CN112323498A - Multifunctional fabric and preparation method and application thereof - Google Patents

Multifunctional fabric and preparation method and application thereof Download PDF

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Publication number
CN112323498A
CN112323498A CN202011203965.2A CN202011203965A CN112323498A CN 112323498 A CN112323498 A CN 112323498A CN 202011203965 A CN202011203965 A CN 202011203965A CN 112323498 A CN112323498 A CN 112323498A
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fabric
preparation
mxene
conductive polymer
multifunctional
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何培富
王腾飞
郑贤宏
王宗乾
牧永权
童忠义
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Wuhu Fuchun Dyeing And Weaving Co ltd
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Wuhu Fuchun Dyeing And Weaving Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/60—Deposition of organic layers from vapour phase
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
    • G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Electromagnetism (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention provides a multifunctional fabric and a preparation method and application thereof. In addition, as MXene can generate active oxygen, lipid peroxidation of bacterial cell membranes and damage of intracellular proteins or genes are caused, the finally prepared conductive polymer/MXene modified fabric has excellent antibacterial performance.

Description

Multifunctional fabric and preparation method and application thereof
Technical Field
The invention belongs to the field of multifunctional textiles, and particularly relates to a multifunctional fabric and a preparation method and application thereof.
Background
Fabric-based wearable electronics are of great interest due to their potential applications in the fields of health monitoring, mobile energy harvesting and storage, wireless communications, and the like. The traditional method is to embed an electronic device into fabric to prepare a wearable device, but the wearable device usually has the defects of steel hardness, poor flexibility, poor comfort, poor washing fastness and the like. In order to solve the above problems, the preparation of multifunctional electronic fabrics by combining functional guest materials with fabrics is considered to be an ideal solution.
At present, the preparation of functional fabrics mainly comprises: the fabric is coated and modified by adopting conductive polymers (polyaniline, polypyrrole and the like), nano-carbon materials (carbon nano tubes, graphene and the like) and metal nano-materials, or functional fabrics woven by adopting metal fibers or carbon fiber blended yarns and the like. Chinese patent CN110344248A published in 2019, 10, 18 and the like carries out graphene and carbon black modification on cotton fabrics, and the prepared fabrics have good electric heating performance; the polypyrrole/cotton fabric supercapacitor electrode is prepared by an in-situ interfacial polymerization method in Chinese patent CN110970236A disclosed in No. 4, month No. 7 and No. 2020; chinese patent CN107233074A published in 2017, 10.10.8 prepares continuous nanofiber yarn by a conjugated electrostatic spinning yarn technology, then a layer of conductive polymer is polymerized and coated on the surface of the fiber in the yarn, the yarn is woven into fabric by a weaving method, and the nanofiber fabric sensor with a sandwich structure is prepared by compounding gel films with conductive copper wires on the upper surface and the lower surface of the fabric; however, the method has the disadvantages of long process flow, complex process, low fabric conductivity and single fabric function.
MXene is two-dimensional layered transition metal carbide or nitride, has good dispersibility, conductivity and electromagnetic shielding performance, and has wide application potential in the fields of energy, catalysis, biology and the like. The document reports that MXene coats yarns and is knitted to prepare an MXene modified fabric supercapacitor (Materials Today 2020,34,17-29), however, the MXene has large loading capacity, so that the fabric has poor hand feeling, and the electromagnetic shielding performance is difficult to obtain due to loose knitting structure; chinese patent CN109868646A disclosed in 6, 11 and 2019 adopts transition metal carbide (MXene) to modify cotton fabric, and electromagnetic shielding fabric with high conductivity is prepared. But the fabric has poor electromagnetic shielding performance and single function.
The Oxidation Chemical Vapor Deposition (OCVD) technology is to generate a conductive polymer film by gradually polymerizing and depositing gaseous conductive polymer monomers on the surface of a sample under the action of an oxidant. The oxidation chemical vapor deposition technology has been widely applied to the fields of thermoelectricity, photoelectricity, energy storage and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a multifunctional fabric, which is used for preparing the multifunctional fabric by using conductive polymer and MXene, and has the advantages of short preparation process flow and simple process.
