably, the second pretreatment step is performed in a bias magnetic control multi-arc ion plating device.
4. Depositing a corrosion-resistant coating: depositing a corrosion-resistant coating 2 on the nitrided first side of the metal substrate 1;
1) Depositing a first metal layer: the vacuum degree of the vacuum chamber is pumped to 3 multiplied by 10 -3 Pa～6×10 -3 Pa, introducing inert gas, setting negative bias voltage to-100 to-500V, opening a metal target, performing ion sputtering on the conductive coating, and depositing a first metal layer on the first surface of the metal substrate.
2) And (3) performing oxidation hole sealing modification treatment: introducing inert gas and oxygen into the vacuum chamber, setting bias voltage to-100 to-500V, and exciting and ionizing the oxygen to bombard the first metal layer by oxygen ions for 1-15 min to obtain a corrosion-resistant coating sealed by the first metal oxide; wherein the pressure of the inert gas is 0.5-1Pa, and the pressure of the oxygen is 0.1-0.5Pa.
Preferably, the first metal comprises one or more of titanium, chromium, tungsten, nickel, aluminum, copper;
preferably, in the step of depositing the corrosion-resistant coating, the temperature of the metal substrate is 350-500 ℃;
preferably, the step of depositing the corrosion-resistant coating is performed in a bias-voltage magnetron multi-arc ion plating apparatus.
5. Depositing a conductive coating: in a vacuum chamber, vacuum is pumped to 3X 10 -3 Pa～6×10- 3 Pa, introducing inert gas of 0.5-1.5 Pa, setting bias voltage of-100 to-500V, and depositing conductive coating 3 containing carbon and second metal on the corrosion-resistant coating 2.
Preferably, the composition of the conductive coating comprises 60-90% of carbon and 10-40% of a second metal in percentage by mass; preferably, the composition of the conductive coating comprises 85-90% carbon and 10-15% of a second metal; preferably, the second metal is titanium;
preferably, in the step of depositing the conductive coating, the temperature of the metal substrate is maintained at 80 to 500 ℃;
preferably, the step of depositing the conductive coating is performed in a bias magnetron multi-arc ion plating apparatus.
6. Surface hydrophobic treatment: a hydrophobic layer 4 is arranged on the surface of the conductive coating 3;
specifically, the surface hydrophobic treatment comprises the following steps: immersing the metal substrate 1 sequentially deposited with the corrosion-resistant coating 2 and the conductive coating 3 into a hydrophobic agent for surface hydrophobic treatment, and forming a hydrophobic layer 4 on the surface of the conductive coating 3; solidifying the hydrophobic layer 4, and naturally cooling to obtain a metal bipolar plate;
preferably, the hydrophobizing agent is PTFE solution with mass percent of 0.1-5%; further preferably 0.5 to 2% of PTFE solution.
Preferably, the surface hydrophobic treatment time is 30 s-5 min;
preferably, the thickness of the hydrophobic layer is 2-20 nm;
preferably, the step of curing the hydrophobic layer comprises: the metal substrate with the hydrophobic layer formed on the surface is heated to 200-450 ℃ (preferably 300-450 ℃), and is subjected to heat treatment for 30 s-10 min (preferably 3-5 min).
The invention is further illustrated by the following specific experimental examples:
experimental example 1
The metal substrate of this embodiment is 316L stainless steel. The metal substrate is deposited with a coating, and the metal bipolar plate is prepared by the following steps:
1) The metal substrate is subjected to a first degreasing treatment with a 1M sodium hydroxide solution at 80 ℃ for 30min, and after cleaning, the metal substrate is subjected to a second degreasing cleaning with alcohol.
2) Placing a metal substrate in an atmosphere furnace, vacuumizing to a relative vacuum degree of-0.1 MPa, introducing nitrogen, and programming to 800 ℃, wherein the temperature rising speed is 5 ℃/min, and the heat preservation time is 1h; and then naturally cooling to room temperature, taking out, placing in pure water for ultrasonic cleaning, placing in the pure water for standby, and cleaning by purging with clean nitrogen before use.
3) The metal substrate after nitriding treatment is sent into a vacuum chamber by adopting bias magnetic control arc ion coating equipment, and is vacuumized to 5 multiplied by 10 -3 Pa, heating the metal substrate to 270 ℃, introducing argon of 1Pa, setting the bias voltage at-1200V, and performing surface ion sputtering and etching activation on the metal substrate for 1min.
