WO2023060739A1 - Self-healing electromagnetic shielding material, preparation method therefor and application thereof - Google Patents

Self-healing electromagnetic shielding material, preparation method therefor and application thereof Download PDF

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WO2023060739A1
WO2023060739A1 PCT/CN2021/137307 CN2021137307W WO2023060739A1 WO 2023060739 A1 WO2023060739 A1 WO 2023060739A1 CN 2021137307 W CN2021137307 W CN 2021137307W WO 2023060739 A1 WO2023060739 A1 WO 2023060739A1
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graphene
electromagnetic shielding
carbon fiber
resin layer
shielding material
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PCT/CN2021/137307
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French (fr)
Chinese (zh)
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胡友根
张浩睿
张陆辉
赵泽宇
韦剑鸿
田锭坤
孙蓉
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中国科学院深圳先进技术研究院
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    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/009—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
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    • C08L2201/04—Antistatic

Definitions

  • the invention relates to the technical field of electromagnetic materials, in particular to a self-healing electromagnetic shielding material and its preparation method and application.
  • Electromagnetic pollution caused by excessive electromagnetic waves will not only affect the accuracy and normal operation of the instrument, but also It will cause harm to the human body, so electromagnetic shielding materials have received more and more attention.
  • electromagnetic shielding materials Compared with traditional metal electromagnetic shielding materials, the advantages of conductive composite materials such as low density, easy processing and functional diversification make them have important application prospects in the pursuit of smaller, lighter and more flexible mobile phones and other portable devices.
  • CN107286591A discloses a kind of preparation method of polythiophene graphene composite electromagnetic material, its disclosed method is the solvent of polymerization reaction with the amide aqueous solution of monomer, graphene oxide, and graphene oxide also participates in the polymerization reaction of thiophene, effectively It improves the compatibility of graphene oxide and polythiophene, effectively reduces agglomeration, and promotes the stability and strength of finished products.
  • CN108192315A discloses an electromagnetic shielding composite material for vehicle instrumentation housings and a preparation method thereof, which belongs to the field of material processing technology.
  • the disclosed composite material is made of the following components in parts by weight: 60-85 parts of thermoplastic resin, 15 parts ⁇ 30 parts of conductive filler, 1.2 ⁇ 2 parts of toughening agent, 0.3 ⁇ 3 parts of coupling agent, 0.5 ⁇ 8 parts of flame retardant, 0.4 ⁇ 3 parts of dispersant, 0.4 ⁇ 1.2 parts of antioxidant, 0.3 ⁇ 0.5 parts of lubrication agent and 0 to 1.5 parts of antibacterial agent.
  • the composite material is used to prepare vehicle instrumentation housings, which can absorb and attenuate electromagnetic radiation permanently and have the advantages of high strength, corrosion resistance, impact resistance, flame retardancy, heat conduction and bacteriostasis. Moreover, the method is simple to operate, has no special requirements on equipment, and is suitable for large-scale production.
  • a single graphene composite material cannot obtain good electromagnetic shielding performance due to its low filling rate and poor electrical conductivity; while a single carbon fiber composite material will release a large amount of heat in a microwave environment due to its good electrical conductivity, causing the material to be blocked. destroy.
  • the object of the present invention is to provide a self-healing electromagnetic shielding material and its preparation method and application, the electromagnetic shielding material has excellent self-healing function, electromagnetic shielding performance and electrical conductivity .
  • the present invention provides a self-healing electromagnetic shielding material, which includes a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
  • the electromagnetic shielding material of the present invention uses thermoplastic resin as the matrix material, graphene and carbon fiber materials are respectively used as conductive filling materials, the upper and lower layers are graphene resin layers, and the middle layer is a carbon fiber material resin layer, which has a sandwich structure; on the one hand, graphite The graphene resin layer can protect the internal carbon fiber material resin layer, reduce its damage during use, and prevent combustion under microwave irradiation or other similar conditions; on the other hand, the graphene resin layer can also be used under microwave irradiation or other similar conditions. The self-healing phenomenon occurs under similar conditions, and the heat transfer drives the internal carbon fiber material resin layer to heal, repairs the conductive network of the material, and restores good electromagnetic shielding performance.
  • the carbon fiber material resin layer is used as the electromagnetic shielding performance providing layer of the material, which can significantly improve the electrical conductivity of the material, enhance the material's ability to reflect electromagnetic waves, and its conductive network is through the overlapping of carbon fiber materials. Formation, good reconnection of the conductive network after self-healing, can restore good electromagnetic shielding performance.
  • the thickness of the first graphene resin layer is 80 ⁇ m-160 ⁇ m, such as 80 ⁇ m, 100 ⁇ m, 120 ⁇ m, 140 ⁇ m, 160 ⁇ m and so on.
  • the carbon fiber material resin layer has a thickness of 80 ⁇ m-150 ⁇ m, such as 80 ⁇ m, 100 ⁇ m, 120 ⁇ m, 140 ⁇ m and the like.
  • the thickness of the second graphene resin layer is 80 ⁇ m-160 ⁇ m, such as 80 ⁇ m, 100 ⁇ m, 120 ⁇ m, 140 ⁇ m, 160 ⁇ m and so on.
  • the graphene resin layer comprises: 1%-10% (such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.) graphene and 90% by mass percentage %-99% (eg, 91%, 92%, 93%, 94%, 95%, 93%, 97%, 98%, etc.) thermoplastic resin.
  • the carbon fiber material resin layer comprises: 10%-60% (such as 20%, 30%, 40%, 50%, etc.) carbon fiber material and 40%-90% (such as 50%, 60%, 70%, 80%, etc.) thermoplastic resin.
  • the graphene includes single-layer graphene and/or multi-layer graphene.
  • the graphene includes any one or a combination of at least two of modified graphene oxide, unmodified graphene oxide or reduced graphene oxide, wherein typical but non-limiting combinations include: modified combination of non-modified graphene oxide and unmodified graphene oxide, combination of unmodified graphene oxide and reduced graphene oxide, modified graphene oxide, unmodified graphene oxide and reduced graphene oxide combinations etc.
  • the carbon fiber material includes any one or a combination of at least two of carbon fibers, carbon nanofibers or carbon nanotubes.
  • the thermoplastic resin includes thermoplastic polyurethane and its derivatives, polyethylene and its derivatives, polypropylene and its derivatives, polyvinyl chloride and its derivatives, polystyrene and its derivatives, polymethacrylate Any one or a combination of at least two of esters and their derivatives, polyoxymethylene and its derivatives, polyamide and its derivatives, polycarbonate and its derivatives, or polytetrafluoroethylene and its derivatives.
  • the present invention provides a method for preparing the self-healing electromagnetic shielding material described in the first aspect, the preparation method comprising the following steps:
  • thermoplastic resin and graphene are dissolved in organic solvent respectively, form thermoplastic resin solution and graphene dispersion liquid;
  • Step 2 mixing the graphene dispersion liquid and the carbon fiber material with the thermoplastic resin solution respectively to form a graphene conductive paste and a carbon fiber material conductive paste;
  • Step 3 coating the graphene conductive paste on the substrate, drying to obtain the first graphene resin layer;
  • the graphene conductive paste is coated on the carbon fiber material resin layer and dried to obtain the electromagnetic shielding material.
  • the invention can prepare the material with both excellent self-healing ability and electromagnetic shielding performance by adopting step-by-step coating and drying methods, and has simple process, convenient manufacture and low cost.
  • the organic solvent includes any one or a combination of at least two of aromatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents, ester organic solvents, ketone organic solvents or amide organic solvents, Typical but non-limiting combinations include: amide organic solvents, aromatic hydrocarbon organic solvents and aliphatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents and ester organic solvents, aromatic hydrocarbon organic solvents, aliphatic hydrocarbon Combinations of organic solvents, ester organic solvents and ketone organic solvents, etc.
  • the organic solvent includes any one of N,N-dimethylformamide, benzene, toluene, xylene, methyl acetate, ethyl acetate, acetone, methyl butanone or methyl isobutyl ketone or a combination of at least two, where typical but non-limiting combinations include: N,N-dimethylformamide and benzene, toluene, xylene and methyl acetate, ethyl acetate, acetone, methyl Combinations of butanone and methyl isobutyl ketone, etc.
  • the mass ratio of the graphene to the organic solvent is 1:(9-49), wherein 9-49 can be 10, 15, 20, 25, 30, 35, 40, 45, etc.
  • the mass ratio of the thermoplastic resin to the organic solvent is 1:(1-9), wherein 1-9 can be 2, 3, 4, 5, 6, 7, 8, etc.
  • the drying method in step 1, step 2 and step 3 includes heating.
  • the heating temperatures in step 1, step 2 and step 3 are each independently 60-120°C, such as 70°C, 80°C, 90°C, 100°C, 110°C, etc.
  • the heating time is each independently 1-4h, such as 2.5h, 3h, 3.5h and so on.
  • the present invention provides an application of the self-healing electromagnetic shielding material described in the first aspect in electronic equipment.
  • the present invention has the following beneficial effects:
  • the electromagnetic shielding material of the invention has excellent self-healing function, electromagnetic shielding performance and conductive performance.
  • the upper and lower layers of the electromagnetic shielding material of the present invention are graphene resin layers, and the middle layer is a carbon fiber material resin layer.
  • the electromagnetic shielding material can provide excellent self-healing properties , and the self-healing speed is fast under microwave irradiation;
  • the carbon fiber material resin layer that the present invention exerts the electromagnetic shielding function is located in the middle layer, and when the thickness is low, good electromagnetic shielding performance can be provided, and the reconnection of the conductive network after self-healing is good, and after self-healing Still has good electrical conductivity and electromagnetic shielding performance;
  • the electromagnetic shielding material of the present invention has a high elongation at break, exhibits good stretchability and flexibility, and can withstand large deformations, such as stretching, bending, folding, winding and twisting;
  • the preparation method of the present invention has simple process, convenient manufacture and low cost
  • the thickness of the first graphene resin layer and the second graphene resin layer is in the range of 80 ⁇ m-160 ⁇ m, and the carbon fiber material resin layer is in the range of 80 ⁇ m-150 ⁇ m, the electromagnetic shielding performance of the initial sample is above 29.6dB, self-healing The electromagnetic shielding performance of the combined sample is above 24dB; the conductivity of the initial sample is above 720S/m, and the conductivity of the self-healing sample is above 310S/m; the self-healing speed is within 10s.
  • Fig. 1 is the scanning electron micrograph of the cross-sectional structure of the electromagnetic shielding material described in embodiment 1;
  • Fig. 2 a is the scanning electron micrograph of the initial sample fracture state of the electromagnetic shielding material described in embodiment 2;
  • Fig. 2b is the scanning electron micrograph of the self-healing sample of the electromagnetic shielding material described in Example 2;
  • Fig. 3 is the initial sample of the electromagnetic shielding material described in embodiment 3 and the stress-strain diagram of the sample after self-healing;
  • Fig. 4 is a diagram of the electromagnetic shielding performance of the initial sample and the self-healed sample of the electromagnetic shielding material described in Example 3.
