WO2023115695A1 - Wave-absorbing thermally-conductive composite material, and preparation method therefor and use thereof - Google Patents

Wave-absorbing thermally-conductive composite material, and preparation method therefor and use thereof Download PDF

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WO2023115695A1
WO2023115695A1 PCT/CN2022/078291 CN2022078291W WO2023115695A1 WO 2023115695 A1 WO2023115695 A1 WO 2023115695A1 CN 2022078291 W CN2022078291 W CN 2022078291W WO 2023115695 A1 WO2023115695 A1 WO 2023115695A1
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wave
absorbing
ink
parts
heat
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PCT/CN2022/078291
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French (fr)
Chinese (zh)
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吴燕如
吉受玉
李廷标
吴培琳
梁伟健
杨涛
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清远高新华园科技协同创新研究院有限公司
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Publication of WO2023115695A1 publication Critical patent/WO2023115695A1/en

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/84—Paper comprising more than one coating on both sides of the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46—Non-macromolecular organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper

Definitions

  • the invention belongs to the field of material technology, and in particular relates to a wave-absorbing and heat-conducting composite material and a preparation method and application thereof.
  • wave-absorbing and heat-conducting composite materials have become increasingly standardized and systematic.
  • Industrial-grade wave-absorbing and heat-conducting composite materials have also been finalized and mass-produced. Their performance has been steadily improved, and they have been applied in the field of military and civilian electronic equipment. But there are still some technical bottlenecks that have not been broken through, restricting the development of the entire industry. For example, the lack of material microstructure and functional unit models, the inability of general design theory to guide actual industrial production, and the lack of single-component fillers with both heat conduction and wave absorption functions have seriously restricted the rapid development of wave-absorbing and heat-conducting composite materials.
  • CN202110576618.2 discloses an electromagnetic wave-absorbing and heat-conducting composition.
  • the generated honeycomb nano-NiO precursor is compounded with nitrogen-doped mesoporous carbon microspheres, and then calcined to obtain nitrogen-doped mesoporous carbon microspheres loaded honeycomb structure.
  • CN202010082833.2 discloses boron nitride graphene polyimide composite wave-absorbing and heat-conducting composite material, which significantly improves wave-absorbing and heat-conducting performance and stability.
  • the filling amount of the heat-conducting particles in the polysiloxane matrix material can be increased, thereby forming an efficient heat conduction network and improving the heat transfer rate .
  • the object of the present invention is to provide a wave-absorbing and heat-conducting composite material whose heat-conducting and wave-absorbing energies cooperate with each other without weakening their respective performances, as well as its preparation method and application.
  • the technical solution adopted by the present invention is: a wave-absorbing and heat-conducting composite material, the wave-absorbing and heat-conducting composite material is a sandwich structure, and the sandwich structure includes a heat-conducting layer, a wave-absorbing layer and a filter paper layer, and the filter paper The layer is located between the heat conducting layer and the wave absorbing layer.
  • the technical solution of the present invention provides a wave-absorbing and heat-conducting composite material with a sandwich structure.
  • a heat-conducting layer and a wave-absorbing layer on both sides of the filter paper.
  • the sandwich structure makes the wave-absorbing layer formed on both sides of the filter paper.
  • the heat conduction layer and the absorbing layer on both sides of the filter paper can be interwoven on the surface of the porous filter paper and have good compatibility, thereby improving the The interfacial compatibility of the sandwich structure and the wave-absorbing and heat-conducting properties on both sides; at the same time, the invention provides a wave-absorbing and heat-conducting composite material with a paper structure, and the material has good flexibility.
  • the heat-conducting layer is coated with boron nitride nanosheet ink A, and the boron nitride nanosheet ink A includes the following raw materials in parts by weight: 5 -40 parts of boron nitride nanosheets, 20-50 parts of tert-butanol, 5-10 parts of glycerin and 0.1-2 parts of silane coupling agent;
  • the absorbing layer is coated with MXene ceramic sheet ink B, and the MXene ceramic sheet ink B includes the following raw materials in parts by weight: 15-50 parts of MXene ceramic sheet, 20-50 parts of tert-butanol, 5-15 parts of glycerin, and 0.1-2 parts of silane coupling agent.
  • the apparent viscosity of the boron nitride nanosheet ink A is 3000-8000mPa*s; the apparent viscosity of the MXene ceramic sheet ink B is 2000-7000mPa *s.
  • the boron nitride nanosheet ink A and MXene ceramic sheet ink B used adopt the raw materials of the above weight parts on the one hand, it can ensure that the apparent viscosity of the prepared boron nitride nanosheet ink A and MXene ceramic sheet ink B is above the above-mentioned Within the range, on the one hand, it can ensure that the thermal conductivity and wave absorption properties of the prepared boron nitride nanosheet ink A and MXene ceramic sheet ink B are in an excellent state; on the other hand, it can also ensure that the prepared boron nitride nanosheet ink A and MXene ceramic sheet ink B have good coating performance when coating and preparing wave-absorbing and heat-conducting composite materials, which reduces the difficulty of the coating operation process and saves the time of the coating process.
  • the silane coupling agent is KH-570.
  • the preparation method of the boron nitride nanosheets comprises the following steps: stirring and dispersing boron nitride in a mixture of isopropanol and deionized water with a mass ratio of 1:1 After centrifuging and dispersing the mixed solvent in the solvent, the supernatant is taken and suction filtered to obtain a filter residue, which is dried to obtain boron nitride nanosheets.
  • the mass volume ratio of the boron nitride and the mixed solvent is 1: (900-1100mL); the stirring speed is 25000r/min, and the stirring time is 2h; the centrifugal speed is 500r/min, and the centrifugal time is 45min; the suction filtration adopts a nylon filter membrane, the diameter of the nylon filter membrane is 40mm, and the aperture is 450nm; the drying is vacuum drying, The drying time is 8 hours, and the drying temperature is 60°C.
  • the mass-to-volume ratio of the boron nitride and the mixed solvent is 1:1000 mL.
  • the preparation method of the MXene ceramic sheet includes the following steps: dissolving NH 4 BF 4 in hydrochloric acid solution, and then adding Ti 3 AlC 2 while stirring, After continuing to stir for 30 minutes, transfer it to a hydrothermal reaction kettle, react at 180°C for 2-16 hours in a nitrogen atmosphere, and then cool it down to room temperature naturally, then centrifuge to collect the black precipitate and wash and dry it to form multi-layer MXene; then multi-layer MXene Add it into ultrapure water, shake it clockwise for 2-3 hours under the protection of nitrogen, and then centrifuge it at 3500r/min for 15 minutes to get a stable upper layer and a stable solution to obtain MXene ceramic sheets.
  • the mass volume ratio of the NH 4 BF 4 , Ti 3 AlC 2 and hydrochloric acid solution is 0.75g:0.25g:15mL; the mass concentration of the hydrochloric acid is 6mol /L;
  • the mass volume ratio of described multilayer MXene and ultrapure water is 0.5g: 10mL.
  • the wave-absorbing and heat-conducting composite material includes the following raw materials in parts by weight: 40-90 parts of boron nitride nanosheet ink A and 20-90 parts of MXene ceramic sheet ink B .
  • the wave-absorbing and heat-conducting composite material includes the following raw materials in parts by weight: 60-80 parts of boron nitride nanosheet ink A and 50-70 parts of MXene ceramic sheet ink B .
  • the parts by weight of boron nitride nanosheet ink A and MXene ceramic sheet ink B are within the above-mentioned range, it can be ensured that the obtained wave-absorbing and heat-conducting composite material has good wave-absorbing and heat-conducting properties; if the weight of boron nitride nanosheet ink A When the number of parts is small, the thermal conductivity of the material will be reduced. If the number of parts by weight of the boron nitride nanosheet ink A is large, the thermal conductivity will be good, but it will make it difficult to mix the ink uniformly and reduce the adhesion strength of the paper surface.
  • the wave-absorbing and heat-conducting composite material includes the following raw materials in parts by weight: 70 parts of boron nitride nanosheet ink A and 60 parts of MXene ceramic sheet ink B.
  • the prepared wave-absorbing and heat-conducting composite material has the best wave-absorbing performance and thermal conductivity, and the thermal conductivity can reach 9.4W/ (m*k), the absorbing performance can reach -18.6dB.
  • the quantitative index of the filter paper used in the filter paper layer is 80-200 g/cm 2 .
  • the quantitative index of the filter paper used in the filter paper layer is 120 g/cm 2 .
