CN101734650B - Method for preparing graphene-carbon nano tube hybrid composite - Google Patents
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Abstract
一种石墨烯-碳纳米管混杂复合材料的制备方法，涉及一种功能高分子材料及器件的制备方法。将石墨烯和碳纳米管经搅拌、超声振荡处理预先形成缠结的网络结构，将其与聚合物颗粒进行充分混合、去除溶剂后，获得石墨烯-碳纳米管网络包裹于聚合物颗粒表面的均匀混合体系；将其放入模具中，热压成型、冷却脱模后得到石墨烯-碳纳米管混杂复合材料。本方法通过石墨烯与碳纳米管预先混杂形成连通网络结构，实现了石墨烯和碳纳米管结构上的优势互补，使得该混杂复合材料具有较好的导电、导热性能。本发明可以在航空航天、交通运输、电子工业、民用设施、建筑及化工等方面具有广泛的应用，并能够工业化规模生产、成本低廉且环境友好。A method for preparing a graphene-carbon nanotube hybrid composite material relates to a method for preparing a functional polymer material and a device. Graphene and carbon nanotubes are stirred and ultrasonically oscillated to form an entangled network structure in advance. After fully mixing them with polymer particles and removing the solvent, a graphene-carbon nanotube network wrapped on the surface of polymer particles is obtained. A uniform mixing system; put it into a mold, hot press molding, cooling and demoulding to obtain a graphene-carbon nanotube hybrid composite material. In the method, graphene and carbon nanotubes are pre-mixed to form a connected network structure, which realizes the complementary advantages in the structure of graphene and carbon nanotubes, and makes the hybrid composite material have better electrical and thermal conductivity properties. The invention can be widely used in aerospace, transportation, electronic industry, civil facilities, construction, chemical industry, etc., and can be produced on an industrial scale, with low cost and environmental friendliness.
Description
技术领域 technical field
本发明涉及一种功能高分子材料及器件技术领域的制备方法，特别是涉及一种石墨烯-碳纳米管混杂复合材料的制备方法。The invention relates to a preparation method in the technical field of functional polymer materials and devices, in particular to a preparation method of a graphene-carbon nanotube hybrid composite material.
背景技术 Background technique
石墨烯(graphene，详见：Novoselov K S，et al.Electric field effects inatomically thin carbon films.Science，2004，306：666-119)是由单层碳原子紧密堆积成二维蜂窝状晶格结构的一种碳质新材料，它是构建其它维度碳质材料(如零维富勒烯、一维碳纳米管、三维石墨)的基本单元。石墨烯具有优异的电学性能和热学性能，其室温电子迁移率可达15000cm2V-1S-1，热导率可达3000Wm-1K-1；此外，石墨烯价格低廉、原料易得，其独特的二维结构能够进行有效的电热传输，有望在高性能电子器件、场发射材料、气体传感器及能量存储等领域获得广泛应用。但由于石墨烯具有二维的片状结构，其在使用过程中特别容易卷曲和高度皱折；尤其是采用熔融共混法制备聚合物复合材料时，石墨烯在剪切力作用下更容易发生卷曲和高度皱折，不利于在基体内形成高效的输运网络。碳纳米管(carbon nanotube，CNT)是1991年由Iijima发现的一种新型碳材料，它可以看成是由石墨烯卷成的无缝中空管体，其长度为数微米至数毫米，直径在几纳米到几十纳米之间。由于其独特的结构，碳纳米管在力学增强和电子长程传输等方面具有显著的优势；但存在易于团聚和成本高等缺点。Graphene (graphene, see: Novoselov K S, et al. Electric field effects inatomically thin carbon films. Science, 2004, 306: 666-119) is a kind of two-dimensional honeycomb lattice structure formed by a single layer of carbon atoms tightly packed. A new carbonaceous material, which is the basic unit for constructing other dimensional carbonaceous materials (such as zero-dimensional fullerenes, one-dimensional carbon nanotubes, and three-dimensional graphite). Graphene has excellent electrical and thermal properties. Its electron mobility at room temperature can reach 15000cm 2 V -1 S -1 , and its thermal conductivity can reach 3000Wm -1 K -1 . In addition, graphene is cheap and its raw materials are readily available. Its unique two-dimensional structure is capable of effective electrothermal transport, and is expected to be widely used in high-performance electronic devices, field emission materials, gas sensors, and energy storage. However, because graphene has a two-dimensional sheet structure, it is particularly prone to curling and highly wrinkled during use; especially when polymer composites are prepared by melt blending, graphene is more likely to occur under shear force. Curled and highly wrinkled, it is not conducive to the formation of efficient transport network in the matrix. Carbon nanotube (carbon nanotube, CNT) is a new type of carbon material discovered by Iijima in 1991. It can be regarded as a seamless hollow tube made of graphene, with a length of several microns to several millimeters and a diameter of between a few nanometers and tens of nanometers. Due to its unique structure, carbon nanotubes have significant advantages in mechanical enhancement and long-distance electron transport; however, they have disadvantages such as easy agglomeration and high cost.