  • This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
  • the thickness is 100 ⁇ m, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455- 203;
  • the thickness is 120 ⁇ m, and it is composed of 40% carbon fiber material and 60% thermoplastic resin in mass percentage.
  • the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455-203.
  • the carbon fiber material is carbon fiber;
  • the thickness is 100 ⁇ m, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, the trade mark is PS455 -20.
  • the preparation method of the electromagnetic shielding material comprises the following steps:
  • Thermoplastic polyurethane and graphene oxide were dissolved in N, N-dimethylformamide, respectively, to prepare a graphene dispersion with a mass fraction of graphene oxide of 2% and a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%. Sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
  • Step 2 preparing graphene conductive paste and carbon fiber material conductive paste
  • Step 3 preparing electromagnetic shielding material
  • the graphene conductive paste is coated on the carbon fiber material resin layer, heated and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
  • This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
  • the thickness is 150 ⁇ m, and it is composed of 5% graphene oxide and 95% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, which is purchased from Huntsman, and the grade is PS455- 203;
  • the carbon fiber material resin layer has a thickness of 100 ⁇ m and is composed of 20% by mass of carbon fiber material and 80% of thermoplastic resin.
  • the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455-203.
  • the carbon fiber material is carbon fiber;
  • the thickness is 150 ⁇ m, and it is composed of 5% graphene oxide and 95% thermoplastic resin by mass percentage.
  • the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the trade mark is PS455 -203.
  • the preparation method of the electromagnetic shielding material comprises the following steps:
  • Thermoplastic polyurethane and graphene oxide were dissolved in N, N-dimethylformamide, respectively, to prepare a graphene dispersion with a mass fraction of graphene oxide of 2% and a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%. Sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
  • Step 2 preparing graphene conductive paste and carbon fiber material conductive paste
  • Step 3 preparing electromagnetic shielding material
  • the graphene conductive paste is coated on the carbon fiber material resin layer, heated and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
  • This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
  • the thickness is 120 ⁇ m, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455- 203;
  • the carbon fiber material resin layer has a thickness of 100 ⁇ m and is composed of 33.3% by mass of carbon fiber material and 66.7% of thermoplastic resin.
  • the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the brand name is PS455-203.
  • the carbon fiber material is carbon fiber;
  • the thickness is 120 ⁇ m, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage.
  • the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the trade mark is PS455 -203.
  • the preparation method of the electromagnetic shielding material comprises the following steps:
  • Thermoplastic polyurethane and graphene oxide were dissolved in N,N-dimethylformamide respectively to prepare graphene dispersion with 10% mass fraction of graphene oxide and thermoplastic resin solution with 20% mass fraction of thermoplastic polyurethane. Sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
  • Step 2 preparing graphene conductive paste and carbon fiber material conductive paste
  • Step 3 preparing electromagnetic shielding material
  • the graphene conductive paste is coated on the carbon fiber material resin layer, heated and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
  • This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
  • the thickness is 160 ⁇ m, and it is composed of 1% reduced graphene oxide and 99% thermoplastic resin in mass percentage, and the thermoplastic resin is polymethyl methacrylate with a mass ratio of 1:1.
  • thermoplastic resin is polymethyl methacrylate with a mass ratio of 1:1.
  • a mixture of ester and polyamide, polymethyl methacrylate is purchased from Yuso, the brand is CM211, and polyamide is purchased from DuPont, the brand is PA66;
  • the carbon fiber material resin layer has a thickness of 100 ⁇ m and is composed of 10% by mass of carbon fiber material and 90% of thermoplastic resin.
  • the thermoplastic resin is polytetrafluoroethylene, purchased from DuPont, and the brand is MT1000.
  • the carbon fiber The material is carbon nanofiber;
  • the thickness is 160 ⁇ m, and it is composed of 1% reduced graphene oxide and 99% thermoplastic resin in mass percentage, and the thermoplastic resin is polymethacrylic acid with a mass ratio of 1:1
  • thermoplastic resin is polymethacrylic acid with a mass ratio of 1:1
  • a mixture of methyl ester and polyamide, polymethyl methacrylate is purchased from Yuso, the brand is CM211, and polyamide is purchased from DuPont, the brand is PA66.
  • the preparation method of the electromagnetic shielding material comprises the following steps:
  • thermoplastic resin was dissolved in toluene, and the reduced graphene oxide was dissolved in ethyl acetate to prepare a graphene dispersion with a mass fraction of 5% and a thermoplastic resin solution with a mass fraction of 50%, and ultrasonicated in an ultrasonic cell disruptor. 60min, until the thermoplastic resin is completely dissolved and the graphene is uniformly dispersed;
  • Step 2 preparing graphene conductive paste and carbon fiber material conductive paste
  • Step 3 preparing electromagnetic shielding material
  • the graphene conductive paste was coated on the resin layer of the carbon fiber material, and dried by heating at 120° C. for 1 hour to obtain the electromagnetic shielding material.
  • This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
  • the thickness is 130 ⁇ m, and it is composed of 10% graphene oxide and 90% thermoplastic resin in mass percentage, and the thermoplastic resin is polyethylene and polycarbonate with a mass ratio of 1:2
  • the thickness is 90 ⁇ m, and the mass percentage is 10% carbon fiber material and 90% thermoplastic resin.
  • the thermoplastic resin is polyoxymethylene, purchased from TYSTRON, and the brand is POM4250.
  • the carbon fiber material is carbon nanotubes;
  • the thickness is 130 ⁇ m, and it is composed of 5% graphene oxide and 95% thermoplastic resin in mass percentage, and the thermoplastic resin is polyvinyl chloride and polyvinyl chloride with a mass ratio of 1:1.
  • the mixture of styrene, polyvinyl chloride was purchased from Tianye Company, the brand is pvc-sg5, and polystyrene was purchased from Chimei Chemical, the brand is PG-33.
  • the preparation method of the electromagnetic shielding material comprises the following steps:
  • Graphene oxide is dissolved in acetone and methyl acetate with a mass ratio of 1:1, and the thermoplastic resins required for each layer are dissolved in methyl butanone respectively to prepare a graphene dispersion with a mass fraction of 2% and The thermoplastic resin solution with a mass fraction of 90% is ultrasonicated in an ultrasonic cell disruptor for 60 minutes until the thermoplastic resin is completely dissolved and the graphene is uniformly dispersed;
  • Step 2 preparing graphene conductive paste and carbon fiber material conductive paste
  • Step 3 preparing electromagnetic shielding material
  • the second graphene conductive paste was coated on the resin layer of the carbon fiber material, and dried by heating at 60° C. for 4 hours to obtain the electromagnetic shielding material.
  • embodiment 6-9 The difference between embodiment 6-9 and embodiment 1 is that the thickness of the first graphene resin layer is respectively 50 ⁇ m (embodiment 6), 200 ⁇ m (embodiment 7), 80 ⁇ m (embodiment 8) and 160 ⁇ m (embodiment 9), All the other are identical with embodiment 1.
  • Example 10 The difference between Examples 10-13 and Example 1 is that the thickness of the carbon fiber material resin layer is 50 ⁇ m (Example 10), 200 ⁇ m (Example 11), 80 ⁇ m (Example 12) and 150 ⁇ m (Example 13), and the rest are all Same as Example 1.
  • Example 1 The difference between this comparative example and Example 1 is that the electromagnetic shielding material does not have the "sandwich structure" described in Example 1, which is composed of carbon fiber, graphene oxide and thermoplastic resin, and the addition amount of each component is the same as that of Example 1 .
  • the preparation method of the above-mentioned electromagnetic shielding material comprises the following steps:
  • Thermoplastic polyurethane and graphene oxide were dissolved in N,N-dimethylformamide, respectively, to prepare a graphene dispersion with a mass fraction of graphene of 2% and a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%. Sonicate in the cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
  • Step 2 preparing graphene conductive paste and carbon fiber material conductive paste
  • Step 3 preparing electromagnetic shielding material
  • the conductive paste was coated on the substrate, and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
  • Example 1 The difference between this comparative example and Example 1 is that the electromagnetic shielding material only contains a carbon fiber material resin layer.
  • the preparation method of the above-mentioned electromagnetic shielding material comprises the following steps:
  • thermoplastic polyurethane Dissolve thermoplastic polyurethane in N,N-dimethylformamide to prepare a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%, and sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved;
  • Step 2 preparing graphene conductive paste and carbon fiber material conductive paste
  • Step 3 preparing electromagnetic shielding material
  • Electromagnetic shielding performance the electromagnetic shielding effectiveness test is carried out by the vector network analyzer (Keysight E5071C) waveguide method;
  • the electromagnetic shielding material of the structure of the present invention has both Excellent self-healing performance, electromagnetic shielding performance and electrical conductivity; when the thickness of the first graphene resin layer and the second graphene resin layer are in the range of 80 ⁇ m-160 ⁇ m, and the carbon fiber material resin layer is in the range of 80 ⁇ m-150 ⁇ m, the initial The electromagnetic shielding performance of the sample is above 29.6dB, and the electromagnetic shielding performance of the sample after self-healing is above 24dB; the conductivity of the initial sample is above 720S/m, and the conductivity of the sample after self-healing is above 310S/m; self-healing Combined speed is within 10s.
  • Comparative Example 1 shows that the performance of Comparative Example 1 is not as good as that of Example 1, which proves that the electromagnetic shielding material with a "sandwich" structure has better performance.
  • Comparative Example 2 shows that the performance of Comparative Example 2 is not as good as that of Example 1, which proves that the electromagnetic shielding material formed by a single graphene or carbon fiber material has poor performance.
  • Examples 6-9 shows that the performance of Examples 6-7 is not as good as that of Examples 8-9, which proves that the performance of the electromagnetic shielding material formed by the thickness of the first graphene resin layer in the range of 80 ⁇ m-160 ⁇ m is better, and the performance of the second graphene resin layer is better. Layers are the same.
  • Examples 10-13 shows that the performance of Examples 10-11 is not as good as that of Examples 12-13, which proves that the performance of the electromagnetic shielding material formed by the carbon fiber material resin layer in the range of 80 ⁇ m-150 ⁇ m is better.
  • Example 1 successfully prepared an electromagnetic shielding material with a "sandwich" structure.
  • the electromagnetic shielding material with the structure of the present invention has excellent self-healing performance in microstructure.
  • the elongation at break of the electromagnetic shielding material with the structure of the present invention is not very different before and after self-healing, which proves that the electromagnetic shielding material with the structure of the present invention has excellent self-healing performance, and the elongation before and after self-healing
  • the high elongation at break of the material proves that the electromagnetic shielding material with the structure of the present invention exhibits good stretchability and flexibility, and can withstand large deformations, such as stretching, bending, folding, winding and twisting.
  • the electromagnetic shielding material with the structure of the present invention has higher electromagnetic shielding effectiveness before and after self-healing, which proves that the electromagnetic shielding material with the structure of the present invention has both excellent self-healing performance and electromagnetic shielding effectiveness.
