CN110687169B - A humidity-sensitive carbon nanotube/graphene/organic composite flexible material, humidity sensor and preparation method thereof - Google Patents
A humidity-sensitive carbon nanotube/graphene/organic composite flexible material, humidity sensor and preparation method thereof Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于柔性功能电子材料及柔性传感器技术领域,具体涉及一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料、柔性湿度传感器及其制备方法。The invention belongs to the technical field of flexible functional electronic materials and flexible sensors, and particularly relates to a humidity-sensitive carbon nanotube/graphene/organic composite flexible material, a flexible humidity sensor and a preparation method thereof.
背景技术Background technique
常见的湿度传感器的工作原理是通过水分子与有机聚合物相互作用引发其介电常数或电导率的改变,通过测量电阻值或电容值的变化来反映湿度的变化。随着近几年传感器应用范围日趋多元化及世界各国在传感器技术领域的发展,湿度传感器在大气监测、工业生产、生物医疗等领域展现出广阔的应用前景。目前,许多智能化的检测设备已经大量地采用了各种各样的传感器,其应用早已渗透到诸如工业生产、海洋探测、环境保护、医学诊断、生物工程、智能家居等方方面面。随着信息时代的应用需求越来越高,对被测量信息的范围、精度和稳定情况等各性能参数的期望值和理想化要求逐步提高。针对特殊环境与特殊信号下湿度的测量需求,新型传感器技术已向以下趋势发展:开发新材料、新工艺和开发新型传感器;实现传感器的集成化和智能化;实现传感技术硬件系统与元器件的微小型化。同时,希望传感器还能够具有透明、柔韧、延展、可自由弯曲甚至折叠、便于携带、可穿戴等特点。而传统的硅基半导体湿度传感器无法柔性化,且制造成本较高、不便于携带。The working principle of common humidity sensors is to change the dielectric constant or conductivity of organic polymers through the interaction of water molecules and organic polymers, and to reflect changes in humidity by measuring changes in resistance or capacitance. With the increasing diversification of sensor applications in recent years and the development of sensor technology in various countries around the world, humidity sensors have shown broad application prospects in atmospheric monitoring, industrial production, biomedical and other fields. At present, many intelligent detection devices have adopted a large number of various sensors, and their applications have already penetrated into various aspects such as industrial production, marine exploration, environmental protection, medical diagnosis, bioengineering, and smart home. With the increasing application requirements in the information age, the expectations and idealization requirements for various performance parameters such as the range, accuracy and stability of the measured information are gradually increasing. In response to the measurement requirements of humidity in special environments and special signals, new sensor technology has developed to the following trends: developing new materials, new processes and developing new sensors; realizing the integration and intelligence of sensors; realizing sensing technology hardware systems and components of miniaturization. At the same time, it is hoped that the sensor can also be transparent, flexible, extensible, freely bendable or even foldable, easy to carry, and wearable. However, the traditional silicon-based semiconductor humidity sensor cannot be flexible, and the manufacturing cost is high and it is not easy to carry.
现有技术报道了一种使用喷墨印刷的方法将聚酰亚胺涂覆到银交叉电极上制备湿度传感器的方法,采用该方法制备的湿度传感器虽然随着湿度变化电阻变化幅度较大,但测量范围有限且湿度灵敏性较差。现有技术还公开了一种通过用叔丁基锂剥离WS2合成2D纳米材料,然后将其沉积在电导陶瓷平台的交叉指状电极上制备湿度传感器的方法,该方法制备的湿度传感器不仅制备成本较高,制造工艺繁杂且传感器响应时间较长。另外还有关于以羧甲基纤维素(CMC)响应于湿度变化而导致机械应变的原理在玻璃纤维基材上制造湿度传感器的报道,虽然该传感器灵敏度较高但适用适用湿度范围较窄,限制了传感器的应用。The prior art reports a method for preparing a humidity sensor by coating polyimide on silver crossed electrodes using inkjet printing. Although the humidity sensor prepared by this method has a large resistance change with humidity, Limited measurement range and poor humidity sensitivity. The prior art also discloses a method for preparing a humidity sensor by exfoliating WS2 with tert-butyl lithium to synthesize 2D nanomaterials, and then depositing it on an interdigitated electrode of a conductive ceramic platform. Higher, the manufacturing process is complicated and the sensor response time is longer. There are also reports on fabricating humidity sensors on glass fiber substrates based on the principle of mechanical strain induced by carboxymethyl cellulose (CMC) in response to changes in humidity. Although the sensor has high sensitivity, it has a narrow range of applicable humidity, which limits the sensor application.