  • the quantitative index of the filter paper used in the filter paper layer is within the above range, especially 120g/ cm2 , it can provide good mechanical strength support and thickness medium for the heat conduction layer and wave absorbing layer on both sides of the paper, which is convenient for the heat conduction layer and wave absorbing layer.
  • the interweaving and blending through the pores of the paper can further improve the overall thermal conductivity and wave absorption of the material, and can avoid excessive contact between the heat conduction layer and the wave absorbing layer and reduce the overall performance due to excessive pores or too thin paper.
  • the present invention also provides a preparation method of the wave-absorbing and heat-conducting composite material, the preparation method comprising the following steps: respectively coating the boron nitride nanosheet ink A and the MXene ceramic sheet ink B on both sides of the filter paper and then drying , to obtain wave-absorbing and heat-conducting composite materials.
  • the coating amount of the coating is 10-100 g/cm 2 .
  • the thickness of the heat-conducting layer and the wave-absorbing layer can be made appropriate.
  • the problem of excessively thin time cost can be avoided, and on the other hand, the heat-conducting layer and wave-absorbing layer caused by too thick
  • the uneven interweaving of layers on both sides of the filter paper makes the overall performance change little, and reduces the benefit in disguise.
  • the preparation method of the boron nitride nanosheet ink A or MXene ceramic sheet ink B comprises the following steps: the raw material of boron nitride nanosheet ink A or MXene ceramic sheet ink B After mixing evenly, add it to a twin-screw mixer for kneading and stirring, and then transfer the stirred mixture to a high-speed shearing machine for high-speed stirring and mixing to obtain boron nitride nanosheet ink A or MXene ceramic sheet ink B.
  • the mixing and stirring speed is 400-600rpm, and the mixing and stirring time is 30-60min; the high-speed stirring speed is 10000-15000rpm, and the high-speed stirring The time is 10-30min.
  • the drying is vacuum drying, and the drying temperature is 80-100°C.
  • the invention also provides the application of the wave-absorbing and heat-conducting composite material in the field of flexible electronic circuits and electronic devices.
  • the sandwich structure of the wave-absorbing and heat-conducting composite material provided by the present invention enables the wave-absorbing layer and the heat-conducting layer formed on both sides of the filter paper to facilitate the independent play of their respective advantages.
  • the filter paper ’s
  • the heat conduction layer and the wave absorbing layer on both sides can be interwoven on the surface of the porous filter paper and have good compatibility, thereby improving the interfacial compatibility of the sandwich structure and the wave absorbing and heat conduction properties of both sides;
  • the wave-absorbing and heat-conducting composite material provided by the technical solution of the present invention adopts the method of coating, which is simple to operate and easy to industrial production;
  • the wave-absorbing and heat-conducting composite material provided by the technical solution of the present invention uses paper as the middle layer of the sandwich, so that the prepared material has good flexibility and can be applied to flexible electronic circuits and electronic devices.
  • This embodiment provides a wave-absorbing and heat-conducting composite material, including the following raw materials in parts by weight: 70 parts of boron nitride nanosheet ink A and 60 parts of MXene ceramic sheet ink B;
  • boron nitride nanosheet ink A includes the following raw materials in parts by weight: 25 parts of boron nitride nanosheets, 30 parts of tert-butanol, 8 parts of glycerin and 0.7 parts of silane coupling agent;
  • MXene ceramic sheet ink B includes the following raw materials in parts by weight: 25 parts of MXene ceramic sheet, 30 parts of tert-butanol, 8 parts of glycerin, and 0.7 part of silane coupling agent;
  • Concrete preparation method comprises the following steps:
  • boron nitride nanosheets Weigh 1g of boron nitride (mass fraction: 99.5%, particle size ⁇ 45 ⁇ m, AlfaAesar) dispersed in 1000 cm of isopropanol (analytical grade, Tianjin Yongda Chemical Reagent Co., Ltd.
  • the precipitate was dried under vacuum at 60°C for 12 hours to obtain multilayer MXene; 0.5 g of the prepared multilayer MXene was weighed and added to a conical flask filled with 10 mL of ultrapure water, and a certain amount of nitrogen gas was introduced Use as a protective gas to prevent MXene from deteriorating; after sealing, shake clockwise for 2-3 hours. Then, centrifuge at a speed of 3500r/min for 15min, and take the stable solution in the upper layer to obtain MXene ceramic sheets;
  • MXene ceramic sheet ink B Weigh 25 parts of MXene ceramic sheet, 30 parts of tert-butanol, 8 parts of glycerin, and 0.7 part of KH-570, mix them evenly, and add them to the twin-screw mixer. Stir for 45min, then transfer it to a high-speed shearing machine, stir for 15min at a rotating speed of 12500rpm to obtain MXene ceramic sheet ink B; carry out according to the standard test method for the freeze-thaw viscosity stability of ASTM D8020-2015 water-based ink and ink carrier Detected, the apparent viscosity of the prepared MXene ceramic sheet ink B was measured to be 4500mPa*s;
  • Boron nitride nanosheet ink A and MXene ceramic sheet ink B are applied to both sides of 120g/ cm2 quantitative filter paper with a coating amount of 50g/ cm2 respectively by screen printing method, and then the coated The finished product was dried in a vacuum drying oven at 80° C. for 1 hour to obtain a wave-absorbing and heat-conducting composite material.
  • Example 1 The only difference between this example and Example 1 is that the parts by weight of the boron nitride nanosheet ink A is 90 parts, and the MXene ceramic sheet ink B is 90 parts.
  • Example 1 The only difference between this example and Example 1 is that the boron nitride nanosheet ink A is 60 parts by weight, and the MXene ceramic sheet ink B is 50 parts by weight.
  • Example 1 The only difference between this example and Example 1 is that the parts by weight of the boron nitride nanosheet ink A is 80 parts, and the MXene ceramic sheet ink B is 70 parts.
  • Example 1 The only difference between this example and Example 1 is that the boron nitride nanosheet ink A is 40 parts by weight, and the MXene ceramic sheet ink B is 20 parts by weight.
  • Example 1 The only difference between this example and Example 1 is that the boron nitride nanosheet ink A is 60 parts by weight, and the MXene ceramic sheet ink B is 40 parts by weight.
  • the boron nitride nanosheet ink A includes the following raw materials in parts by weight: 40 parts of boron nitride nanosheets, 45 parts of tert-butanol, 10 parts of glycerin and 2 parts of silane coupling agent;
  • the apparent viscosity of boron nitride nanosheet ink A is 7500mPa*s;
  • MXene ceramic sheet ink B includes the following raw materials in parts by weight: 45 parts of MXene ceramic sheet, 45 parts of tert-butanol, 14 parts of glycerin, and 1.5 parts of silane coupling agent; the apparent viscosity of MXene ceramic sheet ink B is 6800mPa*s.
  • the boron nitride nanosheet ink A includes the following raw materials in parts by weight: 8 parts of boron nitride nanosheets, 20 parts of tert-butanol, 5 parts of glycerin and 0.2 parts of silane coupling agent,
  • the apparent viscosity of boron nitride nanosheet ink A is 3500mPa*s;
  • MXene ceramic sheet ink B includes the following raw materials in parts by weight: 15 parts of MXene ceramic sheet, 20 parts of tert-butanol, 5 parts of glycerin, and 0.2 part of silane coupling agent; the apparent viscosity of MXene ceramic sheet ink B is 2600mPa*s.
  • Example 1 The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A is 100 parts by weight, and the MXene ceramic sheet ink B is 110 parts by weight.
  • Example 1 The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A is 20 parts by weight, and the MXene ceramic sheet ink B is 15 parts by weight.
  • Example 1 The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A and the MXene ceramic sheet ink B are coated to 120g/cm quantitative filter paper with a coating amount of 200g/ cm2 by screen printing method sides of the .
  • Example 1 The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A and the MXene ceramic sheet ink B are coated to 450g/cm quantitative filter paper with a coating amount of 50g/ cm2 by screen printing method sides of the .
  • Example 1 The only difference between this comparative example and Example 1 is that during the preparation process, 70 parts of boron nitride nanosheet ink A and 60 parts of MXene ceramic sheet ink B were mixed evenly and coated on both sides of the filter paper.
  • Example 1 The only difference between this comparative example and Example 1 is that only 70 parts of the prepared boron nitride nanosheet ink A are coated on both sides of the filter paper.
  • Example 1 The only difference between this comparative example and Example 1 is that only 60 parts of prepared MXene ceramic sheet ink B are coated on both sides of the filter paper.
