WO2018103552A1 - Modal knitted fabric-based stretchable electrically conductive material and application thereof - Google Patents

Modal knitted fabric-based stretchable electrically conductive material and application thereof Download PDF

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Publication number
WO2018103552A1
WO2018103552A1 PCT/CN2017/113116 CN2017113116W WO2018103552A1 WO 2018103552 A1 WO2018103552 A1 WO 2018103552A1 CN 2017113116 W CN2017113116 W CN 2017113116W WO 2018103552 A1 WO2018103552 A1 WO 2018103552A1
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Prior art keywords
stretchable
conductive material
carbonized
modal
knitted fabric
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PCT/CN2017/113116
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French (fr)
Chinese (zh)
Inventor
张莹莹
王春雅
张明超
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清华大学
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Publication of WO2018103552A1 publication Critical patent/WO2018103552A1/en

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/04—Vegetal fibres
    • D06N2201/042—Cellulose fibres, e.g. cotton
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/04—Properties of the materials having electrical or magnetic properties
    • D06N2209/041—Conductive
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • D10B2201/22—Cellulose-derived artificial fibres made from cellulose solutions
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/16—Physical properties antistatic; conductive

Definitions

  • the present invention relates to the field of wearable electronic devices, and in particular to a stretchable conductor based on a knitted fabric and a preparation process and use thereof.
  • a stretchable conductive material refers to a conductive material that retains its high electrical conductivity while undergoing different mechanical deformations.
  • the currently reported stretchable conductive materials are mainly composed of nanomaterials having intrinsic flexibility and conductivity, such as conductive polymer materials, metal nanomaterials, and carbon nanomaterials. Compared with carbon nanomaterials, conductive polymers and metal nanomaterials have poor conductivity and poor chemical stability. Therefore, carbon materials have been widely studied for stretchable conductive materials, which mainly involve three preparation strategies: 1. Dispersing the electrically conductive material in the elastomeric polymer matrix; 2.
  • the present invention provides a stretchable conductive material based on a carbonized Modal knit fabric, characterized in that the carbonized knit fabric is obtained by subjecting an initial modal knit fabric to a high temperature carbonization treatment.
  • the modal knit fabric is a weft-knit modal knit fabric.
  • the production process of the carbonized modal knit fabric comprises: treating the starting modal knit fabric at a high temperature in an inert gas atmosphere or an inert gas-based atmosphere or a vacuum atmosphere, thereby obtaining the carbonized modal Knitted fabric
  • the high temperature treatment comprises: a temperature rising phase, a temperature maintaining phase, and a cooling phase;
  • the temperature in the temperature maintaining phase is 200 ° C to 3000 ° C, preferably 600 ° C to 1200 ° C, especially 900 ° C to 1100 ° C; and the duration is not less than 5 min.
  • the carbonized knit fabric is further composited with other materials.
  • the other materials include: a silicon based polymer, a rubber, a thermoplastic polymer.
  • the inert gas is nitrogen, argon, helium or any combination thereof.
  • the inert gas-based atmosphere may be a mixed gas of an inert gas and hydrogen gas, wherein the ratio of the inert gas to the hydrogen gas is greater than 1:1, for example, greater than 5:1, preferably greater than 10:1, and the inert gas may be, for example, It is argon.
  • the invention also provides for the use of the stretchable electrically conductive material of the invention as an active component of a flexible or stretchable electronic device, or as a wire for a flexible or stretchable electronic device.
  • the stretchable conductive material can be used as an electrode material for a stretchable supercapacitor, or applied to a wearable energy device, or as a heated host material for a stretchable heater, or applied to a wearable thermotherapy device.
  • the present invention also provides a stretchable supercapacitor characterized in that the electrode material comprises the stretchable conductive material of the present invention.
  • the present invention also provides a stretchable heater characterized in that the heating body material comprises the stretchable conductive material of the present invention, the working voltage range is not less than 0.1 V, and the heating temperature range is not lower than 30 °C.
  • the carbonized modal knitted fabric of the invention maintains its knitted structure after high-temperature carbonization treatment, and has flexibility, stretchability and electrical conductivity, and can be directly used as a stretchable conductive material or composited with other materials and used as a stretchable conductive material.
  • the stretchable conductive material has the characteristics of good electrical conductivity, good stretchability, environmental protection, simple preparation, low cost, and the like, and has broad application prospects.
  • FIG. 1 is a flow chart showing a simple production process of a stretchable conductive material based on a knitted fabric according to the present invention.
  • FIG. 2 is a view showing the flexibility and stretchability of a stretchable conductive material using a modal weft knitted fabric as a raw material according to the present invention.
  • FIG. 3 is a scanning electron micrograph of the carbonized knit fabric obtained by heat treatment of a modal weft knitted fabric as a raw material at a high temperature (1050 ° C).
  • FIG. 4 is a microscopic structural representation (transmission electron microscope image) of a carbonized knitted fabric obtained by heat treatment of a modal weft knitted fabric as a raw material at a high temperature (1050 ° C).
  • Figure 5 is a graph showing the change of electrical conductivity of a stretchable conductive material obtained by high temperature heat treatment of a modal weft knitted fabric as a raw material according to different heat treatment temperatures.
  • Figure 6 is a (a) variation of electrical resistance of a tensile conductive material of a carbonized knitted fabric obtained by heat treatment of a modal weft knitted fabric as a raw material according to the present invention at a high temperature (1050 ° C); (b) The elastic polymer composite of the carbonized knitted fabric stretchable conductive material obtained by heat treatment at a high temperature (1050 ° C) using a modal weft knitted fabric as a raw material.
  • Figure 7 is a (a) resistance change stability of a carbon conductive knitted fabric stretchable conductive material obtained by heat treatment at a high temperature (1050 ° C) of a modal weft knitted fabric of the present invention under 50% strain cyclic loading; (b) The resistance change stability of the carbon conductive knitted fabric stretchable conductive material obtained by heat treatment at high temperature (1050 ° C) of the modal weft knitted fabric of the present invention combined with the elastic polymer under 50% strain cycle loading.
  • FIG. 8 is a schematic view of a stretchable supercapacitor in which a stretchable conductive material of a knitted fabric is used as an electrode material and a cyclic voltammetry curve under different tensile strains.
  • Figure 9 is a schematic view of the application of the second embodiment of the present invention, a stretchable heater of a stretchable conductive material for a knitted fabric and its basic electric heating performance.
  • FIG. 10 is a second application example of the present invention.
  • the electric heating temperature of the stretchable heater of the stretchable conductive material of the knitted fabric varies with the tensile strain.
  • Figure 11 is a second embodiment of the application of the present invention, the cycle stability of the electrical heating performance of a stretchable conductive material of a knit fabric.
  • Figure 12 is a second application example of the present invention, and a knit fabric stretchable conductive material stretchable heater wearable application display.
  • Modal is a common man-made fiber and is widely used in the garment industry, especially in the manufacture of underwear. Modal has good softness and excellent hygroscopicity, but its fabric is poorly stiff.
  • a carbonized modal knitted fabric obtained by subjecting a modal knitted fabric to a high-temperature carbonization process has a knit structure maintained, and has particularly excellent stretchability and electrical conductivity, and can be directly used as a stretchable conductive material.
  • the material or composite with other materials is used as a stretchable conductive material.
  • a 1050 ° C carbonized modal weft knitted fabric stretchable conductive material can maintain substantially constant electrical resistance over a 70% tensile strain range, and a 1050 ° C carbonized modal weft knitted fabric in an Ecoflex package.
  • the fabric stretchable conductive material maintains substantially constant electrical resistance over a 125% strain range.
  • One aspect of the present invention provides a stretchable conductive material based on a carbonized modal knit fabric, characterized in that the carbonized modal knit fabric is obtained by subjecting an initial modal knit fabric to a high temperature carbonization process.
  • knitted fabric as used herein has a meaning as is known in the art and refers to the construction of a yarn with a knitting needle.
  • the fabric which is formed into a coil and then the strings are sleeved with each other has the characteristics of being able to extend in all directions and having good elasticity.
