CN107171003B - Conductive super-corrosion-resistant functional coating material - Google Patents
Conductive super-corrosion-resistant functional coating material Download PDFInfo
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- CN107171003B CN107171003B CN201710451138.7A CN201710451138A CN107171003B CN 107171003 B CN107171003 B CN 107171003B CN 201710451138 A CN201710451138 A CN 201710451138A CN 107171003 B CN107171003 B CN 107171003B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0206—Metals or alloys
- H01M8/0208—Alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to the technical field of coatings, in particular to a conductive super-corrosion-resistant functional coating material. The conductive super-corrosion-resistant functional coating material comprises a self-healing layer and a super-corrosion-resistant layer, wherein the self-healing layer is composed of a titanium alloy, and the super-corrosion-resistant layer is a nitride layer composed of the titanium alloy. The conductive super-corrosion-resistant functional coating material prolongs the service life of the metal polar plate of the fuel cell, has the capability of automatically filling the pinholes in the use process, does not need to design a multi-layer structure for avoiding repeated circulation of the pinholes, and can reach lower contact resistance and corrosion current density (the contact resistance can reach 3m omega. cm2-15m omega. cm) than the prior art on the premise of not adding noble metal2The corrosion current density can reach 5 multiplied by 10‑8A/cm2) Greatly reducing the processing cost of the metal polar plate.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a conductive super-corrosion-resistant functional coating material.
Background
The proton exchange membrane fuel cell is used as a new name of a 21 st century new energy automobile, has market promotion prospect which cannot be replaced by the pure electric automobile at present and has great significance for improving the earth environment, has higher energy conversion efficiency than a fuel automobile, does not discharge pollutants in the operation process, and does not have the environmental pollution problem which needs to be considered by the pure electric automobile in the recovery of the cell. Therefore, countries around the world strive to develop related technologies, wherein the selection of the material of the bipolar plate of the fuel cell and the research and development of the surface modification means thereof are particularly outstanding, because the bipolar plate is the core component of the proton exchange membrane fuel cell, which accounts for 70% -80% of the total weight of the fuel cell, and 40% -50% of the manufacturing cost, and is also a key factor restricting the service life of the cell, the development of the novel material of the fuel cell plate is particularly important in order to reduce the total weight of the fuel cell stack, reduce the manufacturing cost, and improve the service life of the cell. At present, the weight problem of bipolar plates is effectively improved, but the base material of the polar plate adopting the lightweight design is mostly stainless steel or titanium alloy which is easy to passivate the surface, so that the surface resistance of the polar plate is easily and rapidly improved in the battery environment, and the standard of the battery use cannot be met, therefore, a large number of coatings and modification technologies aiming at the surface modification of the metal polar plate appear, although some methods really and effectively improve the conductive capacity of the surface of the polar plate, and simultaneously improve the durability of the polar plate to a certain extent, the methods comprise the steps of adopting a multilayer design to plug pin holes, introducing precious metals to improve the corrosion resistance, adopting special means to improve the density of the coatings and the like, although the best technology at present can only meet the use requirement of a fuel battery for 3000 hours, the best technology at present can still not meet the.
Disclosure of Invention
In order to overcome the defects of the existing coating, the invention provides a conductive super-corrosion-resistant functional coating material.
The technical scheme adopted by the invention for solving the technical problems is as follows: the conductive super-corrosion-resistant functional coating material comprises a self-healing layer and a super-corrosion-resistant layer, wherein the self-healing layer is composed of a titanium alloy, and the super-corrosion-resistant layer is a nitride layer composed of the titanium alloy.
According to another embodiment of the present invention, further comprising, the titanium alloy comprises titanium and one or more of vanadium, tantalum, nickel, chromium, zirconium, wherein the titanium content is 30wt% to 80 wt%.
According to another embodiment of the invention, the self-healing layer is arranged on the outer side of the substrate and has a coating thickness of 30nm-500nm, and the mechanical damage part of the self-healing layer automatically forms a filler, and is easy to react with oxygen due to exposure to the outside to automatically form an oxidation filler, and the formed oxidation product has better corrosion resistance and better electric conductivity, so that the further occurrence of corrosion reaction is prevented.
According to another embodiment of the invention, the ultra-corrosion-resistant layer is arranged outside the self-healing layer, and the ultra-corrosion-resistant layer is titanium alloy component nitride, the titanium alloy comprises titanium and one or more of vanadium, tantalum, nickel, chromium and zirconium, wherein the content of the titanium is 3wt% to 70 wt%.