  • the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Abstract

A self-healing electromagnetic shielding material, a preparation method therefor and an application thereof. The electromagnetic shielding material comprises a first graphene resin layer, a carbon fiber material resin layer, and a second graphene resin layer which are sequentially stacked. The electromagnetic shielding material has excellent self-healing function, electromagnetic shielding performance and conductivity.

Description

一种可自愈合的电磁屏蔽材料及其制备方法和应用A self-healing electromagnetic shielding material and its preparation method and application 技术领域technical field
本发明涉及电磁材料技术领域，尤其涉及一种可自愈合的电磁屏蔽材料及其制备方法和应用。The invention relates to the technical field of electromagnetic materials, in particular to a self-healing electromagnetic shielding material and its preparation method and application.
背景技术Background technique
电子行业的快速发展以及手机、电脑等电子设备在生活中的广泛应用，使得电磁污染的问题越来越被人们所重视，过量的电磁波造成的电磁污染不仅会影响仪器的精度和正常运行，还会对人体造成危害，因此电磁屏蔽材料得到了越来越多的关注。与传统金属电磁屏蔽材料相比，导电复合材料的低密度、易加工和功能性多样化等优点使得其在对手机等便携设备追求更小、更轻薄和柔性方面具有重要的应用前景。The rapid development of the electronics industry and the wide application of electronic devices such as mobile phones and computers in daily life have made the problem of electromagnetic pollution more and more people's attention. Electromagnetic pollution caused by excessive electromagnetic waves will not only affect the accuracy and normal operation of the instrument, but also It will cause harm to the human body, so electromagnetic shielding materials have received more and more attention. Compared with traditional metal electromagnetic shielding materials, the advantages of conductive composite materials such as low density, easy processing and functional diversification make them have important application prospects in the pursuit of smaller, lighter and more flexible mobile phones and other portable devices.
由于电子元件在使用过程中会经常受到碰撞与磨损，表面的电磁屏蔽材料会遭到一定程度的破坏，这时电磁波会从破损的缺陷处泄露，材料的电磁屏蔽性能会出现明显的下降，影响电子设备的稳定运行。自愈合电磁屏蔽材料可以在特定条件下产生自愈合现象，修复材料的缺陷，减少电磁波的泄露，延长电子元件的使用寿命。证明了石墨烯在微波照射下会产生适当的热量，在与热塑性树脂复合后具有良好的自愈合效果。Since electronic components are often subject to collision and wear during use, the electromagnetic shielding material on the surface will be damaged to a certain extent. At this time, electromagnetic waves will leak from the damaged defect, and the electromagnetic shielding performance of the material will decline significantly. Stable operation of electronic equipment. Self-healing electromagnetic shielding materials can produce self-healing phenomena under specific conditions, repair material defects, reduce electromagnetic wave leakage, and prolong the service life of electronic components. It is proved that graphene can generate proper heat under microwave irradiation and has good self-healing effect after compounding with thermoplastic resin.
CN107286591A公开了一种聚噻吩石墨烯复合电磁材料的制备方法，其公开的方法以单体、氧化石墨烯的酰胺水溶液为聚合反应的溶剂，将氧化石墨烯也参与到噻吩的聚合反应中，有效的改善了氧化石墨烯与聚噻吩的相容性，有效地降低了团聚，促进了成品的稳定性强度。CN107286591A discloses a kind of preparation method of polythiophene graphene composite electromagnetic material, its disclosed method is the solvent of polymerization reaction with the amide aqueous solution of monomer, graphene oxide, and graphene oxide also participates in the polymerization reaction of thiophene, effectively It improves the compatibility of graphene oxide and polythiophene, effectively reduces agglomeration, and promotes the stability and strength of finished products.
CN108192315A公开了一种车辆仪器仪表壳体用电磁屏蔽复合材料及其制备方法，属于材料加工技术领域，其公开的复合材料按重量份计，由以下成分制成：60～85份热塑性树脂，15～30份导电填料，1.2～2份增韧剂，0.3～3份偶联剂，0.5～8份阻燃剂，0.4～3份分散剂，0.4～1.2份抗氧剂，0.3～0.5份润滑剂和0～1.5份抗菌剂。将该复合材料用于制备车辆仪器仪表壳体，该壳体能够具有持久地吸收和衰减电磁辐射并同时具有高强度、耐腐蚀、抗冲击、 阻燃、导热及抑菌的优点。且该方法操作简单，对设备无特殊要求，适合大规模生产。CN108192315A discloses an electromagnetic shielding composite material for vehicle instrumentation housings and a preparation method thereof, which belongs to the field of material processing technology. The disclosed composite material is made of the following components in parts by weight: 60-85 parts of thermoplastic resin, 15 parts ～30 parts of conductive filler, 1.2～2 parts of toughening agent, 0.3～3 parts of coupling agent, 0.5～8 parts of flame retardant, 0.4～3 parts of dispersant, 0.4～1.2 parts of antioxidant, 0.3～0.5 parts of lubrication agent and 0 to 1.5 parts of antibacterial agent. The composite material is used to prepare vehicle instrumentation housings, which can absorb and attenuate electromagnetic radiation permanently and have the advantages of high strength, corrosion resistance, impact resistance, flame retardancy, heat conduction and bacteriostasis. Moreover, the method is simple to operate, has no special requirements on equipment, and is suitable for large-scale production.
但是单独的石墨烯复合材料由于填充率不高导电性较差，无法得到良好的电磁屏蔽性能；而单独的碳纤维复合材料由于导电性较好，在微波环境中会释放大量的热，导致材料被破坏。However, a single graphene composite material cannot obtain good electromagnetic shielding performance due to its low filling rate and poor electrical conductivity; while a single carbon fiber composite material will release a large amount of heat in a microwave environment due to its good electrical conductivity, causing the material to be blocked. destroy.
因此，如何使材料同时具有自愈合功能和良好的电磁屏蔽性能是一个值得被关注的问题。Therefore, how to make materials with self-healing function and good electromagnetic shielding performance is a problem worthy of attention.
发明内容Contents of the invention
针对现有技术的不足，本发明的目的在于提供一种可自愈合的电磁屏蔽材料及其制备方法和应用，所述电磁屏蔽材料兼具优异的自愈合功能、电磁屏蔽性能和导电性能。In view of the deficiencies in the prior art, the object of the present invention is to provide a self-healing electromagnetic shielding material and its preparation method and application, the electromagnetic shielding material has excellent self-healing function, electromagnetic shielding performance and electrical conductivity .
为达此目的，本发明采用以下技术方案：For reaching this purpose, the present invention adopts following technical scheme:
第一方面，本发明提供一种可自愈合的电磁屏蔽材料，所述电磁屏蔽材料包括依次层叠设置的第一石墨烯树脂层、碳纤维材料树脂层和第二石墨烯树脂层。In a first aspect, the present invention provides a self-healing electromagnetic shielding material, which includes a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
本发明所述电磁屏蔽材料以热塑性树脂作为基体材料，石墨烯和碳纤维材料分别作为导电填充材料，上下两层为石墨烯树脂层，中间层为碳纤维材料树脂层，具有三明治结构；一方面，石墨烯树脂层可以保护内部的碳纤维材料树脂层，减轻其在使用时受到的破坏，防止微波炉照射或其他类似条件下产生燃烧的现象；另一方面，石墨烯树脂层还可以在微波照射下或其他类似条件下产生自愈合现象，传递热量带动内部的碳纤维材料树脂层愈合，修复材料的导电网络，恢复良好的电磁屏蔽性能。除此之外，采用碳纤维材料树脂层作为所述材料的电磁屏蔽性能提供层，可以明显提升材料的导电性能，增强材料对电磁波的反射能力，并且其导电网络是通过碳纤维材料之间的搭接形成，在自愈合后导电网络的重新连接良好，可以恢复良好的电磁屏蔽性能。The electromagnetic shielding material of the present invention uses thermoplastic resin as the matrix material, graphene and carbon fiber materials are respectively used as conductive filling materials, the upper and lower layers are graphene resin layers, and the middle layer is a carbon fiber material resin layer, which has a sandwich structure; on the one hand, graphite The graphene resin layer can protect the internal carbon fiber material resin layer, reduce its damage during use, and prevent combustion under microwave irradiation or other similar conditions; on the other hand, the graphene resin layer can also be used under microwave irradiation or other similar conditions. The self-healing phenomenon occurs under similar conditions, and the heat transfer drives the internal carbon fiber material resin layer to heal, repairs the conductive network of the material, and restores good electromagnetic shielding performance. In addition, the carbon fiber material resin layer is used as the electromagnetic shielding performance providing layer of the material, which can significantly improve the electrical conductivity of the material, enhance the material's ability to reflect electromagnetic waves, and its conductive network is through the overlapping of carbon fiber materials. Formation, good reconnection of the conductive network after self-healing, can restore good electromagnetic shielding performance.
优选地，所述第一石墨烯树脂层的厚度为80μm-160μm，例如80μm、100 μm、120μm、140μm、160μm等。Preferably, the thickness of the first graphene resin layer is 80 μm-160 μm, such as 80 μm, 100 μm, 120 μm, 140 μm, 160 μm and so on.
优选地，所述碳纤维材料树脂层的厚度为80μm-150μm，例如80μm、100μm、120μm、140μm等。Preferably, the carbon fiber material resin layer has a thickness of 80 μm-150 μm, such as 80 μm, 100 μm, 120 μm, 140 μm and the like.
优选地，所述第二石墨烯树脂层的厚度为80μm-160μm，例如80μm、100μm、120μm、140μm、160μm等。Preferably, the thickness of the second graphene resin layer is 80 μm-160 μm, such as 80 μm, 100 μm, 120 μm, 140 μm, 160 μm and so on.
优选地，所述石墨烯树脂层按照质量百分数包括：1％-10％(例如2％、3％、4％、5％、6％、7％、8％、9％等)石墨烯和90％-99％(例如91％、92％、93％、94％、95％、93％、97％、98％等)热塑性树脂。Preferably, the graphene resin layer comprises: 1%-10% (such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.) graphene and 90% by mass percentage %-99% (eg, 91%, 92%, 93%, 94%, 95%, 93%, 97%, 98%, etc.) thermoplastic resin.
优选地，所述碳纤维材料树脂层按照质量百分数包括：10％-60％(例如20％、30％、40％、50％等)碳纤维材料和40％-90％(例如50％、60％、70％、80％等)热塑性树脂。Preferably, the carbon fiber material resin layer comprises: 10%-60% (such as 20%, 30%, 40%, 50%, etc.) carbon fiber material and 40%-90% (such as 50%, 60%, 70%, 80%, etc.) thermoplastic resin.
优选地，所述石墨烯包括单层石墨烯和/或多层石墨烯。Preferably, the graphene includes single-layer graphene and/or multi-layer graphene.