  • the thermal conductivity is tested according to the American standard ASTMD5470 "Standard Test Method for Heat Transfer Characteristics of Thermally Conductive Electrical Insulation Materials". The temperature difference between them can be used to obtain the thermal conductivity of the sample. This test method can better simulate the actual use state and is close to the actual use scene;
  • the absorbing performance is to directly test the electromagnetic wave absorbing performance of the heat-conducting absorbing material according to GJB 2038A-2011 "Radar Absorbing Material Reflectivity Test Method". This method is the most widely used method for evaluating the performance of absorbing materials in China.
  • the electromagnetic wave signal is transmitted by the network analyzer through an antenna during the test, the signal is incident on the sample to be tested and reflected, the reflected signal is received by another antenna and sent to the network analyzer, due to the effect of the absorbing material, the transmission power There is a certain difference between the received power and the received power, and the value converted into dB is the reflectivity of the sample;
  • Table 1 Test data table of heat conduction and wave absorption performance of wave-absorbing and heat-conducting composite materials prepared in Examples 1-8 and Comparative Examples 1-7
  • the thermal conductivity of the composite material obtained is above 7.7W/(m*k), and the wave-absorbing performance is less than -15.2dB, namely It shows excellent heat conduction and wave absorption performance, wherein, comprehensively speaking, the comprehensive effect of heat conduction and wave absorption of the composite material obtained by adopting the parameters and preparation method in Example 1 is the best;
  • Example 1 and Comparative Examples 1-3 when the weight parts of the addition amount of boron nitride nanosheet ink A and MXene ceramic sheet ink B are too much or too little, or increase the coating of both All can make the thermal conductivity and the absorbing property of the composite material prepared obviously decline;
  • embodiment 1 and comparative example 4 when the technical quantitative index of filter paper is not within the scope that the present invention provides, The thermal conductivity and the wave-absorbing performance of the prepared composite material have a certain degree of decline; from the data in Example 1 and Comparative Example 5, it can be seen that when boron nitride nanosheet ink A and MXene ceramic sheet ink B are mixed After coating, although both are added, the performance of the prepared composite material is not as good as that of the composite material prepared separately.

Abstract

The present invention relates to the technical field of materials. Disclosed are a wave-absorbing thermally-conductive composite material, and a preparation method therefor and a use thereof. The wave-absorbing thermally-conductive composite material provided in the present invention is of a sandwich structure, the sandwich structure comprises a thermally-conductive layer, a wave-absorbing layer, and a filter paper layer, and the filter paper layer is located between the thermally-conductive layer and the wave-absorbing layer. On the one hand, the existence of the sandwich structure facilitates the wave-absorbing layer and the thermally-conductive layer exerting respective advantages independently, and on the other hand, the thermally-conductive layer and the wave-absorbing layer on two side surfaces of the filter paper can be interwoven on a surface layer of porous filter paper and have good compatibility, thereby improving interface compatibility of forming the sandwich structure and respective wave-absorbing and thermally-conductive performance of two surfaces. In addition, since a middle layer is the filter paper layer, the prepared material has good flexibility and can be applied to a flexible electronic circuit and an electronic device. Moreover, a coating method is used in the preparation method for the wave-absorbing thermally-conductive composite material provided in the technical solution of the present application, such that the operation is simple and it is easy for industrial production.

Description

一种吸波导热复合材料及其制备方法与应用A wave-absorbing heat-conducting composite material and its preparation method and application 技术领域technical field
本发明属于材料技术领域，尤其涉及一种吸波导热复合材料及其制备方法与应用。The invention belongs to the field of material technology, and in particular relates to a wave-absorbing and heat-conducting composite material and a preparation method and application thereof.
背景技术Background technique
经过十多年发展，吸波导热复合材料已日益标准化、体系化，工业级的吸波导热复合材料产品也已经定型批量生产，其性能稳步提升，已应用在军民电子设备领域。但仍存在一些技术瓶颈没有突破，制约着整个行业的发展。例如，缺乏材料微观结构和功能单元模型、通用设计理论不能指导实际工业生产、尚无兼具导热与吸波功能的单组分填料等问题都严重制约了吸波导热复合材料的快速发展。After more than ten years of development, wave-absorbing and heat-conducting composite materials have become increasingly standardized and systematic. Industrial-grade wave-absorbing and heat-conducting composite materials have also been finalized and mass-produced. Their performance has been steadily improved, and they have been applied in the field of military and civilian electronic equipment. But there are still some technical bottlenecks that have not been broken through, restricting the development of the entire industry. For example, the lack of material microstructure and functional unit models, the inability of general design theory to guide actual industrial production, and the lack of single-component fillers with both heat conduction and wave absorption functions have seriously restricted the rapid development of wave-absorbing and heat-conducting composite materials.
为了改善吸波导热复合材料的结构与性能，人们进行了很多研究。CN202110576618.2公布了一种电磁吸波导热组合物，生成的蜂窝状纳米NiO前驱体与氮掺杂介孔碳微球进行复合，再通过煅烧，得到氮掺杂介孔碳微球负载蜂窝状结构。CN202010082833.2公布了氮化硼石墨烯聚酰亚胺复合吸波导热复合材料，明显提高了吸波导热性能和稳定性能。CN201510992447.6通过平均粒径不同的第一导热粒子和第二导热粒子的搭配,能够提高导热粒子在聚硅氧烷基体材料中的填充量,从而搭接起高效的热传导网络,提高传热率。In order to improve the structure and performance of wave-absorbing and heat-conducting composite materials, many studies have been carried out. CN202110576618.2 discloses an electromagnetic wave-absorbing and heat-conducting composition. The generated honeycomb nano-NiO precursor is compounded with nitrogen-doped mesoporous carbon microspheres, and then calcined to obtain nitrogen-doped mesoporous carbon microspheres loaded honeycomb structure. CN202010082833.2 discloses boron nitride graphene polyimide composite wave-absorbing and heat-conducting composite material, which significantly improves wave-absorbing and heat-conducting performance and stability. CN201510992447.6 Through the collocation of the first heat-conducting particles and the second heat-conducting particles with different average particle diameters, the filling amount of the heat-conducting particles in the polysiloxane matrix material can be increased, thereby forming an efficient heat conduction network and improving the heat transfer rate .
然而，目前针对混合吸波导热结构的制备方法很多，但对于如何制备导热与吸波功能相互配合又不会互相减弱各自的性能发挥，对制备具有三明治功能结构的吸波导热复合材料研究还没有报导。However, there are currently many preparation methods for hybrid wave-absorbing and heat-conducting structures, but there is still no research on how to prepare heat-conducting and wave-absorbing functions to cooperate with each other without weakening their performance. report.
发明内容Contents of the invention
本发明的目的在于提供一种导热和吸波能相互配合又不会相互减弱各自性能发挥的吸波导热复合材料及其制备方法与应用。The object of the present invention is to provide a wave-absorbing and heat-conducting composite material whose heat-conducting and wave-absorbing energies cooperate with each other without weakening their respective performances, as well as its preparation method and application.
为实现上述目的，本发明采取的技术方案为：一种吸波导热复合材料，所述吸波导热复合材料为三明治结构，所述三明治结构包括导热层、吸波层和滤纸层，所述滤纸层位于导热层和吸波层之间。In order to achieve the above object, the technical solution adopted by the present invention is: a wave-absorbing and heat-conducting composite material, the wave-absorbing and heat-conducting composite material is a sandwich structure, and the sandwich structure includes a heat-conducting layer, a wave-absorbing layer and a filter paper layer, and the filter paper The layer is located between the heat conducting layer and the wave absorbing layer.
本发明的技术方案提供了一种具有三明治结构的吸波导热复合材料，在滤纸的两侧面分别有导热层和吸波层，一方面，三明治结构使得产品在滤纸的两侧面形成的吸波层和导热层能够便于两者独立的发挥各自的优势，另一方面，滤纸的两侧面的导热层和吸波层能够在多孔性的滤纸表层进行交织且有很好的相容性，进而提高了形成三明治结构的界面相容性和两面各具的吸波和导热性能；同时，本发明提供的是纸结构的吸波导热复合材料，此材料具有良好的柔性。The technical solution of the present invention provides a wave-absorbing and heat-conducting composite material with a sandwich structure. There are respectively a heat-conducting layer and a wave-absorbing layer on both sides of the filter paper. On the one hand, the sandwich structure makes the wave-absorbing layer formed on both sides of the filter paper The heat conduction layer and the heat conduction layer can facilitate the two to play their respective advantages independently. On the other hand, the heat conduction layer and the absorbing layer on both sides of the filter paper can be interwoven on the surface of the porous filter paper and have good compatibility, thereby improving the The interfacial compatibility of the sandwich structure and the wave-absorbing and heat-conducting properties on both sides; at the same time, the invention provides a wave-absorbing and heat-conducting composite material with a paper structure, and the material has good flexibility.