4) Depositing a corrosion-resistant coating on the surface of the metal substrate; wherein the corrosion-resistant coating comprises chromium. Oxidation modification of the corrosion-resistant coating: introducing a mixed gas of argon of 0.8Pa and oxygen of 0.2Pa into the vacuum chamber, setting the bias voltage at-200V, and carrying out surface ion sputtering and etching for 5min.
5) Vacuum was applied to the vacuum chamber 5X 10 -3 Pa, introducing argon of 1Pa, and maintaining the temperature of the metal substrate at 200 DEG CThe temperature was set at-300V, and a carbon-titanium mixture (i.e., conductive coating) was deposited on the metal substrate for 1h with a carbon content of 90wt% and a titanium content of 10wt% measured after the plating was completed.
6) Immersing the sample after the deposition in the step 5) in 0.3% PTFE aqueous solution, taking out, draining, heating in a 250 ℃ oven for 10min, and naturally cooling to obtain the metal bipolar plate.
Experimental example 2
The metal substrate of this embodiment is 316L stainless steel. The metal substrate is deposited with a coating, and the metal bipolar plate is prepared by the following steps:
1) The metal substrate is subjected to a first degreasing treatment with a 1M sodium hydroxide solution at 80 ℃ for 30min, and after cleaning, the metal substrate is subjected to a second degreasing cleaning with alcohol.
2) Placing a metal substrate in an atmosphere furnace, vacuumizing to a relative vacuum degree of-0.1 MPa, introducing nitrogen, and programming to 800 ℃, wherein the temperature rising speed is 5 ℃/min, and the heat preservation time is 1h; and then naturally cooling to room temperature, taking out, placing in pure water for ultrasonic cleaning, placing in the pure water for standby, and cleaning by purging with clean nitrogen before use.
3) The metal substrate after nitriding treatment is sent into a vacuum chamber by adopting bias magnetic control arc ion coating equipment, and is vacuumized to 5 multiplied by 10 -3 Pa, heating the metal substrate to 270 ℃, introducing argon of 1Pa, setting the bias voltage at-1200V, and performing surface ion sputtering and etching activation on the metal substrate for 1min.
4) Depositing a corrosion-resistant coating on the surface of the metal substrate; wherein the corrosion-resistant coating comprises chromium. Oxidation modification of the corrosion-resistant coating: introducing a mixed gas of argon of 0.7Pa and oxygen of 0.3Pa into the vacuum chamber, setting the bias voltage at-200V, and carrying out surface ion sputtering and etching for 5min.
5) Vacuum was applied to the vacuum chamber 5X 10 -3 Pa, introducing argon of 1Pa, maintaining the temperature of the metal substrate at 250 ℃, setting the bias voltage at 330V, and depositing a carbon-titanium mixture (namely, a conductive coating) on the metal substrate, wherein the carbon content is 80wt% and the titanium content is measured after coating is finished20wt% and a deposition time of 1h.
6) Immersing the sample after the deposition in the step 5) in 0.3% PTFE aqueous solution, taking out, draining, heating in a 250 ℃ oven for 10min, and naturally cooling to obtain the metal bipolar plate.
Experimental example 3
The metal substrate of this embodiment is 316L stainless steel. The metal substrate is deposited with a coating, and the metal bipolar plate is prepared by the following steps:
1) The metal substrate is subjected to a first degreasing treatment with a 1M sodium hydroxide solution at 80 ℃ for 30min, and after cleaning, the metal substrate is subjected to a second degreasing cleaning with alcohol.
2) Placing a metal substrate in an atmosphere furnace, vacuumizing to a relative vacuum degree of-0.1 MPa, introducing nitrogen, programming to 830 ℃, wherein the temperature rising speed is 5 ℃/min, and the heat preservation time is 1h; and then naturally cooling to room temperature, taking out, placing in pure water for ultrasonic cleaning, placing in the pure water for standby, and cleaning by purging with clean nitrogen before use.
3) The metal substrate after nitriding treatment is sent into a vacuum chamber by adopting bias magnetic control arc ion coating equipment, and is vacuumized to 5 multiplied by 10 -3 Pa, heating the metal substrate to 280 ℃, introducing argon of 1Pa, setting bias voltage at-1800V, and performing surface ion sputtering and etching activation on the metal substrate for 1min.
