WO2022188262A1 - 柔性压阻导电材料的制备方法 - Google Patents

柔性压阻导电材料的制备方法 Download PDF

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WO2022188262A1
WO2022188262A1 PCT/CN2021/094096 CN2021094096W WO2022188262A1 WO 2022188262 A1 WO2022188262 A1 WO 2022188262A1 CN 2021094096 W CN2021094096 W CN 2021094096W WO 2022188262 A1 WO2022188262 A1 WO 2022188262A1
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woven fabric
conductive material
flexible piezoresistive
ethylenedioxythiophene
piezoresistive conductive
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French (fr)
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王萍
张佳文
张岩
李媛媛
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Suzhou University
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Suzhou University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/28—Halides of elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Definitions

  • the invention relates to the technical field of conductive material processing, in particular to a preparation method of a flexible piezoresistive conductive material.
  • CNTs carbon nanotubes
  • CNFs carbon nanofibers
  • graphene graphene
  • a series of conductive polymer materials are often used to modify textiles.
  • Flexible electrodes used as sensors.
  • knitted fabrics and woven fabrics are mostly used as the base material of the flexible sensor, and the density of knitted fabrics and woven fabrics is relatively high. less sensitive.
  • a conductive polymer can be attached to the non-woven material, and a flexible sensor material with high conductivity and higher sensitivity to pressure changes can be prepared.
  • uneven distribution of conductive polymers is often prone to occur, thereby affecting the performance of the material.
  • the inventor of the present application proposes a preparation method of a flexible piezoresistive conductive material.
  • the present invention provides a preparation method of a flexible piezoresistive conductive material, which has a large resistance change before and after pressing, has high sensitivity to pressure changes, and has the advantages of preparing a piezoresistive type.
  • the potential of pressure sensors is not limited to, but rather to, but rather to, but rather to, but rather to, but rather to, but rather to, but not to, the present invention.
  • the invention discloses a preparation method of a flexible piezoresistive conductive material, comprising the following steps:
  • the non-woven fabric is immersed in an oxidizing agent solution, and the non-woven fabric is formed by intertwining and intertwining of a plurality of fibers;
  • the preheated nonwoven is arranged in a 3,4-ethylenedioxythiophene gas atmosphere to carry out a polymerization reaction, so as to form poly3,4-ethylenedioxythiophene on the surface of any fiber of the nonwoven;
  • the non-woven fabric after the polymerization reaction is cleaned with an ethanol solution, and the cleaned non-woven fabric is dried until the ethanol solution is volatilized.
  • the density of the non-woven fabric ranges from 0.1 to 0.4 g/cm 3
  • the porosity ranges from 75% to 95%.
  • the dipping treatment time is 20-40 min.
  • the temperature range of the preheating treatment is between 40°C and 50°C.
  • the open mouth containing 3,4-ethylenedioxythiophene is reacted
  • the reactor is placed in the reaction chamber, the first side of the dried non-woven fabric is placed facing the opening of the open reactor, and the temperature in the reaction chamber is controlled to be 50°C to 60°C.
  • the temperature is 50°C to 60°C, the second surface of the non-woven fabric is placed facing the opening of the open reactor, and the reaction is carried out for 2 to 3 hours.
  • the non-woven fabric is one of polyester needle punched cloth, polyimide needle punched cloth and polypropylene needle punched cloth.
  • the drying temperature is 30-50° C., and the drying time is 20-40 minutes.
  • an ethanol solution obtained by mixing 98% ethanol and deionized water in a volume ratio of 1:1 is used to clean the non-woven fabric. cloth for ultrasonic cleaning.
  • the oxidant is one of ferric chloride and ferric p-toluenesulfonate, and the solvent of the oxidant solution is methanol.
  • the preparation method of the flexible piezoresistive conductive material of the present invention adopts a non-woven fabric as the base material prepared by the flexible piezoresistive conductive material, and utilizes the inherent fluffy structure characteristics of the non-woven fabric, when the non-woven fabric is subjected to pressure, the thickness changes greatly, and its The change of fiber structure is more obvious than that of knitted and woven fabrics, so that the prepared flexible piezoresistive conductive material has a large resistance change before and after pressure, and has a high sensitivity to pressure changes, and has the ability to prepare piezoresistive pressure sensors. potential.
