Graphene anticorrosive coating, preparation method thereof and refrigerator

Abstract

The invention discloses a graphene anticorrosive coating, a preparation method thereof and a refrigerator, and belongs to the technical field of non-ferrous metal protection. The graphene anticorrosive coating is composed of benzidine-disuccinimido suberic acid ester modified graphene, and the benzidine-disuccinimido suberic acid ester is combined with the graphene through a pi-pi conjugation effect. The graphene anticorrosive coating is applied to protection of the copper electrode for the refrigerator, the problem that an existing graphene coating for corrosion prevention of the copper electrode cannot give consideration to corrosion prevention performance and conductivity is solved, and the graphene anticorrosive coating has good toughness, excellent corrosion prevention effect and high conductivity.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of non-ferrous metal protection, and particularly relates to a graphene anticorrosive coating, a preparation method thereof and a refrigerator. BACKGROUND

[0002] Due to the advantages of high electrical conductivity and corrosion resistance, copper is widely used as electrode material and contact material. The electrode of the lamp plate used in the light-emitting layer frame in some refrigerators, and the contact material between the electrode of the lamp plate and the power supply part are made of copper, which is carried in the refrigeration space of the refrigerator. The humidity in the refrigeration chamber of the refrigerator is high and various corrosive media exist, which is a harsh corrosive environment for copper electrodes and contacts. In addition, when the light-emitting layer frame is working, the electrode and the contact are in an energized state, which provides electrons for the electrochemical corrosion of copper metal. Especially when the corrosion reaction occurs, the copper contact will generate non-conductive basic copper carbonate, which will cause the copper contact to fail, greatly affecting the service life and reliability of the light-emitting layer frame.

[0003] Therefore, it is necessary to develop an anticorrosive coating that can prevent corrosion of copper contacts and electrodes without affecting their electrical conductivity. Graphene is a typical two-dimensional material, and graphene coating can be prepared by electrophoretic deposition, chemical vapor deposition and evaporation. Graphene has very low resistivity and high electrical conductivity. Due to its excellent shielding effect, graphene coating has excellent corrosion resistance and can block the corrosion of corrosive media to metal substrates.

[0004] However, graphene has high rigidity and poor toughness, and cannot effectively transfer stress when subjected to external stress, which leads to cracking between graphene layers. These cracked positions will become corrosion sites, which will affect the corrosion resistance. SUMMARY

[0005] In view of the deficiencies of the prior art, the technical problem to be solved by the present application is to overcome the problem that the existing graphene coating for copper electrode corrosion prevention cannot balance corrosion resistance and electrical conductivity. The present application provides a graphene anticorrosive coating with good toughness, excellent corrosion resistance and high electrical conductivity, a preparation method thereof and a refrigerator.

[0006] To solve the technical problem, the technical solution adopted by the present application is as follows:

[0007] In one aspect, the present application provides a graphene anticorrosive coating, which is composed of benzidine-disuccinimidyl octanedioate modified graphene. The benzidine-disuccinimidyl octanedioate is combined with graphene through π-π conjugation.

[0008] Preferably, the graphene anticorrosive coating is attached to the surface of the copper electrode and / or contact.

[0009] The application further provides a preparation method of the graphene anticorrosive coating, which comprises the following steps: depositing the biphenylamine-disuccinimidyl octanedioate modified graphene on the surface of a copper electrode and / or a contact by electrophoretic deposition to form the graphene anticorrosive coating with a multilayer structure.

[0010] Preferably, the preparation method comprises the following steps:

[0011] The biphenylamine-disuccinimidyl octanedioate preparation step comprises the following steps: dissolving biphenylamine and disuccinimidyl octanedioate in a dimethylformamide solution, stirring in the dark, reacting at room temperature, washing and drying to obtain the biphenylamine-disuccinimidyl octanedioate.

[0012] The biphenylamine-disuccinimidyl octanedioate modified graphene step comprises the following steps: dispersing the biphenylamine-disuccinimidyl octanedioate and the graphene in a dimethylformamide solution, stirring and reacting at room temperature, washing and drying to obtain the biphenylamine-disuccinimidyl octanedioate modified graphene.

[0013] The electrophoretic deposition step comprises the following steps: depositing the biphenylamine-disuccinimidyl octanedioate modified graphene on the surface of the copper electrode by electrophoretic deposition.