关于石墨烯混杂聚合物复合材料制备技术已有报道，例如：中国专利，CN200910067708.8陈永胜等，《石墨烯与碳纤维复合材料及其制备方法》，其主要特征包括：它是以石墨烯和碳纤维材料为原料，通过涂覆的方法在碳纤维材料表面涂覆石墨烯涂层制备而成，涂层的厚度为1纳米-5微米。中国专利，CN101474897陈永胜等，《石墨烯-有机材料层状组装膜及其制备方法》，其主要特征包括：以石墨烯材料和有机材料为原料，利用石墨烯与有机材料之间的静电、氢键、配位键或电荷转移等相互作用，通过旋涂、喷涂、浸渍-提拉等薄膜制备方法层层叠加成膜。中国专利，CN101474899陈永胜等，《石墨烯-无机材料复合多层薄膜及其制备方法》，其主要特征包括：以石墨烯材料和无机材料为原料，通过喷涂、旋涂、浸渍、化学沉积等常用薄膜制备方法层层叠加成膜，每层膜厚可根据需要控制在10纳米-2毫米。以上方法中，都没有提及利用石墨烯和碳纳米管混杂技术形成缠绕交织网络，而且制备中多采用旋涂技术形成复合薄膜。There have been reports on the preparation technology of graphene hybrid polymer composite materials, for example: Chinese patent, CN200910067708.8 Chen Yongsheng, etc., "Graphene and carbon fiber composite material and its preparation method", its main features include: it is based on graphene and carbon fiber The material is a raw material, prepared by coating a graphene coating on the surface of a carbon fiber material by a coating method, and the thickness of the coating is 1 nanometer to 5 micrometers. Chinese patent, CN101474897 Chen Yongsheng, etc., "Graphene-organic material layered assembly film and its preparation method", its main features include: using graphene materials and organic materials as raw materials, using static electricity and hydrogen between graphene and organic materials Bonds, coordination bonds or charge transfer interactions, layer by layer film formation by spin coating, spray coating, dipping-pulling and other thin film preparation methods. Chinese patent, CN101474899 Chen Yongsheng, etc., "Graphene-inorganic material composite multilayer film and its preparation method", its main features include: using graphene materials and inorganic materials as raw materials, by spraying, spin coating, dipping, chemical deposition and other commonly used The film preparation method is to form a film layer by layer, and the film thickness of each layer can be controlled at 10 nanometers to 2 millimeters as required. In the above methods, there is no mention of the use of graphene and carbon nanotube hybrid technology to form a entangled interweaving network, and the spin coating technology is often used to form a composite film in the preparation.
发明内容 Contents of the invention
本发明的目的在于提出一种石墨烯-碳纳米管混杂复合材料的制备方法，通过在溶剂中搅拌和超声振荡使得碳纳米管与石墨烯形成混杂穿插结构，可以有效地防止石墨烯的卷曲或折皱，充分发挥石墨烯优异的二维电热传输特性；这种石墨烯-碳纳米管的混杂输运网络，可以使石墨烯和碳纳米管在结构和功能设计上形成互补，在满足导热、导电功能的同时，显著降低功能填料的掺量、降低复合材料的成本。此外，由于其输运网络结构可以根据使用要求进行预先设计和构建，具有较大的设计自由度。The object of the present invention is to propose a kind of preparation method of graphene-carbon nanotube hybrid composite material, make carbon nanotube and graphene form hybrid interspersed structure by stirring in solvent and ultrasonic vibration, can effectively prevent the curling of graphene or Wrinkle, give full play to the excellent two-dimensional electrothermal transport characteristics of graphene; this graphene-carbon nanotube hybrid transport network can make graphene and carbon nanotubes complement each other in structure and function design, and meet the needs of thermal and electrical conduction. At the same time, it significantly reduces the dosage of functional fillers and reduces the cost of composite materials. In addition, because its transport network structure can be pre-designed and constructed according to the requirements of use, it has a greater degree of design freedom.