优选地，所述石墨烯包括改性的氧化石墨烯、未改性的氧化石墨烯或还原氧化石墨烯中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：改性的氧化石墨烯和未改性的氧化石墨烯的组合，未改性的氧化石墨烯和还原氧化石墨烯的组合，改性的氧化石墨烯、未改性的氧化石墨烯和还原氧化石墨烯的组合等。Preferably, the graphene includes any one or a combination of at least two of modified graphene oxide, unmodified graphene oxide or reduced graphene oxide, wherein typical but non-limiting combinations include: modified combination of non-modified graphene oxide and unmodified graphene oxide, combination of unmodified graphene oxide and reduced graphene oxide, modified graphene oxide, unmodified graphene oxide and reduced graphene oxide combinations etc.
优选地，所述碳纤维材料包括碳纤维、碳纳米纤维或碳纳米管中的任意一种或至少两种的组合。Preferably, the carbon fiber material includes any one or a combination of at least two of carbon fibers, carbon nanofibers or carbon nanotubes.
优选地，所述热塑性树脂包括热塑性聚氨酯及其衍生物、聚乙烯及其衍生物、聚丙烯及其衍生物、聚氯乙烯及其衍生物、聚苯乙烯及其衍生物、聚甲基丙烯酸甲酯及其衍生物、聚甲醛及其衍生物、聚酰胺及其衍生物、聚碳酸酯及其衍生物或聚四氟乙烯及其衍生物中的任意一种或至少两种的组合。Preferably, the thermoplastic resin includes thermoplastic polyurethane and its derivatives, polyethylene and its derivatives, polypropylene and its derivatives, polyvinyl chloride and its derivatives, polystyrene and its derivatives, polymethacrylate Any one or a combination of at least two of esters and their derivatives, polyoxymethylene and its derivatives, polyamide and its derivatives, polycarbonate and its derivatives, or polytetrafluoroethylene and its derivatives.
第二方面，本发明提供一种第一方面所述的可自愈合的电磁屏蔽材料的制备方法，所述制备方法包括如下步骤：In a second aspect, the present invention provides a method for preparing the self-healing electromagnetic shielding material described in the first aspect, the preparation method comprising the following steps:
步骤1、将热塑性树脂和石墨烯分别溶解于有机溶剂中，形成热塑性树脂 溶液和石墨烯分散液；Step 1, thermoplastic resin and graphene are dissolved in organic solvent respectively, form thermoplastic resin solution and graphene dispersion liquid;
步骤2、将石墨烯分散液和碳纤维材料分别与热塑性树脂溶液混合，形成石墨烯导电浆料和碳纤维材料导电浆料；Step 2, mixing the graphene dispersion liquid and the carbon fiber material with the thermoplastic resin solution respectively to form a graphene conductive paste and a carbon fiber material conductive paste;
步骤3、将石墨烯导电浆料涂覆于基底上，干燥，得到第一石墨烯树脂层；Step 3, coating the graphene conductive paste on the substrate, drying to obtain the first graphene resin layer;
再将碳纤维材料导电浆料涂覆于第一石墨烯树脂层上，干燥，得到碳纤维材料树脂层；Then coating the carbon fiber material conductive paste on the first graphene resin layer and drying to obtain the carbon fiber material resin layer;
最后将石墨烯导电浆料涂覆于碳纤维材料树脂层上，干燥，得到所述电磁屏蔽材料。Finally, the graphene conductive paste is coated on the carbon fiber material resin layer and dried to obtain the electromagnetic shielding material.
本发明采用分步涂覆并干燥的方法即可制备出兼具优异的自愈合能力和电磁屏蔽性能的材料，工艺简单、制作方便且成本低廉。The invention can prepare the material with both excellent self-healing ability and electromagnetic shielding performance by adopting step-by-step coating and drying methods, and has simple process, convenient manufacture and low cost.
优选地，步骤1中，所述有机溶剂包括芳香烃类有机溶剂、脂肪烃类有机溶剂、酯类有机溶剂、酮类有机溶剂或酰胺类有机溶剂中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：酰胺类有机溶剂、芳香烃类有机溶剂和脂肪烃类有机溶剂的组合，脂肪烃类有机溶剂和酯类有机溶剂的组合，芳香烃类有机溶剂、脂肪烃类有机溶剂、酯类有机溶剂和酮类有机溶剂的组合等。Preferably, in step 1, the organic solvent includes any one or a combination of at least two of aromatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents, ester organic solvents, ketone organic solvents or amide organic solvents, Typical but non-limiting combinations include: amide organic solvents, aromatic hydrocarbon organic solvents and aliphatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents and ester organic solvents, aromatic hydrocarbon organic solvents, aliphatic hydrocarbon Combinations of organic solvents, ester organic solvents and ketone organic solvents, etc.
优选地，所述有机溶剂包括N,N-二甲基甲酰胺、苯、甲苯、二甲苯、醋酸甲酯、醋酸乙酯、丙酮、甲基丁酮或甲基异丁酮中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：N,N-二甲基甲酰胺和苯的组合，甲苯、二甲苯和醋酸甲酯的组合，醋酸乙酯、丙酮、甲基丁酮和甲基异丁酮的组合等。Preferably, the organic solvent includes any one of N,N-dimethylformamide, benzene, toluene, xylene, methyl acetate, ethyl acetate, acetone, methyl butanone or methyl isobutyl ketone or a combination of at least two, where typical but non-limiting combinations include: N,N-dimethylformamide and benzene, toluene, xylene and methyl acetate, ethyl acetate, acetone, methyl Combinations of butanone and methyl isobutyl ketone, etc.
优选地，步骤1中，所述石墨烯与有机溶剂的质量比为1:(9-49)，其中9-49可以为10、15、20、25、30、35、40、45等。Preferably, in step 1, the mass ratio of the graphene to the organic solvent is 1:(9-49), wherein 9-49 can be 10, 15, 20, 25, 30, 35, 40, 45, etc.
优选地，步骤1中，所述热塑性树脂与有机溶剂的质量比为1:(1-9)，其中1-9可以为2、3、4、5、6、7、8等。Preferably, in step 1, the mass ratio of the thermoplastic resin to the organic solvent is 1:(1-9), wherein 1-9 can be 2, 3, 4, 5, 6, 7, 8, etc.
优选地，步骤1、步骤2和步骤3中所述干燥的方式包括加热。Preferably, the drying method in step 1, step 2 and step 3 includes heating.
优选地，步骤1、步骤2和步骤3中所述加热的温度各自独立地为60-120℃， 例如70℃、80℃、90℃、100℃、110℃等。Preferably, the heating temperatures in step 1, step 2 and step 3 are each independently 60-120°C, such as 70°C, 80°C, 90°C, 100°C, 110°C, etc.
优选地，所述加热的时间各自独立地为1-4h，例如2.5h、3h、3.5h等。Preferably, the heating time is each independently 1-4h, such as 2.5h, 3h, 3.5h and so on.
第三方面，本发明提供一种第一方面所述的可自愈合的电磁屏蔽材料在电子设备中的应用。In a third aspect, the present invention provides an application of the self-healing electromagnetic shielding material described in the first aspect in electronic equipment.
相对于现有技术，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明所述电磁屏蔽材料兼具优异的自愈合功能、电磁屏蔽性能和导电性能。The electromagnetic shielding material of the invention has excellent self-healing function, electromagnetic shielding performance and conductive performance.
(1)本发明所述电磁屏蔽材料上下两层为石墨烯树脂层，中间层为碳纤维材料树脂层，所述电磁屏蔽材料在碳纤维材料树脂层厚度比较低时就可以提供优秀的自愈合性能，且在微波照射下自愈合速度快；(1) The upper and lower layers of the electromagnetic shielding material of the present invention are graphene resin layers, and the middle layer is a carbon fiber material resin layer. When the thickness of the carbon fiber material resin layer is relatively low, the electromagnetic shielding material can provide excellent self-healing properties , and the self-healing speed is fast under microwave irradiation;
(2)本发明发挥电磁屏蔽功能的碳纤维材料树脂层位于中间层，在厚度较低时就可以提供良好的电磁屏蔽性能，且自愈合后的导电网络的重新连接良好，在自愈合后仍然拥有良好的导电性能和电磁屏蔽性能；(2) The carbon fiber material resin layer that the present invention exerts the electromagnetic shielding function is located in the middle layer, and when the thickness is low, good electromagnetic shielding performance can be provided, and the reconnection of the conductive network after self-healing is good, and after self-healing Still has good electrical conductivity and electromagnetic shielding performance;
(3)本发明所述电磁屏蔽材料断裂伸长率高，表现出良好的可拉伸性与柔性，可承受大幅度形变，如拉伸、弯曲、折叠、卷绕与扭曲等；(3) The electromagnetic shielding material of the present invention has a high elongation at break, exhibits good stretchability and flexibility, and can withstand large deformations, such as stretching, bending, folding, winding and twisting;
(4)本发明的制备方法工艺简单、制作方便且成本低廉；(4) The preparation method of the present invention has simple process, convenient manufacture and low cost;
(5)第一石墨烯树脂层和第二石墨烯树脂层的厚度在80μm-160μm范围内，且碳纤维材料树脂层在80μm-150μm范围内，初始样品的电磁屏蔽性能在29.6dB以上，自愈合后样品的电磁屏蔽性能在24dB以上；初始样品的导电性能在720S/m以上，自愈合后样品的导电性能在310S/m以上；自愈合速度在10s以内。(5) The thickness of the first graphene resin layer and the second graphene resin layer is in the range of 80 μm-160 μm, and the carbon fiber material resin layer is in the range of 80 μm-150 μm, the electromagnetic shielding performance of the initial sample is above 29.6dB, self-healing The electromagnetic shielding performance of the combined sample is above 24dB; the conductivity of the initial sample is above 720S/m, and the conductivity of the self-healing sample is above 310S/m; the self-healing speed is within 10s.
附图说明Description of drawings
图1是实施例1所述的电磁屏蔽材料的截面结构扫描电镜图；Fig. 1 is the scanning electron micrograph of the cross-sectional structure of the electromagnetic shielding material described in embodiment 1;
图2a是实施例2所述的电磁屏蔽材料的初始样品断裂状态的扫描电镜图；Fig. 2 a is the scanning electron micrograph of the initial sample fracture state of the electromagnetic shielding material described in embodiment 2;
图2b是实施例2所述的电磁屏蔽材料的自愈合后样品的扫描电镜图；Fig. 2b is the scanning electron micrograph of the self-healing sample of the electromagnetic shielding material described in Example 2;
图3是实施例3所述的电磁屏蔽材料的初始样品和自愈合后样品的应力应变图；Fig. 3 is the initial sample of the electromagnetic shielding material described in embodiment 3 and the stress-strain diagram of the sample after self-healing;
图4是实施例3所述的电磁屏蔽材料的初始样品和自愈合后样品的电磁屏蔽性能图。Fig. 4 is a diagram of the electromagnetic shielding performance of the initial sample and the self-healed sample of the electromagnetic shielding material described in Example 3.