  • Common knit fabrics include, for example, cotton knit fabrics, modal knit fabrics, and the like.
  • the knit fabric of the present invention is not limited to a particular weaving method.
  • a weft knitted fabric or a warp knitted fabric can be used in the present invention.
  • the term "starting knit fabric” as used herein refers to a knit fabric, such as a cotton knit fabric or a modal knit fabric, which is a raw material for a high temperature carbonization treatment process. In some embodiments of the invention, weft knitted fabrics are particularly suitable.
  • stretchable conductive material means that the conductive material retains its electrical conductivity while being stretched. Stretchable conductive materials are particularly suitable for flexible, stretchable devices such as wearable devices, flexible robots, and the like.
  • the production process of the carbonized knit fabric of the present invention comprises: treating the starting knit fabric at a high temperature in an inert gas atmosphere or an inert gas-based atmosphere or a vacuum atmosphere, thereby obtaining the carbonized knit fabric.
  • the temperature of the high temperature carbonization treatment here is usually 200 ° C to 3000 ° C (for example, 200 ° C, 250 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 600 ° C, 650 ° C, 700 ° C, 750 ° C, 800 ° C, 850 ° C, 900 ° C, 950 ° C, 1000 ° C, 1050 ° C, 1100 ° C, 1150 ° C, 1200 ° C, 1250 ° C, 1300 ° C, 1350 ° C, 1400 ° C, 1450 ° C, 1500 ° C), especially It is 600 to 1050 ° C; the duration of the temperature holding phase is not less than 5 min, for example 100-500 minutes, preferably 150-300 minutes, especially 200 minutes.
  • inert gas atmosphere and “inert atmosphere” are used interchangeably and refer to an atmosphere in which the inert gas ratio exceeds 80%, or even, for example, 90%.
  • inert gas based atmosphere means that the ratio of inert gas to other gases is greater than 1:1, such as greater than 5:1, preferably greater than 10:1.
  • the inert gas-based atmosphere has a ratio of argon:hydrogen of 10:1.
  • vacuum atmosphere refers to an atmosphere having a pressure below one atmosphere.
  • a knitted fabric including natural plant fiber fabrics such as cotton, hemp fabrics, natural animal fiber fabrics such as wool, silk fabrics, Man-made fiber fabrics such as regenerated cellulose fiber fabrics, cellulose ester fiber fabrics, regenerated protein fiber fabrics, synthetic fiber fabrics, and any combination of fiber fabrics are used as raw materials, and are subjected to an inert atmosphere or an inert gas-based atmosphere or a high-temperature heat treatment under a vacuum atmosphere.
  • the process obtains a carbonized knit fabric which maintains the main structural features of the original knit fabric and has flexibility, stretchability and electrical conductivity.
  • the carbonized knit fabric can be directly used as a stretchable conductive material or composited with other materials for use as a stretchable conductive material. material.
  • the carbonized knit fabric-based stretchable conductive material is provided as an active component of a flexible or stretchable electronic device or as a wire of a flexible or stretchable electronic device.
  • an electrode material for a stretchable supercapacitor for a wearable energy device
  • a heating body material for a stretchable heater for a wearable thermotherapy device.
  • the production process of the carbonized knit fabric-based stretchable conductive material of the present invention is:
  • the fibers used for starting the knitted fabric are natural fibers, rayon fibers, synthetic fibers or any combination of fibers;
  • the stretchable, electrically conductive carbonized knit fabric obtained in the step 2) is used directly as a stretchable conductive material or as a stretchable conductive material after being compounded with other materials.
  • the fiber raw material used in the fabric may be natural fiber including natural plant fiber such as cotton, hemp, natural animal fiber such as hair, silk; artificial fiber such as regenerated cellulose fiber, cellulose ester fiber, regenerated protein fiber; synthetic fiber; Or any combination of fibers.
  • the raw material of the fabric is subjected to an inert atmosphere or an inert gas-based atmosphere or a high-temperature heat treatment under a vacuum atmosphere to obtain a carbonized knitted fabric having flexibility, stretchability and electrical conductivity, wherein the inert gas is nitrogen, argon, helium or any combination.
  • the vacuum atmosphere therein refers to any atmosphere having a pressure lower than an atmospheric pressure, wherein the high temperature heat treatment temperature is 200-3000 ° C, wherein the flexible, stretchable and conductive carbonized knitted fabric retains the main structural features of the original fabric.
  • elastomeric polymers or fabrics include elastomeric polymers or fabrics.
  • the elastomeric polymer refers to a polymer having a certain flexibility or stretchability, such as a silicone-based elastomeric polymer, a rubber, a thermoplastic polymer.
  • the stretchable conductive material of the present invention can be used as an active component of a flexible or stretchable electronic device (for example, as an electrode material for a stretchable supercapacitor, for a wearable energy device; for example, as a heating body for a stretchable heater) Materials for wearable thermotherapy devices) or as wires for flexible or stretchable electronics.
  • a flexible or stretchable electronic device for example, as an electrode material for a stretchable supercapacitor, for a wearable energy device; for example, as a heating body for a stretchable heater
  • Materials for wearable thermotherapy devices or as wires for flexible or stretchable electronics.
  • the stretchable conductive material of the present invention can be directly used as an electrode material of a supercapacitor or as a electrode material after being compounded with other electrochemically active materials.
  • Electrochemically active materials refer to materials that can improve the electrochemical performance of supercapacitors, such as polyaniline, polypyrrole, and manganese dioxide.
  • the stretchable electrically conductive material of the present invention may have one or more of the following advantages over existing stretchable electrically conductive materials:
  • the stretchable conductive material of the present invention exhibits excellent properties, that is, its conductivity hardly changes under different deformations.
  • the stretchable conductive material of the present invention exhibits a broad field in the field of flexible or stretchable electronic devices Application prospects.
  • Example 1 Preparation of stretchable conductive material using modal weft knitted fabric as raw material
  • the modal fabric (ROSILY pure color boxer pants) with weft knitted structure is mixed under argon gas (argon gas flow ratio 10:1) or nitrogen atmosphere at different temperatures (600 °C) , 700 ° C, 800 ° C, 900 ° C, 1050 ° C) high temperature heat treatment to obtain a carbonized fabric that maintains its weft knitted structure (specific heating procedure is to increase the temperature to 3 ° C / min to the target temperature for 200min, then naturally cool to room temperature
  • the carbonized knit fabric obtained under the heating process can be directly used as a stretchable conductive material, or can be used as a stretchable conductive material after being compounded with an elastic polymer (specifically, Ecoflex, a silica gel).
  • Figure 1 an elastic polymer
  • the obtained carbonized knitted fabric stretchable conductive material or elastic polymer composite carbonized knitted fabric stretchable conductive material exhibits excellent flexibility and stretchability (see Fig. 2), specifically, the carbonized knitted fabric Or the elastic polymer-encapsulated carbonized knit fabric can withstand the knotting and torsional deformation to prove its excellent flexibility, and its ability to withstand tensile strains of 75% and 100%, respectively, proves its excellent stretchability.
  • the carbonized knit fabric obtained by high temperature heat treatment still retains the weft knitted structure of the original fabric (see Figure 3), and the transmission electron micrograph of the carbonized fabric shows the graphite-like lattice fringe structure and polycrystalline The diffraction ring indicates that it has the microstructure of microcrystalline graphite (see Figure 4), which is why it can have high conductivity.
  • the conductivity of the carbonized knit fabric obtained by the high-temperature heat treatment is increased as the heat treatment temperature is increased (see FIG. 5), for example, specifically, the carbonized knit fabric obtained by heat treatment at a temperature of 1050 ° C has an electric conductivity of up to 15.1 S/cm.
  • the electrical conductivity of the obtained carbonized knit fabric at 600 ° C, 700 ° C, 800 ° C, and 900 ° C was 5.75E-5 S/cm, 0.26 S/cm, 2.48 S/cm, and 5.28 S/cm, respectively. It can be seen that the conductivity increases as the heat treatment temperature increases.