  • the preparation method of the flexible piezoresistive conductive material of the present invention can remove excess oxidant in the non-woven fabric by preheating the impregnated non-woven fabric and then carry out a polymerization reaction, so that the fiber surface of the non-woven fabric can be uniformly adhered to the surface.
  • Oxidant after the polymerization reaction, poly3,4-ethylenedioxythiophene coats the fibers more uniformly, and the coated fibers have a smooth surface, which makes the performance of the prepared flexible piezoresistive conductive material more stable.
  • the preparation method of the flexible piezoresistive conductive material of the present invention can improve the pre-baking effect and maintain the flexibility of the non-woven fabric by setting the pre-baking temperature at 40° C. to 50° C.
  • Fig. 1 is the variation trend diagram of the current released when the flexible piezoresistive conductive material is applied with different pressures in Example 3 of the present invention
  • Example 3 is a scanning electron microscope image of the second region of the flexible piezoresistive conductive material in Example 3 of the present invention.
  • Example 4 is a scanning electron microscope image of a fiber cross-section of a flexible piezoresistive conductive material in Example 3 of the present invention.
  • FIG. 6 is a scanning electron microscope image of the second region of the flexible piezoresistive conductive material in the comparative example of the present invention.
  • the non-woven fabrics used in Examples 1 to 4 of the present invention are polyester needle-punched fabrics with a density of 0.2 g/cm 3 and a porosity of 80% to 85%.
  • the size of the non-woven fabric is adapted to the size of the opening of the open reactor, so that the first side or the second side of the non-woven fabric can be connected with the gaseous 3,4-ethylenedioxythiophene flowing in the open reactor full contact.
  • Step 1 Using iron p-toluenesulfonate as the oxidant, dissolving the iron p-toluenesulfonate powder in the methanol solution, and magnetically stirring it evenly, so that the iron p-toluenesulfonate is completely dissolved in the methanol solution, and the content of the iron p-toluenesulfonate is obtained: 8 wt% oxidant solution.
  • Step 2 Mix deionized water and ethanol with a volume fraction of 98% according to a volume ratio of 1:1 to obtain an ethanol solution.
  • the non-woven fabric was ultrasonically cleaned with an ethanol solution for 15 minutes, and then the non-woven fabric was rinsed three times with 98% ethanol by volume, and the rinsed non-woven fabric was dried in an oven at 40°C until the The weight no longer changes within 20min.
  • Step 3 The non-woven fabric after drying in Step 2 is immersed in an oxidizing agent solution for 30 minutes.
  • the non-woven fabric is formed by intertwining and intertwining a plurality of fibers, and the diameter of any fiber is 15 ⁇ m.
  • Step 4 The impregnated non-woven fabric is rolled with a paddle to remove excess liquid, so that the liquid-carrying rate of the non-woven fabric is 500%.
  • Step 5 Arrange the non-woven fabric with excess liquid removed in an oven for preheating treatment at 40°C for 30 minutes, so that the methanol in the non-woven fabric is completely volatilized, so that excess oxidant can be removed, and the non-woven fabric is pre-baked.
  • the weight gain rate is 60% to 70%.
  • the calculation method of the weight gain rate of the pre-baked non-woven fabric is as follows: the mass of the dried non-woven fabric in step 2 is m 1 , the mass of the pre-baked non-woven fabric in step 5 is m 2 , and the pre-baked non-woven fabric has a mass of m 2 .
  • the weight gain rate of the back non-woven fabric is R 1 , Among them, a total of three groups of parallel experiments were performed, and the average value of the three groups of parallel experiments was taken as the final value.
  • Step 6 The preheated nonwoven is arranged in a 3,4-ethylenedioxythiophene gas atmosphere to carry out a polymerization reaction to form poly3,4-ethylenedioxythiophene (poly3,4-ethylenedioxythiophene) on the surface of any fiber of the nonwoven PEDOT), the thickness of the poly-3,4-ethylenedioxythiophene film layer wrapped on the surface of any fiber is about 500 nm.
