Graphene oxide modified ceramicizable protective heat shielding film and preparation method thereof

Abstract

The application discloses a kind of graphene oxide modified ceramifiable protective heat insulation films and preparation methods thereof, and protective heat insulation film is made by the following mass parts of raw materials by doctor blade coating process: base glue 100-200 parts, graphene oxide modifier 1-5 parts, ceramifiable flame-retardant filler 30-70 parts, heat insulation filler 5-20 parts, auxiliary agent 1-3 parts, graphene oxide modifier is graphene oxide coated with nano silicon carbide, and the auxiliary agent includes directional agent.The tensile strength of the protective heat insulation film can be improved by using the graphene oxide modifier, and since no fiber material is used, a thinner film material can achieve stronger protective heat insulation performance, which is beneficial to improve the space utilization of the film material in practical application and reduce the material cost.The preparation method of the application can make the graphene oxide preferentially parallel to the coating surface by doctor blade coating process, which can effectively improve the tensile strength and heat insulation performance of the prepared protective heat insulation film.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fireproof and heat insulation materials, and particularly relates to a graphene oxide modified ceramifiable protective heat insulation film and a preparation method thereof. BACKGROUND

[0002] The capacity increase of a single cell is an important trend in the development of lithium-ion power battery technology in recent years. The capacity of a single cell of cylindrical cells has increased by more than 5 times from the initial 18650 cell used by Tesla to the 21700 cell to the latest 4680 cell. The capacity of a single cell of soft package cells (mainly used by European car companies) and square cell (mainly used by domestic new energy) widely used by ternary cells is greater, basically exceeding 0.5 degrees of electricity. Such a large single cell capacity puts very high requirements on the performance of thermal runaway protection materials. These requirements are specifically reflected in the need for materials to have good compressibility, high insulation, resistance to high mechanical impact, ability to resist 1000℃-1400℃ flame damage, and ability to prevent high temperature from being transmitted to adjacent cells. The existing mica, super cotton, aerogel and their combinations have been unable to meet such demands.

[0003] Ceramifiable polymer films are a type of fireproof and heat insulation material that is very suitable for new energy lithium batteries. By using different fillers and base glue combinations, good compressibility, insulation, heat resistance and temperature insulation performance can be achieved. The existing technology often adds short fibers or composites with fiber layers to obtain the impact resistance of the ceramifiable polymer film. The problem is that: on the one hand, the addition of short fibers will make the flowability of the raw material worse, making it difficult to form. The composite with the fiber layer makes the overall film material significantly thicker, with a thickness of usually more than 3mm, while the thickness without short glass fibers is generally about 2mm. The addition of short glass fibers reduces the performance of the film material per unit thickness, wasting the space in the car. On the other hand, using fibers as a modification material, there is a risk of fiber residue and fiber falling during the processing process, affecting the safety of the material in the vehicle body construction. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the shortcomings of the prior art and provide a graphene oxide modified ceramifiable protective heat insulation film with small thickness size and good heat insulation performance and a preparation method thereof.

[0005] To solve the above technical problems, the technical scheme adopted by the present application is:

[0006] The application discloses a graphene oxide modified ceramicizable protective heat insulation film, which is prepared from the following raw materials by a doctor blade coating process: base glue 100-200 parts by mass, graphene oxide modifier 1-5 parts by mass, ceramicizable flame-retardant filler 30-70 parts by mass, heat insulation filler 5-20 parts by mass and additive 1-3 parts by mass; the graphene oxide modifier is graphene oxide coated with nano silicon carbide; the thickness of the graphene oxide modified ceramicizable protective heat insulation film is 1-3 mm; and the additive comprises a directional agent.

[0007] Preferably, the graphene oxide is multilayer graphene oxide, the thickness of the multilayer graphene oxide is 1-5 nm, and the flake diameter of the multilayer graphene oxide is 3-10 microns; the mass of the nano silicon carbide is 20-30% of the mass of the multilayer graphene oxide, and the average particle size of the nano silicon carbide is 70-100 nm.

[0008] Preferably, the additive further comprises a coupling agent, a wetting agent and a dispersing agent, the mass ratio of the coupling agent, the wetting agent, the dispersing agent and the directional agent is 5-6:1:1:1.5-2.5; the coupling agent is an organic silicon coupling agent, the wetting agent is an organic silicon wetting agent, the dispersing agent is an organic silicon dispersing agent, and the directional agent is a cellulose directional agent.