  • Example 2 Carbonized Modal weft knitted fabric The electrical resistance of a stretchable conductive material varies with tensile strain
  • the 1050 ° C carbonized modal weft knitted fabric of 1050 ° C can be stretched conductive material and the 1050 ° C carbonized modal weft knitted fabric of Ecoflex package can resist the resistance of the tensile conductive material under tensile strain. See Figure 6).
  • the elastic polymer encapsulated carbonized knit fabric can stretch the conductive material at 125%. The resistance is kept substantially constant within the strain range (see Figure 6b), which demonstrates the superior performance of the two stretchable conductive materials.
  • Example 3 Stability of a stretchable conductive material of a carbonized modal weft knitted fabric under cyclic tensile strain
  • the 1050 ° C carbonized modal weft knitted fabric stretchable conductive material described in column 1 and the 1050 ° C carbonized modal weft knitted fabric of Ecoflex package can be used to stretch the conductive material at 50% cyclic tensile strain. Cycle stability (see Figure 7).
  • Example 4 Carbonized modal weft knitted fabric as a stretchable supercapacitor electrode
  • the carbonized modal weft knitted fabric is used as an electrode material of a supercapacitor, and is assembled with a PVA-H 3 PO 4 gel electrolyte to form a stretchable supercapacitor.
  • the structure diagram is shown in Fig. 8(a), specifically, the supercapacitor
  • the structure is a sandwich structure formed by a two-layer carbonized modal weft knitted fabric as an electrode (a conductive electrode on a fabric is connected to a copper electrode as a test electrode) with a gel electrolyte interposed therebetween.
  • the supercapacitor exhibited excellent electrochemical performance (see Figure 8b), specifically, the area ratio specific capacitance of the supercapacitor was 7.5 mF/cm 2 at a scan rate of 10 mV/s.
  • the electrochemical cyclic volt-ampere curve of the supercapacitor hardly changed at different tensile strains (see Figure 8c), indicating that its electrochemical properties remain unchanged under tensile strain.
  • polyaniline was supported on a carbonized modal weft knitted fabric by electrochemical polymerization deposition method for 5 min (for specific loading methods, see Graphene/polyaniline woven fabric composite films as flexible supercapacitor electrodes.
  • Example 5 Elastomeric polymer encapsulated carbonized modal weft knitted fabric as a wearable heater
  • the carbonized knitted fabric heating element of the polymer package was obtained by connecting the two ends of the carbonized modal weft knitted fabric obtained by the treatment at 1050 ° C described in Example 1 through a conductive silver glue to the copper sheet as an electrode and then encapsulating with the Ecoflex polymer.
  • a wearable heating device can be used for heat application, heat treatment or the like by loading it onto an elastic fabric substrate with a strap structure as shown in Fig. 9a.
  • the heater Through the performance test of the heater, it was found that the heater exhibited excellent electric heating performance, and the temperature at which it can be heated gradually increased as the applied voltage was increased, and when only a DC voltage of 3.5 V was applied, the electric heating was performed.
  • the temperature can reach ⁇ 150 °C in a few seconds (see Figure 9b).
  • the heater Due to the flexibility and stretchability of the heater, it can be used in wearable thermal therapy devices. For example, when the heater is attached to the knee, the heater exhibits better heating performance than knee extension when the knee is bent (see Figure 12), demonstrating its use as a wearable heater for hyperthermia. potential.

Abstract

The invention discloses a carbonized Modal knitted fabric-based stretchable electrically conductive material. The material is characterized in that the carbonized knitted fabric is obtained by performing a high-temperature carbonization treatment on an initial knitted fabric. After the high-temperature carbonization treatment, the carbonized Modal knitted fabric maintains a knitted structure, has flexibility, stretchability and electrical conductivity, and can be directly used as a stretchable electrically conductive material or can be used as a stretchable electrically conductive material after forming a compound with other substances. The stretchable conductive material has features of favorable electrical conductivity, favorable stretchability, and being environmental friendly, easy to manufacture, and low in costs, having wide application prospect.

Description

一种基于莫代尔针织织物的可拉伸导电材料及其用途Stretchable conductive material based on modal knitted fabric and use thereof 技术领域Technical field
本发明涉及可穿戴电子器件技术领域，具体涉及一种基于针织织物的可拉伸导体及其制备工艺与用途。The present invention relates to the field of wearable electronic devices, and in particular to a stretchable conductor based on a knitted fabric and a preparation process and use thereof.
背景技术Background technique
近年来，可穿戴电子器件发展快速，对可拉伸导电材料提出巨大需求。可拉伸导电材料指在承受不同机械变形情况下仍能保持其高导电性的导电材料。目前报道的可拉伸导电材料主要由具有本征柔性、导电性的纳米材料如导电聚合物材料、金属纳米材料、碳纳米材料构成。和碳纳米材料相比，导电聚合物和金属纳米材料分别存在着导电性差、化学稳定性差的问题，所以碳材料被广泛研究用于可拉伸导电材料，其主要涉及三种制备策略：1.将导电材料分散于弹性聚合物基体；2.在弹性聚合物基表面形成具有波浪或屈曲结构的导电材料；3.将导电材料负载到柔性织物基底。但碳纳米材料基可拉伸导电材料仍存在着材料制备过程复杂、价格相对较高、随拉伸应变施加电阻增大等缺点。因此，如何研发制备过程绿色、简便、低成本、低能耗、可大规模生产同时具有优异性能的可拉伸导体材料为其产业化应用面临的重要挑战。In recent years, wearable electronic devices have developed rapidly, placing great demands on stretchable conductive materials. A stretchable conductive material refers to a conductive material that retains its high electrical conductivity while undergoing different mechanical deformations. The currently reported stretchable conductive materials are mainly composed of nanomaterials having intrinsic flexibility and conductivity, such as conductive polymer materials, metal nanomaterials, and carbon nanomaterials. Compared with carbon nanomaterials, conductive polymers and metal nanomaterials have poor conductivity and poor chemical stability. Therefore, carbon materials have been widely studied for stretchable conductive materials, which mainly involve three preparation strategies: 1. Dispersing the electrically conductive material in the elastomeric polymer matrix; 2. forming a conductive material having a wave or buckling structure on the surface of the elastomeric polymer; 3. loading the electrically conductive material onto the flexible fabric substrate. However, carbon nanomaterial-based stretchable conductive materials still have the disadvantages of complicated material preparation process, relatively high price, and increased resistance with tensile strain. Therefore, how to develop a green, simple, low-cost, low-energy, and large-scale production of stretchable conductor materials with excellent performance is an important challenge for industrial applications.
发明内容Summary of the invention
本发明提供了一种基于碳化莫代尔(Modal)针织织物的可拉伸导电材料，其特征在于，所述碳化针织织物通过对起始莫代尔针织织物进行高温碳化处理而获得。The present invention provides a stretchable conductive material based on a carbonized Modal knit fabric, characterized in that the carbonized knit fabric is obtained by subjecting an initial modal knit fabric to a high temperature carbonization treatment.
在一些实施方案中，所述莫代尔针织织物为纬编莫代尔针织织物。In some embodiments, the modal knit fabric is a weft-knit modal knit fabric.
在一些实施方案中，所述碳化莫代尔针织织物的生产工艺流程包括：在惰性气体气氛或惰性气体为主的气氛或真空气氛下，高温处理所述起始莫代尔针织织物，从而得到所述碳化莫代尔针织织物；In some embodiments, the production process of the carbonized modal knit fabric comprises: treating the starting modal knit fabric at a high temperature in an inert gas atmosphere or an inert gas-based atmosphere or a vacuum atmosphere, thereby obtaining the carbonized modal Knitted fabric
其中所述高温处理包括：升温阶段、温度保持阶段和降温阶段；Wherein the high temperature treatment comprises: a temperature rising phase, a temperature maintaining phase, and a cooling phase;
其中所述温度保持阶段的温度为200℃至3000℃，优选600℃至1200℃，特别是900℃至1100℃；持续时间为不低于5min。The temperature in the temperature maintaining phase is 200 ° C to 3000 ° C, preferably 600 ° C to 1200 ° C, especially 900 ° C to 1100 ° C; and the duration is not less than 5 min.
