技术领域technical field
本发明涉及一种柔性导电材料的制备方法，属于功能材料领域。The invention relates to a preparation method of a flexible conductive material, which belongs to the field of functional materials.
背景技术Background technique
近年来，柔性电子织物及储能元件越来越受到人们的青睐，包括柔性的太阳能电池和超级电容器等。用于柔性电子器件制备的材料主要有碳材料、导电聚合物、金属氧化物，而石墨烯、碳纳米管作为主要的碳材料，因具有极大的比表面积、良好的导电性、独特的光学特性以及优秀的机械性能等特性，是其他材料所无法比拟的。符合柔性电子织物及储能元件的要求，在电容器、光电器件、储能电池、电化学传感器和其它领域有着良好的应用前景。In recent years, flexible electronic fabrics and energy storage components have become more and more popular, including flexible solar cells and supercapacitors. The materials used for the preparation of flexible electronic devices mainly include carbon materials, conductive polymers, and metal oxides, and graphene and carbon nanotubes are the main carbon materials because of their large specific surface area, good electrical conductivity, and unique optical properties. Characteristics and excellent mechanical properties are unmatched by other materials. It meets the requirements of flexible electronic fabrics and energy storage components, and has good application prospects in capacitors, photoelectric devices, energy storage batteries, electrochemical sensors and other fields.
纤维素作为天然高分子，广泛存在于植物体中，来源广泛，价格低廉，可以说是一种可再生资源。相比于合成高分子，纤维素易被微生物酵解和转化，无毒、无污染，具有良好的生物相容性。长碳链多羟基结构使得纤维素富有大量的氢键结构，赋予了纤维素材料优异的力学性能，是很好的支架材料。纤维素虽然具有优异的结构性能，但是其功能性却十分有限。石墨烯、碳纳米管作为一种全新的功能型填料，被广泛运用到复合材料中。因此将石墨烯、碳纳米管与纤维素复合，提高纤维素的拉伸性能、导电性能和热学性能等，制备一种柔性导电材料。As a natural polymer, cellulose widely exists in plants, has a wide range of sources, and is cheap, so it can be said to be a renewable resource. Compared with synthetic polymers, cellulose is easily fermented and transformed by microorganisms, non-toxic, non-polluting, and has good biocompatibility. The long carbon chain polyhydroxyl structure makes cellulose rich in a large number of hydrogen bond structures, which endows the cellulose material with excellent mechanical properties and is a good scaffold material. Although cellulose has excellent structural properties, its functionality is very limited. Graphene and carbon nanotubes, as a new functional filler, are widely used in composite materials. Therefore, graphene, carbon nanotubes and cellulose are combined to improve the tensile properties, electrical conductivity and thermal properties of cellulose, and prepare a flexible conductive material.
目前，研究者在石墨烯或碳纳米管与纤维素复合的研究方面，主要采用对石墨烯或碳纳米管进行改性，如中国专利文献CN201710100296.8中公开了一种将棉织物浸入含有羧基化或氨基化的碳纳米管分散液中进行热处理，得到一种基于碳纳米管的导电织物，但是棉织物与碳纳米管只通过范德华力、静电作用结合，作用力比较弱，牢度差，易脱落。为了解决这个问题，一些研究者通过添加粘合剂的方法，将导电碳纳米碳材料固着在纤维上，如中国专利文献CN201710237783.9中公开了一种将水性光固化树脂通过光固化技术将石墨烯包覆固着到织物表面制备成导电织物，虽然提高了石墨烯与织物的牢度，但是织物的柔软性变差，手感粗糙，舒适性下降。At present, researchers mainly modify graphene or carbon nanotubes in the research of graphene or carbon nanotubes and cellulose composites. For example, Chinese patent document CN201710100296.8 discloses a method of soaking cotton fabric containing A conductive fabric based on carbon nanotubes is obtained by heat treatment in the carbon nanotube dispersion liquid that has been oxidized or aminated, but the cotton fabric and carbon nanotubes are only combined by van der Waals force and electrostatic interaction, the force is relatively weak, and the fastness is poor. Easy to fall off. In order to solve this problem, some researchers fix the conductive carbon nanocarbon material on the fiber by adding a binder. Graphene coating is fixed to the fabric surface to prepare a conductive fabric. Although the fastness between graphene and fabric is improved, the softness of the fabric becomes poor, the hand feels rough, and the comfort decreases.