具体实施方式Detailed ways
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。In order to facilitate understanding of the present invention, the present invention enumerates the following examples. It should be clear to those skilled in the art that the embodiments are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.
实施例1Example 1
本实施例提供一种电磁屏蔽材料，所述电磁屏蔽材料由依次层叠设置的第一石墨烯树脂层、碳纤维材料树脂层和第二石墨烯树脂层组成。This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
所述第一石墨烯树脂层中，厚度为100μm，由质量百分数为2％的氧化石墨烯和98％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203；In the first graphene resin layer, the thickness is 100 μm, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455- 203;
所述碳纤维材料树脂层中，厚度为120μm，由质量百分数为40％的碳纤维材料和60％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203，所述碳纤维材料为碳纤维；In the carbon fiber material resin layer, the thickness is 120 μm, and it is composed of 40% carbon fiber material and 60% thermoplastic resin in mass percentage. The thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455-203. The carbon fiber material is carbon fiber;
所述第二层石墨烯树脂层中，厚度为100μm，由质量百分数为2％的氧化石墨烯和98％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-20。In the second layer of graphene resin layer, the thickness is 100 μm, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, the trade mark is PS455 -20.
所述电磁屏蔽材料的制备方法包括以下步骤：The preparation method of the electromagnetic shielding material comprises the following steps:
步骤1、分散石墨烯和热塑性树脂Step 1. Disperse graphene and thermoplastic resin
将热塑性聚氨酯和氧化石墨烯分别溶解于N,N-二甲基甲酰胺中，配制成氧化石墨烯质量分数为2％的石墨烯分散液和热塑性聚氨酯质量分数为20％的热塑性树脂溶液，在超声细胞破碎仪中超声30min，至热塑性树脂完全溶解、石墨烯分散均匀；Thermoplastic polyurethane and graphene oxide were dissolved in N, N-dimethylformamide, respectively, to prepare a graphene dispersion with a mass fraction of graphene oxide of 2% and a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%. Sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
步骤2、制备石墨烯导电浆料和碳纤维材料导电浆料；Step 2, preparing graphene conductive paste and carbon fiber material conductive paste;
将石墨烯分散液、碳纤维分别与热塑性树脂溶液混合，配制成氧化石墨烯 与热塑性聚氨酯质量比为1：49，碳纤维和热塑性聚氨酯质量比为1：1.5的两种溶液，放入清洗机中超声30min至石墨烯、碳纤维均在其溶液中分散均匀，形成石墨烯导电浆料和碳纤维材料导电浆料；Mix the graphene dispersion and carbon fiber with the thermoplastic resin solution respectively to prepare two solutions with a mass ratio of graphene oxide and thermoplastic polyurethane of 1:49, and a mass ratio of carbon fiber and thermoplastic polyurethane of 1:1.5, and put them into a washing machine for ultrasonic 30 minutes until graphene and carbon fiber are uniformly dispersed in the solution to form graphene conductive paste and carbon fiber material conductive paste;
步骤3、制备电磁屏蔽材料Step 3, preparing electromagnetic shielding material
将石墨烯导电浆料涂覆于基底上，在80℃下加热3h完成干燥，得到第一石墨烯树脂层；Coating the graphene conductive paste on the substrate, heating at 80°C for 3h to complete drying, and obtaining the first graphene resin layer;
再将碳纤维材料导电浆料涂覆于第一石墨烯树脂层上，在80℃下加热3h干燥，得到碳纤维材料树脂层；Then coating the carbon fiber material conductive paste on the first graphene resin layer, heating and drying at 80° C. for 3 hours to obtain a carbon fiber material resin layer;
最后将石墨烯导电浆料涂覆于碳纤维材料树脂层上，在80℃下加热3h干燥，得到所述电磁屏蔽材料。Finally, the graphene conductive paste is coated on the carbon fiber material resin layer, heated and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
实施例2Example 2
本实施例提供一种电磁屏蔽材料，所述电磁屏蔽材料由依次层叠设置的第一石墨烯树脂层、碳纤维材料树脂层和第二石墨烯树脂层组成。This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
所述第一石墨烯树脂层中，厚度为150μm，由质量百分数为5％的氧化石墨烯和95％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203；In the first graphene resin layer, the thickness is 150 μm, and it is composed of 5% graphene oxide and 95% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, which is purchased from Huntsman, and the grade is PS455- 203;
所述碳纤维材料树脂层中，厚度为100μm，由质量百分数为20％的碳纤维材料和80％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203，所述碳纤维材料为碳纤维；The carbon fiber material resin layer has a thickness of 100 μm and is composed of 20% by mass of carbon fiber material and 80% of thermoplastic resin. The thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455-203. The carbon fiber material is carbon fiber;
所述第二层石墨烯树脂层中，厚度为150μm，由质量百分数为5％的氧化石墨烯和95％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203。In the second layer of graphene resin layer, the thickness is 150 μm, and it is composed of 5% graphene oxide and 95% thermoplastic resin by mass percentage. The thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the trade mark is PS455 -203.
所述电磁屏蔽材料的制备方法包括以下步骤：The preparation method of the electromagnetic shielding material comprises the following steps:
步骤1、分散石墨烯和热塑性树脂Step 1. Disperse graphene and thermoplastic resin
将热塑性聚氨酯和氧化石墨烯分别溶解于N,N-二甲基甲酰胺中，配制成氧化石墨烯质量分数为2％的石墨烯分散液和热塑性聚氨酯质量分数为20％的热 塑性树脂溶液，在超声细胞破碎仪中超声30min，至热塑性树脂完全溶解、石墨烯分散均匀；Thermoplastic polyurethane and graphene oxide were dissolved in N, N-dimethylformamide, respectively, to prepare a graphene dispersion with a mass fraction of graphene oxide of 2% and a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%. Sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
步骤2、制备石墨烯导电浆料和碳纤维材料导电浆料；Step 2, preparing graphene conductive paste and carbon fiber material conductive paste;
将石墨烯分散液、碳纤维分别与热塑性树脂溶液混合，配制成氧化石墨烯与热塑性聚氨酯质量比为1：19，碳纤维和热塑性聚氨酯质量比为1：4的两种溶液，放入清洗机中超声30min至石墨烯、碳纤维均在其溶液中分散均匀，形成石墨烯导电浆料和碳纤维材料导电浆料；Mix the graphene dispersion and carbon fiber with the thermoplastic resin solution respectively to prepare two solutions with a mass ratio of graphene oxide and thermoplastic polyurethane of 1:19, and a mass ratio of carbon fiber and thermoplastic polyurethane of 1:4, and put them into the washing machine for ultrasonic 30 minutes until graphene and carbon fiber are uniformly dispersed in the solution to form graphene conductive paste and carbon fiber material conductive paste;
步骤3、制备电磁屏蔽材料Step 3, preparing electromagnetic shielding material
将石墨烯导电浆料涂覆于基底上，在80℃下加热3h完成干燥，得到第一石墨烯树脂层；Coating the graphene conductive paste on the substrate, heating at 80°C for 3h to complete drying, and obtaining the first graphene resin layer;
再将碳纤维材料导电浆料涂覆于第一石墨烯树脂层上，在80℃下加热3h干燥，得到碳纤维材料树脂层；Then coating the carbon fiber material conductive paste on the first graphene resin layer, heating and drying at 80° C. for 3 hours to obtain the carbon fiber material resin layer;
最后将石墨烯导电浆料涂覆于碳纤维材料树脂层上，在80℃下加热3h干燥，得到所述电磁屏蔽材料。Finally, the graphene conductive paste is coated on the carbon fiber material resin layer, heated and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
实施例3Example 3
本实施例提供一种电磁屏蔽材料，所述电磁屏蔽材料由依次层叠设置的第一石墨烯树脂层、碳纤维材料树脂层和第二石墨烯树脂层组成。This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
所述第一石墨烯树脂层中，厚度为120μm，由质量百分数为2％的氧化石墨烯和98％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203；In the first graphene resin layer, the thickness is 120 μm, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage, and the thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the grade is PS455- 203;
所述碳纤维材料树脂层中，厚度为100μm，由质量百分数为33.3％的碳纤维材料和66.7％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203，所述碳纤维材料为碳纤维；The carbon fiber material resin layer has a thickness of 100 μm and is composed of 33.3% by mass of carbon fiber material and 66.7% of thermoplastic resin. The thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the brand name is PS455-203. The carbon fiber material is carbon fiber;
所述第二层石墨烯树脂层中，厚度为120μm，由质量百分数为2％的氧化石墨烯和98％的热塑性树脂组成，所述热塑性树脂为热塑性聚氨酯，购于亨斯曼，牌号为PS455-203。In the second layer of graphene resin layer, the thickness is 120 μm, and it is composed of 2% graphene oxide and 98% thermoplastic resin in mass percentage. The thermoplastic resin is thermoplastic polyurethane, purchased from Huntsman, and the trade mark is PS455 -203.