发明内容SUMMARY OF THE INVENTION
针对上述现有技术,本发明提供一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料,基于该柔性材料可以制备出高灵敏度和快速响应的柔性湿度传感器。In view of the above prior art, the present invention provides a humidity-sensitive carbon nanotube/graphene/organic composite flexible material, based on which a flexible humidity sensor with high sensitivity and rapid response can be prepared.
为了达到上述目的,本发明所采用的技术方案是:提供一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料的制备方法,包括以下步骤:In order to achieve the above object, the technical solution adopted in the present invention is: a preparation method of a humidity-sensitive carbon nanotube/graphene/organic composite flexible material is provided, comprising the following steps:
S1:将石墨烯按1g:180~220mL的料液比浸入由浓硫酸与浓硝酸制得的混合酸中,于68~75℃下处理6~8h,再依次进行离心、清洗和干燥处理,得氧化石墨烯;S1: Immerse the graphene in a mixed acid prepared from concentrated sulfuric acid and concentrated nitric acid at a material-to-liquid ratio of 1 g:180 to 220 mL, treat at 68 to 75 ° C for 6 to 8 hours, and then perform centrifugation, cleaning and drying in sequence, get graphene oxide;
S2:将氧化石墨烯和碳纳米管分别分散于溶剂中,得到浓度均为3~7mg/mL的石墨烯分散液和碳纳米管分散液;S2: dispersing graphene oxide and carbon nanotubes in a solvent, respectively, to obtain a graphene dispersion and a carbon nanotube dispersion with a concentration of 3-7 mg/mL;
S3:将柔性衬底依次置于石墨烯分散液和碳纳米管分散液中浸泡,得碳纳米管/石墨烯/有机复合柔性材料。S3: the flexible substrate is soaked in the graphene dispersion solution and the carbon nanotube dispersion solution in turn to obtain a carbon nanotube/graphene/organic composite flexible material.
在上述技术方案的基础上,本发明还可以做如下改进。On the basis of the above technical solutions, the present invention can also be improved as follows.
进一步,混合酸中浓硫酸与浓硝酸的体积比为1:1~5。Further, the volume ratio of concentrated sulfuric acid and concentrated nitric acid in the mixed acid is 1:1-5.
进一步,石墨烯为单层石墨烯或多层石墨烯;碳纳米管为单壁碳纳米管或多壁碳纳米管。Further, the graphene is single-layer graphene or multi-layer graphene; and the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
进一步,S1中清洗所用清洗液为pH≥6的去离子水;干燥温度为55~65℃,干燥时间为12~16h。Further, the cleaning solution used for cleaning in S1 is deionized water with pH≥6; the drying temperature is 55-65° C., and the drying time is 12-16 h.
进一步,S2中分散氧化石墨烯的溶剂为乙醇;分散碳纳米管的溶剂为N,N-二甲基甲酰胺。Further, the solvent for dispersing graphene oxide in S2 is ethanol; the solvent for dispersing carbon nanotubes is N,N-dimethylformamide.
进一步,柔性衬底在浸泡前用无水乙醇超声清洗10~30min。Further, the flexible substrate was ultrasonically cleaned with absolute ethanol for 10-30 min before soaking.
