CN111636085A - Anticorrosive coating and preparation method thereof - Google Patents
Anticorrosive coating and preparation method thereof Download PDFInfo
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- CN111636085A CN111636085A CN202010522589.7A CN202010522589A CN111636085A CN 111636085 A CN111636085 A CN 111636085A CN 202010522589 A CN202010522589 A CN 202010522589A CN 111636085 A CN111636085 A CN 111636085A
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention discloses an anticorrosive coating and a preparation method thereof, wherein the method comprises the following steps: dispersing a conductive polymer monomer and a doped organic matter in a graphene oxide aqueous solution to obtain an electropolymerization electrolyte; and putting the metal bipolar plate into the electropolymerization electrolyte, and introducing current to form an anticorrosive coating on the surface of the metal bipolar plate. The anti-corrosion coating provided by the invention is doped with graphene oxide and organic matters, so that the generation of a passivation film is inhibited, and the conductivity of the anti-corrosion coating is good; the anticorrosive coating formed on the surface of the metal bipolar plate can play a role of a physical barrier, hinder the ion migration process in electrochemical corrosion and improve the corrosion resistance of the metal bipolar plate; the barrier effect can be further enhanced by adding graphene oxide to the anticorrosive coating.
Description
Technical Field
The invention relates to the field of metal corrosion prevention, in particular to an anticorrosive coating and a preparation method thereof.
Background
In recent years, the country has gradually increased the support of policies for the hydrogen energy automobile industry. The hydrogen energy automobile core power part generally adopts a Proton Exchange Membrane Fuel Cell (PEMFC). Bipolar plates are an important functional component of PEMFCs, accounting for about 80% of the mass and 18-28% of the cost of the cell.
The traditional bipolar plate material uses a graphite plate, but the graphite has large brittleness and strong gas permeability, and can meet the mechanical property and air tightness requirements of the bipolar plate only by being generally made to be more than 2 millimeters, so that the improvement of the volume power density and the energy density of the PEMFC is greatly limited; meanwhile, the poor processability also leads to high processing cost of the graphite bipolar plate, and limits the wide application of the graphite bipolar plate. In contrast, the metal material has excellent mechanical properties and processability, can be easily processed to be less than 0.8mm, can be used for providing a fuel flow channel by stamping and forming, has low overall processing cost, and is one of the most promising bipolar plate material types. However, corrosion of the metal and contact resistance problems can dramatically degrade the overall performance of the fuel cell.
Electropolymerization of a layer of conductive polymer on the surface of a metal bipolar plate is one of the main approaches to solve the application problem of the metal bipolar plate. However, the corrosion resistance and contact resistance of the metal bipolar plate are improved to a limited extent by electropolymerizing a single layer of anticorrosive coating, and further improvement of the coating performance is still needed.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an anticorrosive coating and a preparation method thereof, and aims to solve the problem that the existing anticorrosive coating is poor in corrosion resistance and conductivity.
The technical scheme of the invention is as follows:
a method for preparing an anti-corrosive coating, comprising the steps of:
providing a graphene oxide aqueous solution;
dispersing a conductive polymer monomer and a doped organic matter in the graphene oxide aqueous solution to obtain an electropolymerization electrolyte;
and putting the metal bipolar plate into the electropolymerization electrolyte, and introducing current to form an anticorrosive coating on the surface of the metal bipolar plate.
The preparation method of the anticorrosive coating comprises the step of preparing the conductive polymer monomer, wherein the conductive polymer monomer is one or two of pyrrole and aniline.
The preparation method of the anticorrosive coating comprises the step of mixing organic matters, wherein the organic matters are one or more of sodium camphorsulfonate, sodium p-toluenesulfonate, sodium dodecylbenzenesulfonate and sodium dodecylsulfate.
The preparation method of the anticorrosive coating comprises the step of preparing an aqueous solution of graphene oxide, wherein the concentration of the aqueous solution of graphene oxide is 0.5-1.5 g/L.