在一些实施方案中，所述碳化针织织物进一步与其他材料复合。In some embodiments, the carbonized knit fabric is further composited with other materials.
优选地，所述其他材料包括：硅基聚合物、橡胶、热塑性聚合物。Preferably, the other materials include: a silicon based polymer, a rubber, a thermoplastic polymer.
在一些实施方案中，所述惰性气体为氮气、氩气、氦气或其任意组合。 In some embodiments, the inert gas is nitrogen, argon, helium or any combination thereof.
例如，所述惰性气体为主的气氛可以为惰性气体和氢气的混合气体，其中惰性气体和氢气的比例大于1:1，例如大于5:1，优选大于10:1，所述惰性气体可以例如为氩气。For example, the inert gas-based atmosphere may be a mixed gas of an inert gas and hydrogen gas, wherein the ratio of the inert gas to the hydrogen gas is greater than 1:1, for example, greater than 5:1, preferably greater than 10:1, and the inert gas may be, for example, It is argon.
本发明还提供了本发明的可拉伸导电材料作为柔性或可拉伸电子器件的活性组件的应用，或者作为柔性或可拉伸电子器件的导线的应用。The invention also provides for the use of the stretchable electrically conductive material of the invention as an active component of a flexible or stretchable electronic device, or as a wire for a flexible or stretchable electronic device.
例如，所述可拉伸导电材料可以作为可拉伸超级电容器的电极材料，或应用于可穿戴能源器件，或作为可拉伸加热器的加热主体材料，或应用于可穿戴热疗器件。For example, the stretchable conductive material can be used as an electrode material for a stretchable supercapacitor, or applied to a wearable energy device, or as a heated host material for a stretchable heater, or applied to a wearable thermotherapy device.
本发明还提供了一种可拉伸超级电容器，其特征在于其电极材料中包含本发明的可拉伸导电材料。The present invention also provides a stretchable supercapacitor characterized in that the electrode material comprises the stretchable conductive material of the present invention.
本发明还提供了一种可拉伸加热器，其特征在于其加热主体材料中包含本发明的可拉伸导电材料，工作电压范围不低于0.1V，加热温度范围不低于30℃。The present invention also provides a stretchable heater characterized in that the heating body material comprises the stretchable conductive material of the present invention, the working voltage range is not less than 0.1 V, and the heating temperature range is not lower than 30 °C.
本发明碳化莫代尔针织织物在高温碳化处理后保持其针织结构，并且具有柔性、可拉伸性及导电性，可直接用作可拉伸导电材料或与其他物质复合后用作可拉伸导电材料。该可拉伸导电材料具备导电性好、可拉伸性好、绿色环保、制备简便、低成本等特点，具有广阔的应用前景。The carbonized modal knitted fabric of the invention maintains its knitted structure after high-temperature carbonization treatment, and has flexibility, stretchability and electrical conductivity, and can be directly used as a stretchable conductive material or composited with other materials and used as a stretchable conductive material. . The stretchable conductive material has the characteristics of good electrical conductivity, good stretchability, environmental protection, simple preparation, low cost, and the like, and has broad application prospects.
附图说明DRAWINGS
图1为本发明所述基于针织织物的可拉伸导电材料的简单生产工艺流程图。1 is a flow chart showing a simple production process of a stretchable conductive material based on a knitted fabric according to the present invention.
图2为本发明所述以莫代尔纬编针织织物为原材料的可拉伸导电材料的柔性、可拉伸性展示图。(a,c)碳化莫代尔针织织物；(b,d)聚合物封装的碳化莫代尔针织织物。2 is a view showing the flexibility and stretchability of a stretchable conductive material using a modal weft knitted fabric as a raw material according to the present invention. (a, c) carbonized modal knit fabric; (b, d) polymer encapsulated carbonized modal knit fabric.
图3为本发明所述以莫代尔纬编针织织物为原材料高温(1050℃)热处理所得碳化针织织物的扫描电子显微镜图。3 is a scanning electron micrograph of the carbonized knit fabric obtained by heat treatment of a modal weft knitted fabric as a raw material at a high temperature (1050 ° C).
图4为本发明所述以莫代尔纬编针织织物为原材料高温(1050℃)热处理所得碳化针织织物的微观结构表征图(透射电子显微镜图)。4 is a microscopic structural representation (transmission electron microscope image) of a carbonized knitted fabric obtained by heat treatment of a modal weft knitted fabric as a raw material at a high temperature (1050 ° C).
图5为本发明所述以莫代尔纬编针织织物为原材料高温热处理所得可拉伸导电材料的电导率随不同热处理温度的变化。Figure 5 is a graph showing the change of electrical conductivity of a stretchable conductive material obtained by high temperature heat treatment of a modal weft knitted fabric as a raw material according to different heat treatment temperatures.
图6为(a)本发明所述以莫代尔纬编针织织物为原材料高温(1050℃)热处理所得碳化针织织物可拉伸导电材料的电阻随拉伸应变的变化；(b)本发明所述与弹性聚合物复合的以莫代尔纬编针织织物为原材料高温(1050℃)热处理所得碳化针织织物可拉伸导电材料。Figure 6 is a (a) variation of electrical resistance of a tensile conductive material of a carbonized knitted fabric obtained by heat treatment of a modal weft knitted fabric as a raw material according to the present invention at a high temperature (1050 ° C); (b) The elastic polymer composite of the carbonized knitted fabric stretchable conductive material obtained by heat treatment at a high temperature (1050 ° C) using a modal weft knitted fabric as a raw material.
图7为(a)本发明所述以莫代尔纬编针织织物为原材料高温(1050℃)热处理所得碳化针织织物可拉伸导电材料在50％应变循环加载下的电阻变化稳定性； (b)本发明所述与弹性聚合物复合的以莫代尔纬编针织织物为原材料高温(1050℃)热处理所得碳化针织织物可拉伸导电材料在50％应变循环加载下的电阻变化稳定性。Figure 7 is a (a) resistance change stability of a carbon conductive knitted fabric stretchable conductive material obtained by heat treatment at a high temperature (1050 ° C) of a modal weft knitted fabric of the present invention under 50% strain cyclic loading; (b) The resistance change stability of the carbon conductive knitted fabric stretchable conductive material obtained by heat treatment at high temperature (1050 ° C) of the modal weft knitted fabric of the present invention combined with the elastic polymer under 50% strain cycle loading.
图8为本发明所述应用举例一，针织织物可拉伸导电材料作电极材料的可拉伸超级电容器示意图及不同拉伸应变下循环伏安曲线图。(a)可拉伸超级电容器示意图；(b)碳化针织织物作电极材料的可拉伸超级电容器的循环伏安曲线图；(c)碳化针织织物作电极材料的可拉伸超级电容器的不同拉伸应变下循环伏安曲线图；(d)聚苯胺复合碳化针织织物作电极材料的可拉伸超级电容器循环伏安曲线图；(e)聚苯胺复合碳化针织织物作电极材料的可拉伸超级电容器不同拉伸应变下循环伏安曲线图。8 is a schematic view of a stretchable supercapacitor in which a stretchable conductive material of a knitted fabric is used as an electrode material and a cyclic voltammetry curve under different tensile strains. (a) Schematic diagram of a stretchable supercapacitor; (b) Cyclic voltammogram of a stretchable supercapacitor in which a carbonized knitted fabric is used as an electrode material; (c) Different pulls of a stretchable supercapacitor in which a carbonized knitted fabric is used as an electrode material Cyclic voltammetry curve under tensile strain; (d) cyclic voltammetry curve of stretchable supercapacitor with polyaniline composite carbonized knitted fabric as electrode material; (e) stretchable super for polyaniline composite carbonized knitted fabric as electrode material Cyclic voltammograms of capacitors under different tensile strains.