进一步,柔性衬底为聚丙烯、聚丙烯腈、聚乙烯醇缩甲醛、聚酰胺、聚对苯二甲酸乙二酯、聚酰胺或氰基丙烯酸酯Further, the flexible substrate is polypropylene, polyacrylonitrile, polyvinyl formal, polyamide, polyethylene terephthalate, polyamide or cyanoacrylate
进一步,柔性衬底在石墨烯分散液中的浸泡时间为4~7min,浸泡后于60℃下干燥10min,再放入碳纳米管分散液中浸泡3~5min,然后于150℃下干燥0.5h,得碳纳米管/石墨烯/有机复合柔性材料。Further, the soaking time of the flexible substrate in the graphene dispersion liquid is 4-7 min, after soaking, it is dried at 60 °C for 10 min, then put into the carbon nanotube dispersion liquid for soaking for 3-5 min, and then dried at 150 °C for 0.5 h , to obtain carbon nanotube/graphene/organic composite flexible materials.
采用上述方法可以制备出一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料,而且该柔性材料经过剪裁成并涂敷电极后可以得到柔性湿度传感器。Using the above method, a humidity-sensitive carbon nanotube/graphene/organic composite flexible material can be prepared, and the flexible humidity sensor can be obtained after the flexible material is cut and coated with electrodes.
本发明的有益效果是:The beneficial effects of the present invention are:
1.本发明中采用氧化石墨烯和碳纳米管制备复合柔性层,由于二者之间可以形成较强的氢键和范德华力相互作用,因此最终制备的碳纳米管/石墨烯/有机复合多层材料电阻较小,给传感器带来性能稳定的优点。1. In the present invention, graphene oxide and carbon nanotubes are used to prepare the composite flexible layer, because strong hydrogen bonds and van der Waals interaction can be formed between the two, so the carbon nanotube/graphene/organic composite finally prepared is more The resistance of the layer material is small, which brings the advantage of stable performance to the sensor.
2.湿敏元件的特点是在基底上覆盖一层用感湿材料制成的膜,当空气中的水蒸气吸附在感湿膜上时,元件的电阻率和电阻值都发生变化,利用这一特性即可测量湿度。当空气中湿度增大,水分子浓度增加,湿敏膜吸收的水分子变多,导电性能增强,电阻率下降,电阻也就随之降低。当湿敏膜表面的水分子脱落后,电阻也就恢复至原值。然而由于氧化石墨烯本身良好的亲水性能,水分子的脱落所需时间较长,而在氧化石墨烯表面覆盖上碳纳米管后,可以加速水分子的脱落。碳纳米管本身呈管状结构,穿插在石墨烯片层结构之间,由于碳纳米管本身是具有疏水性的,当石墨烯吸附的水分子接触到碳纳米管便会脱落,加速湿敏膜的响应恢复。因此,湿敏膜能够在检测到湿度变化时电阻迅速变小,而湿度变回原值时,湿敏膜表面水分子脱落,电阻也迅速恢复。这样,湿度传感器就具有了灵敏度高,响应恢复快的特点。本发明提供的湿度传感器湿度响应时间小于2秒,恢复时间小于10秒。2. The characteristic of the humidity sensitive element is that the substrate is covered with a film made of moisture-sensitive material. When the water vapor in the air is adsorbed on the moisture-sensitive film, the resistivity and resistance value of the element change. Humidity can be measured with one feature. When the humidity in the air increases, the concentration of water molecules increases, the moisture-sensitive film absorbs more water molecules, the electrical conductivity increases, the resistivity decreases, and the resistance decreases accordingly. When the water molecules on the surface of the humidity sensitive film fall off, the resistance will return to its original value. However, due to the good hydrophilic properties of graphene oxide itself, the shedding of water molecules takes a long time, and the shedding of water molecules can be accelerated after the surface of graphene oxide is covered with carbon nanotubes. Carbon nanotubes have a tubular structure and are interspersed between graphene sheet structures. Since carbon nanotubes are hydrophobic, when the water molecules adsorbed by graphene come into contact with carbon nanotubes, they will fall off, accelerating the moisture-sensitive film. Responsive recovery. Therefore, the resistance of the humidity-sensitive film can quickly decrease when the humidity change is detected, and when the humidity returns to the original value, the water molecules on the surface of the humidity-sensitive film fall off, and the resistance also recovers quickly. In this way, the humidity sensor has the characteristics of high sensitivity and fast response recovery. The humidity response time of the humidity sensor provided by the invention is less than 2 seconds, and the recovery time is less than 10 seconds.