[0009] Preferably, the heat insulation filler is at least one of soda lime borosilicate glass hollow microbeads, zirconium oxide hollow microbeads, zirconium oxide porous microbeads, aluminum oxide hollow microbeads and aluminum oxide porous microbeads.

[0010] Preferably, the heat insulation filler is a mixture of soda lime borosilicate glass hollow microbeads and metal oxide microbeads in a volume ratio of 50-70:20-40; the diameters of the soda lime borosilicate glass hollow microbeads and the metal oxide microbeads are less than or equal to 50 microns; and the metal oxide microbeads are at least one of zirconium oxide hollow microbeads, zirconium oxide porous microbeads, aluminum oxide hollow microbeads and aluminum oxide porous microbeads.

[0011] Preferably, the base glue is at least one of methyl vinyl silicone rubber, methyl silicone rubber and methyl phenyl vinyl silicone rubber.

[0012] Preferably, the ceramicizable flame-retardant filler comprises organic montmorillonite, wollastonite powder, fumed white carbon black, aluminum hydroxide powder, boron oxide powder, aluminum oxide powder, mica powder and silicon carbide powder.

[0013] The graphene oxide modified ceramicizable protective heat insulation film, preferably, the organic montmorillonite is 5-20 parts, the wollastonite powder is 2-10 parts, the fumed white carbon black is 10-50 parts, the aluminum hydroxide powder is 10-50 parts, the boron oxide powder is 1-5 parts, the aluminum oxide powder is 1-10 parts, the mica powder is 5-10 parts, and the silicon carbide powder is 1-10 parts.

[0014] As a general technical concept, the application further provides a preparation method of the graphene oxide modified ceramicizable protective heat insulation film, comprising the following steps:

[0015] (1) mixing the ceramicizable flame-retardant filler, the heat insulation filler, the graphene oxide modifier and the auxiliary agent with the base glue under stirring to obtain a mixture;

[0016] (2) using a doctor blade coating process to coat the mixture on a substrate to form a coating;

[0017] (3) drying and vulcanizing the coating and then winding it up for the next coating;

[0018] (4) repeating steps (2) and (3) until the target thickness is reached.

[0019] The preparation method of the graphene oxide modified ceramicizable protective heat insulation film, in step (1), the mixing process is diluted with a solvent to adjust the viscosity to 20,000-30,000 cps, the solvent is a mixed solvent of xylene, methanol and solvent oil, and the mass ratio of xylene, methanol and solvent oil is 6-8:2:1; in steps (2) and (3), the thickness of the coating in each coating is ≤0.2 mm.

[0020] Compared with the prior art, the application has the following advantages:

[0021] (1) In view of the technical defects of the existing fiber-containing new energy lithium battery fireproof and heat insulation materials, the application provides a graphene oxide modified ceramifiable protective and heat insulation film, which is prepared from a base glue, a graphene oxide modifier, a ceramifiable flame-retardant filler, a heat insulation filler and an additive in specific proportions, wherein the graphene oxide modifier is graphene oxide coated with nano silicon carbide, and the additive contains a directional agent. Through in-depth research on the composition of the existing ceramifiable polymer film of a type of heat insulation material for new energy lithium batteries, the applicant abandons the traditional thinking of using fiber additives and creatively modifies the heat insulation material by using a graphene oxide modifier. Based on the special planar layered structure of graphene oxide, under the action of the directional agent and the scraping force, the graphene oxide will naturally tend to arrange parallel to the film plane when added to the film material to form a coating, which is more conducive to enhancing the tensile and impact resistance of the film material. Further, the graphene oxide modifier of the application is graphene oxide coated with nano silicon carbide. When exposed to high temperature, the nano silicon carbide will form a protective oxide film on the surface of the graphene oxide, improving the high-temperature oxidation resistance of the graphene oxide. After the protective and heat insulation film undergoes a ceramification reaction, the modified graphene oxide can still maintain high mechanical properties. At the same time, coating the graphene oxide with nano silicon carbide can effectively improve the uniformity of the graphene oxide dispersion, thereby uniformly improving the mechanical properties of the film material and reducing the risk of local damage. The modified graphene oxide also has good insulation, which can synergize with the ceramifiable flame-retardant filler and the heat insulation filler while strengthening the ceramifiable heat insulation film material. In summary, the use of the graphene oxide modifier can improve the tensile strength of the protective and heat insulation film, thereby improving the impact resistance. Since no fiber material is used, the safety hazards and processing difficulties caused by fiber residue or shedding are avoided, and the thickness problem caused by the introduction of the fiber layer is avoided. The application can use thinner film materials to achieve stronger protective and heat insulation performance, which is conducive to improving the space utilization of the film material in practical applications, such as reducing the requirements of the protective and heat insulation film on the vehicle interior space and reducing the material cost.

