CN104883756A - Flexible composite electrothermal film - Google Patents
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了一种柔性电热复合膜，其包括发热层和保护层，所述保护层通过热压或涂覆方式与发热层的上、下表面分别固定连接；其中的发热层是由直径为10nm～100nm的碳纳米管形成的厚度为10μm～50μm、孔隙率为45％～75％、面电阻为1.0Ω/cm2～5.0Ω/cm2的碳纳米管薄膜；在所述碳纳米管薄膜的两端分别固定连接有导电电极片。本发明提供的电热复合膜具有柔性好、电热转化率高、发热稳定、能耗低、温度均匀、力学性能好、安全性高、耐腐蚀、轻便易携带、易安装粘合等诸多优点，可通过调整发热层面积或增大电源供给实现各种发热要求，具有非常广泛的应用前景和实用价值。
The invention discloses a flexible electrothermal composite film, which includes a heating layer and a protective layer, and the protective layer is respectively fixedly connected with the upper and lower surfaces of the heating layer by hot pressing or coating; A carbon nanotube film with a thickness of 10 μm to 50 μm, a porosity of 45% to 75%, and a surface resistance of 1.0Ω/cm 2 to 5.0Ω/cm 2 formed by carbon nanotubes of 10nm to 100nm; Both ends of the film are respectively fixedly connected with conductive electrode sheets. The electrothermal composite film provided by the present invention has many advantages such as good flexibility, high electrothermal conversion rate, stable heat generation, low energy consumption, uniform temperature, good mechanical properties, high safety, corrosion resistance, light and easy to carry, easy to install and bond, and many other advantages. By adjusting the area of the heating layer or increasing the power supply to achieve various heating requirements, it has a very wide application prospect and practical value.
Description
技术领域technical field
本发明是涉及一种柔性电热复合膜，属于功能材料技术领域。The invention relates to a flexible electrothermal composite film, which belongs to the technical field of functional materials.
背景技术Background technique
近年来，席卷欧亚多国的强冷空气中，部分地区出现百年来的最低温。在日愈严重的冬季寒冷情况下，工业界和日常生活对供暖的需求越来越高。目前，供暖主要采用燃烧煤化学燃料和电器取暖(如：电暖气、空调等)等两种方式。这种两种取暖方式分别具有污染环境、体积庞大、携带不便等缺陷。在室外严寒情况下应用具有一定局限。In recent years, in the strong cold air that has swept across many countries in Europe and Asia, some areas have experienced the lowest temperature in a century. In the increasingly severe winter cold conditions, the demand for heating in industry and daily life is getting higher and higher. At present, heating mainly adopts two methods such as burning coal chemical fuels and electric heating (such as: electric heaters, air conditioners, etc.). These two heating methods respectively have defects such as polluting the environment, bulky, and inconvenient to carry. There are certain limitations in the application of outdoor severe cold conditions.
碳纳米管的高导电性和高导热性得到了人们越来越多的关注，使得碳纳米管在电热方面有了很大的发展。单壁碳纳米管是目前世界上最好的导热材料，它的导热率3000W/m.K。碳纳米管通过超声波传递热能，其传递速度可达到一万米每秒。碳纳米管也是非金属材料中导电性能最好的物质，主要取决于非定域π电子。炭化、石墨化温度愈高，石墨层面愈发达，形成π键的非定域区愈大，导电性能愈好。因此，碳纳米管电热转换效率在90％以上，节能效果十分显著。但至今未见由碳纳米管制备电热复合膜的相关技术报道。The high electrical conductivity and high thermal conductivity of carbon nanotubes have attracted more and more attention, which has made great development of carbon nanotubes in electric heating. Single-walled carbon nanotubes are currently the best thermally conductive material in the world, with a thermal conductivity of 3000W/m.K. Carbon nanotubes transmit heat energy through ultrasonic waves, and its transmission speed can reach 10,000 meters per second. Carbon nanotubes are also the materials with the best electrical conductivity among non-metallic materials, which mainly depends on delocalized π electrons. The higher the carbonization and graphitization temperature, the more developed the graphite layer, the larger the non-localized area forming π bonds, and the better the conductivity. Therefore, the electrothermal conversion efficiency of carbon nanotubes is above 90%, and the energy saving effect is very remarkable. But so far there is no relevant technical report on the preparation of electrothermal composite membranes from carbon nanotubes.