3.从复合柔性导电织物的制备过程上看,所采用的浸渍涂敷工艺过程简单、生产成本低,效率高,容易实现连续化、规模化生产。3. From the perspective of the preparation process of the composite flexible conductive fabric, the adopted dip coating process is simple, the production cost is low, the efficiency is high, and it is easy to realize continuous and large-scale production.
附图说明Description of drawings
图1为碳纳米管/石墨烯/有机复合柔性材料的湿度-电阻快速响应特性曲线;Fig. 1 is the humidity-resistance fast response characteristic curve of carbon nanotube/graphene/organic composite flexible material;
图2为碳纳米管/石墨烯/有机复合柔性材料灵敏度最佳样品的湿度-电阻响应恢复时间特性曲线;Figure 2 is the humidity-resistance response recovery time characteristic curve of the carbon nanotube/graphene/organic composite flexible material with the best sensitivity;
图3为碳纳米管/石墨烯/有机复合柔性材料的表面SEM图;Fig. 3 is the surface SEM image of carbon nanotube/graphene/organic composite flexible material;
图4为碳纳米管/石墨烯/有机复合柔性材料的湿度梯度-电阻特性曲线;Fig. 4 is the humidity gradient-resistance characteristic curve of carbon nanotube/graphene/organic composite flexible material;
图5为碳纳米管/石墨烯/有机复合柔性材料的湿度点图。Figure 5 is the humidity point diagram of carbon nanotube/graphene/organic composite flexible material.
具体实施方式Detailed ways
本发明制备具有压力/摩擦力传感功能的柔性自粘布过程中所用材料如下:The materials used in the process of preparing the flexible self-adhesive cloth with pressure/friction sensing function in the present invention are as follows:
1.石墨烯:可以为单层石墨烯,也可以为多层石墨烯;1. Graphene: it can be single-layer graphene or multi-layer graphene;
2.碳纳米管:可以为单壁碳纳米管,也可以为多壁碳纳米管;优选多壁碳纳米管,并且多壁碳纳米管的平均直径为10~20nm,平均长度为20μm。2. Carbon nanotubes: can be single-walled carbon nanotubes or multi-walled carbon nanotubes; preferably multi-walled carbon nanotubes, and the average diameter of the multi-walled carbon nanotubes is 10-20 nm, and the average length is 20 μm.
3.柔性衬底:柔性衬底为宽2cm、长10cm,采用高聚物制成,如聚丙烯、聚丙烯腈、聚乙烯醇缩甲醛、聚酰胺、聚对苯二甲酸乙二酯、聚酰胺或氰基丙烯酸酯等。3. Flexible substrate: The flexible substrate is 2cm wide and 10cm long, and is made of high polymers, such as polypropylene, polyacrylonitrile, polyvinyl formal, polyamide, polyethylene terephthalate, polyethylene amides or cyanoacrylates, etc.
下面结合实施例对本发明的具体实施方式做详细的说明。The specific embodiments of the present invention will be described in detail below with reference to the examples.