[0022] (2) The protective and heat insulation film of the application has good flexibility and can better fit the uneven workpiece surface. By optimizing the amounts of the components, the protective and heat insulation film of the application can be re-heat pressed and shaped to achieve better fitting effect.

[0023] (3) The graphene oxide modified ceramifiable protective heat insulation film of the present application can undergo a ceramification reaction when exposed to high temperature, forming a hard ceramic phase layer in the high temperature area to prevent high temperature from further damaging and diffusing through the protective heat insulation film layer. The nanometer silicon carbide forms an oxide film to cover the surface of the layered graphene oxide, and the graphene oxide covered by the nanometer silicon carbide is arranged in parallel in the protective heat insulation film, greatly improving the anti-burn-through performance of the film material. Tests show that the protective heat insulation film of the present application can ensure that the film layer is not penetrated by fire within 30 minutes when the surface temperature does not exceed 1200℃. At the same time, under the condition of free heat dissipation on the cold surface, the cold surface temperature can be less than 350℃ with a film thickness of 1mm.

[0024] (4) The preparation method of the graphene oxide modified ceramifiable protective heat insulation film of the present application. Through the doctor blade coating process, the graphene oxide is preferentially arranged in parallel to the coating direction (see Figure 1 ) under the cooperation of the orienting agent, thereby effectively improving the tensile strength of the prepared protective heat insulation film. The parallel arrangement of the graphene oxide can prevent the formation of a large number of penetrating voids after the graphene oxide is completely oxidized after the high temperature ceramification reaction in subsequent applications. The doctor blade coating process can ensure the precision, flatness and parallel arrangement of the graphene oxide of the coating, and can also better control the thickness of the film product. Therefore, the protective heat insulation film prepared by the preparation method of the present application can achieve stronger protective heat insulation performance with thinner thickness without containing fiber additives.

[0025] The graphene oxide modified ceramifiable protective heat insulation film prepared by the method of the present application is coated with the same thickness of ceramifiable material on both sides of the base material during forming, so that the film layer has uniform performance on both sides, which can reduce the complexity of operation in the application process and prevent misalignment. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The scanning electron microscope image of the graphene oxide modified ceramifiable protective heat insulation film prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0027] The present application will be further described below in conjunction with the drawings and specific preferred embodiments, but the protection scope of the present application is not limited thereby. The materials and instruments used in the following examples are all commercially available.

[0028] Example 1:

[0029] A graphene oxide modified ceramifiable protective heat insulation film of the present application is made from the following raw materials by mass: base glue 100 parts, graphene oxide modifier 1 part, ceramifiable flame retardant filler 50 parts, heat insulation filler 5 parts, and auxiliary agent 1 part.

[0030] In this embodiment, the base glue is methyl vinyl silicone rubber.

[0031] In this embodiment, the graphene oxide has a thickness of 3 nm and a size of 5 μm in flake diameter (the maximum length of the flaky material).

[0032] In this embodiment, the thermal insulation filler is GS40 alkali lime borosilicate glass hollow microsphere from Zhongguang New Material.

[0033] In this embodiment, the auxiliary agent is obtained by mixing KH550 silane coupling agent from Chen Guang New Material, German Degussa 245 silicone wetting agent, German Degussa GS650 dispersant and Eastman CAB 381-0.5 orienting agent in a mass ratio of 5:1:1:2.

[0034] In other embodiments, the silane coupling agent can also be KH570 from Chen Guang New Material or other similar functional types of silane coupling agent; the silicone wetting agent can also be German Degussa 270, Degussa 4100 or other similar functional types of silicone wetting agent; and the dispersant can also be German Degussa 652D dispersant.