图9为本发明所述应用举例二，针织织物可拉伸导电材料可拉伸加热器示意图及其基本电加热性能。Figure 9 is a schematic view of the application of the second embodiment of the present invention, a stretchable heater of a stretchable conductive material for a knitted fabric and its basic electric heating performance.
图10为本发明所述应用举例二，针织织物可拉伸导电材料可拉伸加热器电加热温度随拉伸应变的变化。FIG. 10 is a second application example of the present invention. The electric heating temperature of the stretchable heater of the stretchable conductive material of the knitted fabric varies with the tensile strain.
图11为本发明所述应用举例二，针织织物可拉伸导电材料可拉伸加热器电加热性能的循环稳定性。(a)在2.5V直流电循环开关加载下的电加热循环稳定性；(b)在1.5V直流电压下，加载不同次数循环拉伸应变，该加热器的电加热稳定性。Figure 11 is a second embodiment of the application of the present invention, the cycle stability of the electrical heating performance of a stretchable conductive material of a knit fabric. (a) Electrical heating cycle stability under 2.5V DC cycling switch loading; (b) Loading a different number of cyclic tensile strains at 1.5V DC voltage, the heater's electrical heating stability.
图12为本发明所述应用举例二，针织织物可拉伸导电材料可拉伸加热器可穿戴应用展示。Figure 12 is a second application example of the present invention, and a knit fabric stretchable conductive material stretchable heater wearable application display.
具体实施方式detailed description
莫代尔(Modal)是一种常见的人造纤维，在服装工业特别是内衣制造方面具有广泛应用。莫代尔具有很好的柔软性和优良的吸湿性，但其织物挺括性较差。Modal is a common man-made fiber and is widely used in the garment industry, especially in the manufacture of underwear. Modal has good softness and excellent hygroscopicity, but its fabric is poorly stiff.
发明人意外地发现，通过对莫代尔针织织物进行高温碳化处理而获得的碳化莫代尔针织织物，其针织结构得以保持，并且具有特别优越的可拉伸性及导电性，可直接用作可拉伸导电材料或与其他物质复合后用作可拉伸导电材料。The inventors have unexpectedly discovered that a carbonized modal knitted fabric obtained by subjecting a modal knitted fabric to a high-temperature carbonization process has a knit structure maintained, and has particularly excellent stretchability and electrical conductivity, and can be directly used as a stretchable conductive material. The material or composite with other materials is used as a stretchable conductive material.
例如，在本发明的一些实施方案中，1050℃碳化莫代尔纬编针织织物可拉伸导电材料能在70％的拉伸应变范围内保持电阻基本不变，Ecoflex封装的1050℃碳化莫代尔纬编针织织物可拉伸导电材料能在125％的应变范围内保持电阻基本不变。For example, in some embodiments of the present invention, a 1050 ° C carbonized modal weft knitted fabric stretchable conductive material can maintain substantially constant electrical resistance over a 70% tensile strain range, and a 1050 ° C carbonized modal weft knitted fabric in an Ecoflex package. The fabric stretchable conductive material maintains substantially constant electrical resistance over a 125% strain range.
本发明一方面提供了一种基于碳化莫代尔针织织物的可拉伸导电材料，其特征在于，所述碳化莫代尔针织织物通过对起始莫代尔针织织物进行高温碳化处理而获得。One aspect of the present invention provides a stretchable conductive material based on a carbonized modal knit fabric, characterized in that the carbonized modal knit fabric is obtained by subjecting an initial modal knit fabric to a high temperature carbonization process.
本文所用的术语“针织织物”具有本领域公知的含义，是指用织针将纱线构 成线圈，再把线圈相互串套而成的织物，其具有能在各个方向延伸，弹性好的特点。The term "knitted fabric" as used herein has a meaning as is known in the art and refers to the construction of a yarn with a knitting needle. The fabric which is formed into a coil and then the strings are sleeved with each other has the characteristics of being able to extend in all directions and having good elasticity.
常见的针织织物包括：例如棉针织织物、莫代尔针织织物等。Common knit fabrics include, for example, cotton knit fabrics, modal knit fabrics, and the like.
本发明的针织织物并不局限于特定的编织方法。例如，纬编针织织物或者经编针织织物均可用于本发明。本文所用的术语“起始针织织物”是指作为高温碳化处理工艺的原材料的针织织物，例如棉针织织物或莫代尔针织织物。在本发明的一些具体实施方案中，纬编针织织物是特别合适的。The knit fabric of the present invention is not limited to a particular weaving method. For example, a weft knitted fabric or a warp knitted fabric can be used in the present invention. The term "starting knit fabric" as used herein refers to a knit fabric, such as a cotton knit fabric or a modal knit fabric, which is a raw material for a high temperature carbonization treatment process. In some embodiments of the invention, weft knitted fabrics are particularly suitable.
本文所用的术语“可拉伸导电材料”是指该导电材料在拉伸状态下仍能保持其导电性能。可拉伸导电材料特别适用于柔性、可拉伸器件，例如可穿戴设备、柔性机器人等。The term "stretchable conductive material" as used herein means that the conductive material retains its electrical conductivity while being stretched. Stretchable conductive materials are particularly suitable for flexible, stretchable devices such as wearable devices, flexible robots, and the like.
本发明的碳化针织织物的生产工艺流程包括：在惰性气体气氛或惰性气体为主的气氛或真空气氛下，高温处理所述起始针织织物，从而得到所述碳化针织织物。The production process of the carbonized knit fabric of the present invention comprises: treating the starting knit fabric at a high temperature in an inert gas atmosphere or an inert gas-based atmosphere or a vacuum atmosphere, thereby obtaining the carbonized knit fabric.
此处的高温碳化处理的温度通常为200℃至3000℃(例如200℃、250℃、300℃、350℃、400℃、450℃、500℃、550℃、600℃、650℃、700℃、750℃、800℃、850℃、900℃、950℃、1000℃、1050℃、1100℃、1150℃、1200℃、1250℃、1300℃、1350℃、1400℃、1450℃、1500℃)，尤其是600至1050℃；所述温度保持阶段的持续时间不低于5min，例如100-500分钟，优选150-300分钟，特别是200分钟。The temperature of the high temperature carbonization treatment here is usually 200 ° C to 3000 ° C (for example, 200 ° C, 250 ° C, 300 ° C, 350 ° C, 400 ° C, 450 ° C, 500 ° C, 550 ° C, 600 ° C, 650 ° C, 700 ° C, 750 ° C, 800 ° C, 850 ° C, 900 ° C, 950 ° C, 1000 ° C, 1050 ° C, 1100 ° C, 1150 ° C, 1200 ° C, 1250 ° C, 1300 ° C, 1350 ° C, 1400 ° C, 1450 ° C, 1500 ° C), especially It is 600 to 1050 ° C; the duration of the temperature holding phase is not less than 5 min, for example 100-500 minutes, preferably 150-300 minutes, especially 200 minutes.
本文所用的术语“惰性气体气氛”与“惰性气氛”可互换使用，是指惰性气体占比超过80％、甚至例如90％的气氛。As used herein, the terms "inert gas atmosphere" and "inert atmosphere" are used interchangeably and refer to an atmosphere in which the inert gas ratio exceeds 80%, or even, for example, 90%.
本文所用的术语“惰性气体为主的气氛”是指惰性气体和其他气体的比例大于1:1，例如大于5:1，优选大于10:1。例如，在本发明的一个实施例中，所述惰性气体为主的气氛中，氩气：氢气的比例为10:1。As used herein, the term "inert gas based atmosphere" means that the ratio of inert gas to other gases is greater than 1:1, such as greater than 5:1, preferably greater than 10:1. For example, in one embodiment of the present invention, the inert gas-based atmosphere has a ratio of argon:hydrogen of 10:1.