  • the non-woven fabric has opposite first and second surfaces, and the first surface of the dried non-woven fabric is placed facing the opening of the open reactor, and the temperature in the reaction chamber is controlled to be 60°C.
  • the temperature in the reaction chamber was 60° C.
  • the second surface of the non-woven fabric was placed facing the opening of the open reactor, and the reaction was continued for 3 hours.
  • the temperature in the reaction chamber is controlled to be 60°C, which can make the 3,4-ethylenedioxythiophene (EDOT) monomer in the open reactor evaporate to form a gas, which rises to the surface of the non-woven fabric.
  • EDOT 3,4-ethylenedioxythiophene
  • PEDOT poly-3,4-ethylenedioxythiophene
  • Step 7 Mix deionized water and ethanol with a volume fraction of 98% according to a volume ratio of 1:1 to obtain an ethanol solution.
  • the ethanol solution was used to ultrasonically clean the non-woven fabric after the polymerization reaction for 15 minutes, and the cleaned non-woven fabric was placed in an oven and dried at 40°C for 30 minutes to volatilize the ethanol solution, thereby obtaining a flexible piezoresistive conductive material.
  • the weight gain rate of the resistive conductive material is 20%.
  • the calculation method of the weight gain rate of the flexible piezoresistive conductive material is as follows: the mass of the dried non-woven fabric in step 2 is m 1 , the mass of the flexible piezoresistive conductive material is m 3 , and the weight gain of the flexible piezoresistive conductive material is m 1 .
  • rate R 2 Among them, a total of three groups of parallel experiments were performed, and the average value of the three groups of parallel experiments was taken as the final value.
  • Example 1 The difference between this example and Example 1 is that the content of iron p-toluenesulfonate in the oxidant solution is 10 wt %, and other steps and process parameters are the same as those in Example 1.
  • Example 1 The difference between this example and Example 1 is that the content of iron p-toluenesulfonate in the oxidant solution is 12 wt %, and other steps and process parameters are the same as those in Example 1.
  • Example 1 The difference between this example and Example 1 is that the content of iron p-toluenesulfonate in the oxidant solution is 14 wt %, and other steps and process parameters are the same as those in Example 1.
  • the content of iron p-toluenesulfonate in the oxidant solution was 12 wt %, and in the comparative example, no preheating treatment was performed, but the non-woven fabric from which excess liquid was removed was directly subjected to a polymerization reaction.
  • the flexible piezoresistive conductive materials prepared in Examples 1 to 4 were respectively connected to an electrochemical workstation to conduct electrical performance tests respectively, and the electrical performance data obtained from the tests were recorded.
  • Example 3 Different pressures were applied to the flexible piezoresistive conductive material prepared in Example 3: 40kPa pressure was applied within 10-20s, 30kPa pressure was applied within 30-40s, 20kPa pressure was applied within 50-60s, and 70-80s was applied A pressure of 15kPa was applied, and a pressure of 5kPa was applied within 90-100s to test the current changes when subjected to different pressures. The test results are shown in Tables 2-6 below and Figure 1.
  • the average current output by the flexible piezoresistive conductive material is 0.86mA when a pressure of 5kPa is applied within 90-100s. With the change of the applied pressure value, the output current of the flexible piezoresistive conductive material changes significantly, indicating that the flexible piezoresistive conductive material has high sensitivity to pressure changes and has the potential to prepare a piezoresistive pressure sensor.
  • the flexible piezoresistive conductive material prepared in Example 3 has poly3,4-ethylenedioxythiophene and poly3,4-ethylenedioxythiophene formed on the surface of any fiber.
  • the coating of thiophene on the fiber is uniform, and the surface of the coated fiber is smooth, thereby making the performance of the flexible piezoresistive conductive material better and more stable.
  • the flexible piezoresistive conductive material prepared in the comparative example also formed poly3,4-ethylenedioxythiophene on the surface of any fiber of the non-woven fabric, but appeared on the fiber.
  • the accumulation of poly-3,4-ethylenedioxythiophene agglomerated particles, and the uneven coating of poly-3,4-ethylenedioxythiophene on fibers, and the surface is not smooth, which will affect the performance of flexible piezoresistive conductive materials.