发明内容Contents of the invention
本发明的目的是提供一种由碳纳米管制备的柔性电热复合膜。The purpose of the present invention is to provide a flexible electrothermal composite membrane prepared from carbon nanotubes.
本发明所述的柔性电热复合膜，包括发热层和保护层，所述保护层通过热压或涂覆方式与发热层的上、下表面分别固定连接；其特征在于：所述发热层是由直径为10nm～100nm的碳纳米管形成的厚度为10μm～50μm、孔隙率为45％～75％、面电阻为1.0Ω/cm2～5.0Ω/cm2的碳纳米管薄膜；在所述碳纳米管薄膜的两端分别固定连接有导电电极片。The flexible electrothermal composite film of the present invention includes a heating layer and a protective layer, and the protective layer is fixedly connected to the upper and lower surfaces of the heating layer by hot pressing or coating; it is characterized in that: the heating layer is made of A carbon nanotube film with a thickness of 10 μm to 50 μm, a porosity of 45% to 75%, and a surface resistance of 1.0Ω/cm 2 to 5.0Ω/cm 2 formed by carbon nanotubes with a diameter of 10nm to 100nm; Both ends of the nanotube film are respectively fixedly connected with conductive electrode sheets.
作为一种实施方案，所述的保护层为聚合物薄膜，通过胶粘剂或粘合聚合物与碳纳米管薄膜的上、下表面间进行热压粘接。As an embodiment, the protective layer is a polymer film, which is bonded by thermocompression between the adhesive or bonding polymer and the upper and lower surfaces of the carbon nanotube film.
作为一种优选方案，所述的聚合物薄膜选自聚氨酯薄膜、聚丙烯薄膜、聚酯薄膜和聚氯乙烯薄膜中的至少一种；所述的胶粘剂选自环氧树脂胶粘剂、聚氨酯胶粘剂和丙烯酸胶粘剂中的至少一种；所述的粘合聚合物选自聚乙烯、聚丙烯、聚苯乙烯和聚酯中的至少一种；所述粘合聚合物的形态可以为颗粒、薄膜或粉末。As a preferred version, the polymer film is selected from at least one of polyurethane film, polypropylene film, polyester film and polyvinyl chloride film; the adhesive is selected from epoxy resin adhesive, polyurethane adhesive and acrylic acid At least one of adhesives; the adhesive polymer is selected from at least one of polyethylene, polypropylene, polystyrene and polyester; the form of the adhesive polymer can be particles, films or powders.
作为另一种实施方案，所述的保护层为聚合物涂层，通过直接涂覆方式与碳纳米管薄膜的上、下表面间固定连接。As another embodiment, the protective layer is a polymer coating, which is fixedly connected with the upper and lower surfaces of the carbon nanotube film by direct coating.
作为一种优选方案，所述的聚合物涂层选自聚氨酯涂层、聚氯乙烯涂层、聚丙烯酸酯涂层和有机硅涂层中的至少一种。As a preferred solution, the polymer coating is selected from at least one of polyurethane coating, polyvinyl chloride coating, polyacrylate coating and silicone coating.
作为一种优选方案，所述碳纳米管薄膜为片状结构。As a preferred solution, the carbon nanotube thin film has a sheet structure.
作为进一步优选方案，片状碳纳米管薄膜是由碳纳米管采用条状平行排布方式或之字状排布方式形成。As a further preferred solution, the flaky carbon nanotube film is formed by carbon nanotubes arranged in strips in parallel or zigzag.
作为一种优选方案，所述导电电极片通过导电胶与碳纳米管薄膜的两端固定连接。As a preferred solution, the conductive electrode sheet is fixedly connected to both ends of the carbon nanotube film through conductive glue.
作为一种优选方案，两端的导电电极片分别通过导线与温控器相连接。As a preferred solution, the conductive electrode sheets at both ends are respectively connected to the temperature controller through wires.