[0014] Preferably, the mass ratio of the biphenylamine to the disuccinimidyl octanedioate in the biphenylamine-disuccinimidyl octanedioate preparation step is 5:1.

[0015] Preferably, in the biphenylamine-disuccinimidyl octanedioate modified graphene step, the thickness of the graphene is selected from any value in the range of 1-2 microns, and the flake diameter is selected from any value in the range of 10-30 microns; the mass ratio of the biphenylamine-disuccinimidyl octanedioate to the graphene is 1:30-40.

[0016] Preferably, the electrophoretic deposition step further comprises the following steps:

[0017] The electrolyte is prepared by mixing the biphenylamine-disuccinimidyl octanedioate modified graphene, magnesium nitrate and ethanol, and then ultrasonic stirring to obtain a uniformly distributed modified graphene charged suspension;

[0018] The copper electrode is used as a cathode, and a graphite electrode is used as an anode; the cathode and the anode are inserted into the modified graphene charged suspension in parallel, and the distance between the cathode and the anode is selected from any value in the range of 1-2 cm;

[0019] The electrodes are connected to the positive and negative poles of a direct current power supply, respectively, and the biphenylamine-disuccinimidyl octanedioate modified graphene starts to deposit, and the deposition time lasts for 4 min.

[0020] Preferably, the electrolyte is subjected to ultrasonic stirring, the ultrasonic power is 1 kW, and the ultrasonic time is 1 h.

[0021] Preferably, after the electrophoretic deposition step, the copper electrode is taken out and subjected to drying treatment to obtain the graphene anticorrosion coating, the drying temperature is 60 DEG C, and the drying time is 6 h.

[0022] The application also provides a refrigerator, a lamp plate electrode used by a light-emitting layer shelf carried by a refrigeration space of the refrigerator, and a contact surface between the lamp plate electrode and a power supply part is covered with the graphene anticorrosion coating according to any one of the technical solutions.

[0023] Compared with the prior art, the application has the following beneficial effects:

[0024] The graphene anticorrosion coating has a high specific surface area and is densely distributed, so that the penetration of corrosive media can be hindered and the anticorrosion effect can be achieved, the biphenylamine-disuccinimidyl octanedioate plays a π-π bridging role between adjacent graphene sheets, so that a toughening effect is achieved, in addition, the π-π conjugation between the biphenylamine-disuccinimidyl octanedioate containing a benzene ring and the graphene is beneficial to electron transfer, does not affect the conductivity of the graphene sheet, and instead improves the conductivity through the connection between the bonds, so that good toughness and excellent anticorrosion effect are ensured, and high conductivity is achieved at the same time.

[0025] The application provides a preparation method of a graphene anticorrosion coating, the biphenylamine-disuccinimidyl octanedioate modified graphene is deposited on a copper electrode and / or a contact surface in an electrophoretic deposition manner to form the graphene anticorrosion coating with a multilayer structure, the coating thickness can be controlled by controlling the electrophoretic deposition time, different thicknesses of the graphene anticorrosion coating can be prepared according to specific requirements, and meanwhile, the excellent performance of the prepared graphene anticorrosion coating is ensured.

[0026] The application also provides a refrigerator, a lamp plate electrode used by a light-emitting layer shelf carried by a refrigeration space of the refrigerator, and a contact surface between the lamp plate electrode and a power supply part is covered with the graphene anticorrosion coating according to any one of the technical solutions. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 A schematic view of the graphene anticorrosion coating provided in the embodiments of the application is shown in the drawings.

[0028] In the above drawings, 1 is the graphene anticorrosion coating, 101 is the biphenylamine-disuccinimidyl octanedioate, 102 is the graphene, and 2 is the substrate. DETAILED DESCRIPTION

[0029] The technical solutions in specific embodiments of the present invention will be described in detail and completely below. Obviously, the described embodiments are only some specific implementations of the overall technical solution of the present invention, and not all implementations. Based on the overall concept of the present invention, all other embodiments obtained by those skilled in the art fall within the protection scope of the present invention.