发明内容Contents of the invention
为了解决上述问题，本发明通过化学改性的方法在石墨烯材料表面接枝含有环氧基的活性基团，可以与纤维素反应，将石墨烯材料与纤维素共价键结合，提高石墨烯材料在纤维素表面的牢度，增加纤维素纤维的导电性，同时不影响纤维柔软性和舒适性。In order to solve the above problems, the present invention grafts active groups containing epoxy groups on the surface of graphene materials through chemical modification, which can react with cellulose, and the graphene materials and cellulose are covalently bonded to improve graphene The fastness of the material on the surface of cellulose increases the conductivity of cellulose fibers without affecting the softness and comfort of the fibers.
本发明的第一个目的是提供一种柔性导电材料，所述柔性导电材料是通过在石墨烯表面接枝环氧基作为连接基团，再与纤维素共价结合形成柔性导电材料。The first object of the present invention is to provide a flexible conductive material, which is formed by grafting epoxy groups on the surface of graphene as linking groups, and then covalently bonding with cellulose to form a flexible conductive material.
在本发明的一种实施方式中，所述石墨烯材料为氧化石墨烯。In one embodiment of the present invention, the graphene material is graphene oxide.
在本发明的一种实施方式中，所述纤维素为天然纤维或再生纤维的织物。In one embodiment of the present invention, the cellulose is a fabric of natural fibers or regenerated fibers.
本发明的第二个目的是提供上述柔性导电材料的制备方法，所述方法具体是：The second object of the present invention is to provide the preparation method of above-mentioned flexible conductive material, and described method is specifically:
(1)反应型氧化石墨烯材料的制备：将氧化石墨烯分散于反应介质中，超声剥离分散，然后加入环氧硅烷，氧化石墨烯与环氧硅烷的质量比为1:(1～6)，在氮气的保护下，置于40～120℃下反应4～24小时，制备硅烷化氧化石墨烯材料；(2)柔性导电材料的制备：常温下，将纤维素投入浴比为1:3～30的水中，加入反应型氧化石墨烯材料，超声剥离分散，加入按水每升20～50g/L的Na2SO4，然后升温至60～90℃，加入按水每升10～30g/L的Na2CO3，保温30～90min，取出产物，依次经热水洗、冷水洗及皂洗，烘干，再经120℃热还原4小时得到柔性导电材料。(1) Preparation of reactive graphene oxide material: disperse graphene oxide in the reaction medium, ultrasonically exfoliate and disperse, then add epoxy silane, the mass ratio of graphene oxide to epoxy silane is 1:(1～6) , under the protection of nitrogen, place it at 40-120 ° C for 4-24 hours to prepare silanized graphene oxide material; (2) Preparation of flexible conductive material: at room temperature, put cellulose into the bath ratio of 1:3 ～30°C water, add reactive graphene oxide material, ultrasonically peel and disperse, add 20～50g/L Na2 SO4 per liter of water, then raise the temperature to 60～90°C, add 10～30g/L per liter of water L of Na2 CO3 , keep warm for 30-90 minutes, take out the product, wash with hot water, cold water and soap in sequence, dry, and then heat reduce at 120°C for 4 hours to obtain a flexible conductive material.
在本发明的一种实施方式中，所述的环氧硅烷为γ-缩水甘油醚氧基丙基三乙氧基硅烷或γ-缩水甘油醚氧丙基三甲氧基硅烷。In one embodiment of the present invention, the epoxy silane is γ-glycidoxypropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane.
在本发明的一种实施方式中，所述的反应介质为去离子水、乙醇、四氢呋喃或甲苯。In one embodiment of the present invention, the reaction medium is deionized water, ethanol, tetrahydrofuran or toluene.
在本发明的一种实施方式中，所述反应型氧化石墨烯材料用量为坯布重量的10％～30％。In one embodiment of the present invention, the amount of the reactive graphene oxide material is 10% to 30% of the gray cloth weight.
