Modified graphene silane composite binder, preparation method and application thereof

Abstract

The application provides a modified graphene silane composite binder and a preparation method and application thereof, and the modified graphene silane composite binder comprises 10-20% of silane coupling agent, 5-10% of fluorinated silane and 4-8% of conductive agent by mass fraction, and the rest is solvent; wherein the silane coupling agent comprises gamma-aminopropyl triethoxysilane, tetraethoxysilane, trimethoxysilane propyl methyl acrylate and octamethylcyclotetrasiloxane, and the mass ratio of the four is (8-10):(1-3):(1-3):(1-3). The silane coupling agent, the fluorinated silane and the conductive agent with specific mass ratio are synergized, so that the modified graphene silane composite binder not only enhances the adhesion between the metal and the silicone rubber when bonding the silicone rubber and the metal, but also enhances the conductivity, weather resistance and chemical resistance.

Description

Technical Field

[0001] This invention relates to the field of metal bonding, and more specifically, to a modified graphene silane composite adhesive, its preparation method, and its application. Background Technology

[0002] Silicone rubber is widely used in various industrial fields due to its excellent elasticity, resistance to high and low temperatures, and resistance to chemical corrosion. However, its poor adhesion to metal materials such as copper and aluminum limits its practical applications. Current technologies typically involve coating the metal surface with a coupling agent, cross-linking the silicone rubber and metal at both ends to enhance adhesion. However, existing silane coupling agents still have shortcomings in terms of bond strength, chemical resistance, and weather resistance. Furthermore, existing silane coupling agents are non-conductive, while achieving low resistivity is necessary when bonding semi-conductive silicone rubber to metal locking rings in high-voltage cable accessories. Therefore, providing a modified silane coupling agent that possesses both high bonding performance and conductivity is particularly important. Summary of the Invention

[0003] The main objective of this invention is to provide a modified graphene-silane composite adhesive, its preparation method, and its application, in order to solve the problems of poor adhesion and poor conductivity of silane coupling agents when bonding silicone rubber and metal materials in the prior art.

[0004] To achieve the above objectives, according to one aspect of the present invention, a modified graphene silane composite binder is provided, comprising, by mass fraction, 10-20% silane coupling agent, 5-10% fluorinated silane, 4-8% conductive agent, and the balance being solvent; wherein the silane coupling agent comprises γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane, and the mass ratio of the four is (8-10):(1-3):(1-3):(1-3).

[0005] Furthermore, by mass fraction, the modified graphene silane composite binder contains 11-19% silane coupling agent, 6-10% fluorinated silane, 5-8% conductive agent, and the remainder is solvent.

[0006] Furthermore, in the silane coupling agent, the mass ratio of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane is (8-10):(1-3):(1-3):3.

[0007] Furthermore, the fluorinated silane is 3-fluoropropyltrimethoxysilane.

[0008] Furthermore, the conductive agent includes reduced graphene oxide and carbon nanotubes, and the mass ratio of the two is (4-6):(1-2).

[0009] Furthermore, the particle size of the reduced graphene oxide is 0.5-5 μm.

[0010] Furthermore, the diameter of carbon nanotubes ranges from 1 to 50 nm.

[0011] Furthermore, the solvent includes at least one of n-heptane and ethyl acetate.

[0012] Furthermore, the solvent is a mixed solution of n-heptane and ethyl acetate, and the mass ratio of the two is (50-60):(50-40).

[0013] According to another aspect of the present invention, a method for preparing the modified graphene silane composite binder provided in the first aspect above is provided, comprising the following steps: mixing a silane coupling agent, a fluorinated silane, a conductive agent and the balance solvent to obtain the modified graphene silane composite binder.

[0014] Furthermore, the mixing method is ultrasonic dispersion, the ultrasonic dispersion frequency is 5-20 kHz, and the ultrasonic dispersion time is 1-3 hours.

[0015] According to a third aspect of the present invention, the modified graphene-silane composite adhesive provided in the first aspect or the modified graphene-silane composite adhesive obtained by the preparation method provided in the second aspect is provided for use in metal bonding.