According to another embodiment of the present invention, the titanium alloy composition nitride layer of the super corrosion resistant layer has a coating thickness of 20nm-500nm, and has good conductivity and excellent corrosion resistance, and the contact resistance with carbon paper is 3m Ω cm under a pressure test of 0.6MPa2-15mΩ•cm2(ii) a Electrochemical workstation is adopted to carry out potentiodynamic polarization test, the corrosion potential is 0.5V-1.2V, and the corrosion current density is 0.5 multiplied by 10-7A/cm2-8×10-7A/cm2。
The conductive super-corrosion-resistant functional coating material has the beneficial effects that the service life of the metal polar plate of the fuel cell is prolonged, and the conductive super-corrosion-resistant functional coating material has the capability of automatically filling pinholes in the use process, so that a multi-layer structure for avoiding repeated circulation of the pinholes is not required to be designed, and the contact resistance and the corrosion current density (the contact resistance can reach 3m omega-cm 2-15m omega-cm) which are lower than those of the prior art can be achieved on the premise of not adding noble metal2The corrosion current density can reach 5 multiplied by 10-8A/cm2) Greatly reducing the processing cost of the metal polar plate.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic structural view of the present invention;
in the figure, 1, a substrate, 2, a self-healing layer, 3, an ultra-corrosion-resistant layer, 4, a mechanical damage part, 5 and a filler.
Detailed Description
Referring to fig. 1, which is a schematic structural diagram of the present invention, a conductive super corrosion-resistant functional coating material includes a self-healing layer 2 and a super corrosion-resistant layer 3, the self-healing layer 2 is composed of a titanium alloy, and the super corrosion-resistant layer 3 is a nitride layer of a titanium alloy component.
According to another embodiment of the present invention, further comprising, the titanium alloy comprises titanium and one or more of vanadium, tantalum, nickel, chromium, zirconium, wherein the titanium content is 30wt% to 80 wt%.
According to another embodiment of the invention, the self-healing layer 2 is arranged outside the substrate 1 and has a coating thickness of 30nm-500nm, and the mechanical damage part 4 of the self-healing layer 2 automatically forms the filler 5, and is easy to react with oxygen due to exposure, and automatically forms the oxidized filler 5, and the formed oxidized product has better corrosion resistance and better electric conductivity, so as to prevent further corrosion reaction.
According to another embodiment of the invention, the ultra-corrosion-resistant layer 3 is arranged outside the self-healing layer 2, and the ultra-corrosion-resistant layer 3 is titanium alloy component nitride, the titanium alloy comprises titanium and one or more of vanadium, tantalum, nickel, chromium and zirconium, wherein the content of titanium is 3wt% -70 wt%.
According to another embodiment of the present invention, it is further included that the titanium alloy composition nitride layer of the super corrosion resistant layer 3 has a coating thickness of 20nm to 500nm, and has a good electric conductivity and excellent corrosion resistance, and a contact resistance with carbon paper of 3m Ω cm under a pressure test of 0.6MPa2-15mΩ•cm2(ii) a Electrochemical workstation is adopted to carry out potentiodynamic polarization test, the corrosion potential is 0.5V-1.2V, and the corrosion current density is 0.5 multiplied by 10-7A/cm2-8×10-7A/cm2。
The first embodiment of the invention:
the titanium alloy component composing the self-healing layer is a titanium alloy containing 30wt% of titanium, wherein the titanium is β phase, other additive components can be one or more of vanadium, tantalum, nickel, chromium and zirconium, such as binary, ternary and even multicomponent alloys of titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and tantalum and vanadium, and multicomponent alloys, such as alloys of 30wt% of titanium, 20wt% of vanadium and 50wt% of chromium, and the formed alloy has a BCC structure, the coating thickness is 30nm, and it is worth mentioning that in the present embodiment, the thicker the self-healing layer is, the stronger the self-healing capability is, and the stronger the capability of preventing the corrosion and oxidation of the substrate is.
The alloy component composing the super corrosion-resistant layer is alloy nitride containing 3% of titanium, wherein the titanium is β phase, other additive components can be one or more of vanadium, tantalum, nickel, chromium and zirconium, such as binary, ternary or even multi-component alloy of titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and tantalum and vanadium, super composition, such as alloy of 3wt% of titanium, 10wt% of tantalum and 87wt% of chromium, the coating thickness is 30nm, and it is worth mentioning that the self-healing layer and the super corrosion-resistant layer are obtained by PVD method, including multi-arc ion coating technology, magnetron sputtering coating technology, evaporation coating technology and not limited to one of them.
The coating has good conductivity and excellent corrosion resistance, and the contact resistance with the carbon paper is 15m omega cm under the pressure test of 0.6MPa2The electrochemical workstation is adopted to carry out potentiodynamic polarization test, the corrosion potential is 1.0V, and the corrosion current density is 5 multiplied by 10-6A/cm2。
Embodiment two of the present invention:
the titanium alloy component composing the self-healing layer is a titanium alloy containing 80wt% of titanium, wherein the titanium is β phase, other additive components can be one or more of vanadium, tantalum, nickel, chromium and zirconium, such as binary, ternary and even multicomponent alloys of titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and tantalum and vanadium, such as an alloy composed of 80wt% of titanium and 20wt% of vanadium, and the formed alloy is a BCC structure, the coating thickness is 30nm, and it is worth mentioning that in the embodiment, the thicker the self-healing layer is, the stronger the self-healing capability is, and the stronger the capability of preventing the corrosion and oxidation of the substrate is.
