CN113549979A - Preparation method of graphene coating - Google Patents
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- CN113549979A CN113549979A CN202111046926.0A CN202111046926A CN113549979A CN 113549979 A CN113549979 A CN 113549979A CN 202111046926 A CN202111046926 A CN 202111046926A CN 113549979 A CN113549979 A CN 113549979A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
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- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000001652 electrophoretic deposition Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 26
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000001962 electrophoresis Methods 0.000 claims description 11
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- 239000010936 titanium Substances 0.000 claims description 3
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- 238000005406 washing Methods 0.000 claims description 3
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- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
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- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/02—Electrophoretic coating characterised by the process with inorganic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
Abstract
The invention provides a preparation method of a graphene coating, which comprises the following steps: adding graphene and metal salt into an organic solvent, and performing ultrasonic treatment to obtain a graphene dispersion liquid; and adding the graphene dispersion liquid serving as electrolyte into an electrophoretic deposition tank, and forming a graphene coating on the surface of the negative electrode after electrophoretic deposition. According to the preparation method of the graphene coating, the graphene and the metal salt are mixed and then subjected to ultrasonic treatment, so that metal ions are connected with functional groups at the edge of the graphene, the graphene is subjected to charged modification, and the graphene is provided with positive charges, so that the graphene coating can be prepared by an electrophoretic deposition method.
Description
Technical Field
The invention relates to the technical field of electrodeposition, in particular to a preparation method of a graphene coating.
Background
Graphene has attracted wide attention since the past as a novel material with high mechanical strength, chemical stability and electrical conductivity, has a wide application prospect in the fields of composite materials, solar cells, coatings and the like, and has achieved certain success cases. Particularly in the field of metal material surface corrosion prevention, graphene has great potential by virtue of excellent performance.
Although the corrosion of metal can be relieved by the conventional method of protecting and plating a more corrosion-resistant material by a dense oxide film, the mechanical properties of the material are affected, and once the protective layers on the surfaces of the material have defects in use, the corrosion speed of the base metal is accelerated, so that greater loss is caused. Although studies have reported that the graphene coating is prepared by using a vapor deposition CVD method to prevent corrosion, the vapor deposition method is relatively complex to operate and has higher requirements on equipment, which is not favorable for mass production.
Based on the technical shortcomings of the current graphene coating preparation, there is a need for improvement.
Disclosure of Invention
In view of this, the present invention provides a method for preparing a graphene coating, so as to solve or partially solve the technical problems in the prior art.
In a first aspect, the present invention provides a method for preparing a graphene coating, comprising the following steps:
adding graphene and metal salt into an organic solvent, and performing ultrasonic treatment to obtain a graphene dispersion liquid;
and adding the graphene dispersion liquid serving as electrolyte into an electrophoretic deposition tank, and forming a graphene coating on the surface of the negative electrode after electrophoretic deposition.
Preferably, in the preparation method of the graphene coating, the metal salt is a magnesium salt and/or an aluminum salt, and the organic solvent includes one or more of ethanol, isopropanol, ethylene glycol, and glycerol.
Preferably, in the preparation method of the graphene coating, the electrophoretic deposition process conditions are as follows: the voltage is 10-80V, the electrophoresis temperature is 20-50 ℃, the electrophoresis time is 1-30 min, and the distance between the anode and the cathode is 5-20 mm.
Preferably, in the preparation method of the graphene coating, the concentration of graphene in the graphene dispersion liquid is 0.01-1.0 mg/ml.
Preferably, in the preparation method of the graphene coating, the mass ratio of the metal salt to the graphene is (1-5): 1.
Preferably, the preparation method of the graphene coating further comprises performing surface treatment on the negative electrode before electrophoretic deposition, wherein the surface treatment specifically comprises: and polishing the negative electrode, then placing the negative electrode in a first acid solution for soaking for 2-5 min, then washing the negative electrode with ethanol, and then placing the negative electrode in a second acid solution for soaking for 1-3 min.