[0016] By applying the technical solution of this invention, this application utilizes a specific mass ratio of silane coupling agent, fluorinated silane, and conductive agent to synergistically enhance the bonding ability of the modified graphene silane composite adhesive to both ends of the metal and silicone rubber when bonding metal and silicone rubber, thereby improving the adhesion between the metal and silicone rubber. Simultaneously, it also imparts excellent conductivity, weather resistance, and chemical resistance to the metal and silicone rubber. Furthermore, the silane coupling agent formed by the synergistic interaction of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane in a specific mass ratio further improves the adhesion between the metal and silicone rubber. Moreover, by utilizing the structural differences among the components of the silane coupling agent, the silane coupling agent can form stable chemical bonds with different metal surfaces, further expanding the applicability of the modified graphene silane composite adhesive to various metal surfaces. Detailed Implementation

[0017] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0018] As analyzed in the background section of this application, existing silane coupling agents suffer from poor adhesion and poor conductivity when bonding silicone rubber and metal materials. To solve this problem, this application provides a modified graphene silane composite adhesive, its preparation method, and its application.

[0019] In one typical embodiment of this application, a modified graphene silane composite binder is provided. By mass fraction, the modified graphene silane composite binder comprises 10-20% silane coupling agent, 5-10% fluorinated silane, 4-8% conductive agent, and the balance being solvent. The silane coupling agent comprises γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane, and the mass ratio of the four is (8-10):(1-3):(1-3):(1-3).

[0020] This application utilizes a specific mass ratio of silane coupling agent, fluorinated silane, and conductive agent to synergistically enhance the bonding ability of the modified graphene silane composite adhesive between the metal and silicone rubber at both ends when bonding metal and silicone rubber, thereby improving the adhesion between the metal and silicone rubber. Simultaneously, it also imparts excellent conductivity, weather resistance, and chemical resistance to the metal and silicone rubber. Furthermore, a silane coupling agent formed by the synergistic interaction of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane in a specific mass ratio further improves the adhesion between the metal and silicone rubber. By leveraging the structural differences among the components of the silane coupling agent, it enables the silane coupling agent to form stable chemical bonds with different metal surfaces, further expanding the applicability of the modified graphene silane composite adhesive to various metal surfaces.

[0021] Typically, but not limitingly, the modified graphene-silane composite binder contains, by mass fraction, 10%, 11%, 14%, 16%, 19%, 20%, or any combination of two values ​​for the silane coupling agent; 5%, 6%, 7%, 8%, 9%, 10%, or any combination of two values ​​for the fluorinated silane; and 4%, 5%, 6%, 7%, 8%, or any combination of two values ​​for the conductive agent.

[0022] Typically, but not limitingly, the mass ratios of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane in the silane coupling agent provided in this application are, for example, 8:1.5:1.5:1, 8:1:3:3, 9:2:1:2, 10:3:1:1, or any range of two such values.

[0023] It should be noted that the silane coupling agent in this application does not include fluorinated silanes.

[0024] In some embodiments, the modified graphene silane composite binder contains, by mass fraction, 11-19% silane coupling agent, 6-10% fluorinated silane, and 5-8% conductive agent, with the remainder being solvent, to further enhance the adhesion and conductivity of the modified graphene silane composite binder.

[0025] In some embodiments, the mass ratio of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane in the silane coupling agent is (8-10):(1-3):(1-3):3, to further enhance the adhesion of the modified graphene silane composite binder.

[0026] To further enhance the weather resistance and chemical resistance of the modified graphene silane composite binder, 3-fluoropropyltrimethoxysilane is preferred as the fluorinated silane.

[0027] In some embodiments, the conductive agent comprises reduced graphene oxide and carbon nanotubes, with a mass ratio of (4-6):(1-2). The numerous polar groups on the surface of reduced graphene oxide promote its bonding with the silane coupling agent without delamination, thereby enabling the modified graphene-silane composite binder to form a stable and continuous solution, further improving conductivity. Furthermore, the synergistic conductivity effect formed by the specific mass ratio of reduced graphene oxide and carbon nanotubes further enhances the conductivity of the modified graphene-silane composite binder, achieving high conductivity with a relatively low amount of conductive agent added. In addition, it can further improve the mechanical and thermal properties of the metal-silicone rubber bonding interface, further strengthening the bond strength.