所述电磁屏蔽材料的制备方法包括以下步骤：The preparation method of the electromagnetic shielding material comprises the following steps:
步骤1、分散石墨烯和热塑性树脂Step 1. Disperse graphene and thermoplastic resin
将热塑性聚氨酯和氧化石墨烯分别溶解于N,N-二甲基甲酰胺中，配制成氧化石墨烯质量分数为10％的石墨烯分散液和热塑性聚氨酯质量分数为20％的热塑性树脂溶液，在超声细胞破碎仪中超声30min，至热塑性树脂完全溶解、石墨烯分散均匀；Thermoplastic polyurethane and graphene oxide were dissolved in N,N-dimethylformamide respectively to prepare graphene dispersion with 10% mass fraction of graphene oxide and thermoplastic resin solution with 20% mass fraction of thermoplastic polyurethane. Sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
步骤2、制备石墨烯导电浆料和碳纤维材料导电浆料；Step 2, preparing graphene conductive paste and carbon fiber material conductive paste;
将石墨烯分散液、碳纤维分别与热塑性树脂溶液混合，配制成氧化石墨烯与热塑性聚氨酯质量比为1：49，碳纤维和热塑性聚氨酯质量比为1：2的两种溶液，放入清洗机中超声30min至石墨烯、碳纤维均在其溶液中分散均匀，形成石墨烯导电浆料和碳纤维材料导电浆料；Mix the graphene dispersion and carbon fiber with the thermoplastic resin solution respectively to prepare two solutions with a mass ratio of graphene oxide and thermoplastic polyurethane of 1:49, and a mass ratio of carbon fiber and thermoplastic polyurethane of 1:2, and put them into the washing machine for ultrasonic 30 minutes until graphene and carbon fiber are uniformly dispersed in the solution to form graphene conductive paste and carbon fiber material conductive paste;
步骤3、制备电磁屏蔽材料Step 3, preparing electromagnetic shielding material
将石墨烯导电浆料涂覆于基底上，在80℃下加热3h完成干燥，得到第一石墨烯树脂层；Coating the graphene conductive paste on the substrate, heating at 80°C for 3h to complete drying, and obtaining the first graphene resin layer;
再将碳纤维材料导电浆料涂覆于第一石墨烯树脂层上，在80℃下加热3h干燥，得到碳纤维材料树脂层；Then coating the carbon fiber material conductive paste on the first graphene resin layer, heating and drying at 80° C. for 3 hours to obtain a carbon fiber material resin layer;
最后将石墨烯导电浆料涂覆于碳纤维材料树脂层上，在80℃下加热3h干燥，得到所述电磁屏蔽材料。Finally, the graphene conductive paste is coated on the carbon fiber material resin layer, heated and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
实施例4Example 4
本实施例提供一种电磁屏蔽材料，所述电磁屏蔽材料由依次层叠设置的第一石墨烯树脂层、碳纤维材料树脂层和第二石墨烯树脂层组成。This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
所述第一石墨烯树脂层中，厚度为160μm，由质量百分数为1％的还原氧化石墨烯和99％的热塑性树脂组成，所述热塑性树脂为质量比为1:1的聚甲基丙烯酸甲酯和聚酰胺的混合物，聚甲基丙烯酸甲酯购于优索，牌号为CM211，聚酰胺购于杜邦，牌号为PA66；In the first graphene resin layer, the thickness is 160 μm, and it is composed of 1% reduced graphene oxide and 99% thermoplastic resin in mass percentage, and the thermoplastic resin is polymethyl methacrylate with a mass ratio of 1:1. A mixture of ester and polyamide, polymethyl methacrylate is purchased from Yuso, the brand is CM211, and polyamide is purchased from DuPont, the brand is PA66;
所述碳纤维材料树脂层中，厚度为100μm，由质量百分数为10％的碳纤维 材料和90％的热塑性树脂组成，所述热塑性树脂为聚四氟乙烯，购于杜邦，牌号为MT1000，所述碳纤维材料为碳纳米纤维；The carbon fiber material resin layer has a thickness of 100 μm and is composed of 10% by mass of carbon fiber material and 90% of thermoplastic resin. The thermoplastic resin is polytetrafluoroethylene, purchased from DuPont, and the brand is MT1000. The carbon fiber The material is carbon nanofiber;
所述第二层石墨烯树脂层中，厚度为160μm，由质量百分数为1％的还原氧化石墨烯和99％的热塑性树脂组成，所述热塑性树脂为质量比为1:1的聚甲基丙烯酸甲酯和聚酰胺的混合物，聚甲基丙烯酸甲酯购于优索，牌号为CM211，聚酰胺购于杜邦，牌号为PA66。In the second graphene resin layer, the thickness is 160 μm, and it is composed of 1% reduced graphene oxide and 99% thermoplastic resin in mass percentage, and the thermoplastic resin is polymethacrylic acid with a mass ratio of 1:1 A mixture of methyl ester and polyamide, polymethyl methacrylate is purchased from Yuso, the brand is CM211, and polyamide is purchased from DuPont, the brand is PA66.
所述电磁屏蔽材料的制备方法包括以下步骤：The preparation method of the electromagnetic shielding material comprises the following steps:
步骤1、分散石墨烯和热塑性树脂Step 1. Disperse graphene and thermoplastic resin
将热塑性树脂溶解于甲苯中，将还原氧化石墨烯溶解于醋酸乙酯中，配制成质量分数为5％的石墨烯分散液和质量分数为50％的热塑性树脂溶液，在超声细胞破碎仪中超声60min，至热塑性树脂完全溶解、石墨烯分散均匀；The thermoplastic resin was dissolved in toluene, and the reduced graphene oxide was dissolved in ethyl acetate to prepare a graphene dispersion with a mass fraction of 5% and a thermoplastic resin solution with a mass fraction of 50%, and ultrasonicated in an ultrasonic cell disruptor. 60min, until the thermoplastic resin is completely dissolved and the graphene is uniformly dispersed;
步骤2、制备石墨烯导电浆料和碳纤维材料导电浆料；Step 2, preparing graphene conductive paste and carbon fiber material conductive paste;
将石墨烯分散液、碳纤维分别与各自对应的热塑性树脂溶液按比例混合，将两个混合液放入清洗机中超声60min至石墨烯、碳纳米纤维均在其溶液中分散均匀，形成石墨烯导电浆料和碳纤维材料导电浆料；Mix the graphene dispersion and carbon fiber with their corresponding thermoplastic resin solutions in proportion, put the two mixtures into the washing machine and ultrasonically for 60 minutes until the graphene and carbon nanofibers are evenly dispersed in the solution, forming graphene conductive Paste and carbon fiber material conductive paste;
步骤3、制备电磁屏蔽材料Step 3, preparing electromagnetic shielding material
将石墨烯导电浆料涂覆于基底上，在60℃下加热4h完成干燥，得到第一石墨烯树脂层；Coating the graphene conductive paste on the substrate, heating at 60°C for 4h to complete drying, and obtaining the first graphene resin layer;
再将碳纤维材料导电浆料涂覆于第一石墨烯树脂层上，在80℃下加热3h干燥，得到碳纤维材料树脂层；Then coating the carbon fiber material conductive paste on the first graphene resin layer, heating and drying at 80° C. for 3 hours to obtain a carbon fiber material resin layer;
最后将石墨烯导电浆料涂覆于碳纤维材料树脂层上，在120℃下加热1h干燥，得到所述电磁屏蔽材料。Finally, the graphene conductive paste was coated on the resin layer of the carbon fiber material, and dried by heating at 120° C. for 1 hour to obtain the electromagnetic shielding material.
实施例5Example 5
本实施例提供一种电磁屏蔽材料，所述电磁屏蔽材料由依次层叠设置的第一石墨烯树脂层、碳纤维材料树脂层和第二石墨烯树脂层组成。This embodiment provides an electromagnetic shielding material, and the electromagnetic shielding material is composed of a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
所述第一石墨烯树脂层中，厚度为130μm，由质量百分数为10％的氧化石 墨烯和90％的热塑性树脂组成，所述热塑性树脂为质量比为1:2的聚乙烯和聚碳酸酯的混合物，聚乙烯购于中国石化，牌号为M2320，聚碳酸酯购于Makronlon，牌号为2805；In the first graphene resin layer, the thickness is 130 μm, and it is composed of 10% graphene oxide and 90% thermoplastic resin in mass percentage, and the thermoplastic resin is polyethylene and polycarbonate with a mass ratio of 1:2 The mixture of polyethylene, purchased from Sinopec, the brand is M2320, and polycarbonate is purchased from Makronlon, the brand is 2805;
所述碳纤维材料树脂层中，厚度为90μm，由质量百分数为10％的碳纤维材料和90％的热塑性树脂组成，所述热塑性树脂为聚甲醛，购于TYSTRON，牌号为POM4250，所述碳纤维材料为碳纳米管；In the carbon fiber material resin layer, the thickness is 90 μm, and the mass percentage is 10% carbon fiber material and 90% thermoplastic resin. The thermoplastic resin is polyoxymethylene, purchased from TYSTRON, and the brand is POM4250. The carbon fiber material is carbon nanotubes;
所述第二层石墨烯树脂层中，厚度为130μm，由质量百分数为5％的氧化石墨烯和95％的热塑性树脂组成，所述热塑性树脂为质量比为1:1的聚氯乙烯和聚苯乙烯的混合物，聚氯乙烯购于天业公司，牌号为pvc-sg5，聚苯乙烯购于奇美化工，牌号为PG-33。In the second graphene resin layer, the thickness is 130 μm, and it is composed of 5% graphene oxide and 95% thermoplastic resin in mass percentage, and the thermoplastic resin is polyvinyl chloride and polyvinyl chloride with a mass ratio of 1:1. The mixture of styrene, polyvinyl chloride was purchased from Tianye Company, the brand is pvc-sg5, and polystyrene was purchased from Chimei Chemical, the brand is PG-33.
所述电磁屏蔽材料的制备方法包括以下步骤：The preparation method of the electromagnetic shielding material comprises the following steps:
步骤1、分散石墨烯和热塑性树脂Step 1. Disperse graphene and thermoplastic resin
将氧化石墨烯溶解于质量比为1:1的丙酮和醋酸甲酯中，将各层所需的热塑性树脂分别溶解于甲基丁酮中，配制成质量分数为2％的石墨烯分散液和质量分数为90％的热塑性树脂溶液，在超声细胞破碎仪中超声60min，至热塑性树脂完全溶解、石墨烯分散均匀；Graphene oxide is dissolved in acetone and methyl acetate with a mass ratio of 1:1, and the thermoplastic resins required for each layer are dissolved in methyl butanone respectively to prepare a graphene dispersion with a mass fraction of 2% and The thermoplastic resin solution with a mass fraction of 90% is ultrasonicated in an ultrasonic cell disruptor for 60 minutes until the thermoplastic resin is completely dissolved and the graphene is uniformly dispersed;
步骤2、制备石墨烯导电浆料和碳纤维材料导电浆料；Step 2, preparing graphene conductive paste and carbon fiber material conductive paste;
将各层所需的石墨烯分散液、碳纤维按比例分别与各自对应的热塑性树脂溶液混合，将三个混合液放入清洗机中超声60min至石墨烯、碳纤维均在其溶液中分散均匀，形成第一石墨烯导电浆料、碳纤维材料导电浆料和第二石墨烯导电浆料；Mix the graphene dispersion liquid and carbon fiber required for each layer with their corresponding thermoplastic resin solutions in proportion, put the three mixed liquids into the washing machine and ultrasonically for 60 minutes until the graphene and carbon fiber are uniformly dispersed in the solution, forming The first graphene conductive paste, the carbon fiber material conductive paste and the second graphene conductive paste;
步骤3、制备电磁屏蔽材料Step 3, preparing electromagnetic shielding material
将第一石墨烯导电浆料涂覆于基底上，在100℃下加热1h完成干燥，得到第一石墨烯树脂层；coating the first graphene conductive paste on the substrate, heating at 100° C. for 1 h to complete drying, and obtaining the first graphene resin layer;
再将碳纤维材料导电浆料涂覆于第一石墨烯树脂层上，在100℃下加热2h干燥，得到碳纤维材料树脂层；Then coating the carbon fiber material conductive paste on the first graphene resin layer, heating and drying at 100° C. for 2 hours to obtain a carbon fiber material resin layer;
最后将第二石墨烯导电浆料涂覆于碳纤维材料树脂层上，在60℃下加热4h干燥，得到所述电磁屏蔽材料。Finally, the second graphene conductive paste was coated on the resin layer of the carbon fiber material, and dried by heating at 60° C. for 4 hours to obtain the electromagnetic shielding material.
实施例6-9Example 6-9
实施例6-9与实施例1的区别在于第一石墨烯树脂层的厚度分别为50μm(实施例6)、200μm(实施例7)、80μm(实施例8)和160μm(实施例9)，其余均与实施例1相同。The difference between embodiment 6-9 and embodiment 1 is that the thickness of the first graphene resin layer is respectively 50 μm (embodiment 6), 200 μm (embodiment 7), 80 μm (embodiment 8) and 160 μm (embodiment 9), All the other are identical with embodiment 1.