4) Depositing a corrosion-resistant coating on the surface of the metal substrate; wherein the corrosion-resistant coating comprises tungsten. Oxidation modification of the corrosion-resistant coating: introducing a mixed gas of argon of 0.8Pa and oxygen of 0.2Pa into the vacuum chamber, setting the bias voltage at-480V, and carrying out surface ion sputtering and etching for 5min.
5) Vacuum was applied to the vacuum chamber 5X 10 -3 Pa, introducing argon of 1Pa, maintaining the temperature of the metal substrate at 320 ℃, setting the bias voltage at-280V, and depositing a carbon-titanium mixture (namely, a conductive coating) on the metal substrate, wherein the carbon content is 85wt%, the titanium content is 15wt% and the deposition time is 1h after the coating is finished.
6) Immersing the sample after the deposition in the step 5) in 0.3% PTFE aqueous solution, taking out, draining, heating in a 250 ℃ oven for 10min, and naturally cooling to obtain the metal bipolar plate.
Experimental example 4
The metal substrate of this embodiment is 316L stainless steel. The metal substrate is deposited with a coating, and the metal bipolar plate is prepared by the following steps:
1) The metal substrate is subjected to a first degreasing treatment with a 1M sodium hydroxide solution at 80 ℃ for 30min, and after cleaning, the metal substrate is subjected to a second degreasing cleaning with alcohol.
2) Placing a metal substrate in an atmosphere furnace, vacuumizing to the relative vacuum degree of-0.1 MPa, introducing nitrogen to normal pressure, vacuumizing again to the relative vacuum degree of 0.1MPa, introducing nitrogen, programming to 850 ℃, wherein the temperature rising speed is 5 ℃/min, and the heat preservation time is 1h; and then naturally cooling to room temperature, taking out, placing in pure water for ultrasonic cleaning, placing in the pure water for standby, and cleaning by purging with clean nitrogen before use.
3) The metal substrate after nitriding treatment is sent into a vacuum chamber by adopting bias magnetic control arc ion coating equipment, and is vacuumized to 5 multiplied by 10 -3 Pa, heating the metal substrate to 150 ℃, introducing argon of 1Pa, setting the bias voltage at-800V, and performing surface ion sputtering and etching activation on the metal substrate for 1min.
4) Depositing a corrosion-resistant coating on the surface of the metal substrate; wherein the corrosion-resistant coating comprises titanium. Oxidation modification of the corrosion-resistant coating: introducing a mixed gas of argon of 0.8Pa and oxygen of 0.2Pa into the vacuum chamber, setting the bias voltage at-350V, and carrying out surface ion sputtering and etching for 5min.
5) Vacuum was applied to the vacuum chamber 5X 10 -3 Pa, introducing argon of 1Pa, maintaining the temperature of the metal substrate at 250 ℃, setting the bias voltage at-380V, and depositing a carbon-titanium mixture (namely, a conductive coating) on the metal substrate, wherein the carbon content is 80wt%, the titanium content is 20wt% and the deposition time is 1h after the coating is finished.
6) Immersing the sample after the deposition in the step 5) in a 0.5% PTFE aqueous solution, taking out, draining, heating in a 350 ℃ oven for 5min, and naturally cooling to obtain the metal bipolar plate.
Experimental example 5
The metal substrate of this embodiment is 316L stainless steel. The metal substrate is deposited with a coating, and the metal bipolar plate is prepared by the following steps:
1) The metal substrate is subjected to a first degreasing treatment with a 1M sodium hydroxide solution at 80 ℃ for 30min, and after cleaning, the metal substrate is subjected to a second degreasing cleaning with alcohol.
2) Placing a metal substrate in an atmosphere furnace, vacuumizing to the relative vacuum degree of-0.1 MPa, introducing nitrogen to normal pressure, vacuumizing again to the relative vacuum degree of 0.1MPa, introducing nitrogen, programming to 850 ℃, wherein the temperature rising speed is 5 ℃/min, and the heat preservation time is 1h; and then naturally cooling to room temperature, taking out, placing in pure water for ultrasonic cleaning, placing in the pure water for standby, and cleaning by purging with clean nitrogen before use.
3) The metal substrate after nitriding treatment is sent into a vacuum chamber by adopting bias magnetic control arc ion coating equipment, and is vacuumized to 5 multiplied by 10 -3 Pa, heating the metal substrate to 150 ℃, introducing argon of 1Pa, setting the bias voltage at-800V, and performing surface ion sputtering and etching activation on the metal substrate for 1min.