作为进一步优选方案，所述温控器设有温度显示屏和指示灯。As a further preferred solution, the temperature controller is provided with a temperature display screen and an indicator light.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明通过采用特定的碳纳米管薄膜作为发热层，使得所制备的电热复合膜具有柔性好、电热转化率高、发热稳定、能耗低、温度均匀、力学性能好、安全性高、耐腐蚀、轻便易携带、易安装粘合等诸多优点，既可贴服于曲面形状进行加热，也可与织物进行贴合作为电热服装的理想材料，还可用于潮湿环境，并且还可通过调整发热层面积或增大电源供给实现各种发热要求，具有非常广泛的应用前景和实用价值。The invention adopts a specific carbon nanotube film as the heating layer, so that the prepared electrothermal composite film has good flexibility, high electrothermal conversion rate, stable heat generation, low energy consumption, uniform temperature, good mechanical properties, high safety, and corrosion resistance. , light and easy to carry, easy to install and bond, and many other advantages, it can be attached to the shape of the curved surface for heating, and can also be fitted with fabrics. As an ideal material for electric heating clothing, it can also be used in humid environments, and can also be adjusted by adjusting the heating layer Reducing the area or increasing the power supply to achieve various heating requirements has a very wide application prospect and practical value.
附图说明Description of drawings
图1是本发明提供的一种柔性电热复合膜的截面结构示意图；Fig. 1 is a schematic cross-sectional structure diagram of a flexible electrothermal composite film provided by the present invention;
图2是本发明提供的一种柔性电热复合膜的电路连接结构示意图；Fig. 2 is a schematic diagram of a circuit connection structure of a flexible electrothermal composite film provided by the present invention;
图3是本发明提供的一种发热层的结构示意图；Fig. 3 is a schematic structural view of a heating layer provided by the present invention;
图4是本发明提供的另一种发热层的结构示意图；Fig. 4 is a schematic structural view of another heating layer provided by the present invention;
图中：1、发热层；2、保护层；3、导电电极片；4、导线；5、温控器；51、温度显示屏；52、指示灯。In the figure: 1, heating layer; 2, protective layer; 3, conductive electrode sheet; 4, wire; 5, temperature controller; 51, temperature display screen; 52, indicator light.
具体实施方式Detailed ways
以下将结合本发明的附图，对本发明实施例中的技术方案进行清楚、完整的描述和讨论，显然，这里所描述的仅仅是本发明的一部分实例，并不是全部的实例。下述实施例中所用的碳纳米管薄膜采用立式浮动催化裂解法制备得到，均由苏州捷迪纳米科技有限公司制备提供。The following will clearly and completely describe and discuss the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings of the present invention. Obviously, what is described here is only some examples of the present invention, not all examples. The carbon nanotube films used in the following examples were prepared by a vertical floating catalytic cracking method, and all were prepared and provided by Suzhou Jiedi Nano Technology Co., Ltd.
实施例1Example 1
如图1所示：本实施例提供的柔性电热复合膜，包括发热层1和保护层2。As shown in FIG. 1 : the flexible electrothermal composite film provided in this embodiment includes a heating layer 1 and a protective layer 2 .
本实施例中：In this example:
发热层1是采用由直径为10nm～100nm的碳纳米管形成的厚度为20μm、拉伸断裂强度为200兆帕、孔隙率为50％、面电阻为4Ω/cm2的片状碳纳米管薄膜；The heating layer 1 is a flaky carbon nanotube film with a thickness of 20 μm, a tensile breaking strength of 200 MPa, a porosity of 50%, and a sheet resistance of 4Ω/ cm2 formed by carbon nanotubes with a diameter of 10 nm to 100 nm. ;
保护层2是采用聚酯薄膜(厚度为100微米)；Protective layer 2 adopts polyester film (thickness is 100 microns);
所述保护层通过粘合聚合物(本实施例中采用厚度为30微米的聚乙烯薄膜，也可采用聚乙烯粒子或聚乙烯粉体等)与碳纳米管薄膜的上、下表面间进行热压粘接。The protective layer is heated between the upper and lower surfaces of the adhesive polymer (in this embodiment, a polyethylene film with a thickness of 30 microns can also be used, such as polyethylene particles or polyethylene powder, etc.) and the carbon nanotube film. Pressure bonding.