[0035] The solvent in this embodiment is a mixed solvent of xylene, methanol and solvent oil, and the mass ratio of xylene, methanol and solvent oil is 7:2:1. The solvent oil is No. 120 solvent oil. The solvent is an optional material in the process and is not left in the final product.

[0036] The graphene oxide modifier in this embodiment is obtained by coating the above multi-layer graphene oxide and nano silicon carbide powder, wherein the mass of the nano silicon carbide powder is 20% of the mass of the multi-layer graphene oxide, the average particle size of the nano silicon carbide powder is 90 nm, and the coating is carried out by using a stirring solid coating machine for 30 minutes.

[0037] The ceramicizable flame-retardant filler in this embodiment includes, in parts by mass, 10 parts of organic montmorillonite, 8 parts of wollastonite powder, 10 parts of fumed white carbon black, 20 parts of aluminum hydroxide powder, 5 parts of boron oxide powder, 5 parts of aluminum oxide powder, 10 parts of mica powder and 5 parts of silicon carbide powder.

[0038] A method for preparing a graphene oxide modified ceramicizable protective thermal insulation film according to an embodiment includes the following steps:

[0039] (1) A total of 50 kg of materials is weighed according to the above mass parts, and the above ceramicizable flame-retardant filler, thermal insulation filler, graphene oxide modifier and solvent containing auxiliary agent are sequentially added to the base glue under stirring. An open mill is used to mix them thoroughly at room temperature. During the mixing process, the solvent is diluted to adjust the viscosity to between 20,000 cps and 30,000 cps.

[0040] (2) using a doctor blade process to form, specifically, the mixture prepared in step (1) is evenly coated on the surface of the fluorine plastic release film by a doctor blade coater;

[0041] (3) the coating after doctoring is dried and vulcanized through an oven, and then wound for the next doctoring;

[0042] (4) repeating steps (2) and (3) until the target thickness is reached, and then cutting into a certain shape and size on a slitting machine to obtain the product;

[0043] In steps (2) and (3), the coating thickness of each doctoring is controlled to be ≤0.2 mm.

[0044] Figure 1 The scanning electron microscope image of the graphene oxide modified ceramicizable protective heat insulation film prepared in this example can be seen from Figure 1 It can be seen that the graphene oxide and other fillers are arranged substantially parallel to the film surface. Since the graphene oxide has a planar layered structure, it tends to be arranged parallel to the film plane under the combined action of the orienting agent and the external force of the doctor blade.

[0045] This example uses a comma doctor blade coating, which is suitable for coating liquid with a viscosity of 5000 cps or more, especially liquid with certain solid fillers. The coating thickness can be adjusted, and the coating precision is certain. During the coating process, the force of the doctor blade is parallel to the film surface, which can better ensure that the graphene in the product is arranged parallel to the film plane.

[0046] The graphene oxide modified ceramicizable protective heat insulation film prepared in this example has a thickness of 1.0 mm and a tensile strength of 5.5 Mpa. The flame spray test shows that under the condition that the flame surface temperature does not exceed 1200℃, the film layer can be guaranteed not to be penetrated by the flame within 30 minutes, and the temperature is less than 350℃ under the condition of free heat dissipation on the cold surface.

[0047] Example 2:

[0048] A graphene oxide modified ceramicizable protective heat insulation film of the present application is made from the following raw materials by mass: base glue 100 parts, graphene oxide modifier 2 parts, ceramicizable flame-retardant filler 60 parts, heat insulation filler 10 parts, and auxiliary agent 1 part.

[0049] In this example, the base glue is methylphenylvinyl silicone rubber.

[0050] In this example, the graphene oxide is multi-layer graphene oxide with a thickness of 5 nm and a flake diameter (referring to the maximum length of flaky material) of 7 μm.

[0051] In this example, the heat insulation filler is GS32 soda lime borosilicate glass hollow microsphere of Zhongshan New Material.

[0052] In this embodiment, the adjuvant is obtained by mixing the following materials in a mass ratio of 6:1:1:2: Silane coupling agent of Morningstar KH550, German Degussa 4100 siloxane wetting agent, German Degussa GS650 dispersant, and Eastman CAB 381-0.5 orienting agent.