本发明所采用的技术方案是：The technical scheme adopted in the present invention is:
一种石墨烯-碳纳米管混杂复合材料的制备方法，该制备方法的工艺步骤如下：A kind of preparation method of graphene-carbon nanotube hybrid composite material, the processing step of this preparation method is as follows:
(1)配制包含石墨烯、碳纳米管、分散溶剂的悬浮体系，经搅拌、超声振荡使得石墨烯和碳纳米管相互穿插、缠绕形成连通的网络结构；(1) Prepare a suspension system comprising graphene, carbon nanotubes, and a dispersing solvent, and make graphene and carbon nanotubes interpenetrate and intertwine to form a connected network structure through stirring and ultrasonic oscillation;
(2)加入聚合物颗粒，经搅拌和超声振荡，使得聚合物颗粒表面被石墨烯-碳纳米管交织网络所包裹；(2) adding polymer particles, stirring and ultrasonic vibration, so that the surface of the polymer particles is wrapped by the graphene-carbon nanotube interweaving network;
(3)去除溶剂后，形成石墨烯-碳纳米管包裹于聚合物颗粒表面的均匀混合体系；(3) After the solvent is removed, a uniform mixed system in which graphene-carbon nanotubes are wrapped on the surface of the polymer particles is formed;
(4)将所述混合体系放入模具中，经升温热压成型、冷却脱模后制得石墨烯-碳纳米管混杂复合材料。(4) Put the mixed system into a mould, heat and press to form, cool and demould to prepare a graphene-carbon nanotube hybrid composite material.
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，所用的石墨烯是指单层石墨片、多层石墨片或它们的混合物；所用的碳纳米管是指直径为5-200纳米、长度为0.1-100微米的中空管状碳材料。The preparation method of described a kind of graphene-carbon nanotube hybrid composite material, used graphene refers to single-layer graphite sheet, multilayer graphite sheet or their mixture; Used carbon nanotube refers to diameter is 5-200 Nano, hollow tubular carbon materials with a length of 0.1-100 microns.
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，所用的分散溶剂为无水乙醇、丙酮、甲苯和苯乙烯。In the preparation method of the graphene-carbon nanotube hybrid composite material, the dispersion solvent used is absolute ethanol, acetone, toluene and styrene.
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，经超声振荡后使得石墨烯和碳纳米管预先形成一种交织、缠绕的网络结构。。In the preparation method of the graphene-carbon nanotube hybrid composite material, an interwoven and entangled network structure is formed in advance by graphene and carbon nanotubes after ultrasonic vibration. .
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，聚合物颗粒为聚乙烯、聚氯乙烯、聚丙烯、聚酰胺、聚苯乙烯、聚苯乙烯、聚甲醛、聚四氟乙烯、聚碳酸酯、聚苯醚、聚砜。In the preparation method of a graphene-carbon nanotube hybrid composite material, the polymer particles are polyethylene, polyvinyl chloride, polypropylene, polyamide, polystyrene, polystyrene, polyoxymethylene, polytetrafluoroethylene , polycarbonate, polyphenylene ether, polysulfone.
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，去除溶剂是通过加热或者真空抽滤方法实现的。In the preparation method of the graphene-carbon nanotube hybrid composite material, solvent removal is achieved by heating or vacuum filtration.
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，石墨烯-碳纳米管网络包裹在聚合物颗粒表面，形成沿聚合物颗粒表面分布的连通网络。In the preparation method of the graphene-carbon nanotube hybrid composite material, the graphene-carbon nanotube network is wrapped on the surface of the polymer particles to form a connected network distributed along the surface of the polymer particles.
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，热压温度高于聚合物熔点或软化点20℃以上，成型压力大于10MPa，冷却脱模温度低于60℃。In the preparation method of the graphene-carbon nanotube hybrid composite material, the hot pressing temperature is 20°C higher than the melting point or softening point of the polymer, the molding pressure is higher than 10MPa, and the cooling demoulding temperature is lower than 60°C.
所述的一种石墨烯-碳纳米管混杂复合材料的制备方法，原料的初始用量配比(质量百分数)为：The preparation method of described a kind of graphene-carbon nanotube hybrid composite material, the initial dosage proportion (mass percentage) of raw material is:
石墨烯0.1-10份；0.1-10 parts of graphene;
碳纳米管0.1-10份；0.1-10 parts of carbon nanotubes;
聚合物：100份；Polymer: 100 parts;
分散溶剂：100-500份。Dispersion solvent: 100-500 parts.