作为本发明所述吸波导热复合材料的优选实施方式，所述导热层由氮化硼纳米片油墨A涂布而成，所述氮化硼纳米片油墨A包括以下重量份数的原料：5-40份氮化硼纳米片、20-50份叔丁醇、5-10份甘油和0.1-2份硅烷偶联剂；所述吸波层由MXene陶瓷片油墨B涂布而成，所述MXene陶瓷片油墨B包括以下重量份数的原料：15-50份MXene陶瓷片、20-50份叔丁醇、5-15份甘油、0.1-2份硅烷偶联剂。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the heat-conducting layer is coated with boron nitride nanosheet ink A, and the boron nitride nanosheet ink A includes the following raw materials in parts by weight: 5 -40 parts of boron nitride nanosheets, 20-50 parts of tert-butanol, 5-10 parts of glycerin and 0.1-2 parts of silane coupling agent; the absorbing layer is coated with MXene ceramic sheet ink B, and the MXene ceramic sheet ink B includes the following raw materials in parts by weight: 15-50 parts of MXene ceramic sheet, 20-50 parts of tert-butanol, 5-15 parts of glycerin, and 0.1-2 parts of silane coupling agent.
作为本发明所述吸波导热复合材料的优选实施方式，所述氮化硼纳米片油墨A的表观粘度为3000-8000mPa*s；所述MXene陶瓷片油墨B的表观粘度为2000-7000mPa*s。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the apparent viscosity of the boron nitride nanosheet ink A is 3000-8000mPa*s; the apparent viscosity of the MXene ceramic sheet ink B is 2000-7000mPa *s.
当使用的氮化硼纳米片油墨A和MXene陶瓷片油墨B采用上述重量份的原料时，一方面能够保证制备得到的氮化硼纳米片油墨A和MXene陶瓷片油墨B的表观粘度在上述范围内，一方面能够保证制备得到的氮化硼纳米片油墨A和MXene陶瓷片油墨B的导热和吸波性能处于优异的状态，另一方面，也能保证制备得到的氮化硼纳米片油墨A和MXene陶瓷片油墨B在涂布制备吸波导热复合材料的时候具有良好的涂布性能，减少涂布操作过程的难度、节省涂布过程 的时间。When the boron nitride nanosheet ink A and MXene ceramic sheet ink B used adopt the raw materials of the above weight parts, on the one hand, it can ensure that the apparent viscosity of the prepared boron nitride nanosheet ink A and MXene ceramic sheet ink B is above the above-mentioned Within the range, on the one hand, it can ensure that the thermal conductivity and wave absorption properties of the prepared boron nitride nanosheet ink A and MXene ceramic sheet ink B are in an excellent state; on the other hand, it can also ensure that the prepared boron nitride nanosheet ink A and MXene ceramic sheet ink B have good coating performance when coating and preparing wave-absorbing and heat-conducting composite materials, which reduces the difficulty of the coating operation process and saves the time of the coating process.
作为本发明所述吸波导热复合材料的优选实施方式，所述硅烷偶联剂为KH-570。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the silane coupling agent is KH-570.
作为本发明所述吸波导热复合材料的优选实施方式，所述氮化硼纳米片的制备方法包括以下步骤：将氮化硼搅拌分散在异丙醇和去离子水质量比为1:1的混合溶剂中，接着离心分散后的混合溶剂，取上清液并抽滤，得滤渣，将滤渣干燥，得氮化硼纳米片。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the preparation method of the boron nitride nanosheets comprises the following steps: stirring and dispersing boron nitride in a mixture of isopropanol and deionized water with a mass ratio of 1:1 After centrifuging and dispersing the mixed solvent in the solvent, the supernatant is taken and suction filtered to obtain a filter residue, which is dried to obtain boron nitride nanosheets.
作为本发明所述吸波导热复合材料的优选实施方式，所述氮化硼和混合溶剂的质量体积比为1：(900-1100mL)；所述搅拌的转速为25000r/min，搅拌的时间为2h；所述离心的转速为500r/min，离心的时间为45min；所述抽滤采用的为尼龙滤膜，所述尼龙滤膜的直径为40mm，孔径为450nm；所述干燥为真空干燥，干燥的时间为8h，干燥的温度为60℃。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the mass volume ratio of the boron nitride and the mixed solvent is 1: (900-1100mL); the stirring speed is 25000r/min, and the stirring time is 2h; the centrifugal speed is 500r/min, and the centrifugal time is 45min; the suction filtration adopts a nylon filter membrane, the diameter of the nylon filter membrane is 40mm, and the aperture is 450nm; the drying is vacuum drying, The drying time is 8 hours, and the drying temperature is 60°C.
作为本发明所述吸波导热复合材料的优选实施方式，所述氮化硼和混合溶剂的质量体积比为1：1000mL。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the mass-to-volume ratio of the boron nitride and the mixed solvent is 1:1000 mL.
作为本发明所述吸波导热复合材料的优选实施方式，所述MXene陶瓷片的制备方法包括以下步骤：将NH 4BF 4溶解在盐酸溶液中，接着在搅拌的状态下加入Ti 3AlC 2，继续搅拌30min后转移至水热反应釜中，在氮气的环境下于180℃下反应2-16h后自然冷却至室温，接着离心收集黑色沉淀并洗涤干燥，得多层MXene；接着将多层MXene加入到超纯水中，在氮气的保护下按顺时针的方向震荡2-3h，然后在3500r/min转速下离心15min，取稳定的上层稳定的溶液，得MXene陶瓷片。 As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the preparation method of the MXene ceramic sheet includes the following steps: dissolving NH 4 BF 4 in hydrochloric acid solution, and then adding Ti 3 AlC 2 while stirring, After continuing to stir for 30 minutes, transfer it to a hydrothermal reaction kettle, react at 180°C for 2-16 hours in a nitrogen atmosphere, and then cool it down to room temperature naturally, then centrifuge to collect the black precipitate and wash and dry it to form multi-layer MXene; then multi-layer MXene Add it into ultrapure water, shake it clockwise for 2-3 hours under the protection of nitrogen, and then centrifuge it at 3500r/min for 15 minutes to get a stable upper layer and a stable solution to obtain MXene ceramic sheets.
作为本发明所述吸波导热复合材料的优选实施方式，所述NH 4BF 4、Ti 3AlC 2与盐酸溶液的质量体积比为0.75g：0.25g：15mL；所述盐酸的质量浓度为6mol/L；所述多层MXene与超纯水的质量体积比为0.5g：10mL。 As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the mass volume ratio of the NH 4 BF 4 , Ti 3 AlC 2 and hydrochloric acid solution is 0.75g:0.25g:15mL; the mass concentration of the hydrochloric acid is 6mol /L; The mass volume ratio of described multilayer MXene and ultrapure water is 0.5g: 10mL.
作为本发明所述吸波导热复合材料的优选实施方式，所述吸波导热复合材料包括以下重量份的原料：40-90份氮化硼纳米片油墨A和20-90份MXene陶 瓷片油墨B。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the wave-absorbing and heat-conducting composite material includes the following raw materials in parts by weight: 40-90 parts of boron nitride nanosheet ink A and 20-90 parts of MXene ceramic sheet ink B .
作为本发明所述吸波导热复合材料的优选实施方式，所述吸波导热复合材料包括以下重量份的原料：60-80份氮化硼纳米片油墨A和50-70份MXene陶瓷片油墨B。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the wave-absorbing and heat-conducting composite material includes the following raw materials in parts by weight: 60-80 parts of boron nitride nanosheet ink A and 50-70 parts of MXene ceramic sheet ink B .