[0053] The solvent of this embodiment is a mixed solvent of xylene, methanol and solvent oil, and the mass ratio of xylene, methanol and solvent oil is 7:2:1. The solvent oil is No. 120 solvent oil, which is a selectable material in the process and has no residue in the final product.

[0054] The graphene oxide modifier of this embodiment is obtained by coating the above-mentioned multi-layer graphene oxide with nano silicon carbide powder, wherein the mass of the nano silicon carbide powder is 25% of the mass of the multi-layer graphene oxide, the average particle size of the nano silicon carbide powder is 90 nm, and the coating is carried out using a stirring solid coating machine with a coating time of 30 minutes.

[0055] The ceramicizable flame-retardant filler of this embodiment includes, by mass, 10 parts of organic montmorillonite, 8 parts of wollastonite powder, 10 parts of fumed white carbon black, 20 parts of aluminum hydroxide powder, 5 parts of boron oxide powder, 5 parts of aluminum oxide powder, 10 parts of mica powder, and 5 parts of silicon carbide powder.

[0056] A method for preparing the graphene oxide modified ceramicizable protective heat insulation film of this embodiment includes the following steps:

[0057] (1) A total of 50 kg of materials is taken according to the above mass, and the ceramicizable flame-retardant filler, heat insulation filler, graphene oxide modifier and solvent containing adjuvant are added to the base glue in turn under stirring conditions. An open mill is used to mix them thoroughly at room temperature. During the mixing process, the solvent is diluted to adjust the viscosity to between 20,000 cps and 30,000 cps.

[0058] (2) The mixture prepared in step (1) is uniformly coated on the surface of a fluoroplastic release film using a doctor blade coater by a doctor blade coating process.

[0059] (3) The coated layer after doctor blade coating is dried and vulcanized through an oven, and then wound up for the next doctor blade coating.

[0060] (4) Steps (2) and (3) are repeated until the target thickness is reached, and then the product is cut into a certain shape and size on a slitting machine.

[0061] In steps (2) and (3), the thickness of the coating layer for each doctor blade coating should be controlled to be ≤0.2 mm.

[0062] The embodiment adopts comma doctor blade coating, is suitable for coating liquid with viscosity of 5000cps or more, especially suitable for liquid with certain solid filler, coating thickness can be adjusted, has certain coating precision, and the doctor blade force is parallel to the film surface during coating, which can better guarantee that the graphene in the oxygen product is parallel to the film plane.

[0063] The thickness of the graphene oxide modified ceramicizable protective heat insulation film prepared in the embodiment is 1.6mm; the tensile strength is 5.8MPa, flame spraying test is carried out, under the condition that the flame surface temperature does not exceed 1200℃, the film layer can be guaranteed not to be penetrated by the flame within 30 minutes, and the temperature is less than 350℃ under the condition that the cold surface freely radiates heat.

[0064] Embodiment 3:

[0065] A graphene oxide modified ceramicizable protective heat insulation film of the application is prepared from the following raw materials by mass fraction: base glue 100 parts, graphene oxide modifier 3 parts, ceramicizable flame-retardant filler 50 parts, heat insulation filler 6 parts, and auxiliary agent 2 parts.

[0066] In the embodiment, the base glue is methyl vinyl silicone rubber.

[0067] In the embodiment, the graphene oxide is multi-layer graphene oxide with a thickness of 3nm and a flake diameter (referring to the maximum length of flaky material) of 5μm.

[0068] In the embodiment, the heat insulation filler is GS46 soda lime borosilicate glass hollow microsphere of Zhonggang New Material.

[0069] In the embodiment, the auxiliary agent is obtained by mixing silane coupling agent of morning light new material KH550, German Degao 270 siloxane wetting agent, German Degao 652D dispersant and Eastman CAB 381-0.5 orienting agent according to a mass ratio of 5:1:1:2.

[0070] The solvent of the embodiment is a mixed solvent of xylene, methanol and solvent oil, the mass ratio of xylene, methanol and solvent oil is 7:2:1, the solvent oil is 120# solvent oil, and the solvent is a selectable material in the process, which does not remain in the final product.