The preparation method of the anticorrosive coating comprises the step of preparing an electropolymerization electrolyte, wherein the concentration of a conductive polymer monomer is 0.1-0.5 mol/L.
The preparation method of the anticorrosive coating comprises the step of preparing an electropolymerization electrolyte, wherein the concentration of the doped organic matter is 0.1-0.5 mol/L.
The preparation method of the anticorrosive coating comprises the steps of putting the metal bipolar plate into the electropolymerization electrolyte and introducing current, wherein the introduced current density is 0.5-2 mA-cm2。
The preparation method of the anticorrosive coating comprises the steps of placing the metal bipolar plate into the electropolymerization electrolyte and introducing current for 5-30 min.
An anticorrosive coating, wherein, the anticorrosive coating is prepared by the preparation method of the invention.
The application of the anticorrosive coating is to prevent metal corrosion.
Has the advantages that: according to the invention, the metal bipolar plate is put into electropolymerization electrolyte consisting of a conductive polymer monomer, a doped organic matter and a graphene oxide aqueous solution, and current is introduced, so that an anticorrosive coating is formed on the surface of the metal bipolar plate. The conductive polymer monomer is electropositive during electropolymerization, both the doped organic matter and the graphene oxide are negative ion functional groups during electropolymerization, and the conductive polymer monomer can be combined with the doped organic matter and the graphene oxide through ionic bonds after forming a polymer to form an anticorrosive coating. The corrosion-resistant coating provided by the invention is doped with specific organic matters, so that the generation of the passivation film can be inhibited, and the conductivity of the corrosion-resistant coating is good; the anticorrosive coating formed on the surface of the metal bipolar plate can play a role of a physical barrier, hinder the ion migration process in electrochemical corrosion and improve the corrosion resistance of the metal bipolar plate; the barrier effect can be further enhanced by adding graphene oxide to the anticorrosive coating.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of a method for preparing an anticorrosive coating according to the present invention.
FIG. 2 is a plot of the polarization of the coatings of example 1 of the present invention and comparative examples 1-2.
FIG. 3 is a graph showing the results of contact resistance test performance of the coatings of example 1 of the present invention and comparative examples 1-2.
Detailed Description
The present invention provides an anticorrosive coating and a method for preparing the same, and the present invention is further described in detail below in order to make the objects, technical schemes, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of an anticorrosive coating, as shown in figure 1, comprising the following steps:
s10, providing a graphene oxide aqueous solution;
s20, dispersing a conductive polymer monomer and a doped organic matter in the graphene oxide aqueous solution to obtain an electropolymerization electrolyte;
and S30, putting the metal bipolar plate into the electropolymerization electrolyte, and introducing current to form an anticorrosive coating on the surface of the metal bipolar plate.
In this embodiment, an anti-corrosion coating is formed on the surface of the metal bipolar plate by placing the metal bipolar plate into an electropolymerization electrolyte composed of a conductive polymer monomer, a doped organic compound and a graphene oxide aqueous solution and passing current. The conductive polymer is electropositive during electropolymerization, both the doped organic matter and the graphene oxide are negative ion functional groups during electropolymerization, and the conductive polymer monomer can be combined with the doped organic matter and the graphene oxide through ionic bonds after the electropositive polymer is formed to form the anticorrosive coating. Because the existing metal bipolar plate can form a passive film when being corroded, the passive film seriously influences the conductivity of the metal bipolar plate, the anticorrosive coating provided by the embodiment is doped with specific organic matters, so that the generation of the passive film can be inhibited, and the conductivity of the anticorrosive coating is good; the anticorrosive coating formed on the surface of the metal bipolar plate can play a role of a physical barrier, hinder the ion migration process in electrochemical corrosion and improve the corrosion resistance of the metal bipolar plate; the barrier effect can be further enhanced by adding graphene oxide to the anticorrosive coating. That is to say, in the embodiment, the corrosion resistance and the electrical conductivity of the anti-corrosion coating are improved by simultaneously using two means of organic macromolecule doping and graphene oxide compounding, so as to obtain the anti-corrosion coating metal bipolar plate with enhanced electrical conductivity and corrosion resistance.