Preferably, in the preparation method of the graphene coating, the first acid solution is an acetic acid solution, and the second acid solution is a hydrochloric acid solution or a sulfuric acid solution.
Preferably, in the preparation method of the graphene coating, the concentration of an acetic acid solution is 0.1-0.2 mol/L, the concentration of a hydrochloric acid solution is 0.1-1 mol/L, and the concentration of a sulfuric acid solution is 0.05-0.5 mol/L.
Preferably, in the preparation method of the graphene coating, the cathode material used in the electrophoretic deposition process is noble metal or titanium, and the anode material is copper.
Preferably, in the preparation method of the graphene coating, graphene and metal salt are added into an organic solvent, and the graphene dispersion liquid is obtained by performing ultrasonic treatment at the power of 80-120W for 30-60 min.
Compared with the prior art, the boron-nitrogen co-doped porous carbon material has the following beneficial effects:
(1) according to the preparation method of the graphene coating, the graphene and the metal salt are mixed and then subjected to ultrasonic treatment, so that metal ions are connected with functional groups at the edge of the graphene, the graphene is subjected to charged modification, and the graphene is provided with positive charges, so that the graphene coating by an electrophoretic deposition method can be realized;
(2) according to the preparation method of the graphene coating, the graphene coating with high binding force is deposited on the surface of the metal material, so that the corrosion resistance of a metal matrix can be remarkably improved;
(3) compared with a reduced graphene oxide coating (rGO), the graphene coating prepared by electrophoretic deposition has fewer defects and better performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a macroscopic view of a copper sheet before and after electrophoretic deposition in example 2 of the present invention;
FIG. 2 is an SEM image of a copper sheet after electrophoretic deposition in example 2 of the present invention;
FIG. 3 is an EDS map at spectrum1 in FIG. 2;
FIG. 4 is an EDS map at spectrum2 in FIG. 2;
FIG. 5 is an EDS map at spectrum3 in FIG. 2;
FIG. 6 is a graph of electrochemical impedance of a copper strip before and after electrophoretic deposition in example 2 of the present invention;
FIG. 7 is a graph showing the polarization curves before and after the electrophoretic deposition of the copper sheet in example 2 of the present invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a preparation method of a graphene coating, which comprises the following steps:
s1, adding graphene and metal salt into an organic solvent, and performing ultrasonic treatment to obtain a graphene dispersion liquid;
and S2, adding the graphene dispersion liquid serving as electrolyte into an electrophoretic deposition tank, and forming a graphene coating on the surface of the negative electrode after electrophoretic deposition.
It should be noted that, in the preparation method of the graphene coating in the embodiment of the present application, since graphene itself has no electric charge, the method of direct electrophoretic deposition after solution preparation cannot be implemented; according to the preparation method, the graphene and the metal salt are mixed and then subjected to ultrasonic treatment, so that the metal ions are connected with the functional groups at the edge of the graphene, the graphene is subjected to charged modification, and as a result, the graphene is positively charged, so that the graphene coating by an electrophoretic deposition method can be realized.
In some embodiments, the metal salt is a magnesium and/or aluminum salt and the organic solvent comprises one or more of ethanol, isopropanol, ethylene glycol, or glycerol.
In some embodiments, the process conditions for electrophoretic deposition are: the voltage is 10-80V, the electrophoresis temperature is 20-50 ℃, the electrophoresis time is 1-30 min, and the distance between the anode and the cathode is 5-20 mm.
In some embodiments, the concentration of graphene in the graphene dispersion is 0.01-1.0 mg/ml.
In some embodiments, the mass ratio of the metal salt to the graphene is (1-5): 1.