4) Depositing a corrosion-resistant coating on the surface of the metal substrate; wherein the corrosion-resistant coating comprises titanium. Oxidation modification of the corrosion-resistant coating: introducing a mixed gas of argon of 0.8Pa and oxygen of 0.2Pa into the vacuum chamber, setting the bias voltage at-350V, and carrying out surface ion sputtering and etching for 5min.
5) Vacuum was applied to the vacuum chamber 5X 10 -3 Pa, introducing argon of 1Pa, maintaining the temperature of the metal substrate at 250 ℃, setting the bias voltage at-380V, and depositing a carbon-titanium mixture (namely, a conductive coating) on the metal substrate, wherein the carbon content is 80wt%, the titanium content is 20wt% and the deposition time is 1h after the coating is finished, so as to obtain the metal bipolar plate.
Comparative example 1
The metal substrate of comparative example 1 was selected from 316L stainless steel. The metal substrate is deposited with a coating, and the metal bipolar plate is prepared by the following steps:
1) The metal substrate is subjected to a first degreasing treatment with a 1M sodium hydroxide solution at 80 ℃ for 30min, and after cleaning, the metal substrate is subjected to a second degreasing cleaning with alcohol.
2) Adopting bias magnetic control arc ion plating equipment to send the metal substrate into a vacuum chamber, and vacuumizing to 5X 10 - 3 Pa, heating the metal substrate to 270 ℃, introducing argon of 1Pa, setting the bias voltage at-1200V, and performing surface ion sputtering and etching activation on the metal substrate for 1min. Then depositing a corrosion-resistant coating on the surface of the metal substrate; wherein the corrosion-resistant coating comprises chromium.
3) Vacuum was applied to the vacuum chamber 5X 10 -3 Pa, introducing argon of 1Pa, maintaining the temperature of the metal substrate at 200 ℃, setting the bias voltage at-300V, and depositing a carbon film on the metal substrate to obtain the metal bipolar plate.
The metal bipolar plates prepared in experimental examples 1 to 5 and comparative example 1 were subjected to performance test, and the test results are shown in table 1.
Table 1 shows the results of the performance test of the metallic bipolar plates prepared in experimental examples 1 to 5 and comparative example 1
From the experimental results in table 1, it can be seen that:
1. according to the embodiment of the invention, the first surface of the metal substrate is subjected to high-temperature nitriding treatment, so that the corrosion resistance and the conductivity of the first surface of the metal substrate and the binding force between the first surface of the metal substrate and the corrosion-resistant coating can be improved.
2. According to the embodiment of the invention, the corrosion resistance of the metal bipolar plate is further improved by carrying out oxidation modification on the corrosion-resistant coating.
3. According to the embodiment of the invention, the conductive coating is doped with a small amount of titanium, so that the titanium can form oxide under the action of a small amount of oxygen to block pinholes in the conductive coating, and the corrosion resistance of the metal bipolar plate is further improved.
4. According to the embodiment of the invention, the second conductive coating is provided with the hydrophobic layer, so that the corrosion resistance is further improved.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (22)
1. A metal bipolar plate, the metal bipolar plate comprising:
a metal substrate including a first surface subjected to nitriding treatment;
a corrosion-resistant coating deposited on a first side of the metal substrate; the composition of the corrosion-resistant coating comprises a first metal; the first metal comprises one or more of titanium, chromium, tungsten, nickel, aluminum, and copper; the corrosion-resistant coating has a plurality of first pinholes; wherein the first pinholes are distributed on the surface and inside of the corrosion-resistant coating; the first pinholes are plugged with an oxide formed by the first metal;
a conductive coating deposited on the corrosion-resistant coating;
the preparation method of the metal bipolar plate comprises the following steps:
the first step of pretreatment: carrying out oil removal treatment on the metal substrate;
nitriding: performing high-temperature nitridation treatment on the metal substrate;
depositing a corrosion-resistant coating: depositing a corrosion-resistant coating on the nitrided first side of the metal substrate;
depositing a conductive coating: depositing a conductive coating on the corrosion-resistant coating of the metal substrate;
wherein the step of depositing a corrosion-resistant coating comprises:
depositing a first metal layer: the vacuum degree of the vacuum chamber is pumped to 3 multiplied by 10 -3 Pa～6×10 -3 Pa, introducing inert gas, setting negative bias voltage to-100 to-500V, opening a metal target, performing ion sputtering on the conductive coating, and forming a metal substrate on the metal targetDepositing a first metal layer on the first side of the substrate;
and (3) performing oxidation hole sealing modification treatment: introducing inert gas and oxygen into the vacuum chamber, setting bias voltage to-100 to-500V, and exciting and ionizing the oxygen to bombard the first metal layer by oxygen ions for 1-15 min to obtain a corrosion-resistant coating sealed by the first metal oxide; wherein the pressure of the inert gas is 0.5-1Pa, and the pressure of the oxygen is 0.1-0.5Pa.