所述柔性电热复合膜的具体制作工艺如下：The specific manufacturing process of the flexible electrothermal composite film is as follows:
将作为上保护层的聚酯薄膜、起粘合作用的聚乙烯薄膜、作为发热层的片状碳纳米管薄膜、作为下保护层的聚酯薄膜自上至下依次叠置，然后采用热压工艺进行粘合：热压机上下底板温度均设置为110℃，压强为3兆帕，预热时间为1分钟，热压时间为1分钟；热压结束后，置于50℃的硫化机上冷压2分钟。The polyester film as the upper protective layer, the polyethylene film as the adhesive, the sheet-like carbon nanotube film as the heat-generating layer, and the polyester film as the lower protective layer are stacked sequentially from top to bottom, and then heat-pressed Process bonding: the temperature of the upper and lower bottom plates of the hot press is set to 110°C, the pressure is 3 MPa, the preheating time is 1 minute, and the hot pressing time is 1 minute; Press for 2 minutes.
然后通过导电胶在片状碳纳米管薄膜1的两端分别粘接导电电极片3，并将两端导电电极片3通过导线4与温控器5相连(详见图2所示)。Then, the conductive electrode sheets 3 are respectively bonded to both ends of the sheet carbon nanotube film 1 through conductive glue, and the conductive electrode sheets 3 at both ends are connected to the temperature controller 5 through the wire 4 (see FIG. 2 for details).
所述的温控器5优选具有温度显示屏51和工作状态指示灯52，以方便温度监控和调节。The temperature controller 5 preferably has a temperature display screen 51 and a working status indicator light 52 to facilitate temperature monitoring and adjustment.
经测试：该柔性电热复合膜(30mm×30mm)在3.2W功率条件下30秒内，温度可上升到45～55℃。可根据实际用途，通过调整电压来调整加热温度。After testing: the temperature of the flexible electrothermal composite film (30mm×30mm) can rise to 45-55°C within 30 seconds under the condition of 3.2W power. According to the actual use, the heating temperature can be adjusted by adjusting the voltage.
实施例2Example 2
如图1所示：本实施例提供的柔性电热复合膜，包括发热层1和保护层2。As shown in FIG. 1 : the flexible electrothermal composite film provided in this embodiment includes a heating layer 1 and a protective layer 2 .
本实施例中：In this example:
发热层1是采用长为20mm、宽为5mm、拉伸断裂强度为200兆帕、孔隙率为50％、面电阻为4Ω/cm2的条状碳纳米管薄膜按间距为3mm平行排布形成(如图3所示)；The heating layer 1 is formed by arranging strip-shaped carbon nanotube films with a length of 20 mm, a width of 5 mm, a tensile breaking strength of 200 MPa, a porosity of 50%, and a surface resistance of 4 Ω/ cm2 in parallel at a distance of 3 mm. (As shown in Figure 3);
保护层2是采用聚氨酯涂层(厚度为100微米)。Protective layer 2 is a polyurethane coating (thickness 100 microns).
所述柔性电热复合膜的具体制作工艺如下：The specific manufacturing process of the flexible electrothermal composite film is as follows:
将作为保护层2的水溶性聚氨酯涂料直接涂覆在碳纳米管薄膜1的上、下表面，然后置于通风橱中静置24小时。The water-soluble polyurethane coating used as the protective layer 2 is directly coated on the upper and lower surfaces of the carbon nanotube film 1, and then placed in a fume hood and left to stand for 24 hours.
再通过导电胶在片状碳纳米管薄膜1的两端分别粘接导电电极片3，并将两端导电电极片3通过导线4与温控器5相连(结合图3和图2所示)。Then, the two ends of the sheet carbon nanotube film 1 are bonded with conductive electrode sheets 3 respectively by conductive glue, and the conductive electrode sheets 3 at both ends are connected to the temperature controller 5 by wire 4 (shown in conjunction with Fig. 3 and Fig. 2 ) .
经测试：该柔性电热复合膜(20mm×32mm)在3.8W功率条件下30秒内温度可上升到50～70℃。After testing: the temperature of the flexible electrothermal composite film (20mm×32mm) can rise to 50-70°C within 30 seconds under the condition of 3.8W power.