本发明的有益效果是：The beneficial effects of the present invention are:
1.本发明采用石墨烯-碳纳米管混杂技术，通过超声振荡使得碳纳米管与石墨烯进行相互穿插和缠绕，利用石墨烯成本低、电学性能优异的优势，借助碳纳米管刚度大、长径比高的特点来防止二维石墨烯片的卷曲；充分发挥石墨烯和碳纳米管的结构特点、形成优势互补，有助于形成高效的三维电热输运网络。1. The present invention adopts graphene-carbon nanotube hybrid technology to interpenetrate and entangle carbon nanotubes and graphene through ultrasonic vibration, and utilizes the advantages of low cost and excellent electrical performance of graphene, and with the help of carbon nanotubes with high rigidity and long The characteristics of high diameter ratio prevent the curling of two-dimensional graphene sheets; give full play to the structural characteristics of graphene and carbon nanotubes, form complementary advantages, and help form an efficient three-dimensional electrothermal transport network.
2.通过预先设计和构建输运网络，可以有效地避免传统熔融共混制备过程中出现的聚合物对功能填料的包裹、填料间接触电(热)阻增加、导电(热)性能降低的局限性。本发明中输运网络的预先构建有助于形成功能填料间的有效搭界、提高输运网络的电、导热传输效率。2. By pre-designing and constructing the transport network, it is possible to effectively avoid the limitations of the encapsulation of polymers on functional fillers, the increase of contact electrical (thermal) resistance between fillers, and the decrease of electrical conductivity (thermal) properties that occur in the traditional melt blending preparation process. . The pre-construction of the transportation network in the present invention helps to form an effective interface between functional fillers and improve the electricity and heat transfer efficiency of the transportation network.
3.结合石墨烯-碳纳米管网络与聚合物颗粒的混杂技术，使得石墨烯-碳纳米管网络包裹在聚合物颗粒表面，形成三维的输运网络，显著提高填料在电热传输增强方面的有效利用率，只需要很低的掺量，混杂复合材料就能够具有较好的导电(热)性能，显著降低复合材料的成本。此外，若采用高结晶性聚合物的基体，混杂复合材料会具有一定的正温度系数效应，可以在热敏电阻及器件领域得到广泛的应用。。3. Combining the hybrid technology of graphene-carbon nanotube network and polymer particles, the graphene-carbon nanotube network is wrapped on the surface of polymer particles to form a three-dimensional transport network, which significantly improves the effectiveness of fillers in enhancing electrothermal transmission. The utilization rate requires only a very low dosage, and the hybrid composite material can have better electrical conductivity (thermal) performance, which significantly reduces the cost of the composite material. In addition, if a highly crystalline polymer matrix is used, the hybrid composite material will have a certain positive temperature coefficient effect, and can be widely used in thermistor and device fields. .
4.本发明将石墨烯-碳纳米管导电网络与聚合物基体通过溶剂共混、热压成型的方式制备混杂复合材料，设备简单，操作流程简易，可用于多种热塑性聚合物与石墨烯-碳纳米管混杂复合材料的制备。选择不同基体材料、颗粒分布以及填料用量，可根据实际使用需求，预先设计并制造具有特定网络结构的功能性复合材料，具有极大的设计自由度。4. In the present invention, the graphene-carbon nanotube conductive network and the polymer matrix are prepared by solvent blending and hot pressing to form a hybrid composite material. The equipment is simple and the operation process is simple. It can be used for various thermoplastic polymers and graphene- Preparation of carbon nanotube hybrid composites. By choosing different matrix materials, particle distributions and filler dosages, functional composite materials with specific network structures can be pre-designed and manufactured according to actual use requirements, with great design freedom.
具体实施方式 Detailed ways
实施例1：Example 1:
将0.01克石墨烯和0.01克碳纳米管分散于10克无水乙醇中，超声2小时后形成稳定的悬浮液；将10克高密度聚乙烯超细粉末加入到该悬浮液中，超声30分钟，待石墨烯-碳纳米管包裹在高密度聚乙烯粉末表面并形成均匀混合体系时，升温至60℃进行干燥以除去溶剂。将其转移至模具中，升温至170℃，并于10MPa条件下热压成型5分钟，冷却至室温、脱模得到石墨烯-碳纳米管混杂复合材料。测量复合材料体积电阻，计算其电阻率为7.09×106ohm·cm。Disperse 0.01 g of graphene and 0.01 g of carbon nanotubes in 10 g of absolute ethanol, and form a stable suspension after ultrasonication for 2 hours; add 10 g of high-density polyethylene ultrafine powder to the suspension, and ultrasonicate for 30 minutes , when the graphene-carbon nanotubes are wrapped on the surface of the high-density polyethylene powder and a uniform mixed system is formed, the temperature is raised to 60°C for drying to remove the solvent. Transfer it to a mold, raise the temperature to 170° C., and hot press for 5 minutes under the condition of 10 MPa, cool to room temperature, and demould to obtain a graphene-carbon nanotube hybrid composite material. The volume resistance of the composite material was measured, and its resistivity was calculated to be 7.09×10 6 ohm·cm.