2. The metallic bipolar plate of claim 1, wherein the nitriding process is a gas nitriding process.
3. The metallic bipolar plate of claim 1 wherein the corrosion-resistant coating has a thickness of 20nm to 5um.
4. The metallic bipolar plate of claim 1 wherein the composition of the conductive coating comprises, in mass percent, 60-90% carbon and 10-40% of the second metal.
5. The metallic bipolar plate of claim 4 wherein the composition of the conductive coating comprises, in mass percent, 85-90% carbon and 10-15% of the second metal.
6. The metallic bipolar plate of claim 5 wherein the second metal is titanium.
7. The metallic bipolar plate of claim 4 wherein the conductive coating has a plurality of second pinholes, the second pinholes being plugged with an oxide formed from the second metal.
8. The metallic bipolar plate of claim 1 wherein the metallic bipolar plate further comprises a hydrophobic layer; wherein the hydrophobic layer is disposed on the conductive coating.
9. The metallic bipolar plate of claim 8 wherein the composition of the hydrophobic layer comprises PTFE.
10. The metallic bipolar plate of claim 1, wherein the first step of pretreatment is specifically: and (3) carrying out first oil removal treatment on the metal substrate by adopting a sodium hydroxide solution, and carrying out second oil removal treatment on the metal substrate by adopting alcohol.
11. The metallic bipolar plate of claim 1 wherein,
the nitriding step comprises the following steps: performing heat treatment on the metal substrate under nitriding gas; wherein the temperature of the heat treatment is 450-850 ℃, and the time of the heat treatment is 0.5-4 h.
12. The metallic bipolar plate of claim 11 wherein,
the temperature of the heat treatment is 800-850 ℃, and the time of the heat treatment is 1-2 h.
13. The metallic bipolar plate of claim 11 wherein,
the nitriding step is performed in an atmosphere furnace.
14. The metallic bipolar plate of claim 1, further comprising a second pretreatment step after the nitriding step and before the depositing the corrosion-resistant coating step to increase the roughness of the first side of the metallic substrate.
15. The metallic bipolar plate of claim 14 wherein,
the second step of preprocessing comprises the following steps: heating the metal substrate subjected to nitriding treatment in a vacuum chamber, introducing working gas, setting negative bias, and performing ion sputtering on the first surface of the metal substrate; and/or
The vacuum degree of the vacuum chamber is 3 multiplied by 10 -3 Pa～6×10 -3 Pa; the working gas is inert gas; the pressure of the working gas is 0.5Pa to 1.5Pa; the negative bias voltage is set to be-200 to-3200V; the temperature of the metal substrate is 120-300 ℃; the ion sputtering time is 1-3 min; and/or
The second pretreatment step is carried out in a bias magnetic control multi-arc ion plating device.
16. The metallic bipolar plate of claim 1, wherein the step of depositing a corrosion-resistant coating comprises:
in the step of depositing the corrosion-resistant coating, the temperature of the metal substrate is 350-500 ℃; and/or
The step of depositing the corrosion-resistant coating is performed in a biased magnetically controlled multi-arc ion plating device.
17. The metallic bipolar plate of claim 1, wherein the step of depositing a conductive coating comprises:
in a vacuum chamber, vacuum is pumped to 3X 10 -3 Pa～6×10 -3 Pa, introducing inert gas of 0.5-1.5 Pa, setting bias voltage of-100 to-500V, and depositing conductive coating containing carbon and second metal on the corrosion-resistant coating.
18. The method for producing a metallic bipolar plate as claimed in claim 17, wherein,
in the step of depositing the conductive coating, the temperature of the metal substrate is maintained at 80-500 ℃; and/or
The step of depositing the conductive coating is performed in a bias magnetic control multi-arc ion plating device.
19. The metallic bipolar plate of claim 8 wherein the method of making the metallic bipolar plate further comprises the steps of:
and carrying out surface hydrophobic treatment, and arranging a hydrophobic layer on the surface of the conductive coating.