In some embodiments, graphene oxide is prepared from graphite as a raw material, and the prepared graphene oxide is placed in deionized water for ultrasonic dispersion to obtain a graphene oxide aqueous solution. In some specific embodiments, the concentration of the aqueous graphene oxide solution is 0.5-1.5 g/L. Within this concentration range, the aqueous graphene oxide solution is uniformly dispersed and easily doped into a polymer formed of a conductive polymer monomer.
In some embodiments, the conductive polymer monomer is one or both of pyrrole and aniline, but is not limited thereto. In some embodiments, the concentration of the conductive polymer monomer is 0.1 to 0.5mol/L, and within this concentration range, the conductive polymer monomer can polymerize to form a uniform polymer film upon application of an electric current. If the concentration of the conductive polymer monomer is too low (less than 0.1mol/L), it is not easy to form a polymer film upon polymerization; if the concentration of the conductive polymer monomer is too high (more than 0.5mol/L), it is liable to cause voids when polymerized to form a polymer film.
In some embodiments, the doped organic is one or more of sodium camphorsulfonate, sodium p-toluenesulfonate, sodium dodecylbenzenesulfonate and sodium dodecylsulfate, but is not limited thereto. In some embodiments, the concentration of the doping organic is 0.1 to 0.5 mol/L.
In some embodiments, a metallic bipolar plate is placed in the electropolymerization electrolyte and an electric current is passed to induce polymerization of the conductive polymer monomer in the electropolymerization electrolyte. In some embodiments, the polymerization of the conductive polymer monomer is induced by constant current polarization, and the current density is 0.5-2 mA-cm2The prepared anticorrosive coating can be compact in the current range.
In some specific embodiments, the metal bipolar plate is placed into the electropolymerization electrolyte at the temperature of 20-25 ℃ and is electrified for 5-30min to obtain the anticorrosive coating.
In some embodiments, an anticorrosive coating is also provided, which is prepared by the preparation method of the anticorrosive coating.
In some embodiments, the invention also provides application of the anticorrosion coating, and the anticorrosion coating is used for metal anticorrosion.
In some embodiments, the metallic bipolar plate can be made of various stainless steel grades, such as 904L, 304L, and the like.
The preparation of an anticorrosive coating according to the invention and its metal corrosion protection properties are explained further below by means of specific examples:
example 1
1) 316L stainless steel is used as a sample, 1g/L GO, 0.4mol/L sodium camphorsulfonate and 0.4mol/L pyrrole aqueous solution are used as electrolyte, the electropolymerization temperature is 20 ℃, and the constant current polarization current density is selected to be 1 mA-cm-2Electropolymerization time is 15min, and camphor sulfonate doped Ppy/GO complex is obtained on the surface of 316L stainless steelAnd a strengthening coating.
Comparative example 1
1) 316L stainless steel is used as a sample, 0.4mol/L pyrrole aqueous solution is used as electrolyte, the electropolymerization temperature is 20 ℃, and the constant current polarization current density is selected to be 1 mA-cm-2Electropolymerization time is 15min, and Ppy coating is obtained on the surface of 316L stainless steel.
Ppy coated stainless steels prepared in example 1 and comparative example 1 were placed at 0.5M H2SO4+2ppm HF in a 25 deg.C solution, simulating the PEMFC operating environment, the polarization curve was determined as shown in FIG. 2. As can be seen from FIG. 2, the corrosion resistance of the camphorsulfonate doped Ppy/GO composite strengthened coating in example 1 is the strongest, the corrosion resistance of the Ppy coating is the second lowest, and the corrosion resistance of the 316L stainless steel substrate is the worst.