  • the gaps and intervals between the fibers of the non-woven fabric are much larger than those of knitted fabrics and woven fabrics. Especially in the stacking and intersecting areas of the fibers, there will be too much accumulation of oxidant solution. If the polymerization reaction is carried out directly without preheating treatment, excessive accumulation of poly-3,4-ethylenedioxythiophene agglomerate particles will preferentially occur in these areas.
  • the solvent in the oxidant solution can be volatilized and the excess oxidant can be taken away, so that the oxidant attached to the surface of the fiber is more uniform, so that after the polymerization reaction, poly3,4-ethylenedioxythiophene is effective for the fiber package.
  • the coating is more uniform, and the surface of the coated fiber is smooth.
  • the preparation method of the present invention has the advantages of simple process flow, no need for vacuum and high temperature environment, easy operation, low requirements for operating devices, and the used base material is ordinary polyester needle-punched non-woven fabric, which is easy to obtain and low in cost.
  • Resistive conductive materials have good piezoresistive properties and can be used to prepare piezoresistive flexible pressure sensors.
  • the surface of the fiber of the non-woven fabric is covered with poly-3,4-ethylenedioxythiophene.
  • Poly-3,4-ethylenedioxythiophene is a highly stable conductive polymer, which has High electrical conductivity, and its electrical conductivity exhibits remarkable stability under various environmental conditions, so that the prepared flexible piezoresistive conductive material has better comprehensive properties.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonwoven Fabrics (AREA)
  • Treatment Of Fiber Materials (AREA)

Abstract