氮化硼纳米片油墨A和MXene陶瓷片油墨B的重量份数在上述范围内时，能够保证得到的吸波导热复合材料具有良好的吸波导热性能；若氮化硼纳米片油墨A的重量份数较少时，会使得材料的导热性能下降，若氮化硼纳米片油墨A的重量份数较多时，导热性能好，但是会使得油墨混合难以均匀且使得纸面的粘附强度降低，不利于后续的利用以及吸波导热材料的稳定储存；若MXene陶瓷片油墨B的重量份数较少时，会使得材料的吸波性能下降，若MXene陶瓷片油墨B的重量份数较多时，会使得油墨难以混合均匀且粘度下降，反而降低材料的吸波性能。When the parts by weight of boron nitride nanosheet ink A and MXene ceramic sheet ink B are within the above-mentioned range, it can be ensured that the obtained wave-absorbing and heat-conducting composite material has good wave-absorbing and heat-conducting properties; if the weight of boron nitride nanosheet ink A When the number of parts is small, the thermal conductivity of the material will be reduced. If the number of parts by weight of the boron nitride nanosheet ink A is large, the thermal conductivity will be good, but it will make it difficult to mix the ink uniformly and reduce the adhesion strength of the paper surface. It is not conducive to subsequent utilization and stable storage of wave-absorbing and heat-conducting materials; if the weight fraction of MXene ceramic sheet ink B is small, the wave-absorbing performance of the material will be reduced; if the weight fraction of MXene ceramic sheet ink B is large, It will make it difficult for the ink to mix evenly and the viscosity will drop, which will reduce the absorbing performance of the material.
作为本发明所述吸波导热复合材料的优选实施方式，所述吸波导热复合材料包括以下重量份的原料：70份氮化硼纳米片油墨A和60份MXene陶瓷片油墨B。As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the wave-absorbing and heat-conducting composite material includes the following raw materials in parts by weight: 70 parts of boron nitride nanosheet ink A and 60 parts of MXene ceramic sheet ink B.
当氮化硼纳米片油墨A和MXene陶瓷片油墨B的重量份数为上述值时，制备得到的吸波导热复合材料的吸波性能和导热性能均最优，其中导热性能可达9.4W/(m*k)，吸波性能可达-18.6dB。When the weight parts of boron nitride nanosheet ink A and MXene ceramic sheet ink B are the above values, the prepared wave-absorbing and heat-conducting composite material has the best wave-absorbing performance and thermal conductivity, and the thermal conductivity can reach 9.4W/ (m*k), the absorbing performance can reach -18.6dB.
作为本发明所述吸波导热复合材料的优选实施方式，所述滤纸层使用的滤纸的定量指标为80-200g/cm 2。 As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the quantitative index of the filter paper used in the filter paper layer is 80-200 g/cm 2 .
作为本发明所述吸波导热复合材料的优选实施方式，所述滤纸层使用的滤纸的定量指标为120g/cm 2。 As a preferred embodiment of the wave-absorbing and heat-conducting composite material of the present invention, the quantitative index of the filter paper used in the filter paper layer is 120 g/cm 2 .
当滤纸层使用的滤纸的定量指标在上述范围内尤其是120g/cm 2时，能够给纸张两侧面的导热层和吸波层提供良好的机械强度支撑及厚度媒介，方便导热层和吸波层通过纸张的孔隙进行交织和交融，进一步提升材料整体的导热性和吸波性，又能避免孔隙过大或纸张过薄使得导热层和吸波层过多接触相互影响 而降低整体的性能。 When the quantitative index of the filter paper used in the filter paper layer is within the above range, especially 120g/ cm2 , it can provide good mechanical strength support and thickness medium for the heat conduction layer and wave absorbing layer on both sides of the paper, which is convenient for the heat conduction layer and wave absorbing layer. The interweaving and blending through the pores of the paper can further improve the overall thermal conductivity and wave absorption of the material, and can avoid excessive contact between the heat conduction layer and the wave absorbing layer and reduce the overall performance due to excessive pores or too thin paper.
另外，本发明还提供了所述吸波导热复合材料的制备方法，所述制备方法包括以下步骤：将氮化硼纳米片油墨A和MXene陶瓷片油墨B分别涂布在滤纸的两侧面后干燥，得吸波导热复合材料。In addition, the present invention also provides a preparation method of the wave-absorbing and heat-conducting composite material, the preparation method comprising the following steps: respectively coating the boron nitride nanosheet ink A and the MXene ceramic sheet ink B on both sides of the filter paper and then drying , to obtain wave-absorbing and heat-conducting composite materials.
作为本发明所述制备方法的优选实施方式，所述涂布的涂布量为10-100g/cm 2。 As a preferred embodiment of the preparation method of the present invention, the coating amount of the coating is 10-100 g/cm 2 .
当涂布量在上述范围内时，能够使得导热层和吸波层的厚度适宜，一方面能够避免过薄的时间成本过高的问题，另一方面能够避免过厚导致的导热层和吸波层在滤纸两侧面进行交织的不均匀而使得整体性能改变不大，变相的降低了效益。When the coating amount is within the above range, the thickness of the heat-conducting layer and the wave-absorbing layer can be made appropriate. On the one hand, the problem of excessively thin time cost can be avoided, and on the other hand, the heat-conducting layer and wave-absorbing layer caused by too thick The uneven interweaving of layers on both sides of the filter paper makes the overall performance change little, and reduces the benefit in disguise.
作为本发明所述制备方法的优选实施方式，所述氮化硼纳米片油墨A或MXene陶瓷片油墨B的制备方法包括以下步骤：将氮化硼纳米片油墨A或MXene陶瓷片油墨B的原料混合均匀后加入到双螺杆混合器中混炼搅拌，接着将搅拌后的混合物转移至高速剪切机中高速搅拌混合，得氮化硼纳米片油墨A或MXene陶瓷片油墨B。As a preferred embodiment of the preparation method of the present invention, the preparation method of the boron nitride nanosheet ink A or MXene ceramic sheet ink B comprises the following steps: the raw material of boron nitride nanosheet ink A or MXene ceramic sheet ink B After mixing evenly, add it to a twin-screw mixer for kneading and stirring, and then transfer the stirred mixture to a high-speed shearing machine for high-speed stirring and mixing to obtain boron nitride nanosheet ink A or MXene ceramic sheet ink B.
作为本发明所述制备方法的优选实施方式，所述混炼搅拌的转速为400-600rpm，混炼搅拌的时间为30-60min；所述高速搅拌的转速为10000-15000rpm，所述高速搅拌的时间为10-30min。As a preferred embodiment of the preparation method of the present invention, the mixing and stirring speed is 400-600rpm, and the mixing and stirring time is 30-60min; the high-speed stirring speed is 10000-15000rpm, and the high-speed stirring The time is 10-30min.
作为本发明所述制备方法的优选实施方式，所述干燥为真空干燥，所述干燥的温度为80-100℃。As a preferred embodiment of the preparation method of the present invention, the drying is vacuum drying, and the drying temperature is 80-100°C.
另外，本发明还提供了所述吸波导热复合材料在柔性电子电路与电子器件领域上的应用。In addition, the invention also provides the application of the wave-absorbing and heat-conducting composite material in the field of flexible electronic circuits and electronic devices.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
第一：本发明提供的吸波导热复合材料具有的三明治结构一方面使得产品在滤纸的两侧面形成的吸波层和导热层能够便于两者独立的发挥各自的优势， 另一方面，滤纸的两侧面的导热层和吸波层能够在多孔性的滤纸表层进行交织且有很好的相容性，进而提高了形成三明治结构的界面相容性和两面各具的吸波和导热性能；First: The sandwich structure of the wave-absorbing and heat-conducting composite material provided by the present invention enables the wave-absorbing layer and the heat-conducting layer formed on both sides of the filter paper to facilitate the independent play of their respective advantages. On the other hand, the filter paper’s The heat conduction layer and the wave absorbing layer on both sides can be interwoven on the surface of the porous filter paper and have good compatibility, thereby improving the interfacial compatibility of the sandwich structure and the wave absorbing and heat conduction properties of both sides;
第二：本发明的技术方案提供的吸波导热复合材料采用涂布的方式，操作简单，易于工业生产；Second: The wave-absorbing and heat-conducting composite material provided by the technical solution of the present invention adopts the method of coating, which is simple to operate and easy to industrial production;
第三：本发明的技术方案提供的吸波导热复合材料以纸为三明治的中间层，使得制备得到的材料具有良好的柔性，能够应用于柔性电子电路与电子器件上。Third: The wave-absorbing and heat-conducting composite material provided by the technical solution of the present invention uses paper as the middle layer of the sandwich, so that the prepared material has good flexibility and can be applied to flexible electronic circuits and electronic devices.
具体实施方式Detailed ways
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific examples.