20. The metallic bipolar plate of claim 19 wherein,
the surface hydrophobic treatment comprises the following steps: immersing the metal substrate sequentially deposited with the corrosion-resistant coating and the conductive coating into a hydrophobizing agent for surface hydrophobizing treatment, and forming a hydrophobic layer on the surface of the conductive coating; and solidifying the hydrophobic layer, and cooling to obtain the metal bipolar plate.
21. The metallic bipolar plate of claim 20 wherein,
the surface hydrophobic treatment time is 30 s-5 min; and/or
The thickness of the hydrophobic layer is 2-20 nm; and/or
The hydrophobizing agent is PTFE solution with mass fraction of 0.1-5%; and/or
The step of curing the hydrophobic layer is as follows: and heating the metal substrate with the hydrophobic layer formed on the surface to 200-450 ℃ and performing heat treatment for 30 s-10 min.
22. A fuel cell comprising the metallic bipolar plate of any of claims 1-21.
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| CN110289428B (en) * | 2019-06-19 | 2020-10-13 | 北京科技大学 | Preparation and surface modification method of stainless steel bipolar plate of fuel cell |
| CN112038652B (en) * | 2020-07-28 | 2021-11-12 | 江苏科技大学 | Fuel cell bipolar plate and preparation method thereof |
| CN114525475A (en) * | 2021-12-08 | 2022-05-24 | 常州翊迈新材料科技有限公司 | Functional coating material and preparation method thereof |
| CN116727205B (en) * | 2023-05-31 | 2024-04-02 | 麓丰新材料(广东)有限公司 | Corrosion prevention treatment method for metal bipolar plate |
| CN117587357B (en) * | 2024-01-19 | 2024-04-09 | 北京开元新能科技有限公司 | Metal bipolar plate for proton exchange membrane fuel cell and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003092139A2 (en) * | 2002-04-26 | 2003-11-06 | President And Fellows Of Harvard College | Durable bipolar plates for fuel cells |
| CN101552342A (en) * | 2009-04-09 | 2009-10-07 | 上海交通大学 | Method of compositely manufacturing proton exchange membrane fuel cell bipolar plate and membrane electrode assembly |
| CN101800318A (en) * | 2010-04-09 | 2010-08-11 | 新源动力股份有限公司 | Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof |
| CN102130341A (en) * | 2011-01-18 | 2011-07-20 | 大连理工大学 | Bipolar plate of fuel cell and method for preparing carbon titanium nanocomposite film on surface thereof |
| CN103614693A (en) * | 2013-12-02 | 2014-03-05 | 新源动力股份有限公司 | Pore blocking method for surface modified layer of fuel cell polar plate |
| CN104577144A (en) * | 2015-01-27 | 2015-04-29 | 大连理工常州研究院有限公司 | Fuel-cell bipolar plate with nitrified and enhanced surface and preparation method thereof |
| CN209401743U (en) * | 2018-12-26 | 2019-09-17 | 浙江锋源氢能科技有限公司 | A kind of metal double polar plates and fuel cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9136545B2 (en) * | 2008-02-27 | 2015-09-15 | GM Global Technology Operations LLC | Low cost fuel cell bipolar plate and process of making the same |
-
2018
- 2018-12-26 CN CN201811600340.2A patent/CN109755592B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003092139A2 (en) * | 2002-04-26 | 2003-11-06 | President And Fellows Of Harvard College | Durable bipolar plates for fuel cells |
| CN101552342A (en) * | 2009-04-09 | 2009-10-07 | 上海交通大学 | Method of compositely manufacturing proton exchange membrane fuel cell bipolar plate and membrane electrode assembly |
| CN101800318A (en) * | 2010-04-09 | 2010-08-11 | 新源动力股份有限公司 | Metal bipolar plate for proton exchange membrane fuel cell and preparation method thereof |
| CN102130341A (en) * | 2011-01-18 | 2011-07-20 | 大连理工大学 | Bipolar plate of fuel cell and method for preparing carbon titanium nanocomposite film on surface thereof |
| CN103614693A (en) * | 2013-12-02 | 2014-03-05 | 新源动力股份有限公司 | Pore blocking method for surface modified layer of fuel cell polar plate |
| CN104577144A (en) * | 2015-01-27 | 2015-04-29 | 大连理工常州研究院有限公司 | Fuel-cell bipolar plate with nitrified and enhanced surface and preparation method thereof |
| CN209401743U (en) * | 2018-12-26 | 2019-09-17 | 浙江锋源氢能科技有限公司 | A kind of metal double polar plates and fuel cell |
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