本文所用的术语“真空气氛”是指压强低于一个大气压的气氛。本发明的一些实施方案中提供了一种制备可拉伸导电材料的方法，包含：以针织织物(包括天然植物纤维织物如棉、麻织物，天然动物纤维织物如毛类、桑蚕丝类织物，人造纤维织物如再生纤维素纤维织物、纤维素酯纤维织物、再生蛋白质纤维织物，合成纤维织物以及任意组合纤维织物)为原材料，经过惰性气氛或惰性气体为主的气氛或真空气氛下的高温热处理过程得到保持原针织织物主要结构特征并具有柔性、可拉伸性及导电性的碳化针织织物，该碳化针织织物可直接用作可拉伸导电材料或与其他物质复合后用作可拉伸导电材料。The term "vacuum atmosphere" as used herein refers to an atmosphere having a pressure below one atmosphere. Some embodiments of the present invention provide a method of preparing a stretchable conductive material, comprising: a knitted fabric (including natural plant fiber fabrics such as cotton, hemp fabrics, natural animal fiber fabrics such as wool, silk fabrics, Man-made fiber fabrics such as regenerated cellulose fiber fabrics, cellulose ester fiber fabrics, regenerated protein fiber fabrics, synthetic fiber fabrics, and any combination of fiber fabrics are used as raw materials, and are subjected to an inert atmosphere or an inert gas-based atmosphere or a high-temperature heat treatment under a vacuum atmosphere. The process obtains a carbonized knit fabric which maintains the main structural features of the original knit fabric and has flexibility, stretchability and electrical conductivity. The carbonized knit fabric can be directly used as a stretchable conductive material or composited with other materials for use as a stretchable conductive material. material.
本发明的一些实施方案中提供了该基于碳化针织织物的可拉伸导电材料作为柔性或可拉伸电子器件的活性组件或作为柔性或可拉伸电子器件的导线的应 用。例如作为可拉伸超级电容器的电极材料，用于可穿戴能源器件；再如作为可拉伸加热器的加热主体材料，用于可穿戴热疗器件。In some embodiments of the present invention, the carbonized knit fabric-based stretchable conductive material is provided as an active component of a flexible or stretchable electronic device or as a wire of a flexible or stretchable electronic device. use. For example, as an electrode material for a stretchable supercapacitor, for a wearable energy device; and as a heating body material for a stretchable heater, for a wearable thermotherapy device.
在一些实施方案中，本发明的基于碳化针织织物的可拉伸导电材料的生产工艺流程为：In some embodiments, the production process of the carbonized knit fabric-based stretchable conductive material of the present invention is:
(1)利用起始针织织物为原材料，起始针织织物所采用的纤维为天然纤维、人造纤维、合成纤维或任意组合纤维；(1) using the starting knitted fabric as a raw material, and the fibers used for starting the knitted fabric are natural fibers, rayon fibers, synthetic fibers or any combination of fibers;
(2)经过惰性气氛或惰性气体为主的气氛或真空气氛下的高温热处理过程得到具有柔性、可拉伸性及导电性的碳化针织织物；(2) obtaining a carbonized knit fabric having flexibility, stretchability and electrical conductivity by an inert atmosphere or an inert gas-based atmosphere or a high-temperature heat treatment process under a vacuum atmosphere;
(3)步骤2)得到的可拉伸、导电的碳化针织织物直接用作可拉伸导电材料或与其他物质复合后用作可拉伸导电材料。(3) The stretchable, electrically conductive carbonized knit fabric obtained in the step 2) is used directly as a stretchable conductive material or as a stretchable conductive material after being compounded with other materials.
织物所采用的纤维原材料可以为天然纤维包括天然植物纤维如棉、麻，天然动物纤维如毛类、桑蚕丝类；人造纤维如再生纤维素纤维、纤维素酯纤维、再生蛋白质纤维；合成纤维；或任意组合纤维。The fiber raw material used in the fabric may be natural fiber including natural plant fiber such as cotton, hemp, natural animal fiber such as hair, silk; artificial fiber such as regenerated cellulose fiber, cellulose ester fiber, regenerated protein fiber; synthetic fiber; Or any combination of fibers.
织物原材料经过惰性气氛或惰性气体为主的气氛或真空气氛下的高温热处理得到具有柔性、可拉伸性及导电性的碳化针织织物，其中的惰性气为氮气、氩气、氦气或任意组合，其中的真空气氛为指压强低于一个大气压力的任意气氛，其中的高温热处理温度为200-3000℃，其中的柔性、可拉伸性及导电性碳化针织织物保留原织物的主要结构特征。The raw material of the fabric is subjected to an inert atmosphere or an inert gas-based atmosphere or a high-temperature heat treatment under a vacuum atmosphere to obtain a carbonized knitted fabric having flexibility, stretchability and electrical conductivity, wherein the inert gas is nitrogen, argon, helium or any combination. The vacuum atmosphere therein refers to any atmosphere having a pressure lower than an atmospheric pressure, wherein the high temperature heat treatment temperature is 200-3000 ° C, wherein the flexible, stretchable and conductive carbonized knitted fabric retains the main structural features of the original fabric.
可以与本发明的可拉伸导电材料复合的其他物质包括弹性聚合物或织物。其中弹性聚合物是指具有一定柔性或可拉伸性的聚合物，例如硅基弹性聚合物、橡胶、热塑性聚合物。Other materials that may be combined with the stretchable electrically conductive materials of the present invention include elastomeric polymers or fabrics. The elastomeric polymer refers to a polymer having a certain flexibility or stretchability, such as a silicone-based elastomeric polymer, a rubber, a thermoplastic polymer.
本发明的可拉伸导电材料可以用作柔性或可拉伸电子器件的活性组件(例如作为可拉伸超级电容器的电极材料，用于可穿戴能源器件；例如作为可拉伸加热器的加热主体材料，用于可穿戴热疗器件)或用作柔性或可拉伸电子器件的导线。The stretchable conductive material of the present invention can be used as an active component of a flexible or stretchable electronic device (for example, as an electrode material for a stretchable supercapacitor, for a wearable energy device; for example, as a heating body for a stretchable heater) Materials for wearable thermotherapy devices) or as wires for flexible or stretchable electronics.
本发明的可拉伸导电材料可以直接用作超级电容器的电极材料或与其他电化学活性材料复合后用作电极材料。电化学活性材料指可以改善超级电容器电化学性能的材料，例如聚苯胺、聚吡咯、二氧化锰均属于此类材料。The stretchable conductive material of the present invention can be directly used as an electrode material of a supercapacitor or as a electrode material after being compounded with other electrochemically active materials. Electrochemically active materials refer to materials that can improve the electrochemical performance of supercapacitors, such as polyaniline, polypyrrole, and manganese dioxide.
在本发明的优选实施例中，本发明的可拉伸导电材料与现有的可拉伸导电材料相比，可以具有以下一个或多个优点：In a preferred embodiment of the invention, the stretchable electrically conductive material of the present invention may have one or more of the following advantages over existing stretchable electrically conductive materials:
(1)所采用的织物原材料来源广泛、价格低廉；(1) The fabrics used have a wide range of raw materials and low prices;
(2)所采用的制备工艺简单、绿色环保；(2) The preparation process adopted is simple and green;
(3)本发明的可拉伸导电材料表现出优异的性能，即在不同的变形下，其导电性几乎不发生变化。(3) The stretchable conductive material of the present invention exhibits excellent properties, that is, its conductivity hardly changes under different deformations.
(4)本发明的可拉伸导电材料在柔性或可拉伸电子器件领域表现出广阔的 应用前景。(4) The stretchable conductive material of the present invention exhibits a broad field in the field of flexible or stretchable electronic devices Application prospects.
为了更清楚地展现本发明，以下结合实施例及附图对本发明进行进一步的描述。此处所述的实施例不用于限定本发明而只是对本发明进行更直观的解释说明。In order to present the present invention more clearly, the present invention will be further described in conjunction with the embodiments and the accompanying drawings. The embodiments described herein are not intended to limit the invention but are merely illustrative of the invention.