[0028] Typically, but not limitingly, in the conductive agent provided in this application, the mass ratio of reduced graphene oxide to carbon nanotubes is, for example, 4:1, 4:2, 5:1.5, 6:1, 6:2, or any range of two values.

[0029] The reduced graphene oxide used in this application can be obtained commercially (e.g., Beijing Meiston Technology Development Co., Ltd., product model SY-rGO-S), or it can be prepared by the following steps: Step (1), providing natural graphene, and using a mixed solution of potassium sulfate and sulfuric acid at 50°C to perform a mild oxidation treatment on the natural graphene, causing partial oxidation of the graphene to obtain graphene oxide. The mild oxidation treatment can not only introduce polar functional groups such as hydroxyl and carboxyl groups on the graphene surface to ensure the activity of subsequent chemical reactions, but also reduce the damage to the graphene sheet structure caused by excessive oxidation. Step (2), heating the graphene oxide to 400°C under nitrogen protection for reduction treatment to obtain reduced graphene. The reduction treatment restores some conductivity, ensuring that the graphene material has high conductivity, reducing defects in graphite, and improving the mechanical strength of the graphene material. Step (3), using plasma treatment technology to activate the surface of the reduced graphene to obtain reduced graphene oxide. Plasma treatment technology can give the surface of reduced graphene oxide a large number of reaction sites. These reaction sites help silane coupling agents form stable chemical bonds with the surface of reduced graphene oxide, thereby improving the dispersibility and stability of reduced graphene oxide.

[0030] To further ensure uniform dispersion of reduced graphene oxide in the silane coupling agent and avoid agglomeration and sedimentation caused by excessively large particle size of reduced graphene oxide, which would affect the conductivity of the modified graphene-silane composite binder, the particle size of the modified graphene is preferably 0.5-5 μm.

[0031] To further improve the conductivity of carbon nanotubes, the diameter of the carbon nanotubes is preferably 1-50 nm.

[0032] Typical, but not limiting, reduced graphene oxide particle sizes are 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm or any combination of two values; carbon nanotube diameters are 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm or any combination of two values.

[0033] When the number of polar groups on the surface of reduced graphene oxide is small, it is easy to cause the modified graphene and silane coupling agent to separate, which reduces the conductivity. In order to better combine and uniformly disperse the reduced graphene oxide and silane coupling agent, the number of polar groups on the surface of reduced graphene oxide can be increased in practical applications to further improve the conductivity of the modified graphene silane composite binder.

[0034] To further promote the dissolution of silane coupling agents, fluorinated silanes, and conductive agents in solvents and to achieve green and environmentally friendly results, organic compounds are preferred as solvents, including any one or more of n-heptane and ethyl acetate.

[0035] To further promote the dissolution and dispersion of silane coupling agent, fluorinated silane, and conductive agent, the solvent is preferably a mixture of n-heptane and ethyl acetate, with a mass ratio of (50-60):(50-40).

[0036] Typical, but not limiting, the mass ratio of n-heptane to ethyl acetate in the solvent is, for example, 50:50, 52:48, 54:46, 56:44, 58:42, 60:40, or any range of two such values.

[0037] In practical applications, those skilled in the art can appropriately add the above-mentioned solvents to the modified graphene silane composite binder for dilution according to the actual application environment or purpose, so as to ensure the actual use effect of the product.

[0038] In another typical embodiment of this application, a method for preparing the modified graphene silane composite binder provided in the first typical embodiment above is provided, comprising the following steps: mixing a silane coupling agent, a fluorinated silane, a conductive agent and the remaining solvent to obtain the modified graphene silane composite binder.

[0039] The preparation method provided in this application is simple to operate and suitable for industrial production.

[0040] To further promote the dissolution and dispersion of each component in the solvent, the preferred mixing method is ultrasonic dispersion, with an ultrasonic dispersion frequency of 5-20 kHz and an ultrasonic dispersion time of 1-3 h.

[0041] In a third typical embodiment of this application, the modified graphene silane composite adhesive provided in the first typical embodiment or the modified graphene silane composite adhesive obtained by the preparation method provided in the second typical embodiment is provided for use in metal bonding.