实施例一Example 1
一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料的制备方法,包括以下步骤:A preparation method of a humidity-sensitive carbon nanotube/graphene/organic composite flexible material, comprising the following steps:
S1:取浓硫酸(98%)150mL和浓硝酸(65%)50mL,将两者混合得混合酸200mL;向上述混合酸中加入1g多层石墨烯,搅拌均匀并加热至70℃,保持反应7h。待上述反应体系冷却后经6000rpm离心3min,然后用pH≥6的去离子水清洗4次,再在60℃下干燥14h,制得氧化石墨烯;S1: take 150 mL of concentrated sulfuric acid (98%) and 50 mL of concentrated nitric acid (65%), and mix the two to obtain 200 mL of mixed acid; add 1 g of multi-layer graphene to the above mixed acid, stir evenly and heat to 70 ° C to keep the reaction 7h. After the reaction system was cooled, the reaction system was centrifuged at 6000 rpm for 3 min, then washed with deionized water with pH ≥ 6 for 4 times, and then dried at 60 °C for 14 h to obtain graphene oxide;
S2:将制得的氧化石墨烯分散于无水乙醇中,得浓度为5mg/mL的氧化石墨烯分散液;将多壁碳纳米管分散于N,N-二甲基甲酰胺(DMF)中,得浓度为5mg/mL的碳纳米管分散液;S2: Disperse the prepared graphene oxide in absolute ethanol to obtain a graphene oxide dispersion liquid with a concentration of 5 mg/mL; disperse the multi-walled carbon nanotubes in N,N-dimethylformamide (DMF) , to obtain a carbon nanotube dispersion with a concentration of 5 mg/mL;
S3:将聚丙烯无纺布的双面经过无水乙醇超声清洗10min;S3: ultrasonically clean both sides of the polypropylene non-woven fabric with absolute ethanol for 10 minutes;
S4:将清洗后的聚丙烯无纺布置于氧化石墨烯分散液中浸泡5min,然后60℃下干燥10min,制得氧化石墨烯包覆的无纺布;S4: soak the cleaned polypropylene non-woven fabric in the graphene oxide dispersion for 5 min, and then dry at 60° C. for 10 min to obtain a graphene oxide-coated non-woven fabric;
S5:将得到的氧化石墨烯包覆的无纺布置于碳纳米管分散液中浸泡20s,然后在150℃下干燥0.5h,制得碳纳米管/石墨烯/有机复合多层包覆的无纺布。S5: The obtained graphene oxide-coated non-woven fabric was soaked in carbon nanotube dispersion for 20 s, and then dried at 150° C. for 0.5 h to obtain a carbon nanotube/graphene/organic composite multilayer coated Non-woven.
实施例二Embodiment 2
一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料的制备方法,氧化石墨烯包覆的无纺布在碳纳米管分散液中浸泡1min,其余操作与实施例相同。A preparation method of a humidity-sensitive carbon nanotube/graphene/organic composite flexible material, the graphene oxide-coated non-woven fabric is soaked in a carbon nanotube dispersion for 1 min, and the rest of the operations are the same as in the embodiment.
实施例三Embodiment 3
一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料的制备方法,氧化石墨烯包覆的无纺布在碳纳米管分散液中浸泡3min,其余操作与实施例相同。A preparation method of a humidity-sensitive carbon nanotube/graphene/organic composite flexible material, the graphene oxide-coated non-woven fabric is soaked in a carbon nanotube dispersion liquid for 3 minutes, and the remaining operations are the same as those in the embodiment.
实施例四Embodiment 4
一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料的制备方法,氧化石墨烯包覆的无纺布在碳纳米管分散液中浸泡10min,其余操作与实施例相同。A preparation method of a humidity-sensitive carbon nanotube/graphene/organic composite flexible material, the graphene oxide-coated non-woven fabric is soaked in a carbon nanotube dispersion for 10 minutes, and the rest of the operations are the same as in the embodiment.
实施例五Embodiment 5
一种湿度敏感的碳纳米管/石墨烯/有机复合柔性材料的制备方法,氧化石墨烯包覆的无纺布在碳纳米管分散液中浸泡5min,其余操作与实施例相同。A preparation method of a humidity-sensitive carbon nanotube/graphene/organic composite flexible material, the graphene oxide-coated non-woven fabric is soaked in a carbon nanotube dispersion liquid for 5 minutes, and the rest of the operations are the same as in the embodiment.