[0030] This invention provides a graphene anti-corrosion coating 1, such as... Figure 1 As shown, the graphene anti-corrosion coating 1 is composed of graphene 102 modified with benzidine-disuccinimidyl octanoate 101. The benzidine-disuccinimidyl octanoate 101 is bonded to the graphene 102 through π-π conjugation. The high specific surface area graphene anti-corrosion coating 1 is densely distributed, which can hinder the penetration of corrosive media and play an anti-corrosion role. Among them, benzidine-disuccinimidyl octanoate 101 plays a π-π bridging role between adjacent graphene 102 sheets, which plays a toughening role. In addition, the π-π conjugation between benzidine-disuccinimidyl octanoate 101 containing benzene rings and graphene 102 is conducive to electron transfer and does not affect the conductivity of the graphene 102 sheets. On the contrary, it improves the conductivity through the connection between bonds, thus ensuring good toughness and excellent anti-corrosion effect while having high conductivity.

[0031] The graphene anticorrosion coating 1 can significantly improve the problem of copper rust and reduced conductivity of copper electrodes and contacts caused by accelerated corrosion during electrification. The graphene anticorrosion coating 1 is composed of graphene 102 modified by benzidine-disuccinimidyl suberate 101 and is attached to the surface of copper electrodes and contacts by electrophoretic deposition, having good toughness and excellent anticorrosion effect, as well as high conductivity. The graphene 102 has a large specific surface area, high electrical conductivity, excellent mechanical properties and chemical stability, so the graphene 102 can be used as an anticorrosion coating material with excellent conductivity. Benzidine and disuccinimidyl suberate undergo condensation reaction to form amide bonds to prepare benzidine-disuccinimidyl suberate 101. Benzidine-disuccinimidyl suberate 101 is combined with graphene 102 through π-π conjugation to obtain benzidine-disuccinimidyl suberate 101 modified graphene 102. The modified graphene 102 is deposited on the surface of copper electrodes or contacts by electrophoretic deposition to form a multilayer graphene 102 coating. Benzidine-disuccinimidyl suberate 101 plays a bridging role between graphene 102 layers through π-π, which can improve the toughness of the graphene 102 coating. When subjected to external force impact, the graphene 102 layers in the pure graphene 102 coating begin to crack under the action of external force. When the benzidine-disuccinimidyl suberate 101 modified graphene 102 coating is subjected to external force impact, the long chain plays a role in preventing crack propagation, which can effectively resist external force impact, thereby achieving the effect of toughening. At the same time, the π-π conjugation between benzidine-disuccinimidyl suberate 101 containing benzene rings and graphene 102 is conducive to electron transfer. Specifically, the graphene 102 coating itself has ultra-high conductivity, and the benzidine-disuccinimidyl suberate 101 connected between the graphene 102 layers also has conductivity, which improves the conductivity through the connection between the bonds.

[0032] In a preferred embodiment, the graphene anticorrosion coating 1 is attached to the surface of copper electrodes and / or contacts.

[0033] In another aspect, the application provides a method for preparing the graphene anticorrosion coating 1 according to any of the above technical solutions, which comprises depositing the diphenylamine-disuccinimidyl suberate 101 modified graphene 102 on the surface of a copper electrode and / or contact by electrophoretic deposition to form the graphene anticorrosion coating 1 with a multi-layer structure. The method for preparing the graphene anticorrosion coating 1 with a multi-layer structure by electrophoretic deposition of the diphenylamine-disuccinimidyl suberate 101 modified graphene 102 on the surface of a copper electrode and / or contact can control the thickness of the coating by controlling the electrophoretic deposition time, which is conducive to the preparation of graphene anticorrosion coatings 1 with different thicknesses according to specific needs while ensuring the excellent performance of the prepared graphene anticorrosion coating 1.

[0034] In a preferred embodiment, the method comprises:

[0035] The step of preparing the diphenylamine-disuccinimidyl suberate 101 comprises dissolving diphenylamine and disuccinimidyl suberate in a dimethylformamide solution, stirring in the dark, reacting at room temperature, washing and drying to prepare the diphenylamine-disuccinimidyl suberate 101; wherein the mass fraction of the diphenylamine and the disuccinimidyl suberate is 5:1.

[0036] The step of preparing the diphenylamine-disuccinimidyl suberate 101 modified graphene 102 comprises dispersing the diphenylamine-disuccinimidyl suberate 101 and the graphene 102 in a dimethylformamide solution, stirring and reacting at room temperature, washing and drying to prepare the diphenylamine-disuccinimidyl suberate 101 modified graphene 102; wherein the thickness of the graphene 102 is selected from any value in the range of 1-2 μm, and the flake diameter is selected from any value in the range of 10-30 μm; the mass fraction of the diphenylamine-disuccinimidyl suberate 101 and the graphene 102 is 1:30-40. It can be understood that the thickness of the graphene 102 can also be 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm, and any point value in the range thereof, the flake diameter can also be 15 μm, 20 μm, 25 μm, and any point value in the range thereof, and the mass fraction of the diphenylamine-disuccinimidyl suberate 101 and the graphene 102 can also be 1:32, 1:34, 1:36, 1:38, and any point value in the range thereof.