[0042] The beneficial effects of this application will be further illustrated below with reference to embodiments and comparative examples.

[0043] It should be noted that in the following examples and comparative examples, "%" refers to "wt%".

[0044] Example 1

[0045] This embodiment provides a modified graphene-silane composite binder, which, by mass fraction, comprises 12% silane coupling agent, 6% fluorinated silane, 5% conductive agent, and the balance being solvent. The silane coupling agent includes γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane, with a mass ratio of 8:1.5:1.5:1. The fluorinated silane is 3-fluoropropyltrimethoxysilane; the conductive agent includes reduced graphene oxide (purchased from Beijing Meiston Technology Development Co., Ltd., product model SY-rGO-S) and carbon nanotubes (particle size 30 nm), with a mass ratio of 4:1; the solvent is a mixed solution of n-heptane and ethyl acetate, with a mass ratio of 52:48.

[0046] The modified graphene-silane composite binder was prepared according to the following steps: γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane were mixed with 50 wt% solvent and uniformly dispersed using ultrasonic dispersion technology at a frequency of 10 kHz for 1.5 h. Then, reduced graphene oxide, carbon nanotubes, and 3-fluoropropyltrimethoxysilane were added sequentially, and the components were uniformly dispersed using ultrasonic dispersion technology at a frequency of 10 kHz for 1.5 h. Finally, 50 wt% solvent was added and stirred until homogeneous to obtain the modified graphene-silane composite binder.

[0047] Example 2

[0048] The difference between Example 2 and Example 1 is that the content of each component in the modified graphene silane composite binder is adjusted by mass fraction, so that the modified graphene silane composite binder includes 10% silane coupling agent, 10% fluorinated silane, 8% conductive agent, and the balance is solvent.

[0049] Example 3

[0050] The difference between Example 3 and Example 1 is that the content of each component in the modified graphene silane composite binder is adjusted by mass fraction so that the modified graphene silane composite binder includes 20% silane coupling agent, 5% fluorinated silane, 4% conductive agent, and the balance is solvent.

[0051] Example 4

[0052] The difference between Example 4 and Example 1 is that the content of each component in the modified graphene silane composite binder is adjusted by mass fraction, so that the modified graphene silane composite binder includes 11% silane coupling agent, 10% fluorinated silane, 8% conductive agent, and the balance is solvent.

[0053] Example 5

[0054] The difference between Example 5 and Example 1 is that the content of each component in the modified graphene silane composite binder is adjusted by mass fraction so that the modified graphene silane composite binder includes 19% silane coupling agent, 6% fluorinated silane, 5% conductive agent, and the balance is solvent.

[0055] Example 6

[0056] The difference between Example 6 and Example 1 is that the mass ratio of each component in the silane coupling agent is adjusted so that the mass ratio of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane in the silane coupling agent is 8:1:3:3.

[0057] Example 7

[0058] The difference between Example 7 and Example 1 is that the mass ratio of each component in the silane coupling agent is adjusted so that the mass ratio of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane in the silane coupling agent is 10:3:1:1.

[0059] Example 8

[0060] The difference between Example 8 and Example 1 is that the mass ratio of each component in the conductive agent was adjusted so that the mass ratio of modified graphene to carbon nanotubes in the conductive agent is 4:2.

[0061] Example 9

[0062] The difference between Example 9 and Example 1 is that the mass ratio of each component in the conductive agent is adjusted so that the mass ratio of modified graphene to carbon nanotubes in the conductive agent is 6:1.

[0063] Example 10

[0064] The difference between Example 10 and Example 1 is that the mass ratio of each component in the conductive agent is adjusted so that the mass ratio of modified graphene to carbon nanotubes in the conductive agent is 7:0.5.

[0065] Example 11

[0066] The difference between Example 11 and Example 1 is that the mass ratio of each component in the conductive agent is adjusted so that the mass ratio of modified graphene to carbon nanotubes in the conductive agent is 2:4.

[0067] Example 12

[0068] The difference between Example 12 and Example 1 is that the modified graphene in the conductive agent is removed, so that the conductive agent is carbon nanotubes.