[0071] The graphene oxide modifier of the embodiment is obtained by coating the above multi-layer graphene oxide and nano silicon carbide powder, wherein the mass of the nano silicon carbide powder is 30% of the mass of the multi-layer graphene oxide, the average particle size of the nano silicon carbide powder is 90nm, the coating device is a stirring type solid coating machine, and the coating time is 30min.

[0072] The ceramicizable flame-retardant filler of the present embodiment comprises, in parts by mass, 10 parts of organically modified montmorillonite, 8 parts of wollastonite powder, 10 parts of fumed white carbon black, 20 parts of aluminum hydroxide powder, 5 parts of boron oxide powder, 5 parts of aluminum oxide powder, 10 parts of mica powder, and 5 parts of silicon carbide powder.

[0073] A preparation method of the graphene oxide modified ceramicizable protective heat insulation film of the present embodiment comprises the following steps:

[0074] (1) A total of 50 kg of materials is taken according to the above mass parts. The ceramicizable flame-retardant filler, heat insulation filler, graphene oxide modifier, and solvent containing additives are sequentially added to the base glue under stirring conditions. An open mill is used to mix them thoroughly at room temperature. The viscosity is adjusted to 20,000-30,000 cps during the mixing process by dilution with solvent.

[0075] (2) The mixture prepared in step (1) is uniformly coated on the surface of a fluoroplastic release film using a doctor blade coater.

[0076] (3) The coated layer is dried and vulcanized through an oven, and then wound up for the next coating.

[0077] (4) Steps (2) and (3) are repeated until the target thickness is reached, and then the product is cut into a certain shape and size on a slitting machine.

[0078] In steps (2) and (3), the thickness of each coating layer should be controlled to be ≤0.2 mm.

[0079] The comma doctor blade coating method of the present embodiment is suitable for coating liquid with a viscosity of 5,000 cps or higher and a certain degree of flowability, especially for liquid with a certain amount of solid filler. The coating thickness can be adjusted, and the coating process has a certain coating precision. The force of the doctor blade during coating is parallel to the film surface, which can better ensure that the graphene in the product is arranged parallel to the film plane.

[0080] The graphene oxide modified ceramicizable protective heat insulation film prepared in the present embodiment has a thickness of 1.8 mm and a tensile strength of 6.1 MPa. The flame spray test shows that the film layer can be penetrated by the flame within 30 minutes when the flame surface temperature does not exceed 1,200℃, and the temperature on the cold side is less than 350℃ under the condition of free heat dissipation.

[0081] Comparative Example 1

[0082] A graphene oxide modified ceramifiable protective heat insulation film is basically the same as that of Example 1, with the only difference being that the graphene oxide modifier is graphene oxide without nano-silicon carbide powder coating treatment. The graphene oxide modified ceramifiable protective heat insulation film obtained has a thickness of 1.0 mm and a tensile strength of 3.2 MPa, and can ensure that the film layer is not penetrated by the flame within 30 minutes under the condition that the flame surface temperature is not more than 1200℃, and the temperature of the cold surface is not less than 370℃ under the condition of free heat dissipation.

[0083] Comparative Example 2:

[0084] A graphene oxide modified ceramifiable protective heat insulation film is basically the same as that of Example 1, with the only difference being that no glass hollow microbeads are added. The graphene oxide modified ceramifiable protective heat insulation film obtained has a thickness of 1.0 mm and a tensile strength of 5.2 MPa, and can ensure that the film layer is not penetrated by the flame within 30 minutes under the condition that the flame surface temperature is not more than 1200℃, and the temperature of the cold surface is not less than 400℃ under the condition of free heat dissipation.

[0085] Comparative Example 3:

[0086] A graphene oxide modified ceramifiable protective heat insulation film is basically the same as that of Example 1, with the only difference being that no directional agent is used in the additive. The graphene oxide modified ceramifiable protective heat insulation film obtained has a thickness of 1.0 mm and a tensile strength of 4.3 MPa, and can ensure that the film layer is not penetrated by the flame within 30 minutes under the condition that the flame surface temperature is not more than 1200℃, and the temperature of the cold surface is not less than 380℃ under the condition of free heat dissipation.