In some embodiments, before the electrophoretic deposition, the method further includes performing surface treatment on the negative electrode, where the surface treatment specifically includes: and polishing the negative electrode, then placing the negative electrode in a first acid solution for soaking for 2-5 min, then washing the negative electrode with ethanol, and then placing the negative electrode in a second acid solution for soaking for 1-3 min. In the embodiment of the application, the surface treatment is carried out on the surface of the negative electrode, so that the binding force between the graphene coating and the surface of the negative electrode can be improved; specifically, the surface of the negative electrode material can be polished by adopting 800-1200-mesh sand paper or a polishing machine.
In some embodiments, the first acid solution is an acetic acid solution and the second acid solution is a hydrochloric acid solution or a sulfuric acid solution.
In some embodiments, the concentration of the acetic acid solution is 0.1-0.2 mol/L, the concentration of the hydrochloric acid solution is 0.1-1 mol/L, and the concentration of the sulfuric acid solution is 0.05-0.5 mol/L.
In some embodiments, the positive electrode material used in the electrophoretic deposition process is a noble metal or titanium and the negative electrode material is copper. Specifically, the noble metal is one of gold, silver, and platinum group metals (ruthenium, rhodium, palladium, osmium, iridium, platinum), etc., and the negative electrode material may be stainless steel, etc., in addition to copper.
In some embodiments, graphene and metal salt are added into an organic solvent, and the mixture is subjected to ultrasonic treatment at a power of 80-120W for 30-60 min to obtain a graphene dispersion liquid.
According to the preparation method of the graphene coating, the raw materials of the used reagents are easy to obtain and non-toxic, so that the preparation method does not harm operators in the preparation and production process, the link of gas defense is omitted, and the waste liquid is not too harmful to the natural environment during treatment; the preparation method disclosed by the invention is simple and controllable in operation, the preparation of the graphene dispersion liquid is very convenient, and meanwhile, the thickness of the graphene coating can be easily controlled by adjusting the voltage and the electrophoresis time, so that the application field of the product disclosed by the invention is further expanded; the corrosion resistance of a metal matrix can be remarkably improved by depositing the graphene coating with high binding force on the surface of a metal material (namely a negative electrode); the preparation method and the electrophoretic deposition method of the graphene dispersion liquid provided by the invention are suitable for preparing graphene coatings of metals with different shapes and sizes, such as flaky and linear metals; compared with the method of electrophoretic deposition of a graphene oxide coating, namely a reduction coating, which is widely used at present, the method can obtain the graphene coating more simply, and the reduced graphene oxide (rGO) has a large number of defects and functional groups on the surface, such as carboxyl, hydroxyl, epoxy and other oxygen-containing functional groups, so that the reduced graphene oxide (rGO) is easy to combine with organic matters for reaction; the properties of graphene (Gr) are similar to those of the original graphite, without functional groups, which makes the graphene molecular structure very stable. Therefore, in the actual preparation, the coating obtained by reducing graphene oxide on the metal surface has poor bonding force, so that the electrochemical test is difficult to perform, and graphene can be easily deposited on the metal surface and has good bonding force.
The following further describes the preparation method of the graphene coating according to the present application with specific examples.
Example 1
A preparation method of a graphene coating comprises the following steps:
s1, adding 30mg of graphene and 60mg of magnesium chloride hexahydrate into 60ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 60min under the power of 100W to obtain 0.5mg/ml of graphene dispersion liquid with positive charges;
s2, polishing a copper wire with the diameter of 0.5mm by using 1000-mesh abrasive paper, soaking the copper wire in 0.1mol/L acetic acid solution for 3min, then cleaning the copper wire by using absolute ethyl alcohol, and finally soaking and cleaning the copper wire in 1mol/L hydrochloric acid solution for 1 min;
s3, placing the graphene dispersion liquid obtained in the S1 into an electrophoretic deposition tank as electrolyte, taking a platinum sheet as a positive electrode, taking a copper wire obtained in the S2 as a negative electrode, and performing electrophoretic deposition, wherein the electrophoretic deposition process conditions are as follows: the direct current voltage is 60V, the distance between the anode and the cathode is 10mm, the electrophoresis temperature is 20 ℃, and the electrophoresis time is 1 min; and forming a graphene coating on the surface of the copper wire after electrophoretic deposition, and drying the copper wire deposited with the graphene coating in a vacuum drying oven for 1h to obtain the graphene coating on the copper wire.