[0069] Example 13

[0070] The difference between Example 13 and Example 1 is that the carbon nanotubes in the conductive agent are removed, so that the conductive agent is modified graphene.

[0071] Comparative Example 1

[0072] The difference between Comparative Example 1 and Example 1 is that the content of each component in the modified graphene silane composite binder was adjusted by mass fraction so that the modified graphene silane composite binder includes 7% silane coupling agent, 13% fluorinated silane, 9% conductive agent, and the balance being solvent.

[0073] Comparative Example 2

[0074] The difference between Comparative Example 2 and Example 1 is that the content of each component in the modified graphene silane composite binder was adjusted by mass fraction so that the modified graphene silane composite binder includes 23% silane coupling agent, 2% fluorinated silane, 2% conductive agent, and the balance being solvent.

[0075] Comparative Example 3

[0076] The difference between Comparative Example 3 and Example 1 is that the mass ratio of each component in the silane coupling agent was adjusted so that the mass ratio of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane in the silane coupling agent is 12:0.5:0.5:4.

[0077] Comparative Example 4

[0078] The difference between Comparative Example 4 and Example 1 is that the mass ratio of each component in the silane coupling agent was adjusted so that the mass ratio of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane in the silane coupling agent is 6:4:5:0.5.

[0079] Comparative Example 5

[0080] The difference between Comparative Example 5 and Example 1 is that tetraethoxysilane in the silane coupling agent is removed, so that the silane coupling agent includes γ-aminopropyltriethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane, and the mass ratio of the three is 8:1.5:2.5.

[0081] Comparative Example 6

[0082] The difference between Comparative Example 6 and Example 1 is that the trimethoxysilylpropylmethacrylic acid in the silane coupling agent is removed, so that the silane coupling agent includes γ-aminopropyltriethoxysilane, tetraethoxysilane and octamethylcyclotetrasiloxane, and the mass ratio of the three is 8.5:2:1.5.

[0083] Comparative Example 7

[0084] The difference between Comparative Example 7 and Example 1 is that the trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane in the silane coupling agent are removed, so that the silane coupling agent includes γ-aminopropyltriethoxysilane and tetraethoxysilane, and the mass ratio of the two is 9:3.

[0085] Test case

[0086] The modified graphene-silane composite adhesive samples provided in the embodiments and comparative examples of this application were coated onto the surface of a copper metal sheet and air-dried at room temperature to obtain a copper metal sheet to be bonded. The thickness of the modified graphene-silane composite adhesive coating layer on the copper metal sheet to be bonded was 0.1 mm. Subsequently, semi-conductive liquid silicone rubber (model 1523) was poured onto the copper metal sheet to be bonded to obtain a silicone rubber and copper metal composite sheet to be tested. Its tensile shear strength and volume resistivity were tested, and the results are shown in Table 1.

[0087] Tensile shear strength test method: The test shall be conducted in accordance with the requirements of the national standard GB / T 13936-2014.

[0088] Volume resistivity test method: Refer to GB / T 3048.3 for testing.

[0089] Table 1

[0090]

[0091]

[0092] The experimental data from Examples 1, 2, 3, 4, 5 and Comparative Examples 1, 2 show that when the modified graphene-silane composite binder includes 10-20 wt% silane coupling agent, 5-10 wt% fluorinated silane, 4-8 wt% conductive agent, and the balance being solvent, the tensile shear strength between the metal and silicone rubber is relatively high, and the volume resistivity of the modified graphene-silane composite binder is relatively low, indicating strong adhesion and conductivity between the metal and silicone rubber. When the composition or proportion of the modified graphene-silane composite binder is changed, it becomes impossible to simultaneously achieve excellent adhesion and conductivity.

[0093] The experimental data from Examples 6 and 7 and Comparative Examples 3, 4, 5, 6, and 7 show that when the silane coupling agent includes γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane, and the mass ratio of the four is (8-10):(1-3):(1-3):(1-3), the tensile shear strength between the metal and silicone rubber is relatively high, and the volume resistivity of the modified graphene silane composite binder is relatively low, indicating that the adhesion and conductivity between the metal and silicone rubber are strong. When the composition or ratio of the silane coupling agent is changed, the tensile shear strength between the metal and silicone rubber decreases, indicating that the adhesion between the metal and silicone rubber decreases.