[0037] The electrophoretic deposition step comprises depositing the biphenylamine-disuccinimidyl suberate 101 modified graphene 102 on the surface of the copper electrode by electrophoretic deposition. Further, the electrophoretic deposition step further comprises: configuring an electrolyte comprising the biphenylamine-disuccinimidyl suberate 101 modified graphene 102, magnesium nitrate, and ethanol, ultrasonic stirring the electrolyte to obtain a uniformly distributed charged suspension of the modified graphene 102; wherein the ultrasonic power is 1 kW, and the ultrasonic time is 1 h; taking the copper electrode as the cathode and the graphite electrode as the anode, inserting the cathode and the anode into the charged suspension of the modified graphene 102 in parallel, and the distance between the cathode and the anode is selected as any value in the range of 1-2 cm; and connecting the electrodes with the positive and negative poles of a direct current power supply, respectively, so that the biphenylamine-disuccinimidyl suberate 101 modified graphene 102 starts to deposit, and the deposition time lasts for 4 min.

[0038] In a preferred embodiment, after the electrophoretic deposition step, the copper electrode is taken out and dried to obtain the graphene anticorrosion coating 1, the drying temperature is 60 DEG C, and the drying time is 6 h.

[0039] The application also provides a refrigerator, wherein the light plate electrode of the light-emitting shelf carried by the refrigerating space of the refrigerator and the contact surface between the light plate electrode and the power supply part are covered with the graphene anticorrosion coating 1 according to any one of the technical solutions, so that good anticorrosion effect is achieved in a humid environment on the basis of ensuring the conductive performance.

[0040] In order to more clearly and specifically introduce the graphene anticorrosion coating 1, the preparation method thereof and the refrigerator provided in the embodiments of the application, the following will be described in combination with specific embodiments.

[0041] Embodiment 1

[0042] A preparation method of a graphene anticorrosion coating 1 for a copper electrode and a contact point, comprising the following steps:

[0043] (1) 184 mg of biphenylamine and 36.8 mg of disuccinimidyl suberate are weighed and dissolved in 40 mL of dimethylformamide solution. Stirring is performed under light-proof conditions, and room temperature reaction is performed for 10 h. After washing with dimethylformamide solution for several times, 60 DEG C drying is performed for 12 h, so as to prepare biphenylamine-disuccinimidyl suberate 101.

[0044] (2) 2 mg of biphenylamine-disuccinimidyl suberate 101 and 80 mg of graphene 102 are weighed and dispersed into 40 mL of dimethylformamide solution, stirring is performed under room temperature conditions, and reaction is performed for 12 h. After washing with dimethylformamide solution for several times, 60 DEG C drying is performed for 12 h, so as to prepare biphenylamine-disuccinimidyl suberate 101 modified graphene 102.

[0045] (3) 25 mg of modified graphene 102, 25 mg of magnesium nitrate, and 500 mL of ethanol were used as raw materials, and stirring was performed under 1000 W ultrasonic for 1 h to obtain a uniformly distributed charged suspension of modified graphene 102. A copper electrode was used as a cathode, and a graphite electrode was used as an anode. The cathode and the anode were inserted into the charged suspension of modified graphene 102 in parallel, and the distance between the cathode and the anode was adjusted to 1-2 cm. The two electrodes were connected to the positive and negative poles of a direct current power supply, respectively, at this time, the modified graphene 102 began to deposit, and the deposition time lasted for 4 min.

[0046] (4) The copper electrode was taken out, and drying treatment was performed at 60°C for 6 h to obtain a modified graphene 102 coating deposited on the surface of the copper electrode.

[0047] Example 2

[0048] A method for preparing a graphene corrosion-resistant coating 1 for a copper electrode and a contact point includes the following steps:

[0049] (1) 184 mg of benzidine and 36.8 mg of disuccinimidyl suberate were weighed and dissolved in 40 mL of dimethylformamide solution. Stirring was performed under light shielding conditions, and reaction was performed at room temperature for 10 h. After washing with dimethylformamide solution for several times, drying was performed at 60°C for 12 h to prepare benzidine-disuccinimidyl suberate 101.