本发明的有益效果：本发明提供一种具有高耐久性、良好热性能、柔软手感和保持纤维或织物较好强度等性能的柔性导电材料的制备方法，应用前景良好。Beneficial effects of the present invention: the present invention provides a method for preparing a flexible conductive material with high durability, good thermal performance, soft hand feeling and good strength of fibers or fabrics, etc., and has a good application prospect.
具体实施方式Detailed ways
为了能够更清楚地理解本发明的技术内容，特举以下实施例详细说明，其目的仅在于更好理解本发明的内容而非限制本发明的保护范围。In order to understand the technical content of the present invention more clearly, the following examples are given in detail, the purpose of which is only to better understand the content of the present invention but not to limit the protection scope of the present invention.
本发明中未作特殊说明的原料均为市售。The raw materials not specified in the present invention are all commercially available.
本发明中列举出的实施例中涉及到的部分化合物如下所示：Part of the compounds involved in the examples listed in the present invention are as follows:
1.GO:氧化石墨1.GO: graphite oxide
2.KH560：γ-缩水甘油醚氧丙基三甲氧基硅烷2. KH560: γ-glycidyl etheroxypropyltrimethoxysilane
3.KH561：γ-缩水甘油醚氧丙基三乙氧基硅烷3. KH561: γ-glycidyl etheroxypropyltriethoxysilane
4.KH560-GO或KH561-GO4. KH560-GO or KH561-GO
KH560R＝OCH3，KH561R＝OCH2CH3.KH560R＝OCH3 , KH561R＝OCH2 CH3 .
本发明涉及的各物性参数的测试方法如下：The test method of each physical parameter that the present invention relates to is as follows:
(1)织物弯曲性能(弯曲刚度越小，织物手感越软)(1) Fabric bending properties (the smaller the bending stiffness, the softer the fabric feels)
取20cm×20cm试样，在温度为20±2℃，相对湿度为65％±2％的条件用KES—FB2风格仪测试织物在低负荷作用下的弯曲刚度。Take a 20cm×20cm sample, and use the KES-FB2 style meter to test the bending stiffness of the fabric under low load at a temperature of 20±2°C and a relative humidity of 65%±2%.
(2)皂洗牢度(2) Soaping fastness
GB/T 3921:2008纺织品色牢度试验耐皂洗色牢度。GB/T 3921:2008 Tests for color fastness of textiles Color fastness to soaping.
(3)摩擦牢度(3) Rubbing fastness
GB/T3920-2008纺织品色牢度试验耐皂洗色牢度。GB/T3920-2008 Tests for color fastness of textiles Color fastness to soaping.
实施例1Example 1
称取0.25gGO放入100ml乙醇和20ml水中超声分散，将0.25g KH560溶于50ml乙醇中慢慢滴加到反应体系中，在氮气的保护下，置于40℃下，反应24h，用无水乙醇清洗两次，去离子水清洗一次，真空烘干，得到KH560-GO。Weigh 0.25g of GO into 100ml of ethanol and 20ml of water for ultrasonic dispersion, dissolve 0.25g of KH560 in 50ml of ethanol and slowly drop into the reaction system, under the protection of nitrogen, place it at 40°C for 24 hours, and use anhydrous Washed twice with ethanol, once with deionized water, and dried in vacuum to obtain KH560-GO.
称取1.50g粘胶纤维投入浴比为1:3的水中，加入0.15g的KH560-GO，超声剥离分散，加入按水20g/L的Na2SO4，然后升温至90℃，加入按水10g/L的Na2CO3，保温30min，取出产物，依次经热水洗、冷水洗及皂洗，烘干，再经120℃热还原4h，制备具有高耐久性、柔软手感的粘胶基导电材料，该材料的弯曲刚度为4.5×10-2cN.cm2/cm，皂洗牢度3级，干摩擦牢度4级，湿摩擦牢度3级。Weigh 1.50g of viscose fiber into water with a bath ratio of 1:3, add 0.15g of KH560-GO, ultrasonically peel and disperse, add 20g/L of Na2 SO4 by water, then raise the temperature to 90°C, add 10g of water /L of Na2 CO3 , keep warm for 30min, take out the product, wash in hot water, cold water and soap in sequence, dry, and then heat reduction at 120°C for 4h to prepare a viscose-based conductive material with high durability and soft touch , the bending stiffness of the material is 4.5×10-2 cN.cm2 /cm, the soaping fastness is grade 3, the dry rubbing fastness is grade 4, and the wet rubbing fastness is grade 3.