当所述发热层1是采用采用长为30mm、宽为5mm、拉伸断裂强度为200兆帕、孔隙率为50％、面电阻为4Ω/cm2的条状碳纳米管薄膜按间距为3mm平行排布形成，其余均同以上所述时；经测试：所得柔性电热复合膜(30mm×48mm)在3.2W功率条件下30秒内温度可上升到50～65℃。When the heating layer 1 adopts a strip carbon nanotube film with a length of 30 mm, a width of 5 mm, a tensile strength of 200 MPa, a porosity of 50%, and a sheet resistance of 4 Ω/cm , the spacing is 3 mm Formed in parallel arrangement, the rest are the same as above; after testing: the temperature of the obtained flexible electrothermal composite film (30mm×48mm) can rise to 50-65°C within 30 seconds under the condition of 3.2W power.
实施例3Example 3
如图1所示：本实施例提供的柔性电热复合膜，包括发热层1和保护层2。As shown in FIG. 1 : the flexible electrothermal composite film provided in this embodiment includes a heating layer 1 and a protective layer 2 .
本实施例中：In this example:
发热层1是采用由长为20mm、宽为5mm、拉伸断裂强度为200兆帕、孔隙率为50％、面电阻为4Ω/cm2的条状碳纳米管薄膜按之字形排布形成(如图4所示)；The heating layer 1 adopts a strip carbon nanotube film with a length of 20 mm, a width of 5 mm, a tensile breaking strength of 200 MPa, a porosity of 50%, and a surface resistance of 4 Ω/cm in a zigzag arrangement ( As shown in Figure 4);
保护层2是采用聚氨酯薄膜(厚度为100微米)；Protective layer 2 adopts polyurethane film (thickness is 100 microns);
所述保护层通过胶粘剂(本实施例中采用聚氨酯胶粘剂)与碳纳米管薄膜的上、下表面间进行热压粘接。The protective layer is thermally pressure bonded to the upper and lower surfaces of the carbon nanotube film through an adhesive (polyurethane adhesive is used in this embodiment).
所述柔性电热复合膜的具体制作工艺如下：The specific manufacturing process of the flexible electrothermal composite film is as follows:
将作为保护层的聚氨酯薄膜用聚氨酯胶粘剂分别粘帖在作为发热层的片状碳纳米管薄膜的上、下表面，然后采用热压工艺进行粘合：热压机上下底板温度均设置为110℃，压强为3兆帕，预热时间为1分钟，热压时间为1分钟；热压结束后，置于50℃的硫化机上冷压2分钟。Paste the polyurethane film as the protective layer on the upper and lower surfaces of the sheet-like carbon nanotube film as the heat-generating layer with polyurethane adhesive, and then use hot pressing process to bond: the temperature of the upper and lower bottom plates of the hot press is set to 110°C , the pressure is 3 MPa, the preheating time is 1 minute, and the hot pressing time is 1 minute; after the hot pressing is finished, place it on a vulcanizing machine at 50°C for 2 minutes for cold pressing.
然后通过导电胶在片状碳纳米管薄膜1的两端分别粘接导电电极片3，并将两端导电电极片3通过导线4与温控器5相连(结合图4和图2所示)。Then, the conductive electrode sheets 3 are bonded respectively at the two ends of the sheet-like carbon nanotube film 1 by conductive glue, and the conductive electrode sheets 3 at both ends are connected to the thermostat 5 by the wire 4 (shown in conjunction with Fig. 4 and Fig. 2 ) .
经测试：该柔性电热复合膜(20mm×32mm)在3.2W功率条件下30秒内温度可上升到50～65℃。After testing: the temperature of the flexible electrothermal composite film (20mm×32mm) can rise to 50-65° C. within 30 seconds under the condition of 3.2W power.
综上实施例可见：本发明所述的柔性电热复合膜，可通过调整其发热层面积或增大电源供给实现各种发热要求。From the above examples, it can be seen that the flexible electrothermal composite film of the present invention can realize various heating requirements by adjusting the area of the heating layer or increasing the power supply.
最后有必要在此说明的是，以上所述仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。Finally, it is necessary to explain here that the above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any easily conceivable changes or substitutions within the scope of the present invention shall be covered within the protection scope of the present invention.
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