实施例2：Example 2:
将0.1克石墨烯和0.1克碳纳米管分散于10克丙酮中，超声2小时后形成稳定的悬浮液；将10克聚丙烯颗粒加入到该悬浮液中，超声30分钟，待石墨烯-碳纳米管包裹在高密度聚丙烯颗粒表面并形成均匀混合体系时，于常温下进行真空抽滤除去溶剂。将其转移至模具中，升温至200℃，并于10MPa条件下热压成型5分钟，冷却至室温脱模、得到石墨烯-碳纳米管混杂复合材料。测量复合材料体积电阻，计算其电阻率为2.00×104ohm·cm。Disperse 0.1 g of graphene and 0.1 g of carbon nanotubes in 10 g of acetone, and form a stable suspension after ultrasonication for 2 hours; add 10 g of polypropylene particles to the suspension, and ultrasonicate for 30 minutes, and the graphene-carbon When nanotubes are wrapped on the surface of high-density polypropylene particles to form a uniform mixed system, the solvent is removed by vacuum filtration at room temperature. Transfer it to a mold, raise the temperature to 200°C, and hot press for 5 minutes under the condition of 10MPa, cool to room temperature and release the mold to obtain a graphene-carbon nanotube hybrid composite material. The volume resistance of the composite material was measured, and its resistivity was calculated to be 2.00×10 4 ohm·cm.
实施例3：Example 3:
将0.5克石墨烯和0.5克碳纳米管分散于25克无水乙醇中，超声2小时后形成稳定的悬浮液；将10克聚甲基丙烯酸甲酯颗粒加入到该悬浮液中，超声30分钟，待石墨烯-碳纳米管包裹在聚甲基丙烯酸甲酯颗粒表面并形成均匀混合体系时，于常温下进行真空抽滤以除去溶剂。将其转移至模具中，升温至180℃，并于10MPa条件下热压成型5分钟，冷却至室温脱模、得到石墨烯-碳纳米管混杂复合材料。测量复合材料体积电阻，计算其电阻率为8.84×102ohm·cm。Disperse 0.5 g of graphene and 0.5 g of carbon nanotubes in 25 g of absolute ethanol, and form a stable suspension after ultrasonication for 2 hours; add 10 g of polymethyl methacrylate particles to the suspension, and ultrasonicate for 30 minutes , when the graphene-carbon nanotubes are wrapped on the surface of polymethyl methacrylate particles and form a uniform mixed system, vacuum filtration is performed at room temperature to remove the solvent. Transfer it to a mold, raise the temperature to 180°C, and hot press for 5 minutes under the condition of 10MPa, cool to room temperature and release the mold to obtain a graphene-carbon nanotube hybrid composite material. The volume resistance of the composite material was measured, and its resistivity was calculated to be 8.84×10 2 ohm·cm.
实施例4：Example 4:
将1克石墨烯和1克碳纳米管分散于50克无水乙醇中，超声2小时后形成稳定的悬浮液；将10克聚苯乙烯颗粒加入到该悬浮液中，超声30分钟，待石墨烯-碳纳米管包裹在聚苯乙烯颗粒表面并形成均匀混合体系时，升温至60℃进行加热干燥以除去溶剂。进一步转移至模具中，升温至160℃，并于10MPa条件下热压成型5分钟，冷却至室温脱模、得到石墨烯-碳纳米管混杂复合材料。测量复合材料体积电阻，计算其电阻率为4.55×101ohm·cm。Disperse 1 gram of graphene and 1 gram of carbon nanotubes in 50 grams of absolute ethanol, and form a stable suspension after ultrasonication for 2 hours; add 10 grams of polystyrene particles to the suspension, ultrasonic for 30 minutes, and the When the olefin-carbon nanotubes are wrapped on the surface of the polystyrene particles and form a homogeneous mixed system, the temperature is raised to 60°C for heating and drying to remove the solvent. It was further transferred to a mold, heated to 160°C, and hot-pressed at 10MPa for 5 minutes, cooled to room temperature and demolded to obtain a graphene-carbon nanotube hybrid composite material. The volume resistance of the composite material was measured, and its resistivity was calculated to be 4.55×10 1 ohm·cm.
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