实施例2Example 2
称取0.25gGO放入50ml甲苯中超声分散，将1.50g KH561溶于50ml甲苯中慢慢滴加到反应体系中，在氮气的保护下，置于120℃下，反应4h，用甲苯清洗两次，真空烘干，得到KH561-GO。Weigh 0.25g GO into 50ml toluene for ultrasonic dispersion, dissolve 1.50g KH561 in 50ml toluene and slowly add dropwise to the reaction system, under the protection of nitrogen, place at 120°C, react for 4h, wash with toluene twice , and dried in vacuum to obtain KH561-GO.
称取1.50g的莫代尔织物投入浴比为1:30的水中，加入0.45g的KH561-GO，超声剥离分散，加入按水50g/L的Na2SO4，然后升温至60℃，加入按水30g/L的Na2CO3，保温90min，取出产物，依次经热水洗、冷水洗及皂洗，烘干，再经120℃热还原4h，制备具有高耐久性、柔软手感的莫代尔基导电材料，该材料的弯曲刚度为4.2×10-2cN.cm2/cm，皂洗牢度3级，干摩擦牢度3-4级，湿摩擦牢度3级。Weigh 1.50g of modal fabric into water with a bath ratio of 1:30, add 0.45g of KH561-GO, ultrasonically peel and disperse, add 50g/L of Na2 SO4 in water, then raise the temperature to 60°C, add in water 30g/L Na2 CO3 , heat preservation for 90min, take out the product, wash in hot water, cold water and soap in sequence, dry, and then heat reduction at 120℃ for 4h to prepare a modal-based conductive material with high durability and soft touch , the bending stiffness of the material is 4.2×10-2 cN.cm2 /cm, the soaping fastness is grade 3, the dry rubbing fastness is 3-4 grade, and the wet rubbing fastness is grade 3.
实施例3：Example 3:
称取0.25gGO放入100ml乙醇和20ml水中超声分散，将0.5g KH560和0.5gKH561溶于50ml乙醇中慢慢滴加到反应体系中，在氮气的保护下，置于60℃下，反应12h，用无水乙醇清洗两次，去离子水清洗一次，真空烘干，得到KH560/KH561-GO。Weigh 0.25g of GO into 100ml of ethanol and 20ml of water for ultrasonic dispersion, dissolve 0.5g of KH560 and 0.5g of KH561 in 50ml of ethanol and slowly add to the reaction system dropwise, under the protection of nitrogen, place it at 60°C and react for 12h. Wash twice with absolute ethanol, once with deionized water, and dry in vacuum to obtain KH560/KH561-GO.
称取1.50g棉织物投入浴比为1:10的水中，加入0.30g的KH560/KH561-GO，超声剥离分散，加入按水30g/L的Na2SO4，然后升温至80℃，加入按水25g/L的Na2CO3，保温60min，取出产物，依次经热水洗、冷水洗及皂洗，烘干，再经120℃热还原4h，制备具有高耐久性、柔软手感的粘胶基导电材料。该材料的弯曲刚度为5.0×10-2cN.cm2/cm，皂洗牢度3级，干摩擦牢度4级，湿摩擦牢度3级。Weigh 1.50g of cotton fabric into water with a bath ratio of 1:10, add 0.30g of KH560/KH561-GO, ultrasonically peel and disperse, add 30g/L of Na2 SO4 in water, then raise the temperature to 80°C, add Water 25g/L Na2 CO3 , keep warm for 60min, take out the product, wash in hot water, cold water and soap in sequence, dry, and then heat reduction at 120℃ for 4h to prepare a viscose base with high durability and soft touch conductive material. The bending stiffness of the material is 5.0×10-2 cN.cm2 /cm, the soaping fastness is grade 3, the dry rubbing fastness is grade 4, and the wet rubbing fastness is grade 3.