图1为碳纳米管/石墨烯/有机复合柔性材料的湿度-电阻快速响应特性曲线,A~E分别为实施例一~实施例五所得柔性材料的湿度-电阻响应特性曲线。从图1可以看出,碳纳米管/石墨烯/有机复合柔性材料的电阻值随相对湿度的增加而减小,并且灵敏度高;而且从图1中的曲线A~C以及E可以看出,随着氧化石墨烯包覆的无纺布在碳纳米管分散液中浸泡时间的延长,其电阻-湿度变化灵敏度也随之增加;从图1中曲线D可以看出碳纳米管/石墨烯/有机复合柔性材料的电阻值变化率大大减小,但是其电阻-湿度变化灵敏度仍在上升,这个结果说明湿敏膜表面的疏水性能已经很强了,再继续延长浸泡时间湿敏膜的亲水性会被破坏,具有疏水的特性。Fig. 1 is the humidity-resistance fast response characteristic curve of carbon nanotube/graphene/organic composite flexible material, A to E are respectively the humidity-resistance response characteristic curve of the flexible material obtained in Example 1 to Example 5. It can be seen from Figure 1 that the resistance value of the carbon nanotube/graphene/organic composite flexible material decreases with the increase of relative humidity, and the sensitivity is high; and it can be seen from the curves A to C and E in Figure 1 that, With the prolongation of the soaking time of the graphene oxide-coated non-woven fabric in the carbon nanotube dispersion, its resistance-humidity change sensitivity also increases; it can be seen from the curve D in Figure 1 that the carbon nanotube/graphene/ The resistance value change rate of the organic composite flexible material is greatly reduced, but its resistance-humidity change sensitivity is still increasing. This result shows that the hydrophobicity of the surface of the humidity-sensitive film is already very strong, and the hydrophilicity of the humidity-sensitive film is prolonged by continuing to prolong the soaking time. Sexuality is disrupted and has hydrophobic properties.
图2为实施例五制得的碳纳米管/石墨烯/有机复合柔性材料,此时湿度传感器灵敏度达到最佳,响应时间为1s,恢复时间为7s,其响应恢复曲线如图2所示。Figure 2 shows the carbon nanotube/graphene/organic composite flexible material prepared in Example 5. At this time, the sensitivity of the humidity sensor reaches the best, the response time is 1s, and the recovery time is 7s. The response recovery curve is shown in Figure 2.
图3为实施例二制得的碳纳米管/石墨烯/有机复合柔性材料的表面SEM图。从图中可以看出,碳纳米管和石墨烯形成了具有一定连续性的导电网络。3 is a SEM image of the surface of the carbon nanotube/graphene/organic composite flexible material prepared in Example 2. As can be seen from the figure, carbon nanotubes and graphene form a conductive network with certain continuity.
图4为碳纳米管/石墨烯/有机复合柔性材料的湿度梯度-电阻特性曲线。从图中可以看出通过多次改变测试环境湿度,湿敏膜电阻在对应湿度处的电阻值没有太大变化,说明该复合湿敏材料稳定性好。Figure 4 is the humidity gradient-resistance characteristic curve of the carbon nanotube/graphene/organic composite flexible material. It can be seen from the figure that by changing the humidity of the test environment for many times, the resistance value of the humidity-sensitive film resistor at the corresponding humidity does not change much, indicating that the composite humidity-sensitive material has good stability.
图5为碳纳米管/石墨烯/有机复合柔性材料的湿度点图。从图中可以看出,低湿区敏感度比高湿区高,电阻变化幅度更大。从相对湿度45%RH到95%RH,平均每上升1%RH电阻下降436kΩ。Figure 5 is the humidity point diagram of carbon nanotube/graphene/organic composite flexible material. It can be seen from the figure that the sensitivity of the low humidity area is higher than that of the high humidity area, and the resistance change is larger. From 45%RH to 95%RH relative humidity, the resistance drops by 436kΩ for every 1%RH rise on average.
虽然结合实施例对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。Although the specific embodiments of the present invention have been described in detail with reference to the examples, they should not be construed as limiting the protection scope of the present patent. Within the scope described in the claims, various modifications and variations that can be made by those skilled in the art without creative efforts still belong to the protection scope of this patent.
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