实施例1Example 1
本实施例提供了一种吸波导热复合材料，包括以下重量份的原料：70份氮化硼纳米片油墨A和60份MXene陶瓷片油墨B；This embodiment provides a wave-absorbing and heat-conducting composite material, including the following raw materials in parts by weight: 70 parts of boron nitride nanosheet ink A and 60 parts of MXene ceramic sheet ink B;
其中，氮化硼纳米片油墨A包括以下重量份的原料：25份氮化硼纳米片、30份叔丁醇、8份甘油和0.7份硅烷偶联剂；Wherein, boron nitride nanosheet ink A includes the following raw materials in parts by weight: 25 parts of boron nitride nanosheets, 30 parts of tert-butanol, 8 parts of glycerin and 0.7 parts of silane coupling agent;
MXene陶瓷片油墨B包括以下重量份数的原料：25份MXene陶瓷片、30份叔丁醇、8份甘油、0.7份硅烷偶联剂；MXene ceramic sheet ink B includes the following raw materials in parts by weight: 25 parts of MXene ceramic sheet, 30 parts of tert-butanol, 8 parts of glycerin, and 0.7 part of silane coupling agent;
具体制备方法包括以下步骤：Concrete preparation method comprises the following steps:
(1)氮化硼纳米片的制备：称取1g氮化硼(质量分数为99.5％，粒径＜45μm，AlfaAesar)分散在1000cm 3的异丙醇(分析纯，天津永大化学试剂有限公司)与去离子水的质量比为1:1的混合溶剂中，用玻璃棒搅拌均匀后放置于HR3653搅拌机中处理2h，使用VC6326P激光测速仪测得其转速约为25000r/min；将处理后的混合溶液以500r/min离心45min，取上层90％(体积分数)的清液，采用直径为40mm，孔径为450nm的尼龙滤膜进行真空抽滤；将滤膜上的粉体转移至玻璃培养皿，放置于60℃真空干燥箱中干燥8h，得氮化硼纳米片； (1) Preparation of boron nitride nanosheets: Weigh 1g of boron nitride (mass fraction: 99.5%, particle size <45 μm, AlfaAesar) dispersed in 1000 cm of isopropanol (analytical grade, Tianjin Yongda Chemical Reagent Co., Ltd. ) and deionized water in a mixed solvent with a mass ratio of 1:1, stirred evenly with a glass rod, and placed in a HR3653 mixer for 2 hours, and the rotational speed was measured by a VC6326P laser velocimeter at about 25000r/min; The mixed solution was centrifuged at 500r/min for 45min, and the supernatant of 90% (volume fraction) of the upper layer was taken, and a nylon filter membrane with a diameter of 40mm and a pore size of 450nm was used for vacuum filtration; the powder on the filter membrane was transferred to a glass petri dish , placed in a vacuum oven at 60°C and dried for 8 hours to obtain boron nitride nanosheets;
(2)MXene陶瓷片的制备：称取0.75g NH 4BF 4溶解在15mL 6M的HCl溶液中，然后在剧烈搅拌下将0.25g Ti 3AlC 2粉末加入上述溶液中，搅拌30min，混合均匀；之后将反应混合物转移到在50mL的水热反应釜中，并通入一定量的氮气，在180℃下反应2-16h，然后自然冷却至室温。离心收集黑色沉淀，用去离子水和无水乙醇洗涤数次。最后，沉淀物在60℃真空下干燥12小时，得到多层的MXene；称取0.5g制备好的多层MXene加入到盛有10mL超纯水的锥形瓶中，并通入一定量的氮气作保护气，防止MXene变质；封口后，按顺时针方向摇晃2-3h。然后，通过3500r/min的转速离心15min，取上层稳定的溶液，得MXene陶瓷片； (2) Preparation of MXene ceramic sheet: Weigh 0.75g NH 4 BF 4 and dissolve in 15mL 6M HCl solution, then add 0.25g Ti 3 AlC 2 powder into the above solution under vigorous stirring, stir for 30min, and mix well; Afterwards, the reaction mixture was transferred to a 50 mL hydrothermal reactor, and a certain amount of nitrogen gas was passed through, and the reaction was performed at 180° C. for 2-16 h, and then naturally cooled to room temperature. The black precipitate was collected by centrifugation and washed several times with deionized water and absolute ethanol. Finally, the precipitate was dried under vacuum at 60°C for 12 hours to obtain multilayer MXene; 0.5 g of the prepared multilayer MXene was weighed and added to a conical flask filled with 10 mL of ultrapure water, and a certain amount of nitrogen gas was introduced Use as a protective gas to prevent MXene from deteriorating; after sealing, shake clockwise for 2-3 hours. Then, centrifuge at a speed of 3500r/min for 15min, and take the stable solution in the upper layer to obtain MXene ceramic sheets;
(3)氮化硼纳米片油墨A的制备：称取25份氮化硼纳米片、30份叔丁醇、8份甘油和0.7份KH-570混合均匀后加入到双螺杆混合器中，在500rpm的转速下搅拌45min，接着将其转移至高速剪切机中，在12500rpm的转速下搅拌15min，得氮化硼纳米片油墨A；按照ASTM D8020-2015水性油墨和油墨载体的冻融粘度稳定性的标准试验方法进行检测，测得制备得到的氮化硼纳米片油墨A表观粘度为5500mPa*s；(3) Preparation of boron nitride nanosheet ink A: Weigh 25 parts of boron nitride nanosheets, 30 parts of tert-butanol, 8 parts of glycerin and 0.7 part of KH-570 and mix them evenly, then add them to the twin-screw mixer, Stir for 45min at a speed of 500rpm, then transfer it to a high-speed shear, and stir for 15min at a speed of 12500rpm to obtain boron nitride nanosheet ink A; according to ASTM D8020-2015, the freeze-thaw viscosity of water-based ink and ink carrier is stable According to the standard test method, the apparent viscosity of the prepared boron nitride nanosheet ink A is 5500mPa*s;
(4)MXene陶瓷片油墨B的制备：称取25份MXene陶瓷片、30份叔丁醇、8份甘油、0.7份KH-570混合均匀后加入到双螺杆混合器中，在500rpm的转速下搅拌45min，接着将其转移至高速剪切机中，在12500rpm的转速下搅拌15min，得MXene陶瓷片油墨B；按照ASTM D8020-2015水性油墨和油墨载体的冻融粘度稳定性的标准试验方法进行检测，测得制备得到的MXene陶瓷片油墨B表观粘度为4500mPa*s；(4) Preparation of MXene ceramic sheet ink B: Weigh 25 parts of MXene ceramic sheet, 30 parts of tert-butanol, 8 parts of glycerin, and 0.7 part of KH-570, mix them evenly, and add them to the twin-screw mixer. Stir for 45min, then transfer it to a high-speed shearing machine, stir for 15min at a rotating speed of 12500rpm to obtain MXene ceramic sheet ink B; carry out according to the standard test method for the freeze-thaw viscosity stability of ASTM D8020-2015 water-based ink and ink carrier Detected, the apparent viscosity of the prepared MXene ceramic sheet ink B was measured to be 4500mPa*s;
(5)采用丝网印刷方法将氮化硼纳米片油墨A和MXene陶瓷片油墨B分别以50g/cm 2的涂布量涂布至120g/cm 2定量的滤纸的两侧面，接着将涂布后的产品置于80℃的真空干燥箱中干燥1h，得吸波导热复合材料。 (5) Boron nitride nanosheet ink A and MXene ceramic sheet ink B are applied to both sides of 120g/ cm2 quantitative filter paper with a coating amount of 50g/ cm2 respectively by screen printing method, and then the coated The finished product was dried in a vacuum drying oven at 80° C. for 1 hour to obtain a wave-absorbing and heat-conducting composite material.
实施例2Example 2
本实施例与实施例1的唯一区别在于氮化硼纳米片油墨A的重量份数为90份、MXene陶瓷片油墨B为90份。The only difference between this example and Example 1 is that the parts by weight of the boron nitride nanosheet ink A is 90 parts, and the MXene ceramic sheet ink B is 90 parts.
实施例3Example 3
本实施例与实施例1的唯一区别在于氮化硼纳米片油墨A的重量份数为60 份、MXene陶瓷片油墨B为50份。The only difference between this example and Example 1 is that the boron nitride nanosheet ink A is 60 parts by weight, and the MXene ceramic sheet ink B is 50 parts by weight.
实施例4Example 4
本实施例与实施例1的唯一区别在于氮化硼纳米片油墨A的重量份数为80份、MXene陶瓷片油墨B为70份。The only difference between this example and Example 1 is that the parts by weight of the boron nitride nanosheet ink A is 80 parts, and the MXene ceramic sheet ink B is 70 parts.
实施例5Example 5
本实施例与实施例1的唯一区别在于氮化硼纳米片油墨A的重量份数为40份、MXene陶瓷片油墨B为20份。The only difference between this example and Example 1 is that the boron nitride nanosheet ink A is 40 parts by weight, and the MXene ceramic sheet ink B is 20 parts by weight.