[0050] (2) 2 mg of benzidine-disuccinimidyl suberate 101 and 60 mg of graphene 102 were dispersed in 35 mL of dimethylformamide solution, and stirring was performed at room temperature, and reaction was performed for 12 h. After washing with dimethylformamide solution for several times, drying was performed at 60°C for 12 h to prepare benzidine-disuccinimidyl suberate 101 modified graphene 102.

[0051] (3) 25 mg of modified graphene 102, 25 mg of magnesium nitrate, and 500 mL of ethanol were used as raw materials, and stirring was performed under 1000 W ultrasonic for 1 h to obtain a uniformly distributed charged suspension of modified graphene 102. A copper electrode was used as a cathode, and a graphite electrode was used as an anode. The cathode and the anode were inserted into the charged suspension of modified graphene 102 in parallel, and the distance between the cathode and the anode was adjusted to 1-2 cm. The two electrodes were connected to the positive and negative poles of a direct current power supply, respectively, at this time, the modified graphene 102 began to deposit, and the deposition time lasted for 4 min.

[0052] (4) The copper electrode was taken out, and drying treatment was performed at 60°C for 6 h to obtain a modified graphene 102 coating deposited on the surface of the copper electrode.

[0053] Comparative Example 1

[0054] A method for preparing a graphene corrosion-resistant coating 1 for a copper electrode and a contact point includes the following steps:

[0055] (1) Take 25 mg of graphene 102, 25 mg of magnesium nitrate, and 500 mL of ethanol as raw materials, and stir under 1000 W ultrasonic for 1 h to obtain a uniformly distributed graphene 102 charged suspension. Take a copper electrode as the cathode and a graphite electrode as the anode, and insert the cathode and the anode into the graphene 102 charged suspension in parallel, and adjust the distance between the cathode and the anode to 1-2 cm. Connect the two electrodes to the positive and negative poles of a direct current power source respectively, at this time the graphene 102 starts to deposit, and the deposition time lasts for 4 min.

[0056] (2) Take out the copper electrode, and dry at 60°C for 6 h to obtain a graphene 102 coating deposited on the surface of the copper electrode.

[0057] Performance test

[0058] The graphene 102 coating of Example 1-2 and Comparative Example 1 is peeled off from the copper electrode, and cut into a sample of 5*20 mm. The universal testing machine is used to perform static tension on the coating sample, and the toughness of the coating is measured.

[0059] A three-electrode system is prepared with the copper electrode on which the graphene anticorrosion coating 1 is deposited as the working electrode, Ag / AgCl as the reference electrode, and platinum electrode as the counter electrode, and the area of the copper electrode is 1*1 cm. The potentiodynamic polarization test is used to characterize the corrosion behavior of the graphene anticorrosion coating 1 system in 3.5% NaCl solution.

[0060] The conductivity of the graphene 102 coating of Example 1-2 and Comparative Example 1 is measured by means of conductivity meter by double probe method. The test results are shown in Table 1.

[0061] Table 1 Performance test results of Example 1-2 and Comparative Example 1

[0062] Item Example 1 Example 2 Comparative Example 1 Toughness (MJ-m -3 ) 25.9 37.3 2.6 corrosion current (pA-cm -2 )]]> 0.59 0.56 0.67 conductivity (S-cm -1 )]]> 2636 2814 2352

[0063] From the results in Table 1, it can be found that:

[0064] Compared with the pure graphene 102 coating of Comparative Example 1, the toughness of the modified graphene 102 coating of Example 1-2 is obviously improved, because when subjected to external force impact, the biphenylamine-disuccinimidyl octanedioate 101 between the graphene 102 layers can preferentially undergo plastic deformation to resist the external force. The high toughness of the modified graphene 102 coating is more conducive to maintaining the integrity of the coating in the application process, avoiding damage to the coating caused by external force and affecting the anticorrosion ability of the coating.

[0065] The smaller the corrosion current density, the greater the charge transfer resistance, and the better the corrosion resistance of the material. The corrosion current density of the modified graphene 102 coating of Example 1-2 is lower than that of the pure graphene 102 coating of Comparative Example 1, due to the π-π conjugation between the benzidine-disuccinimidyl suberate 101 and the graphene 102, which increases the interlayer binding force, making the coating more dense and more conducive to resisting the penetration of corrosive media.