一种柔性压阻导电材料的制备方法，包括以下步骤：将非织造布置于氧化剂溶液中浸渍处理，非织造布由多根纤维相互交织缠绕而成；将浸渍处理后的非织造布除去多余液体，再进行预热处理；将预热处理后的非织造布置于3，4-乙烯二氧噻吩气体气氛中进行聚合反应，以在非织造布的任意一根纤维表面形成聚3，4-乙烯二氧噻吩；将经过聚合反应后的非织造布采用乙醇溶液进行清洗后再干燥至乙醇溶液挥发。柔性压阻导电材料的制备方法，在加压前后的电阻变化量大，对压力变化具有较高的敏锐性，具有制备压阻型压力传感器的潜力。

Description

柔性压阻导电材料的制备方法
交叉参考相关引用
本申请要求2021年3月10日提交的申请号为2021102619618、名称为“柔性压阻导电材料的制备方法”的中国专利申请的优先权，上述申请参考并入本文。
技术领域
本发明涉及导电材料加工技术领域，具体的是一种柔性压阻导电材料的制备方法。
背景技术
近年来，智能纺织品，可穿戴电子设备和软体机器人已成为研究的热点。可穿戴电子设备的关键组件之一是柔性传感器。传感器可以感应周围的刺激(如温度、压力、拉力、酸碱度等)并做出响应。由柔性材料制成的柔性传感器具有良好的柔韧性和延展性，甚至可以自由弯曲或折叠，能够满足测量条件的各种需要。目前，柔性传感器在电子皮肤，医疗保健，运动器材，纺织品，航空航天，环境监测等各领域均有应用。
金属、碳纳米管(CNT)，碳纳米纤维(CNF)，石墨烯和一系列导电聚合物材料常用于对纺织品修饰处理，而通过导电材料的修饰，能够赋予纺织品出色的导电性，使其可以用作传感器的柔性电极。
现有技术中，多采用针织物、机织物作为柔性传感器的基底材料，而针织物、机织物的密度较高，因此，以用针织物、机织物为基底材料的柔性传感器，其对压力变化的敏感性较差。
本申请发明人经过研究发现，采用气相聚合法，在非织造材料中附着导电聚合物，能够制备得到高电导率，且对压力变化的敏感程度更高的柔性传感器用材料。而在非织造材料中附着导电聚合物，常容易出现导电聚合物分布不均，从而影响材料的性能。
基于上述，本申请发明人提出了一种柔性压阻导电材料的制备方法。
申请内容
为了克服现有技术中的缺陷，本发明提供了一种柔性压阻导电材料的制备方法，其在加压前后的电阻变化量大，对压力变化具有较高的敏锐性，具有制备压阻型压力传感器的潜力。
本发明公开了一种柔性压阻导电材料的制备方法，包括以下步骤：
将非织造布置于氧化剂溶液中浸渍处理，所述非织造布由多根纤维相互交织缠绕而成；
将浸渍处理后的非织造布除去多余液体，再进行预热处理，以去除过量氧化剂；
将预热处理后的非织造布置于3，4-乙烯二氧噻吩气体气氛中进行聚合反应，以在所述非织造布的任意一根纤维表面形成聚3，4-乙烯二氧噻吩；
将经过聚合反应后的非织造布采用乙醇溶液进行清洗，将清洗后的非织造布干燥至乙醇溶液挥发。
作为优选，所述非织造布的密度范围值在0.1～0.4g/cm 3之间，孔隙率范围值在75％～95％之间。
作为优选，所述步骤“将非织造布置于氧化剂溶液中浸渍处理”中，浸渍处理时间为20～40min。
作为优选，所述预热处理的温度范围值在40℃～50℃之间。
作为优选，所述步骤“将预热处理后的非织造布置于3，4-乙烯二氧噻吩气体气氛中进行聚合反应”中，将盛放有3，4-乙烯二氧噻吩的敞口反应器置于反应室内，将干燥处理后的非织造布的第一面面向敞口反应器的开口处放置，控制反应室内的温度为50℃～60℃，反应2～3h后，保持反应室内的温度为50℃～60℃，将所述非织造布的第二面面向敞口反应器的开口处放置，反应2～3h。
作为优选，所述非织造布为涤纶针刺布、聚酰亚胺针刺布、丙纶针刺布中的一种。
作为优选，所述步骤“将清洗后的非织造布干燥至乙醇溶液挥发”中，干燥温度为30～50℃，干燥时间为20～40min。
作为优选，所述步骤“将经过聚合反应后的非织造布采用乙醇溶液进行清洗”中，采用体积分数98％的乙醇与去离子水按照体积比1:1混合而成的乙醇溶液对非织造布进行超声清洗。
作为优选，所述氧化剂为三氯化铁和对甲苯磺酸铁中的一种，所述氧化剂溶液的溶剂为甲醇。
本发明的有益效果如下：
本发明柔性压阻导电材料的制备方法采用非织造布作为柔性压阻导电材料制备的基底材料，利用非织造布固有的蓬松结构特性，非织造布在受到压力时，厚度变化较大，且其纤维结构的变化比针织、机织物更加明显，从而使得制备得到的柔性压阻导电材料在加压前后的电阻变化量较大，对压力变化具有较高的敏锐性，具有制备压阻型压力传感器的潜力。
本发明柔性压阻导电材料的制备方法通过对浸渍后的非织造布进行预热处理后，再进行聚合反应，能够去除非织造布中过量的氧化剂，从而使得非织造布的纤维表面均匀的附着氧化剂，在聚合反应后，聚3，4-乙烯二氧噻吩对纤维包覆更均匀，包覆后的纤维表面平滑，使得制备得到的柔性压阻导电材料的性能更加稳定。