实施例6Example 6
本实施例与实施例1的唯一区别在于氮化硼纳米片油墨A的重量份数为60份、MXene陶瓷片油墨B为40份。The only difference between this example and Example 1 is that the boron nitride nanosheet ink A is 60 parts by weight, and the MXene ceramic sheet ink B is 40 parts by weight.
实施例7Example 7
本实施例与实施例1的唯一区别在于氮化硼纳米片油墨A包括以下重量份的原料：40份氮化硼纳米片、45份叔丁醇、10份甘油和2份硅烷偶联剂；氮化硼纳米片油墨A的表观粘度为7500mPa*s；The only difference between this embodiment and Example 1 is that the boron nitride nanosheet ink A includes the following raw materials in parts by weight: 40 parts of boron nitride nanosheets, 45 parts of tert-butanol, 10 parts of glycerin and 2 parts of silane coupling agent; The apparent viscosity of boron nitride nanosheet ink A is 7500mPa*s;
MXene陶瓷片油墨B包括以下重量份数的原料：45份MXene陶瓷片、45份叔丁醇、14份甘油、1.5份硅烷偶联剂；MXene陶瓷片油墨B的表观粘度为6800mPa*s。MXene ceramic sheet ink B includes the following raw materials in parts by weight: 45 parts of MXene ceramic sheet, 45 parts of tert-butanol, 14 parts of glycerin, and 1.5 parts of silane coupling agent; the apparent viscosity of MXene ceramic sheet ink B is 6800mPa*s.
实施例8Example 8
本实施例与实施例1的唯一区别在于氮化硼纳米片油墨A包括以下重量份的原料：8份氮化硼纳米片、20份叔丁醇、5份甘油和0.2份硅烷偶联剂，氮化硼纳米片油墨A的表观粘度为3500mPa*s；The only difference between this embodiment and Example 1 is that the boron nitride nanosheet ink A includes the following raw materials in parts by weight: 8 parts of boron nitride nanosheets, 20 parts of tert-butanol, 5 parts of glycerin and 0.2 parts of silane coupling agent, The apparent viscosity of boron nitride nanosheet ink A is 3500mPa*s;
MXene陶瓷片油墨B包括以下重量份数的原料：15份MXene陶瓷片、20份叔丁醇、5份甘油、0.2份硅烷偶联剂；MXene陶瓷片油墨B的表观粘度为2600mPa*s。MXene ceramic sheet ink B includes the following raw materials in parts by weight: 15 parts of MXene ceramic sheet, 20 parts of tert-butanol, 5 parts of glycerin, and 0.2 part of silane coupling agent; the apparent viscosity of MXene ceramic sheet ink B is 2600mPa*s.
对比例1Comparative example 1
本对比例与实施例1的唯一区别在于氮化硼纳米片油墨A的重量份数为100份、MXene陶瓷片油墨B为110份。The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A is 100 parts by weight, and the MXene ceramic sheet ink B is 110 parts by weight.
对比例2Comparative example 2
本对比例与实施例1的唯一区别在于氮化硼纳米片油墨A的重量份数为20份、MXene陶瓷片油墨B为15份。The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A is 20 parts by weight, and the MXene ceramic sheet ink B is 15 parts by weight.
对比例3Comparative example 3
本对比例与实施例1的唯一区别在于采用丝网印刷方法将氮化硼纳米片油墨A和MXene陶瓷片油墨B分别以200g/cm 2的涂布量涂布至120g/cm 2定量的滤纸的两侧面。 The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A and the MXene ceramic sheet ink B are coated to 120g/cm quantitative filter paper with a coating amount of 200g/ cm2 by screen printing method sides of the .
对比例4Comparative example 4
本对比例与实施例1的唯一区别在于采用丝网印刷方法将氮化硼纳米片油墨A和MXene陶瓷片油墨B分别以50g/cm 2的涂布量涂布至450g/cm 2定量的滤纸的两侧面。 The only difference between this comparative example and Example 1 is that the boron nitride nanosheet ink A and the MXene ceramic sheet ink B are coated to 450g/cm quantitative filter paper with a coating amount of 50g/ cm2 by screen printing method sides of the .
对比例5Comparative example 5
本对比例与实施例1的唯一区别在于制备的过程中，将制备得到的70份氮化硼纳米片油墨A和60份MXene陶瓷片油墨B混合均匀后涂布到滤纸的两侧面。The only difference between this comparative example and Example 1 is that during the preparation process, 70 parts of boron nitride nanosheet ink A and 60 parts of MXene ceramic sheet ink B were mixed evenly and coated on both sides of the filter paper.
对比例6Comparative example 6
本对比例与实施例1的唯一区别在于在滤纸的两侧面只涂布制备得到的70份氮化硼纳米片油墨A。The only difference between this comparative example and Example 1 is that only 70 parts of the prepared boron nitride nanosheet ink A are coated on both sides of the filter paper.
对比例7Comparative example 7
本对比例与实施例1的唯一区别在于在滤纸的两侧面只涂布制备得到的60份MXene陶瓷片油墨B。The only difference between this comparative example and Example 1 is that only 60 parts of prepared MXene ceramic sheet ink B are coated on both sides of the filter paper.
效果例Effect example
将实施例1-8和对比例1-7制备得到的吸波导热复合材料进行导热性能和吸波性能的测试；The wave-absorbing and heat-conducting composite materials prepared in Examples 1-8 and Comparative Examples 1-7 were tested for thermal conductivity and wave-absorbing properties;
其中，导热性能按照美国标准ASTMD5470《热导性电绝缘材料热传输特性标准试验方法》测试进行，测试原理是通过对样品施加一定的热流量、压力来测试样品的厚度和在热板/冷板间的温度差，从而得到样品的导热系数，这种测 试方式更能模拟实际的使用状态，接近实际使用场景；Among them, the thermal conductivity is tested according to the American standard ASTMD5470 "Standard Test Method for Heat Transfer Characteristics of Thermally Conductive Electrical Insulation Materials". The temperature difference between them can be used to obtain the thermal conductivity of the sample. This test method can better simulate the actual use state and is close to the actual use scene;
吸波性能是按照GJB 2038A-2011《雷达吸波材料反射率测试方法》直接对导热吸波材料进行电磁波吸收性能的测试，该方法是国内对吸波材料性能进行评价使用最广泛的一种方法，测试时电磁波信号由网络分析仪通过一个天线发射，信号入射到待测样品并被反射出去，反射后的信号被另一个天线接收并送至网络分析仪，由于吸波材料的作用，发射功率和接收功率存在一定差值，这一差值转化成dB为单位的数值就是样品的反射率；The absorbing performance is to directly test the electromagnetic wave absorbing performance of the heat-conducting absorbing material according to GJB 2038A-2011 "Radar Absorbing Material Reflectivity Test Method". This method is the most widely used method for evaluating the performance of absorbing materials in China. , the electromagnetic wave signal is transmitted by the network analyzer through an antenna during the test, the signal is incident on the sample to be tested and reflected, the reflected signal is received by another antenna and sent to the network analyzer, due to the effect of the absorbing material, the transmission power There is a certain difference between the received power and the received power, and the value converted into dB is the reflectivity of the sample;
测试得到的性能参数如表1所示；The performance parameters obtained by the test are shown in Table 1;
表1：实施例1-8和对比例1-7制备得到的吸波导热复合材料的导热吸波性能测试数据表Table 1: Test data table of heat conduction and wave absorption performance of wave-absorbing and heat-conducting composite materials prepared in Examples 1-8 and Comparative Examples 1-7
Figure PCTCN2022078291-appb-000001
Figure PCTCN2022078291-appb-000001
从表1中可以看出，当采用的制备参数在本发明给出的范围内时，得到的复合材料的导热性能在7.7W/(m*k)以上，吸波性能小于-15.2dB，即显示出了优异的导热吸波性能，其中，综合来看，采用实施例1中的参数和制备方法得到的复合材料的导热吸波综合效果最优；As can be seen from Table 1, when the preparation parameters adopted are within the scope given by the present invention, the thermal conductivity of the composite material obtained is above 7.7W/(m*k), and the wave-absorbing performance is less than -15.2dB, namely It shows excellent heat conduction and wave absorption performance, wherein, comprehensively speaking, the comprehensive effect of heat conduction and wave absorption of the composite material obtained by adopting the parameters and preparation method in Example 1 is the best;