实施例1：以莫代尔纬编针织织物为原材料制备可拉伸导电材料Example 1: Preparation of stretchable conductive material using modal weft knitted fabric as raw material
将具有纬编针织结构的莫代尔织物(ROSILY莫代尔纯色平角裤)在以氩气为主的氩气氢气(氩气氢气流量比例10:1)混合气氛下或氮气氛围下，不同温度下(600℃、700℃、800℃、900℃、1050℃)高温热处理得到保持其纬编针织结构的碳化织物(具体升温程序为以3℃/min的升温速率升到目标温度保持200min，然后自然降温至室温)，该升温程序下得到的碳化针织织物可直接用作可拉伸导电材料，也可与弹性聚合物(具体为Ecoflex，一种硅胶)复合后用作可拉伸导电材料，制备工艺流程见附图1。所得到的碳化针织织物可拉伸导电材料或弹性聚合物复合碳化针织织物可拉伸导电材料均表现出优异的柔性及可拉伸性(见附图2)，具体而言，该碳化针织织物或弹性聚合物封装碳化针织织物能够承受打结、扭转变形证明其优异的柔性，而且其能够分别承受75％和100％的拉伸应变证明其优异的可拉伸性。值得提出的是，经过高温热处理得到的碳化针织织物仍保留原织物的纬编针织结构(见附图3)，且该碳化织物的透射电子显微图展示类石墨的晶格条纹结构及多晶衍射环说明其具有微晶石墨的微观结构(见附图4)，这是其能够具有高导电性的原因。另外，高温热处理得到的碳化针织织物的导电性随热处理温度的提高而提高，(见附图5)，例如，具体而言1050℃的温度下热处理所得碳化针织织物的电导率高达15.1S/cm，而600℃、700℃、800℃、900℃温度下所得碳化针织织物的电导率则分别为5.75E-5S/cm、0.26S/cm、2.48S/cm、5.28S/cm。由此可见，其导电性随热处理温度的升高而增大。The modal fabric (ROSILY pure color boxer pants) with weft knitted structure is mixed under argon gas (argon gas flow ratio 10:1) or nitrogen atmosphere at different temperatures (600 °C) , 700 ° C, 800 ° C, 900 ° C, 1050 ° C) high temperature heat treatment to obtain a carbonized fabric that maintains its weft knitted structure (specific heating procedure is to increase the temperature to 3 ° C / min to the target temperature for 200min, then naturally cool to room temperature The carbonized knit fabric obtained under the heating process can be directly used as a stretchable conductive material, or can be used as a stretchable conductive material after being compounded with an elastic polymer (specifically, Ecoflex, a silica gel). Figure 1. The obtained carbonized knitted fabric stretchable conductive material or elastic polymer composite carbonized knitted fabric stretchable conductive material exhibits excellent flexibility and stretchability (see Fig. 2), specifically, the carbonized knitted fabric Or the elastic polymer-encapsulated carbonized knit fabric can withstand the knotting and torsional deformation to prove its excellent flexibility, and its ability to withstand tensile strains of 75% and 100%, respectively, proves its excellent stretchability. It is worth mentioning that the carbonized knit fabric obtained by high temperature heat treatment still retains the weft knitted structure of the original fabric (see Figure 3), and the transmission electron micrograph of the carbonized fabric shows the graphite-like lattice fringe structure and polycrystalline The diffraction ring indicates that it has the microstructure of microcrystalline graphite (see Figure 4), which is why it can have high conductivity. In addition, the conductivity of the carbonized knit fabric obtained by the high-temperature heat treatment is increased as the heat treatment temperature is increased (see FIG. 5), for example, specifically, the carbonized knit fabric obtained by heat treatment at a temperature of 1050 ° C has an electric conductivity of up to 15.1 S/cm. The electrical conductivity of the obtained carbonized knit fabric at 600 ° C, 700 ° C, 800 ° C, and 900 ° C was 5.75E-5 S/cm, 0.26 S/cm, 2.48 S/cm, and 5.28 S/cm, respectively. It can be seen that the conductivity increases as the heat treatment temperature increases.
实施例2：碳化莫代尔纬编针织织物可拉伸导电材料的电阻随拉伸应变变化Example 2: Carbonized Modal weft knitted fabric The electrical resistance of a stretchable conductive material varies with tensile strain
实施例1中所述的1050℃碳化莫代尔纬编针织织物可拉伸导电材料及Ecoflex封装的1050℃碳化莫代尔纬编针织织物可拉伸导电材料在拉伸应变下，其电阻基本不发生变化(见附图6)。例如对于碳化针织织物可拉伸导电材料其能在70％的拉伸应变范围内保持电阻基本不变(见附图6a)，弹性聚合物封装的碳化针织织物可拉伸导电材料能在125％的应变范围内保持电阻基本不变(见附图6b)，这表明了两种可拉伸导电材料优异的性能。The 1050 ° C carbonized modal weft knitted fabric of 1050 ° C can be stretched conductive material and the 1050 ° C carbonized modal weft knitted fabric of Ecoflex package can resist the resistance of the tensile conductive material under tensile strain. See Figure 6). For example, for a carbonized knit fabric stretchable conductive material that maintains a substantially constant resistance over a 70% tensile strain range (see Figure 6a), the elastic polymer encapsulated carbonized knit fabric can stretch the conductive material at 125%. The resistance is kept substantially constant within the strain range (see Figure 6b), which demonstrates the superior performance of the two stretchable conductive materials.
实施例3：碳化莫代尔纬编针织织物可拉伸导电材料在循环拉伸应变下的稳定性 Example 3: Stability of a stretchable conductive material of a carbonized modal weft knitted fabric under cyclic tensile strain
实施列1中所述的1050℃碳化莫代尔纬编针织织物可拉伸导电材料及Ecoflex封装的1050℃碳化莫代尔纬编针织织物可拉伸导电材料在50％循环拉伸应变下，其电阻保持优异的循环稳定性(见附图7)。The 1050 ° C carbonized modal weft knitted fabric stretchable conductive material described in column 1 and the 1050 ° C carbonized modal weft knitted fabric of Ecoflex package can be used to stretch the conductive material at 50% cyclic tensile strain. Cycle stability (see Figure 7).
实施例4：碳化莫代尔纬编针织织物作可拉伸超级电容器电极Example 4: Carbonized modal weft knitted fabric as a stretchable supercapacitor electrode
碳化莫代尔纬编针织织物用作超级电容器的电极材料，与PVA-H3PO4凝胶电解质组装形成可拉伸超级电容器，其结构示意图见附图8(a)，具体而言，该超级电容器的结构是由两层碳化莫代尔纬编针织织物作电极(织物上通过导电银胶连接铜片作测试电极)中间夹有凝胶电解质形成的三明治结构。该超级电容器表现出优异的电化学性能(见附图8b)，具体而言，在10mV/s的扫描速率下，该超级电容器的面积比电容达7.5mF/cm2。在不同的拉伸应变下，该超级电容器的电化学循环伏安曲线几乎不发生变化(见附图8c)，表明其电化学性能在拉伸应变下保持不变。另外，通过电化学聚合沉积方法在碳化莫代尔纬编针织织物上负载聚苯胺5min(具体负载方法可参见文献Graphene/polyaniline woven fabric composite films asflexible supercapacitor electrodes.Nanoscale,2015,7,7318–7322)，然后将其用作超级电容器电极材料，该超级电容器表现出较碳化针织织物明显提高的电化学性能(见附图8d)。具体而言，在10mV/s的扫描速率下，该超级电容器的面积比电容达246.3mF/cm2，为碳化莫代尔纬编针织织物的～33倍。而且在不同的拉伸应变下，该超级电容器的电化学循环伏安曲线几乎不发生变化(见附图8e)，表明其可拉伸性。The carbonized modal weft knitted fabric is used as an electrode material of a supercapacitor, and is assembled with a PVA-H 3 PO 4 gel electrolyte to form a stretchable supercapacitor. The structure diagram is shown in Fig. 8(a), specifically, the supercapacitor The structure is a sandwich structure formed by a two-layer carbonized modal weft knitted fabric as an electrode (a conductive electrode on a fabric is connected to a copper electrode as a test electrode) with a gel electrolyte interposed therebetween. The supercapacitor exhibited excellent electrochemical performance (see Figure 8b), specifically, the area ratio specific capacitance of the supercapacitor was 7.5 mF/cm 2 at a scan rate of 10 mV/s. The electrochemical cyclic volt-ampere curve of the supercapacitor hardly changed at different tensile strains (see Figure 8c), indicating that its electrochemical properties remain unchanged under tensile strain. In addition, polyaniline was supported on a carbonized modal weft knitted fabric by electrochemical polymerization deposition method for 5 min (for specific loading methods, see Graphene/polyaniline woven fabric composite films as flexible supercapacitor electrodes. Nanoscale, 2015, 7, 7318-7322), and then It was used as a supercapacitor electrode material which exhibited significantly improved electrochemical performance compared to carbonized knit fabrics (see Figure 8d). Specifically, at a scan rate of 10 mV/s, the area ratio of the supercapacitor is 246.3 mF/cm 2 , which is ~33 times that of a carbonized modal weft knitted fabric. Moreover, the electrochemical cyclic voltammetry curve of the supercapacitor hardly changed under different tensile strains (see Fig. 8e), indicating its stretchability.