[0087] The above is only a preferred embodiment of the present application, and does not limit the present application in any form. Although the present application has been disclosed as above with a preferred embodiment, it is not intended to limit the present application. Any skilled person in the art can make many possible changes and modifications to the technical solution of the present application, or modify it as an equivalent embodiment, without departing from the spirit and technical solution of the present application, using the disclosed methods and technical contents. Therefore, any simple modification, equivalent replacement, equivalent change and modification of the above embodiments made in accordance with the technical essence of the present application, without departing from the technical solution of the present application, are still within the scope of protection of the present application.

Claims

1. A graphene oxide modified ceramifiable protective thermal barrier film, characterized in that, The graphene oxide modified ceramicizable flame-retardant protective heat insulation film is prepared from the following raw materials by a scraping process: base glue 100-200 parts, graphene oxide modifier 1-5 parts, ceramicizable flame-retardant filler 30-70 parts, heat insulation filler 5-20 parts, and auxiliary agent 1-3 parts; the graphene oxide modifier is graphene oxide coated with nano silicon carbide, the thickness of the graphene oxide modified ceramicizable protective heat insulation film is 1-3 mm; the auxiliary agent includes a directional agent; the graphene oxide is multilayer graphene oxide, the mass of the nano silicon carbide is 20-30% of the mass of the multilayer graphene oxide; the ceramicizable flame-retardant filler includes organic montmorillonite, wollastonite powder, fumed white carbon black, aluminum hydroxide powder, boron oxide powder, aluminum oxide powder, mica powder, and silicon carbide powder; the heat insulation filler is at least one of soda lime borosilicate glass hollow microsphere, zirconium oxide hollow microsphere, zirconium oxide porous microsphere, aluminum oxide hollow microsphere, and aluminum oxide porous microsphere; the base glue is at least one of methyl vinyl silicone rubber, methyl silicone rubber, and methyl phenyl vinyl silicone rubber. The preparation method of the graphene oxide modified ceramicizable protective heat insulation film comprises the following steps: (1) mixing the ceramicizable flame-retardant filler, heat insulation filler, graphene oxide modifier, and auxiliary agent with the base glue under stirring to obtain a mixture; (2) forming a coating layer on a substrate by scraping the mixture using a scraping process; (3) drying and vulcanizing the coating layer and then winding it for the next scraping; (4) repeating steps (2) and (3) until the target thickness is reached; In step (1), the mixture is diluted with a solvent to adjust the viscosity to 20,000-30,000 cps, the solvent is a mixed solvent of xylene, methanol, and solvent oil, and the mass ratio of xylene, methanol, and solvent oil is 6-8:2:1; in steps (2) and (3), the thickness of the coating layer scraped each time is ≤0.2 mm.

2. The graphene oxide modified ceramifiable protective thermal barrier film according to claim 1, wherein, The thickness of the multilayer graphene oxide is 1-5 nm, and the flake diameter of the multilayer graphene oxide is 3-10 μm; the average particle size of the nano silicon carbide is 70-100 nm.

3. The graphene oxide modified ceramifiable protective thermal barrier film according to claim 1, wherein, The auxiliary agent further includes a coupling agent, wetting agent, and dispersant, and the mass ratio of the coupling agent, wetting agent, dispersant, and directional agent is 5-6:1:1:1.5-2.5; the coupling agent is an organic silicon coupling agent, the wetting agent is an organic silicon wetting agent, the dispersant is an organic silicon dispersant, and the directional agent is a cellulose directional agent.

4. The graphene oxide modified ceramifiable protective thermal barrier film according to claim 1, wherein, The heat insulation filler is a mixture of soda lime borosilicate glass hollow microspheres and metal oxide microspheres in a volume ratio of 50-70:20-40, the diameters of the soda lime borosilicate glass hollow microspheres and the metal oxide microspheres are both ≤50 μm, and the metal oxide microspheres are at least one of zirconium oxide hollow microspheres, zirconium oxide porous microspheres, aluminum oxide hollow microspheres, and aluminum oxide porous microspheres.

5. The graphene oxide modified ceramifiable protective thermal barrier film according to any one of claims 1 to 4, characterized in that, The organic montmorillonite is 5-20 parts, the wollastonite powder is 2-10 parts, the fumed white carbon black is 10-50 parts, the aluminum hydroxide powder is 10-50 parts, the boron oxide powder is 1-5 parts, the aluminum oxide powder is 1-10 parts, the mica powder is 5-10 parts, and the silicon carbide powder is 1-10 parts.

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