从实施例1和对比例1-3的数据可以看出来，当氮化硼纳米片油墨A和MXene陶瓷片油墨B的添加量的重量份数过多或过少、或者增加两者的涂布量都会使得制备得到的复合材料的导热性能和吸波性有明显的下降；从实施例1和对比例4的数据中可以看出来，滤纸的技术定量指标不在本发明给出的范围 内时，制备得到的复合材料的导热性能和吸波性能有一定程度的下降；从实施例1和对比例5中的数据中可以看出，当将氮化硼纳米片油墨A和MXene陶瓷片油墨B混合后涂布，虽然两者都有添加，但制备得到的复合材料的性能却不如分别涂布制备得到的复合材料性能那么优异，这直观的说明了，两者混合涂布会对导热吸波性能产生干扰，而本发明的三明治结构能够很好的避免这个干扰现象的出现；从实施例1和对比例6-7的数据中可以看出，当分别只采用氮化硼纳米片油墨A或MXene陶瓷片油墨B涂布时，得到的产品也只具有导热或吸波性能，并且具有的导热和吸波性能不如将两者分别涂布后的性能，这直观的说明了本发明提出的三明治结构的复合材料的导热性能和吸波性能并不是简单的叠加的效果，其由于滤纸的多孔性结构，两者油墨涂布干燥时产生了一定的交织，从而相互提升了彼此的导热和吸波性能。As can be seen from the data of Example 1 and Comparative Examples 1-3, when the weight parts of the addition amount of boron nitride nanosheet ink A and MXene ceramic sheet ink B are too much or too little, or increase the coating of both All can make the thermal conductivity and the absorbing property of the composite material prepared obviously decline; As can be seen from the data of embodiment 1 and comparative example 4, when the technical quantitative index of filter paper is not within the scope that the present invention provides, The thermal conductivity and the wave-absorbing performance of the prepared composite material have a certain degree of decline; from the data in Example 1 and Comparative Example 5, it can be seen that when boron nitride nanosheet ink A and MXene ceramic sheet ink B are mixed After coating, although both are added, the performance of the prepared composite material is not as good as that of the composite material prepared separately. This intuitively shows that the mixed coating of the two will affect the thermal conductivity and wave absorption performance Interference occurs, and the sandwich structure of the present invention can well avoid the occurrence of this interference phenomenon; as can be seen from the data of Example 1 and Comparative Examples 6-7, when only using boron nitride nanosheet ink A or MXene When ceramic sheet ink B is coated, the obtained product also only has heat conduction or wave absorption properties, and the heat conduction and wave absorption properties are not as good as those after the two are coated separately, which intuitively illustrates the sandwich structure proposed by the present invention The thermal conductivity and microwave absorption performance of the composite material is not a simple superimposed effect. Due to the porous structure of the filter paper, a certain degree of interweaving occurs when the two inks are coated and dried, thereby enhancing each other's thermal conductivity and microwave absorption performance. .
最后应当说明的是，以上实施例以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above examples are to illustrate the technical solutions of the present invention rather than limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the present invention can be Modifications or equivalent replacements shall be made to the technical solutions without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

  1. 一种吸波导热复合材料，其特征在于，所述吸波导热复合材料为三明治结构，所述三明治结构包括导热层、吸波层和滤纸层，所述滤纸层位于导热层和吸波层之间。A wave-absorbing and heat-conducting composite material, characterized in that the wave-absorbing and heat-conducting composite material is a sandwich structure, and the sandwich structure includes a heat-conducting layer, a wave-absorbing layer, and a filter paper layer, and the filter paper layer is located between the heat-conducting layer and the wave-absorbing layer between.
  2. 根据权利要求1所述的吸波导热复合材料，其特征在于，所述导热层由氮化硼纳米片油墨A涂布而成，所述氮化硼纳米片油墨A包括以下重量份数的原料：5-40份氮化硼纳米片、20-50份叔丁醇、5-10份甘油和0.1-2份硅烷偶联剂；The wave-absorbing and heat-conducting composite material according to claim 1, wherein the heat-conducting layer is coated with boron nitride nanosheet ink A, and the boron nitride nanosheet ink A includes the following raw materials in parts by weight : 5-40 parts of boron nitride nanosheets, 20-50 parts of tert-butanol, 5-10 parts of glycerin and 0.1-2 parts of silane coupling agent;
    所述吸波层由MXene陶瓷片油墨B涂布而成，所述MXene陶瓷片油墨B包括以下重量份数的原料：15-50份MXene陶瓷片、20-50份叔丁醇、5-15份甘油、0.1-2份硅烷偶联剂。The absorbing layer is formed by coating MXene ceramic sheet ink B, and the MXene ceramic sheet ink B includes the following raw materials in parts by weight: 15-50 parts of MXene ceramic sheet, 20-50 parts of tert-butanol, 5-15 Parts of glycerin, 0.1-2 parts of silane coupling agent.
  3. 根据权利要求2所述的吸波导热复合材料，其特征在于，所述氮化硼纳米片油墨A的表观粘度为3000-8000mPa*s；所述MXene陶瓷片油墨B的表观粘度为2000-7000mPa*s。The wave-absorbing and heat-conducting composite material according to claim 2, wherein the apparent viscosity of the boron nitride nanosheet ink A is 3000-8000mPa*s; the apparent viscosity of the MXene ceramic sheet ink B is 2000 -7000mPa*s.
  4. 根据权利要求2所述的吸波导热复合材料，其特征在于，所述吸波导热复合材料包括以下重量份的原料：40-90份氮化硼纳米片油墨A和20-90份MXene陶瓷片油墨B。The wave-absorbing and heat-conducting composite material according to claim 2, wherein the wave-absorbing and heat-conducting composite material comprises the following raw materials in parts by weight: 40-90 parts of boron nitride nanosheet ink A and 20-90 parts of MXene ceramic sheet Ink B.
  5. 根据权利要求2所述的吸波导热复合材料，其特征在于，所述吸波导热复合材料包括以下重量份的原料：60-80份氮化硼纳米片油墨A和50-70份MXene陶瓷片油墨B。The wave-absorbing and heat-conducting composite material according to claim 2, wherein the wave-absorbing and heat-conducting composite material comprises the following raw materials in parts by weight: 60-80 parts of boron nitride nanosheet ink A and 50-70 parts of MXene ceramic sheet Ink B.
  6. 根据权利要求1所述的吸波导热复合材料，其特征在于，所述滤纸层使用的滤纸的定量指标为80-200g/cm 2。 The wave-absorbing and heat-conducting composite material according to claim 1, characterized in that the quantitative index of the filter paper used in the filter paper layer is 80-200g/cm 2 .
  7. 如权利要求1-6任一项所述的吸波导热复合材料的制备方法，其特征在于，所述制备方法包括以下步骤：将氮化硼纳米片油墨A和MXene陶瓷片油墨B分别涂布在滤纸的两侧面后干燥，得吸波导热复合材料。The preparation method of the wave-absorbing and heat-conducting composite material according to any one of claims 1-6, wherein the preparation method comprises the following steps: coating boron nitride nanosheet ink A and MXene ceramic sheet ink B respectively After drying on both sides of the filter paper, a wave-absorbing and heat-conducting composite material is obtained.
  8. 根据权利要求7所述的制备方法，其特征在于，所述涂布的涂布量为 10-100g/cm 2。 The preparation method according to claim 7, characterized in that, the coating amount of the coating is 10-100 g/cm 2 .
  9. 根据权利要求7所述的制备方法，其特征在于，所述氮化硼纳米片油墨A或MXene陶瓷片油墨B的制备方法包括以下步骤：将氮化硼纳米片油墨A或MXene陶瓷片油墨B的原料混合均匀后加入到双螺杆混合器中混炼搅拌，接着将搅拌后的混合物转移至高速剪切机中高速搅拌混合，得氮化硼纳米片油墨A或MXene陶瓷片油墨B。The preparation method according to claim 7, wherein the preparation method of the boron nitride nanosheet ink A or MXene ceramic sheet ink B comprises the following steps: making the boron nitride nanosheet ink A or the MXene ceramic sheet ink B After the raw materials are mixed evenly, they are added to a twin-screw mixer for kneading and stirring, and then the stirred mixture is transferred to a high-speed shearing machine for high-speed stirring and mixing to obtain boron nitride nanosheet ink A or MXene ceramic sheet ink B.
  10. 如权利要求1-6任一项所述的吸波导热复合材料在柔性电子电路与电子器件领域上的应用。The application of the wave-absorbing and heat-conducting composite material according to any one of claims 1-6 in the field of flexible electronic circuits and electronic devices.
PCT/CN2022/078291 2021-12-23 2022-02-28 Wave-absorbing thermally-conductive composite material, and preparation method therefor and use thereof WO2023115695A1 (en)

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