[0066] Both Example 1-2 and Comparative Example 1 show high electrical conductivity. The electrical conductivity of Examples 1 and 2 is slightly higher than that of Comparative Example 1, and the π-π conjugation between the benzidine-disuccinimidyl suberate 101 and the graphene 102 facilitates electron transfer, while the benzidine-disuccinimidyl suberate 101 connects adjacent graphene 102 sheets through π-π interaction, accelerating the transfer of electrons. Therefore, the deposition of the modified graphene 102 coating on the surface of the copper electrode does not affect its electrical conductivity.

Claims

1. A graphene anticorrosive coating, characterized by, The graphene anticorrosion coating is composed of benzidine-disuccinimidyl suberate modified graphene, and the benzidine-disuccinimidyl suberate is combined with graphene through π-π conjugation.

2. The graphene anticorrosion coating according to claim 1, characterized in that, The graphene anticorrosion coating is attached to the surface of copper electrodes and / or contacts.

3. The method of claim 1 or 2, wherein the graphene anticorrosive coating is prepared by a method comprising: The method comprises depositing the benzidine-disuccinimidyl suberate modified graphene on the surface of copper electrodes and / or contacts by electrophoretic deposition to form the graphene anticorrosion coating with a multilayer structure.

4. The method of claim 3, wherein the graphene anticorrosive coating is prepared by a process comprising: The method comprises: The benzidine-disuccinimidyl suberate preparation step comprises dissolving benzidine and disuccinimidyl suberate in a dimethylformamide solution, stirring in the dark, reacting at room temperature, washing and drying to obtain the benzidine-disuccinimidyl suberate; The benzidine-disuccinimidyl suberate modified graphene step comprises dispersing the benzidine-disuccinimidyl suberate and the graphene in a dimethylformamide solution, stirring and reacting at room temperature, washing and drying to obtain the benzidine-disuccinimidyl suberate modified graphene; The electrophoretic deposition step comprises depositing the benzidine-disuccinimidyl suberate modified graphene on the surface of the copper electrodes by electrophoretic deposition.

5. The method of claim 4, wherein the graphene anticorrosive coating is prepared by a process comprising: The mass fraction of the benzidine to the disuccinimidyl suberate in the benzidine-disuccinimidyl suberate preparation step is 5:

1.

6. The method of claim 4, wherein the graphene anticorrosive coating is prepared by a process comprising: In the benzidine-disuccinimidyl suberate modified graphene step, the thickness of the graphene is selected from any value in the range of 1-2 μm, and the flake diameter is selected from any value in the range of 10-30 μm; the mass fraction of the benzidine-disuccinimidyl suberate to the graphene is 1:30-40.

7. The method of claim 4, wherein the graphene anticorrosive coating is prepared by a process comprising: The electrophoretic deposition step further comprises: The electrolyte is prepared by mixing the benzidine-disuccinimidyl suberate modified graphene, magnesium nitrate and ethanol, and the electrolyte is subjected to ultrasonic stirring to obtain a uniformly distributed modified graphene charged suspension; The copper electrode is used as the cathode, and the graphite electrode is used as the anode; the cathode and the anode are inserted into the modified graphene charged suspension in parallel, and the distance between the cathode and the anode is selected from any value in the range of 1-2 cm; The electrodes are connected to the positive and negative poles of a direct current power supply, respectively, and the benzidine-disuccinimidyl suberate modified graphene starts to deposit, and the deposition time lasts for 4 min.

8. The method of claim 7, wherein the graphene anticorrosive coating is prepared by a process comprising: The electrolyte is subjected to ultrasonic stirring, the ultrasonic power is 1 kW, and the ultrasonic time is 1 h.

9. The method of claim 4, wherein the graphene anticorrosive coating is prepared by a process comprising: After the electrophoretic deposition step, the copper electrode is taken out and dried to obtain the graphene anticorrosion coating, the drying temperature is 60°C, and the drying time is 6 h.

10. A refrigerator characterized by comprising: The light plate electrode used in the light-emitting layer shelf of the refrigeration space of the refrigerator, and the contact surface between the light plate electrode and the power supply part are covered with the graphene anticorrosion coating according to claim 1 or 2.

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