Example 2
A preparation method of a graphene coating comprises the following steps:
s1, adding 30mg of graphene and 30mg of magnesium chloride hexahydrate into 60ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 60min under the power of 100W to obtain 0.5mg/ml of graphene dispersion liquid with positive charges;
s2, polishing a 10 x 1mm copper sheet (namely 10mm in length, 10mm in width and 1mm in thickness) by using 1000-mesh sand paper, soaking the copper sheet in 0.1mol/L acetic acid solution for 3min, then cleaning the copper sheet by using absolute ethyl alcohol, and finally soaking and cleaning the copper sheet in 0.5mol/L sulfuric acid solution for 1 min;
s3, putting the graphene dispersion liquid obtained in the S1 into an electrophoretic deposition tank as an electrolyte, taking a platinum sheet as a positive electrode, taking a copper sheet obtained in the S2 as a negative electrode, and performing electrophoretic deposition, wherein the electrophoretic deposition process conditions are as follows: the direct current voltage is 20V, the distance between the anode and the cathode is 20mm, the electrophoresis temperature is 20 ℃, and the electrophoresis time is 20 min; and forming a graphene coating on the surface of the copper sheet after electrophoretic deposition, and drying the copper sheet deposited with the graphene coating in a vacuum drying oven for 1h to obtain the graphene coating on the copper sheet.
FIG. 1 is a schematic view of the morphology of the negative electrode of example 2 before and after electrophoretic deposition. FIG. 1 (a) is a schematic diagram of a graphene coating formed after electrophoretic deposition on the surface of a copper sheet in example 2; FIG. 1 (b) is a schematic diagram of the copper sheet of example 2 before surface electrophoretic deposition.
Fig. 2 to 5 are EDS spectra of graphene coatings prepared on the copper sheets in example 2, wherein fig. 3 to 5 correspond to spectra 1, 2 and 3 in fig. 2, respectively.
Wherein, in fig. 3, the atomic percentages are: 80.4% of C, 8.5% of O, 7.5% of Cu and 3.6% of Mg; in fig. 4, the atomic percentages are: 73.7% of C, 9.2% of O, 14.3% of Cu and 2.8% of Mg; in fig. 5, the atomic percentages are: 73.4% of C, 5.3% of O, 19.0% of Cu and 2.3% of Mg.
The negative copper sheet used before the electrophoretic deposition in example 2 and the copper sheet forming the graphene coating after the electrophoretic deposition in example 2 were respectively placed in 3.5 wt% NaCl solution, and subjected to electrochemical impedance (frequency 100000 Hz-0.01 Hz, amplitude 10mV) and polarization test (open circuit potential ± 250mV, scanning rate 1mV/s), and the results are shown in fig. 6-7.
In fig. 6, b is a negative electrode copper sheet used before electrophoretic deposition, and a is a copper sheet forming a graphene coating after electrophoretic deposition.
In fig. 7, a is a negative electrode copper sheet used before electrophoretic deposition, and b is a copper sheet forming a graphene coating after electrophoretic deposition.
As can be seen from fig. 6, the electrochemical resistance of the copper sheet forming the graphene coating after electrophoretic deposition is greater than that of the negative electrode copper sheet used before electrophoretic deposition. As can be seen from FIG. 7, the self-corrosion potential of the copper sheet forming the graphene coating after electrophoretic deposition is shifted forward, and the corrosion current density is reduced, which proves that the graphene coating is prepared on the substrate through electrophoretic deposition, and the corrosion resistance of the substrate is greatly improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a graphene coating is characterized by comprising the following steps:
adding graphene and metal salt into an organic solvent, and performing ultrasonic treatment to obtain a graphene dispersion liquid;
and adding the graphene dispersion liquid serving as electrolyte into an electrophoretic deposition tank, and forming a graphene coating on the surface of the negative electrode after electrophoretic deposition.