本发明柔性压阻导电材料的制备方法通过设置预烘温度40℃～50℃，可以提高预烘效果，并能保持非织造布的柔性性能。
为让本发明的上述和其他目的、特征和优点能更明显易懂，下文特举较佳实施例，并配合所附图式，作详细说明如下。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例3中柔性压阻导电材料被施加不同大小压力时所释放电流的变化趋势图；
图2是本发明实施例3中柔性压阻导电材料第一区域的扫描电镜图；
图3是本发明实施例3中柔性压阻导电材料第二区域的扫描电镜图；
图4是本发明实施例3中柔性压阻导电材料的纤维截面的扫描电镜图；
图5是本发明对比例中柔性压阻导电材料第一区域的扫描电镜图；
图6是本发明对比例中柔性压阻导电材料第二区域的扫描电镜图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基 于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明实施例1～4中所采用的非织造布为涤纶针刺布，密度为0.2g/cm 3，孔隙率为80％～85％之间。非织造布的尺寸与敞口反应器的开口尺寸相适配，以使得非织造布的第一面或第二面能够与敞口反应器中流动的气体状的3，4-乙烯二氧噻吩充分接触。
实施例1
步骤一：采用对甲苯磺酸铁为氧化剂，将对甲苯磺酸铁粉末溶解于甲醇溶液中，磁力搅拌均匀，使得对甲苯磺酸铁完全溶解于甲醇溶液中，得到对甲苯磺酸铁含量为8wt％的氧化剂溶液。
步骤二：将去离子水和体积分数为98％的乙醇按照体积比1:1混合，得到乙醇溶液。采用乙醇溶液对非织造布超声清洗15min，再用体积分数为98％的乙醇对所述非织造布进行冲洗3次，将冲洗后的非织造布在40℃烘箱中进行干燥，直至非织造布的重量在20min内不再发生变化。
步骤三：将步骤二中干燥后的非织造布置于氧化剂溶液中浸渍处理30min，非织造布由多根纤维相互交织缠绕而成，任意一根纤维的直径为15μm。
步骤四：将浸渍处理后的非织造布采用轧车轧去多余液体，使得非织造布的带液率为500％。
步骤五：将轧去多余液体的非织造布置于烘箱内进行预热处理，40℃预热处理30min，使得非织造布中的甲醇完全挥发，从而能够去除过量的氧化剂，预烘后非织造布的增重率为60％～70％。
其中，预烘后非织造布的增重率的计算方法为：步骤二中干燥后的非织造布的质量为m 1，步骤五中预烘后的非织造布的质量为m 2，预烘后非织造布的的增重率为R 1，
Figure PCTCN2021094096-appb-000001
其中，共做三组平行试验，取三组平行试验的平均值作为最终值。
步骤六：将预热处理后的非织造布置于3，4-乙烯二氧噻吩气体气氛中进行聚合反应，以在非织造布的任意一根纤维表面形成聚3，4-乙烯二氧噻吩(PEDOT)，任意一根纤维表面包裹的聚3，4-乙烯二氧噻吩膜层的厚度约为500nm。具体为：
将盛放有3，4-乙烯二氧噻吩的敞口反应器放置于反应室内。
非织造布具有相对的第一面和第二面，将干燥处理后的非织造布的第一面面向敞口反应器的开口处放置，控制反应室内的温度为60℃，反应3h后，保持反应室内的温度为60℃，将非织造布的第二面面向敞口反应器的开口处放置，再反应3h。
控制反应室内的温度为60℃，能够使得敞口反应器中的3，4-乙烯二氧噻吩(EDOT)单体蒸发形成气体，上升到非织造布表面，在非织造布中的氧化剂的作用下，直接在非织造布的任意一根纤维的表面生成聚3，4乙烯二氧噻吩(PEDOT)。而将非织造布的第一面和第二面分别面向敞口反应器的开口处放置反应，能够使得3，4-乙烯二氧噻吩单体能够更充分的渗入非织造布中，从而使得氧化反应更充分。
步骤七：将去离子水和体积分数为98％的乙醇按照体积比1:1混合，得到乙醇溶液。采用所述乙醇溶液对经过聚合反应后的非织造布进行超声清洗15min，将清洗后的非织造布置于烘箱中，40℃干燥30min，使得乙醇溶液挥发，从而得到柔性压阻导电材料，柔性压阻导电材料的增重率20％。
其中，柔性压阻导电材料的增重率的计算方法为：步骤二中干燥后的非织造布的质量为m 1，柔性压阻导电材料的质量为m 3，柔性压阻导电材料的增重率为R 2，
Figure PCTCN2021094096-appb-000002
其中，共做三组平行试验，取三组平行试验的平均值作为最终值。
实施例2