实施例10-13Examples 10-13
实施例10-13与实施例1的区别在于碳纤维材料树脂层的厚度分别为50μm(实施例10)、200μm(实施例11)、80μm(实施例12)和150μm(实施例13)，其余均与实施例1相同。The difference between Examples 10-13 and Example 1 is that the thickness of the carbon fiber material resin layer is 50 μm (Example 10), 200 μm (Example 11), 80 μm (Example 12) and 150 μm (Example 13), and the rest are all Same as Example 1.
对比例1Comparative example 1
本对比例与实施例1的区别在于所述电磁屏蔽材料不具备实施例1所述“三明治结构”，其由碳纤维、氧化石墨烯和热塑性树脂组成，各组分的添加量与实施例1相同。The difference between this comparative example and Example 1 is that the electromagnetic shielding material does not have the "sandwich structure" described in Example 1, which is composed of carbon fiber, graphene oxide and thermoplastic resin, and the addition amount of each component is the same as that of Example 1 .
上述电磁屏蔽材料的制备方法包括如下步骤：The preparation method of the above-mentioned electromagnetic shielding material comprises the following steps:
步骤1、分散石墨烯和热塑性树脂Step 1. Disperse graphene and thermoplastic resin
将热塑性聚氨酯和氧化石墨烯分别溶解于N,N-二甲基甲酰胺中，配制成石墨烯质量分数为2％的石墨烯分散液和热塑性聚氨酯质量分数为20％的热塑性树脂溶液，在超声细胞破碎仪中超声30min，至热塑性树脂完全溶解、石墨烯分散均匀；Thermoplastic polyurethane and graphene oxide were dissolved in N,N-dimethylformamide, respectively, to prepare a graphene dispersion with a mass fraction of graphene of 2% and a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%. Sonicate in the cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved and the graphene is evenly dispersed;
步骤2、制备石墨烯导电浆料和碳纤维材料导电浆料；Step 2, preparing graphene conductive paste and carbon fiber material conductive paste;
将石墨烯分散液、碳纤维与热塑性树脂溶液混合，放入清洗机中超声30min至氧化石墨烯和碳纤维在热塑性树脂溶液中分散均匀，形成导电浆料；Mix the graphene dispersion, carbon fiber and thermoplastic resin solution, put it into a cleaning machine and ultrasonically for 30 minutes until the graphene oxide and carbon fiber are evenly dispersed in the thermoplastic resin solution to form a conductive paste;
步骤3、制备电磁屏蔽材料Step 3, preparing electromagnetic shielding material
将导电浆料涂覆于基底上，在80℃下加热3h完成干燥，得到所述电磁屏蔽材料。The conductive paste was coated on the substrate, and dried at 80° C. for 3 hours to obtain the electromagnetic shielding material.
对比例2Comparative example 2
本对比例与实施例1的区别在于所述电磁屏蔽材料仅含有碳纤维材料树脂层。The difference between this comparative example and Example 1 is that the electromagnetic shielding material only contains a carbon fiber material resin layer.
上述电磁屏蔽材料的制备方法包括如下步骤：The preparation method of the above-mentioned electromagnetic shielding material comprises the following steps:
步骤1、分散石墨烯和热塑性树脂Step 1. Disperse graphene and thermoplastic resin
将热塑性聚氨酯溶解于N,N-二甲基甲酰胺中，配制成热塑性聚氨酯质量分数为20％的热塑性树脂溶液，在超声细胞破碎仪中超声30min，至热塑性树脂完全溶解；Dissolve thermoplastic polyurethane in N,N-dimethylformamide to prepare a thermoplastic resin solution with a mass fraction of thermoplastic polyurethane of 20%, and sonicate in an ultrasonic cell disruptor for 30 minutes until the thermoplastic resin is completely dissolved;
步骤2、制备石墨烯导电浆料和碳纤维材料导电浆料；Step 2, preparing graphene conductive paste and carbon fiber material conductive paste;
将碳纤维与热塑性树脂溶液混合，配制成碳纤维和热塑性聚氨酯质量比为1：1.5的溶液，放入清洗机中超声30min至碳纤维在其溶液中分散均匀，形成碳纤维材料导电浆料；Mix carbon fiber and thermoplastic resin solution to prepare a solution with a mass ratio of carbon fiber and thermoplastic polyurethane of 1:1.5, put it into a washing machine and ultrasonically 30min until the carbon fiber is evenly dispersed in the solution, and form a conductive paste of carbon fiber material;
步骤3、制备电磁屏蔽材料Step 3, preparing electromagnetic shielding material
将碳纤维材料导电浆料涂覆于基底上，在80℃下加热3h干燥，得到碳纤维材料树脂层，即得到所述电磁屏蔽材料。Coating the conductive paste of carbon fiber material on the substrate, heating and drying at 80° C. for 3 hours, to obtain a resin layer of carbon fiber material, that is, to obtain the electromagnetic shielding material.
性能测试Performance Testing
将实施例1-13和对比例1-2所述电磁屏蔽材料进行如下测试：The electromagnetic shielding materials described in Examples 1-13 and Comparative Examples 1-2 are tested as follows:
(1)形貌表征：通过扫描电子显微镜(FEI Nova Nano SEM 450)进行观察；(1) Morphological characterization: observation by scanning electron microscope (FEI Nova Nano SEM 450);
(2)拉伸性能：通过电子万能试验机(Reger 4050)进行拉伸测试；(2) Tensile performance: carry out tensile test by electronic universal testing machine (Reger 4050);
(3)电磁屏蔽性能：通过矢量网分仪(Keysight E5071C)波导法进行电磁屏蔽效能测试；(3) Electromagnetic shielding performance: the electromagnetic shielding effectiveness test is carried out by the vector network analyzer (Keysight E5071C) waveguide method;
(4)导电性能：通过精密万能电用表测试电阻，通过刻度尺和螺旋测微器进行长宽厚的测量，通过电导率公式(δ＝lR*S)计算出电导率。(4) Conductivity: Test the resistance with a precision universal meter, measure the length, width and thickness with a scale and a screw micrometer, and calculate the conductivity through the conductivity formula (δ=lR*S).
测试结果汇总于表1和图1-4中。The test results are summarized in Table 1 and Figures 1-4.
表1Table 1
Figure PCTCN2021137307-appb-000001
Figure PCTCN2021137307-appb-000001
Figure PCTCN2021137307-appb-000002
Figure PCTCN2021137307-appb-000002
分析表1中数据可知，实施例1-5，实施例8-9和实施例12-13中，本发明所述结构的电磁屏蔽材料在具有较好的断裂伸长率的前提下，兼具优异的自愈合性能、电磁屏蔽性能和导电性能；当第一石墨烯树脂层和第二石墨烯树脂层的厚度在80μm-160μm范围内，且碳纤维材料树脂层在80μm-150μm范围内，初始样品的电磁屏蔽性能在29.6dB以上，自愈合后样品的电磁屏蔽性能在24dB以上；初始样品的导电性能在720S/m以上，自愈合后样品的导电性能在310S/m以上；自愈合速度在10s以内。Analysis of the data in Table 1 shows that in Examples 1-5, 8-9 and 12-13, the electromagnetic shielding material of the structure of the present invention has both Excellent self-healing performance, electromagnetic shielding performance and electrical conductivity; when the thickness of the first graphene resin layer and the second graphene resin layer are in the range of 80 μm-160 μm, and the carbon fiber material resin layer is in the range of 80 μm-150 μm, the initial The electromagnetic shielding performance of the sample is above 29.6dB, and the electromagnetic shielding performance of the sample after self-healing is above 24dB; the conductivity of the initial sample is above 720S/m, and the conductivity of the sample after self-healing is above 310S/m; self-healing Combined speed is within 10s.
分析对比例1与实施例1可知，对比例1性能不如实施例1，证明具有“三明治”结构的电磁屏蔽材料性能更佳。Analysis of Comparative Example 1 and Example 1 shows that the performance of Comparative Example 1 is not as good as that of Example 1, which proves that the electromagnetic shielding material with a "sandwich" structure has better performance.
分析对比例2与实施例1可知，对比例2性能不如实施例1，证明单一石墨烯或者碳纤维材料形成的电磁屏蔽材料性能较差。Analysis of Comparative Example 2 and Example 1 shows that the performance of Comparative Example 2 is not as good as that of Example 1, which proves that the electromagnetic shielding material formed by a single graphene or carbon fiber material has poor performance.
分析实施例6-9可知，实施例6-7性能不如实施例8-9，证明第一石墨烯树脂层的厚度在80μm-160μm范围内形成的电磁屏蔽材料性能更佳，第二石墨烯树脂层同理。Analysis of Examples 6-9 shows that the performance of Examples 6-7 is not as good as that of Examples 8-9, which proves that the performance of the electromagnetic shielding material formed by the thickness of the first graphene resin layer in the range of 80 μm-160 μm is better, and the performance of the second graphene resin layer is better. Layers are the same.
分析实施例10-13可知，实施例10-11性能不如实施例12-13，证明碳纤维材料树脂层在80μm-150μm范围内形成的电磁屏蔽材料性能更佳。Analysis of Examples 10-13 shows that the performance of Examples 10-11 is not as good as that of Examples 12-13, which proves that the performance of the electromagnetic shielding material formed by the carbon fiber material resin layer in the range of 80 μm-150 μm is better.
由图1可知，实施例1成功制备了具有“三明治”结构的电磁屏蔽材料。It can be seen from Figure 1 that Example 1 successfully prepared an electromagnetic shielding material with a "sandwich" structure.
由图2a和图2b可知，本发明所述结构的电磁屏蔽材料在微观结构上具有优异的自愈合性能。It can be seen from Fig. 2a and Fig. 2b that the electromagnetic shielding material with the structure of the present invention has excellent self-healing performance in microstructure.
由图3可知，本发明所述结构的电磁屏蔽材料自愈合前后的断裂伸长率差距不大，证明本发明所述结构的电磁屏蔽材料具有优异的自愈合性能，自愈合前后的材料断裂伸长率较高，证明本发明所述结构的电磁屏蔽材料表现出良好的可拉伸性与柔性，可承受大幅度形变，如拉伸、弯曲、折叠、卷绕与扭曲等。As can be seen from Fig. 3, the elongation at break of the electromagnetic shielding material with the structure of the present invention is not very different before and after self-healing, which proves that the electromagnetic shielding material with the structure of the present invention has excellent self-healing performance, and the elongation before and after self-healing The high elongation at break of the material proves that the electromagnetic shielding material with the structure of the present invention exhibits good stretchability and flexibility, and can withstand large deformations, such as stretching, bending, folding, winding and twisting.