2. The method for preparing the graphene coating according to claim 1, wherein the metal salt is a magnesium salt and/or an aluminum salt, and the organic solvent includes one or more of ethanol, isopropanol, ethylene glycol or glycerol.
3. The method for preparing the graphene coating according to claim 1, wherein the electrophoretic deposition process conditions are as follows: the voltage is 10-80V, the electrophoresis temperature is 20-50 ℃, the electrophoresis time is 1-30 min, and the distance between the anode and the cathode is 5-20 mm.
4. The method for preparing the graphene coating according to claim 1, wherein the concentration of graphene in the graphene dispersion liquid is 0.01-1.0 mg/ml.
5. The method for preparing the graphene coating according to claim 1, wherein the mass ratio of the metal salt to the graphene is (1-5): 1.
6. The preparation method of the graphene coating according to claim 1, further comprising performing surface treatment on the negative electrode before the electrophoretic deposition, wherein the surface treatment specifically comprises: and polishing the negative electrode, then placing the negative electrode in a first acid solution for soaking for 2-5 min, then washing the negative electrode with ethanol, and then placing the negative electrode in a second acid solution for soaking for 1-3 min.
7. The method for preparing the graphene coating according to claim 6, wherein the first acid solution is an acetic acid solution, and the second acid solution is a hydrochloric acid solution or a sulfuric acid solution.
8. The method for preparing the graphene coating according to claim 7, wherein the concentration of the acetic acid solution is 0.1-0.2 mol/L, the concentration of the hydrochloric acid solution is 0.1-1 mol/L, and the concentration of the sulfuric acid solution is 0.05-0.5 mol/L.
9. The method for preparing the graphene coating according to claim 1, wherein a positive electrode material used in the electrophoretic deposition process is a noble metal or titanium, and the negative electrode material is copper.
10. The preparation method of the graphene coating according to claim 1, wherein graphene and metal salt are added into an organic solvent, and the mixture is subjected to ultrasonic treatment at a power of 80-120W for 30-60 min to obtain a graphene dispersion liquid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115787032A (en) * | 2022-12-12 | 2023-03-14 | 宁波市新光货架有限公司 | Surface treatment process for metal goods shelf |
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| CN103590089A (en) * | 2013-11-20 | 2014-02-19 | 上海应用技术学院 | Preparation method of graphene/silver composite material |
| CN104711655A (en) * | 2015-03-26 | 2015-06-17 | 兰州明仁智能科技有限公司 | Method for preparing graphene-based anti-corrosion and wear-resistant coating on magnesium alloy surface through liquid phase electrophoretic deposition method |
| US20160053398A1 (en) * | 2014-08-22 | 2016-02-25 | Luminit Llc | Graphene Anti-Corrosion Coating and Method of Application Thereof |
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| CN103590089A (en) * | 2013-11-20 | 2014-02-19 | 上海应用技术学院 | Preparation method of graphene/silver composite material |
| US20160053398A1 (en) * | 2014-08-22 | 2016-02-25 | Luminit Llc | Graphene Anti-Corrosion Coating and Method of Application Thereof |
| CN104711655A (en) * | 2015-03-26 | 2015-06-17 | 兰州明仁智能科技有限公司 | Method for preparing graphene-based anti-corrosion and wear-resistant coating on magnesium alloy surface through liquid phase electrophoretic deposition method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115787032A (en) * | 2022-12-12 | 2023-03-14 | 宁波市新光货架有限公司 | Surface treatment process for metal goods shelf |
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Application publication date: 20211026 |