[0094] The experimental data from Examples 8, 9, 10, 11, 12, and 13 show that when the conductive agent includes reduced graphene oxide and carbon nanotubes in a mass ratio of (4-6):(1-2), the tensile shear strength between the metal and silicone rubber is high, and the volume resistivity of the modified graphene-silane composite binder is low, indicating strong adhesion and conductivity between the metal and silicone rubber. When the composition or ratio of the conductive agent is changed, the volume resistivity of the modified graphene-silane composite binder increases, indicating a decrease in conductivity between the metal and silicone rubber.

[0095] As can be seen from the above description, the embodiments of the present invention achieve the following technical effects:

[0096] This application utilizes a specific mass ratio of silane coupling agent, fluorinated silane, and conductive agent to synergistically enhance the bonding ability of the modified graphene silane composite adhesive between the metal and silicone rubber at both ends when bonding metal and silicone rubber, thereby improving the adhesion between the metal and silicone rubber. Simultaneously, it also imparts excellent conductivity, weather resistance, and chemical resistance to the metal and silicone rubber. Furthermore, a silane coupling agent formed by the synergistic interaction of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane in a specific mass ratio further improves the adhesion between the metal and silicone rubber. By leveraging the structural differences among the components of the silane coupling agent, it enables the silane coupling agent to form stable chemical bonds with different metal surfaces, further expanding the applicability of the modified graphene silane composite adhesive to various metal surfaces.

[0097] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A modified graphene-silane composite binder, characterized in that, By mass fraction, the modified graphene silane composite binder comprises 10-20% silane coupling agent, 5-10% fluorinated silane, 4-8% conductive agent, and the balance being solvent; wherein, the silane coupling agent comprises γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid, and octamethylcyclotetrasiloxane, and the mass ratio of the four is (8-10):(1-3):(1-3):(1-3); the conductive agent comprises reduced graphene oxide and carbon nanotubes, and the mass ratio of the two is (4-6):(1-2).

2. The modified graphene-silane composite binder according to claim 1, characterized in that, By mass fraction, the modified graphene silane composite binder contains 11-19% silane coupling agent, 6-10% fluorinated silane, 5-8% conductive agent, and the remainder is solvent.

3. The modified graphene-silane composite binder according to claim 1 or 2, characterized in that, In the silane coupling agent, the mass ratio of γ-aminopropyltriethoxysilane, tetraethoxysilane, trimethoxysilylpropylmethacrylic acid and octamethylcyclotetrasiloxane is (8-10):(1-3):(1-3):

3.

4. The modified graphene-silane composite binder according to claim 1 or 2, characterized in that, The fluorinated silane is 3-fluoropropyltrimethoxysilane.

5. The modified graphene-silane composite binder according to claim 1, characterized in that, The reduced graphene oxide has a particle size of 0.5-5 μm.

6. The modified graphene-silane composite binder according to claim 1, characterized in that, The diameter of the carbon nanotubes is 1-50 nm.

7. The modified graphene-silane composite binder according to claim 1 or 2, characterized in that, The solvent includes at least one of n-heptane and ethyl acetate.

8. The modified graphene-silane composite binder according to claim 7, characterized in that, The solvent is a mixed solution of n-heptane and ethyl acetate, and the mass ratio of the two is (50-60):(50-40).

9. The method for preparing the modified graphene-silane composite binder according to any one of claims 1 to 8, characterized in that, Includes the following steps: The silane coupling agent, the fluorinated silane, the conductive agent, and the remaining solvent are mixed to obtain the modified graphene silane composite binder.

10. The method for preparing the modified graphene silane composite binder according to claim 9, characterized in that, The mixing method is ultrasonic dispersion, the ultrasonic dispersion frequency is 5~20KHz, and the ultrasonic dispersion time is 1~3h.

11. The application of the modified graphene silane composite adhesive according to any one of claims 1 to 8 or the modified graphene silane composite adhesive obtained by the preparation method according to claim 9 or 10 in metal bonding.

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