由图4可知，本发明所述结构的电磁屏蔽材料自愈合前后的电磁屏蔽效能均较高，证明本发明所述结构的电磁屏蔽材料兼具优异的自愈合性能和电磁屏蔽效能。It can be seen from FIG. 4 that the electromagnetic shielding material with the structure of the present invention has higher electromagnetic shielding effectiveness before and after self-healing, which proves that the electromagnetic shielding material with the structure of the present invention has both excellent self-healing performance and electromagnetic shielding effectiveness.
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。The applicant declares that the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (10)

  1. 一种可自愈合的电磁屏蔽材料，其特征在于，所述电磁屏蔽材料包括依次层叠设置的第一石墨烯树脂层、碳纤维材料树脂层和第二石墨烯树脂层。A self-healing electromagnetic shielding material is characterized in that the electromagnetic shielding material comprises a first graphene resin layer, a carbon fiber material resin layer and a second graphene resin layer stacked in sequence.
  2. 根据权利要求1所述的可自愈合的电磁屏蔽材料，其特征在于，所述第一石墨烯树脂层的厚度为80μm-160μm；The self-healing electromagnetic shielding material according to claim 1, wherein the thickness of the first graphene resin layer is 80 μm-160 μm;
    优选地，所述碳纤维材料树脂层的厚度为80μm-150μm；Preferably, the carbon fiber material resin layer has a thickness of 80 μm-150 μm;
    优选地，所述第二石墨烯树脂层的厚度为80μm-160μm。Preferably, the thickness of the second graphene resin layer is 80 μm-160 μm.
  3. 根据权利要求1或2所述的可自愈合的电磁屏蔽材料，其特征在于，所述石墨烯树脂层按照质量百分数包括：1％-10％石墨烯和90％-99％热塑性树脂；The self-healing electromagnetic shielding material according to claim 1 or 2, wherein the graphene resin layer comprises: 1%-10% graphene and 90%-99% thermoplastic resin in terms of mass percentage;
    优选地，所述碳纤维材料树脂层按照质量百分数包括：10％-60％碳纤维材料和40％-90％热塑性树脂。Preferably, the carbon fiber material resin layer includes: 10%-60% carbon fiber material and 40%-90% thermoplastic resin in terms of mass percentage.
  4. 根据权利要求1-3任一项所述的可自愈合的电磁屏蔽材料，其特征在于，所述石墨烯包括单层石墨烯和/或多层石墨烯；The self-healing electromagnetic shielding material according to any one of claims 1-3, wherein the graphene comprises single-layer graphene and/or multi-layer graphene;
    优选地，所述石墨烯包括改性的氧化石墨烯、未改性的氧化石墨烯或还原氧化石墨烯中的任意一种或至少两种的组合。Preferably, the graphene includes any one or a combination of at least two of modified graphene oxide, unmodified graphene oxide or reduced graphene oxide.
  5. 根据权利要求1-4任一项所述的可自愈合的电磁屏蔽材料，其特征在于，所述碳纤维材料包括碳纤维、碳纳米纤维或碳纳米管中的任意一种或至少两种的组合。The self-healing electromagnetic shielding material according to any one of claims 1-4, wherein the carbon fiber material comprises any one or a combination of at least two of carbon fibers, carbon nanofibers or carbon nanotubes .
  6. 根据权利要求1-5任一项所述的可自愈合的电磁屏蔽材料，其特征在于，所述热塑性树脂包括热塑性聚氨酯及其衍生物、聚乙烯及其衍生物、聚丙烯及其衍生物、聚氯乙烯及其衍生物、聚苯乙烯及其衍生物、聚甲基丙烯酸甲酯及其衍生物、聚甲醛及其衍生物、聚酰胺及其衍生物、聚碳酸酯及其衍生物或聚四氟乙烯及其衍生物中的任意一种或至少两种的组合。The self-healing electromagnetic shielding material according to any one of claims 1-5, wherein the thermoplastic resin comprises thermoplastic polyurethane and its derivatives, polyethylene and its derivatives, polypropylene and its derivatives , polyvinyl chloride and its derivatives, polystyrene and its derivatives, polymethyl methacrylate and its derivatives, polyoxymethylene and its derivatives, polyamide and its derivatives, polycarbonate and its derivatives or Any one or a combination of at least two of polytetrafluoroethylene and its derivatives.
  7. 一种权利要求1-6任一项所述的可自愈合的电磁屏蔽材料的制备方法，其特征在于，所述制备方法包括如下步骤：A preparation method of the self-healing electromagnetic shielding material according to any one of claims 1-6, characterized in that the preparation method comprises the steps of:
    步骤1、将热塑性树脂和石墨烯分别溶解于有机溶剂中，形成热塑性树脂溶液和石墨烯分散液；Step 1, dissolving the thermoplastic resin and graphene in an organic solvent respectively to form a thermoplastic resin solution and a graphene dispersion;
    步骤2、将石墨烯分散液和碳纤维材料分别与热塑性树脂溶液混合，形成石墨烯导电浆料和碳纤维材料导电浆料；Step 2, mixing the graphene dispersion liquid and the carbon fiber material with the thermoplastic resin solution respectively to form a graphene conductive paste and a carbon fiber material conductive paste;
    步骤3、将石墨烯导电浆料涂覆于基底上，干燥，得到第一石墨烯树脂层；Step 3, coating the graphene conductive paste on the substrate, drying to obtain the first graphene resin layer;
    再将碳纤维材料导电浆料涂覆于第一石墨烯树脂层上，干燥，得到碳纤维材料树脂层；Then coating the carbon fiber material conductive paste on the first graphene resin layer and drying to obtain the carbon fiber material resin layer;
    最后将石墨烯导电浆料涂覆于碳纤维材料树脂层上，干燥，得到所述电磁屏蔽材料。Finally, the graphene conductive paste is coated on the carbon fiber material resin layer and dried to obtain the electromagnetic shielding material.
  8. 根据权利要求7所述的制备方法，其特征在于，步骤1中，所述有机溶剂包括芳香烃类有机溶剂、脂肪烃类有机溶剂、酯类有机溶剂、酮类有机溶剂或酰胺类有机溶剂中的任意一种或至少两种的组合；The preparation method according to claim 7, wherein in step 1, the organic solvent includes aromatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents, ester organic solvents, ketone organic solvents or amide organic solvents. Any one or a combination of at least two of
    优选地，所述有机溶剂包括N,N-二甲基甲酰胺、苯、甲苯、二甲苯、醋酸甲酯、醋酸乙酯、丙酮、甲基丁酮或甲基异丁酮中的任意一种或至少两种的组合；Preferably, the organic solvent includes any one of N,N-dimethylformamide, benzene, toluene, xylene, methyl acetate, ethyl acetate, acetone, methyl butanone or methyl isobutyl ketone or a combination of at least two;
    优选地，步骤1中，所述石墨烯与有机溶剂的质量比为1:(9-49)；Preferably, in step 1, the mass ratio of described graphene and organic solvent is 1:(9-49);
    优选地，步骤1中，所述热塑性树脂与有机溶剂的质量比为1:(1-9)。Preferably, in step 1, the mass ratio of the thermoplastic resin to the organic solvent is 1:(1-9).
  9. 根据权利要求7或8所述的制备方法，其特征在于，步骤1、步骤2和步骤3中所述干燥的方式包括加热；The preparation method according to claim 7 or 8, characterized in that, the drying method described in step 1, step 2 and step 3 includes heating;
    优选地，步骤1、步骤2和步骤3中所述加热的温度各自独立地为60-120℃；Preferably, the heating temperatures in step 1, step 2 and step 3 are each independently 60-120°C;
    优选地，所述加热的时间各自独立地为1-4h。Preferably, the heating time is each independently 1-4h.
  10. 一种权利要求1-6任一项所述的可自愈合的电磁屏蔽材料在电子设备中的应用。An application of the self-healing electromagnetic shielding material according to any one of claims 1-6 in electronic equipment.
PCT/CN2021/137307 2021-10-12 2021-12-12 Self-healing electromagnetic shielding material, preparation method therefor and application thereof WO2023060739A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105038055A (en) * 2015-08-06 2015-11-11 中国人民解放军军械工程学院 Method for preparing graded carbon fiber-graphene based shell layered bionic electromagnetic shielding film
KR20170002949A (en) * 2015-06-30 2017-01-09 한국과학기술연구원 Ultraviolet induced thermoplastic based self-healing composites and method for preparing the same
KR20170043157A (en) * 2015-10-13 2017-04-21 한국기계연구원 Polymer composite with electromagnetic shielding and absorbing ability and manufacturing method of the same
CN108659693A (en) * 2018-06-08 2018-10-16 常熟理工学院 The preparation method and restorative procedure of selfreparing graphene/thermoplastic resin coating
CN108948995A (en) * 2018-07-09 2018-12-07 常熟理工学院 The preparation of nano gold/graphene oxide self-repair material and restorative procedure
CN111231439A (en) * 2020-01-10 2020-06-05 上海大学 Heat-conducting graphene-high polymer material composite film and preparation method thereof
CN111391440A (en) * 2020-03-17 2020-07-10 四川大学 Insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding function and preparation method thereof
CN111851068A (en) * 2020-08-12 2020-10-30 四川大学 Method for repairing surface interface of modified carbon fiber and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105505054A (en) * 2015-12-07 2016-04-20 宁波墨西科技有限公司 Preparation method for electromagnetic shielding coating
CN107216587A (en) * 2017-07-19 2017-09-29 北京工商大学 A kind of sandwich structure polymer matrix electromagnetic shielding composite material and preparation method thereof
CN107627678B (en) * 2017-09-07 2019-05-14 大连理工大学 The electromagnetic shielding material and preparation method thereof of the low reflection of high-selenium corn
CN110278702B (en) * 2019-06-04 2021-02-19 江南石墨烯研究院 High-stretch high-elasticity electromagnetic shielding composite material and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170002949A (en) * 2015-06-30 2017-01-09 한국과학기술연구원 Ultraviolet induced thermoplastic based self-healing composites and method for preparing the same
CN105038055A (en) * 2015-08-06 2015-11-11 中国人民解放军军械工程学院 Method for preparing graded carbon fiber-graphene based shell layered bionic electromagnetic shielding film
KR20170043157A (en) * 2015-10-13 2017-04-21 한국기계연구원 Polymer composite with electromagnetic shielding and absorbing ability and manufacturing method of the same
CN108659693A (en) * 2018-06-08 2018-10-16 常熟理工学院 The preparation method and restorative procedure of selfreparing graphene/thermoplastic resin coating
CN108948995A (en) * 2018-07-09 2018-12-07 常熟理工学院 The preparation of nano gold/graphene oxide self-repair material and restorative procedure
CN111231439A (en) * 2020-01-10 2020-06-05 上海大学 Heat-conducting graphene-high polymer material composite film and preparation method thereof
CN111391440A (en) * 2020-03-17 2020-07-10 四川大学 Insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding function and preparation method thereof
CN111851068A (en) * 2020-08-12 2020-10-30 四川大学 Method for repairing surface interface of modified carbon fiber and application thereof

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