实施例4：Example 4:
称取0.25gGO放入50ml四氢呋喃中超声分散，将1.5g KH560溶于50ml四氢呋喃中慢慢滴加到反应体系中，在氮气的保护下，置于80℃的温度下，反应6h，用四氢呋喃清洗两次，真空烘干，得到KH560-GO。Weigh 0.25g GO into 50ml THF for ultrasonic dispersion, dissolve 1.5g KH560 in 50ml THF and slowly add dropwise to the reaction system, under the protection of nitrogen, place at 80°C, react for 6h, and wash with THF Twice, vacuum drying to get KH560-GO.
称取1.5gLyocell纱线投入浴比为1:10的水中，加入0.30gKH560-GO，超声剥离分散，加入按水40g/L的Na2SO4，然后升温至80℃，加入按水30g/L的Na2CO3，保温60min，取出产物，依次经热水洗、冷水洗及皂洗，烘干，再经120℃热还原10h，制备具有高耐久性、柔软手感的Lyocell基导电材料。该材料的弯曲刚度为4.6×10-2cN.cm2/cm，皂洗牢度3-4级，干摩擦牢度4级，湿摩擦牢度3级。Weigh 1.5g Lyocell yarn into water with a bath ratio of 1:10, add 0.30g KH560-GO, ultrasonically peel and disperse, add 40g/L Na2 SO4 by water, then raise the temperature to 80°C, add 30g/L water Na2 CO3 , keep warm for 60min, take out the product, wash with hot water, cold water and soap in sequence, dry, and then heat reduction at 120℃ for 10h to prepare Lyocell-based conductive material with high durability and soft hand feeling. The bending stiffness of the material is 4.6×10-2 cN.cm2 /cm, the soaping fastness is 3-4 grades, the dry rubbing fastness is 4 grades, and the wet rubbing fastness is 3 grades.
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Any person familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore The scope of protection of the present invention should be defined by the claims.
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| CN201711417148.5ACN108103772B (en) | 2017-12-25 | 2017-12-25 | A kind of preparation method of flexible conducting material |
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| CN201711417148.5ACN108103772B (en) | 2017-12-25 | 2017-12-25 | A kind of preparation method of flexible conducting material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109183392B (en)* | 2018-08-09 | 2021-02-23 | 青岛大学 | Graphene modified conductive cellulose fiber and preparation method and application thereof |
| CN109295699A (en)* | 2018-09-30 | 2019-02-01 | 河南工程学院 | A method for improving the electrical conductivity, electrical conductivity uniformity and durability of graphene-finished fabrics |
| CN112982013B (en)* | 2021-02-18 | 2022-05-20 | 陕西科技大学 | Preparation method of cellulose-based flexible electronic material |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627139B (en)* | 2013-09-25 | 2015-10-28 | 杭州师范大学 | A kind of preparation method of functional graphene oxide/epoxy resin nano composites |
| CN103806266B (en)* | 2013-11-25 | 2016-01-13 | 江南大学 | A kind of method utilizing ultraviolet light to prepare graphene oxide conductive cellulose fabric |
| CN104674573B (en)* | 2015-03-10 | 2018-10-16 | 北京安墨烯科技有限责任公司 | A kind of flexible wire and preparation method thereof, conductive fabric, heating fabric |
| CN106854832A (en)* | 2016-12-05 | 2017-06-16 | 嘉兴学院 | A kind of compliant conductive waterproof fabric based on Graphene layer assembly and preparation method thereof |
| CN107286553A (en)* | 2017-06-12 | 2017-10-24 | 安徽省颍上县正泰电器有限责任公司 | A kind of preparation method of the plain cross-linked material of water-retaining type graphene nano fiber |
| CN107287883B (en)* | 2017-07-26 | 2020-01-07 | 山东圣泉新材料股份有限公司 | Preparation method of modified cotton fiber, obtained product and application |
| Publication number | Publication date |
|---|---|
| CN108103772A (en) | 2018-06-01 |
| Publication | Publication Date | Title |
|---|---|---|
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