本实施例与实施例1的区别在于氧化剂溶液中的对甲苯磺酸铁含量为10wt％，其他步骤、工艺参数均与实施例1相同。
实施例3
本实施例与实施例1的区别在于氧化剂溶液中的对甲苯磺酸铁含量为12wt％，其他步骤、工艺参数均与实施例1相同。
实施例4
本实施例与实施例1的区别在于氧化剂溶液中的对甲苯磺酸铁含量为14wt％，其他步骤、工艺参数均与实施例1相同。
对比例
对比例与实施例1的区别在于：
氧化剂溶液中的对甲苯磺酸铁含量为12wt％，以及，对比例中不进行预热处理，而是将轧去多余液体的非织造布直接进行聚合反应。
分别将实施例1～4中制备得到的柔性压阻导电材料与电化学工作站连接，以分别进行电学性能测试，记录测试所得的电学性能数据。
分别对实施例1～4中制备得到的柔性压阻导电材料施加40KPa的压力，测试其在受压前后的电阻变化情况，测试结果参见表1。
  初始电阻R 0(Ω) 加压40kPa后电阻R(Ω) 电阻变化率△R/R 0(％)
实施例1 2952.45±339.88 350.29±61.23 87.68±2.68
实施例2 1759.35±303.59 199.48±18.65 88.27±2.05
实施例3 3525.54±320.41 157.97±10.91 95.44±0.58
实施例4 4026.28±427.86 354.64±118.23 91.09±1.72
表1实施例1～4中柔性压阻导电材料电阻变化情况测试结果
对实施例3中制备得到的柔性压阻导电材料分别施加不同大小压力：在10～20s内施加40kPa压力，在30～40s内施加30kPa压力，在50～60s施加20kPa压力，在70～80s内施加15kPa压力，在90～100s内施加5kPa压力，测试其在受到不同压力时的电流变化情况，测试结果参见下表2-6以及附图1。
表2 10～20s内的电流变化情况
时间/s 11 12 13 14 15 16 17 18 19 平均电流/mA
电流/mA 6.40 6.14 6.16 5.79 5.79 5.79 5.82 5.92 5.97 5.93
表3 30～40s内的电流变化情况
时间/s 31 32 33 34 35 36 37 38 39 平均电流/mA
电流/mA 4.47 4.35 4.58 4.59 4.57 4.56 4.49 4.58 4.51 4.52
表4 50～60s内的电流变化情况
时间/s 51 52 53 54 55 56 57 58 59 平均电流/mA
电流/mA 3.86 3.86 3.70 3.69 3.71 3.62 3.60 3.67 3.69 3.71
表5 70～80s内的电流变化情况
时间/s 71 72 73 74 75 76 77 78 79 平均电流/mA
电流/mA 3.00 3.13 2.89 2.99 2.90 2.69 2.49 2.45 2.31 2.76
表6 90～100s内的电流变化情况
时间/s 91 92 93 94 95 96 97 98 99 平均电流/mA
电流/mA 0.70 0.85 0.86 0.88 0.87 0.89 0.88 0.88 0.89 0.86
由表1中的测试结果可知，实施例3中制备的柔性压阻导电材料，在加压前后的电阻变化率最高，对压力变化具有更高的敏锐性，能达到最佳的使用效果。
由表2-6和附图1可知，向实施例3中制备的柔性压阻导电材料施加压力时，施加的压力值越大，柔性压阻导电材料的电阻越小，其输出的电流越大。
对实施例3中制备得到的柔性压阻导电材料分别施加不同大小压力，在10～20s内施加40kPa压力，柔性压阻导电材料的输出的平均电流为5.93mA。在30～40s内施加30kPa压力，柔性压阻导电材料的输出的平均电流为4.52mA。在50～60s施加20kPa压力，柔性压阻导电材料的输出的平均电流为3.71mA。在70～80s内施加15kPa压力，柔性压阻导电材料的输出的平均电流为2.76mA。在90～100s内施加5kPa压力，柔性压阻导电材料的输出的平均电流为0.86mA。随着所施加压力值的变化，柔性压阻导电材料的输出电流是呈明显变化的，表明柔性压阻导电材料对压力的变化具有高敏感性，具有制备压阻型压力传感器的潜力。
图1中柔性压阻导电材料的输出电流呈阶梯式变化，由此也可反推出所施加压力的阶梯式变化趋势，表征了所制备的柔性压阻导电材料具有制备压阻型压力传感器的潜力。
由附图2～4可知，实施例3中制备得到的柔性压阻导电材料，其任意一根纤维的表面均形成了聚3，4-乙烯二氧噻吩，且聚3，4-乙烯二氧噻吩对纤维的包覆均匀，包覆后的纤维表面平滑，由此使得柔性压阻导电材料性能更佳稳定。