The coatings prepared in example 1 and comparative example 1 were subjected to contact resistance performance tests, and the results are shown in fig. 3, and it can be seen from fig. 3 that the contact resistance of the camphorsulfonate doped Ppy/GO composite reinforced coating in example 1 is the smallest (i.e. the strongest conductivity), the contact resistance of the 316L stainless steel substrate is the second smallest, and the contact resistance of Ppy coating is the largest (i.e. the worst conductivity).
In summary, the metal bipolar plate is placed in the electropolymerization electrolyte composed of the conductive polymer monomer, the doped organic matter and the graphene oxide aqueous solution, and current is introduced, so that the anticorrosive coating is formed on the surface of the metal bipolar plate. The conductive polymer is electropositive during electropolymerization, both the doped organic matter and the graphene oxide are negative ion functional groups during electropolymerization, and the conductive polymer monomer can be combined with the doped organic matter and the graphene oxide through ionic bonds after forming a polymer to form an anticorrosive coating. The corrosion-resistant coating provided by the invention is doped with specific organic matters, so that the generation of the passivation film can be inhibited, and the conductivity of the corrosion-resistant coating is good; the electropolymeric coating formed on the surface of the metal bipolar plate can play a role of a physical barrier, hinder the ion migration process in electrochemical corrosion and improve the corrosion resistance of the metal bipolar plate; the barrier effect can be further enhanced by adding graphene oxide to the anticorrosive coating.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for preparing an anticorrosive coating, characterized by comprising the steps of:
providing a graphene oxide aqueous solution;
dispersing a conductive polymer monomer and a doped organic matter in the graphene oxide aqueous solution to obtain an electropolymerization electrolyte;
and putting the metal bipolar plate into the electropolymerization electrolyte, and introducing current to form an anticorrosive coating on the surface of the metal bipolar plate.
2. The method for preparing an anticorrosive coating according to claim 1, wherein the conductive polymer monomer is one or both of pyrrole and aniline.
3. The method of claim 1, wherein the doped organic material is one or more of sodium camphorsulfonate, sodium p-toluenesulfonate, sodium dodecylbenzenesulfonate and sodium dodecylsulfate.
4. The method for preparing the anticorrosive coating according to claim 1, wherein the concentration of the aqueous graphene oxide solution is 0.5 to 1.5 g/L.
5. The method for preparing the corrosion-resistant coating according to claim 1, wherein the concentration of the conductive polymer monomer in the electropolymerization electrolyte is 0.1 to 0.5 mol/L.
6. The method for preparing the corrosion-resistant coating according to claim 1, wherein the concentration of the doped organic compound in the electropolymerization electrolyte is 0.1-0.5 mol/L.
7. The method for preparing the corrosion-resistant coating according to claim 1, wherein the step of placing the metal bipolar plate in the electropolymerization electrolyte and applying a current with a current density of 0.5 to 2 mA-cm2。
8. The method for preparing the corrosion-resistant coating according to claim 7, wherein the step of placing the metal bipolar plate into the electropolymerization electrolyte and applying current for 5-30 min.
9. An anti-corrosion coating, characterized in that it is produced by the method of any one of claims 1 to 8.
10. Use of a corrosion protection coating according to claim 9 for the protection of metals against corrosion.
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| CN112341848A (en) * | 2020-11-05 | 2021-02-09 | 上海理工大学 | Graphene coating and preparation method of graphene conductive corrosion-resistant coating |
| CN113045958A (en) * | 2021-04-30 | 2021-06-29 | 深圳大学 | Graphene-based marine anticorrosive paint and preparation method and application thereof |
| CN114665102A (en) * | 2022-03-21 | 2022-06-24 | 北京氢沄新能源科技有限公司 | Metal bipolar plate of fuel cell and preparation method thereof |
| CN115433914A (en) * | 2022-11-07 | 2022-12-06 | 江苏金亚隆科技有限公司 | Preparation process of high-temperature-resistant and antioxidant graphite product coating |
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Application publication date: 20200908 |