实施例5：弹性聚合物封装碳化莫代尔纬编针织织物作可穿戴加热器Example 5: Elastomeric polymer encapsulated carbonized modal weft knitted fabric as a wearable heater
通过将实施例1中所述1050℃处理所得碳化莫代尔纬编针织织物两端通过导电银胶连接铜片作电极然后利用Ecoflex聚合物进行封装，得聚合物封装的碳化针织织物加热元件，然后可通过将其负载到带有绑带结构的弹性织物基底上即得可穿戴加热器件如附图9a所示，可用于热敷、热疗等。通过对该加热器进行性能测试发现该加热器表现优异的电加热性能，随着对其施加电压的增大其能够加热的温度逐渐增加，而且当只施加3.5V的直流电压时，其电加热温度能在数秒内达到～150℃(见附图9b)。另外，在3.0V的直流电压下，当对该加热器施加拉伸应变时，随着施加的拉伸应变不断增大，该加热器的电加热温度逐渐缓慢升高(见附图10)，表明其在拉伸状态下仍能保持优异的电加热性能，说明其可在拉伸状态下工作另外，该加热器表现出稳定的电加热-冷却循环稳定性，具体如附图11a所示，当对施加在该加热器上的2.5V直流电进行开关循环时，该加热器表现出稳定的温度加热-冷却循环稳定性。而且，该加热器在承受循环的拉伸应变加载时，其电加热性能几乎保持不变(见附图11b)，l两者均说明了该可 拉伸加热器的高稳定性。The carbonized knitted fabric heating element of the polymer package was obtained by connecting the two ends of the carbonized modal weft knitted fabric obtained by the treatment at 1050 ° C described in Example 1 through a conductive silver glue to the copper sheet as an electrode and then encapsulating with the Ecoflex polymer. A wearable heating device can be used for heat application, heat treatment or the like by loading it onto an elastic fabric substrate with a strap structure as shown in Fig. 9a. Through the performance test of the heater, it was found that the heater exhibited excellent electric heating performance, and the temperature at which it can be heated gradually increased as the applied voltage was increased, and when only a DC voltage of 3.5 V was applied, the electric heating was performed. The temperature can reach ~150 °C in a few seconds (see Figure 9b). In addition, at a DC voltage of 3.0 V, when a tensile strain is applied to the heater, as the tensile strain applied increases, the electric heating temperature of the heater gradually increases (see FIG. 10). It is shown that it can maintain excellent electric heating performance under the tensile state, indicating that it can work under the tensile state. In addition, the heater exhibits stable electric heating-cooling cycle stability, as shown in Fig. 11a. When a switching cycle of 2.5 V DC applied to the heater was performed, the heater exhibited stable temperature heating-cooling cycle stability. Moreover, the electric heating performance of the heater is almost unchanged when subjected to cyclic tensile strain loading (see Figure 11b), both of which illustrate the High stability of the stretching heater.
由于该加热器的柔性、拉伸性，其可用于可穿戴热疗器件。例如，当将该加热器绑到膝盖上，在膝盖弯曲时，该加热器表现出优于膝盖伸直时的加热性能(见附图12)，证明了其作为可穿戴加热器用于热疗的潜力。 Due to the flexibility and stretchability of the heater, it can be used in wearable thermal therapy devices. For example, when the heater is attached to the knee, the heater exhibits better heating performance than knee extension when the knee is bent (see Figure 12), demonstrating its use as a wearable heater for hyperthermia. potential.

Claims (9)

  1. 一种基于碳化莫代尔针织织物的可拉伸导电材料，其特征在于，所述碳化针织织物通过对起始莫代尔针织织物进行高温碳化处理而获得。A stretchable electrically conductive material based on a carbonized modal knit fabric, characterized in that the carbonized knit fabric is obtained by subjecting an initial modal knit fabric to a high temperature carbonization process.
  2. 权利要求1的可拉伸导电材料，其中所述莫代尔针织织物为纬编莫代尔针织织物。The stretchable electrically conductive material of claim 1 wherein said modal knit fabric is a weft-knit modal knit fabric.
  3. 权利要求1-2之任一项的可拉伸导电材料，其中所述碳化莫代尔针织织物的生产工艺流程包括：在惰性气体气氛或惰性气体为主的气氛或真空气氛下，高温处理所述起始莫代尔针织织物，从而得到所述碳化莫代尔针织织物；The stretchable conductive material according to any one of claims 1 to 2, wherein the production process of the carbonized modal knitted fabric comprises: under an inert gas atmosphere or an inert gas-based atmosphere or a vacuum atmosphere, the high temperature treatment Starting a Modal knit fabric to obtain the carbonized modal knit fabric;
    其中所述高温处理包括：升温阶段、温度保持阶段和降温阶段；Wherein the high temperature treatment comprises: a temperature rising phase, a temperature maintaining phase, and a cooling phase;
    其中所述温度保持阶段的温度为200℃至3000℃，持续时间为不低于5min。The temperature in the temperature maintaining phase is 200 ° C to 3000 ° C, and the duration is not less than 5 min.
  4. 权利要求1-3之任一项的可拉伸导电材料，其中所述碳化针织织物进一步与其他材料复合。The stretchable electrically conductive material of any one of claims 1 to 3, wherein the carbonized knit fabric is further compounded with other materials.
  5. 权利要求4的可拉伸导电材料，其中所述其他材料包括：硅基聚合物、橡胶、热塑性聚合物。The stretchable electrically conductive material of claim 4 wherein said other material comprises: a silicon based polymer, a rubber, a thermoplastic polymer.
  6. 权利要求1-5之任一项的可拉伸导电材料作为柔性或可拉伸电子器件的活性组件的应用，或者作为柔性或可拉伸电子器件的导线的应用。Use of the stretchable electrically conductive material of any of claims 1-5 as an active component of a flexible or stretchable electronic device, or as a wire for a flexible or stretchable electronic device.
  7. 权利要求6的应用，其中所述可拉伸导电材料作为可拉伸超级电容器的电极材料，或应用于可穿戴能源器件，或作为可拉伸加热器的加热主体材料，或应用于可穿戴热疗器件。The use of claim 6 wherein said stretchable electrically conductive material is used as an electrode material for a stretchable supercapacitor, or as a wearable energy device, or as a heated body material for a stretchable heater, or for wearable heat Treatment device.
  8. 一种可拉伸超级电容器，其特征在于其电极材料中包含权利要求1-5之任一项的可拉伸导电材料。A stretchable supercapacitor characterized in that the electrode material comprises the stretchable conductive material of any one of claims 1-5.
  9. 一种可拉伸加热器，其特征在于其加热主体材料中包含权利要求1-5之任一项的可拉伸导电材料，工作电压范围不低于0.1V，加热温度范围不低于30℃。 A stretchable heater characterized in that the heating body material comprises the stretchable conductive material according to any one of claims 1 to 5, the working voltage range is not less than 0.1 V, and the heating temperature range is not lower than 30 ° C. .
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