由附图5～6可知，对比例中制备得到的柔性压阻导电材料，其在非织造布的任意一根纤维表面也形成了聚3，4-乙烯二氧噻吩，但在纤维上出现了聚3，4-乙烯二氧噻吩团聚颗粒的堆积，且聚3，4-乙烯二氧噻吩对纤维的包覆不均匀，表面不光滑，由此会影响柔性压阻导电材料的性能。
由于本发明采用了非织造布为基材，非织造布的纤维之间的空隙和间隔比针织物、机织物大很多，在经过氧化剂溶液浸渍后，填充在纤维间隔空隙内的氧化剂的量比较多，尤其在纤维的堆叠交叉区域，会过多的囤积氧化剂溶液，若不经过预热处理，直接进行聚合反应，则会在这些区域优先发生聚3，4-乙烯二氧噻吩团聚颗粒过量堆积，而通过预热处理，在氧化剂溶液中溶剂挥发的同时能够带走过量的氧化剂，使得纤维表面所依附的氧化剂更加均匀，从而在聚合反应后，聚3，4-乙烯二氧噻吩对纤维包覆更加均匀，包覆后的纤维表面平滑。
综上，本发明制备方法工艺流程简单、无需真空、高温环境，易于操作，对操作装置的要求低，所用基材为普通的涤纶针刺非织造布，易于获得且成本低廉，制备的柔性压阻导电材料具有较好的压阻性能，可用于制备压阻型柔性压力传感器。
本发明在非织造物的纤维表面包覆了聚3，4-乙烯二氧噻吩，聚3，4-乙烯二氧噻吩是一种高度稳定的导电聚合物，其相对于其他聚合物而言具有较高的电导率，且其导电性能在各种环境条件下都表面出显著的稳定性，因此使得制备得到的柔性压阻导电材料具有较佳的综合性能。
本发明中应用了具体实施例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。

Claims (9)

  1. 一种柔性压阻导电材料的制备方法，其特征在于，包括以下步骤：
    将非织造布置于氧化剂溶液中浸渍处理，所述非织造布由多根纤维相互交织缠绕而成；
    将浸渍处理后的非织造布除去多余液体，再进行预热处理，以去除过量氧化剂；
    将预热处理后的非织造布置于3，4-乙烯二氧噻吩气体气氛中进行聚合反应，以在所述非织造布的任意一根纤维表面形成聚3，4-乙烯二氧噻吩；
    将经过聚合反应后的非织造布采用乙醇溶液进行清洗，将清洗后的非织造布干燥至乙醇溶液挥发。
  2. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述非织造布的密度范围值在0.1～0.4g/cm 3之间，孔隙率范围值在75％～95％之间。
  3. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述步骤“将非织造布置于氧化剂溶液中浸渍处理”中，浸渍处理时间为20～40min。
  4. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述预热处理的温度范围值在40℃～50℃之间。
  5. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述步骤“将预热处理后的非织造布置于3，4-乙烯二氧噻吩气体气氛中进行聚合反应”中，将盛放有3，4-乙烯二氧噻吩的敞口反应器置于反应室内，将干燥处理后的非织造布的第一面面向敞口反应器的开口处放置，控制反应室内的温度为50℃～60℃，反应2～3h后，保持反应室内的温度为50℃～60℃，将所述非织造布的第二面面向敞口反应器的开口处放置，反应2～3h。
  6. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述非织造布为涤纶针刺布、聚酰亚胺针刺布、丙纶针刺布中的一种。
  7. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述步骤“将清洗后的非织造布干燥至乙醇溶液挥发”中，干燥温度为30～50℃，干燥时间为20～40min。
  8. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述步骤“将经过聚合反应后的非织造布采用乙醇溶液进行清洗”中，采用体积分数98％的乙醇与去离子水按照体积比1:1混合而成的乙醇溶液对非织造布进行超声清洗。
  9. 根据权利要求1所述的柔性压阻导电材料的制备方法，其特征在于，所述氧化剂 为三氯化铁和对甲苯磺酸铁中的一种，所述氧化剂溶液的溶剂为甲醇。
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