The titanium alloy component composing the super corrosion-resistant layer is titanium alloy nitride containing 70% of titanium, wherein the titanium is β phase, other additive components can be one or more of vanadium, tantalum, nickel, chromium and zirconium, such as titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and tantalum and vanadium, binary, ternary and even multicomponent alloy with excessive composition, such as alloy composed of 80wt% of titanium and 20wt% of vanadium, and the formed alloy is BCC structure, the coating thickness is 30nm, and it is worth mentioning that the self-healing layer and the super corrosion-resistant layer are obtained by PVD method, including multi-arc ion coating technology, magnetron sputtering coating technology, evaporation coating technology and not limited to one of them.
The coating has good conductivity and excellent corrosion resistance, and the contact resistance with the carbon paper is 3m omega cm under the pressure test of 0.6MPa2The electrochemical workstation is adopted to carry out potentiodynamic polarization test, the corrosion potential is 1.2V, and the corrosion current is denseDegree of 8X 10-7A/cm2。
The third embodiment of the invention:
the titanium alloy component composing the self-healing layer is a titanium alloy containing 60wt% of titanium, wherein the titanium is β phase, other additive components can be one or more of vanadium, tantalum, nickel, chromium and zirconium, such as binary, ternary and even multicomponent alloys of titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and tantalum and vanadium, such as an alloy composed of 60wt% of titanium and 40wt% of vanadium, and the formed alloy is a BCC structure, the coating thickness is 30nm, and it is worth mentioning that in the embodiment, the thicker the self-healing layer is, the stronger the self-healing capability is, and the stronger the capability of preventing the corrosion and oxidation of the substrate is.
The titanium alloy component composing the super corrosion-resistant layer is titanium alloy nitride containing 50% of titanium, wherein the titanium is β phase, other additive components can be one or more of vanadium, tantalum, nickel, chromium and zirconium, such as titanium and vanadium, titanium and tantalum, titanium and chromium, titanium and tantalum and vanadium, binary, ternary and even multicomponent alloy with excessive composition, such as alloy composed of 50wt% of titanium and 50wt% of vanadium, and the formed alloy is BCC structure, the coating thickness is 30nm, and it is worth mentioning that the self-healing layer and the super corrosion-resistant layer are obtained by PVD method, including multi-arc ion coating technology, magnetron sputtering coating technology, evaporation coating technology and not limited to one of them.
The coating has good conductivity and excellent corrosion resistance, and the contact resistance with the carbon paper is 10m omega cm under the pressure test of 0.6MPa2The electrochemical workstation is adopted to carry out potentiodynamic polarization test, the corrosion potential is 0.7V, and the corrosion current density is 1 multiplied by 10-6A/cm2。
The foregoing description is intended to be illustrative rather than limiting, and it will be appreciated by those skilled in the art that many modifications, variations or equivalents may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (2)
1. A conductive super-corrosion-resistant functional coating material is characterized in that the coating comprises a self-healing layer (2) and a super-corrosion-resistant layer (3), wherein the self-healing layer (2) is made of titanium alloy, and the super-corrosion-resistant layer (3) is a nitride layer made of titanium alloy components;
the titanium alloy comprises titanium and one or more of vanadium, tantalum, nickel, chromium and zirconium, wherein the content of the titanium is 30-80 wt%;
the super-corrosion-resistant layer (3) is arranged outside the self-healing layer (2), and the super-corrosion-resistant layer (3) is titanium alloy component nitride, the titanium alloy comprises titanium and one or more of vanadium, tantalum, nickel, chromium and zirconium, wherein the content of the titanium is 3wt% -70 wt%;
the self-healing layer (2) is arranged on the outer side of the base body (1) and has a coating thickness of 30nm-500nm, the filler (5) is automatically formed at the mechanical damage part (4) of the self-healing layer (2), the filler is easy to react with oxygen due to exposure, the oxidized filler (5) is automatically formed, and the formed oxidation product has better corrosion resistance and better conductivity, so that further occurrence of corrosion reaction is prevented.
2. The conductive ultra corrosion-resistant functional coating material as claimed in claim 1, wherein the titanium alloy component nitride layer of the ultra corrosion-resistant layer (3) has a coating thickness of 20nm-500nm, and has good conductivity and excellent corrosion resistance, and a contact resistance with carbon paper of 3m Ω. cm under a pressure test of 0.6MPa2-15mΩ•cm2(ii) a Electrochemical workstation is adopted to carry out potentiodynamic polarization test, the corrosion potential is 0.5V-1.2V, and the corrosion current density is 0.5 multiplied by 10-7A/cm2-8×10-7A/cm2。
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| CN109023231A (en) * | 2018-09-10 | 2018-12-18 | 常州翊迈新材料科技有限公司 | The preparation method of superconduction graphene coating and the coating manufactured using this method |
| CN114214658A (en) * | 2021-12-14 | 2022-03-22 | 中国科学院大连化学物理研究所 | Composite coating for water electrolysis metal bipolar plate and preparation method thereof |
| CN115663224B (en) * | 2022-11-16 | 2023-05-02 | 上海治臻新能源股份有限公司 | Metal composite coating of bipolar plate of proton exchange membrane fuel cell and preparation method thereof |
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