The invention also aims to provide the multifunctional fabric prepared by the method, and the prepared fabric has the electrochemical storage performance, the electromagnetic shielding performance, the electric heating performance and the sensing performance, and simultaneously keeps the original flexibility and the air permeability of the fabric, so that the technical problems are solved.
The last purpose of the invention is to provide the application of the multifunctional fabric, which is used for manufacturing electrode materials of super capacitors, electrothermal materials, strain sensors, electromagnetic shielding materials or antibacterial textiles.
The specific technical scheme of the invention is as follows:
a preparation method of the multifunctional fabric comprises the following steps:
1) conducting polymer is deposited by chemical vapor deposition of fabric oxidation;
2) infrared grafting of MXene.
Further, the conductive polymer in step 1) includes, but is not limited to, polyaniline, polypyrrole, poly-3 hexyl thiophene, poly-3 methyl thiophene or poly-3, 4-ethylenedioxythiophene; preferably poly 3, 4-ethylenedioxythiophene;
the fabric in the step 1) includes but is not limited to cotton fabric, hemp fabric, wool fabric, silk fabric, chemical fiber fabric, blended fabric or carbon fiber fabric.
Preferably, the oxidant used in the process of oxidizing the fabric in the step 1) and chemically vapor depositing the conductive polymer is vanadium oxytrichloride (VOCl)3) Ferric chloride (FeCl)3) Or iron p-toluenesulfonate.
Further, the deposition conditions of the fabric oxidation chemical vapor deposition conductive polymer in the step 1) are as follows: reacting at 60-160 deg.c for 10-300 min.
Further, in the step 1), the fabric is fixed with a pre-tension of 0.1-20cN, and then the oxidation chemical vapor deposition of the conductive polymer is carried out.
Preferably, in the step 1), in the process of chemical vapor deposition of the conductive polymer by fabric oxidation, the gas phase temperature of the conductive polymer monomer is kept at 140-200 ℃, and the flow rate is 5-20 standard ml/min; the gas phase temperature of the oxidant is maintained at 30-90 ℃ and the flow rate is 5-20 standard ml/min.
Further, in the step 1), the pressure is kept to be 0.1-10Torr all the time in the process of oxidizing the fabric and depositing the conductive polymer by chemical vapor deposition.
Preferably, the specific method for the fabric oxidation chemical vapor deposition of the conductive polymer in the step 1) is as follows: fixing the fabric on a heating table in an oxidation chemical vapor deposition reactor with the pre-tension of 0.1-20cN, respectively conveying gaseous conductive high molecular monomer and gaseous oxidant into the reactor at certain flow rate and temperature, and polymerizing on the fabric surface for 10-300 minutes at 60-160 ℃ to prepare the conductive high molecular modified fabric; wherein the temperature of the conductive polymer monomer gas phase transfer pipeline is maintained at 140-200 ℃, and the temperature of the oxidant gas phase transfer pipeline is maintained at 30-90 ℃. The gas phase flow of the conductive polymer monomer is 5-20 standard ml/min, the gas phase flow of the oxidant is 5-20 standard ml/min, and the pressure of the whole reactor is kept at 0.1-10 Torr.
Most preferably, step 1) is specifically: fixing the fabric on a heating table in an oxidation chemical vapor deposition reactor with the pre-tension of 0.1-20cN, respectively conveying gaseous 3, 4-ethylenedioxythiophene and gaseous oxidant into the reactor at certain flow rate and temperature, and polymerizing on the surface of the fabric for 10-300 minutes at 60-160 ℃ to prepare the conductive polymer modified fabric; wherein the temperature of the conductive polymer monomer gas phase transfer pipeline is maintained at 140-200 ℃, and the temperature of the oxidant gas phase transfer pipeline is maintained at 30-90 ℃; the gas phase flow of the conductive polymer monomer is 5-20 standard ml/min, the gas phase flow of the oxidant is 5-20 standard ml/min, and the pressure of the whole reactor is kept at 0.1-10 Torr.
The fabric is fixed in a pre-tension of 0.1-20cN, then the conductive polymer film is deposited, and then the pre-tension is released, and the conductive polymer film deposited on the surface of the fiber in the fabric is coated on the surface of the fiber in a micro-wrinkle mode. The main principle of the oxidation chemical vapor deposition conductive polymer is a stepped growth mechanism: under the action of gaseous oxidant, the gaseous conductive high molecular monomer gradually generates dimer, tetramer and the like on the surface of the sample to cause the molecular weight to gradually increase, and finally generates a uniform conductive high molecular film on the surface of the sample. The uniform conductive polymer film on the surface of the sample can promote the continuous transmission of electrons on the surface of the sample, and the conductivity of the sample can be greatly improved.
Furthermore, the tension device with the sensor and the controller is arranged on the hot table, so that the tension can be monitored in real time, and the effects that: (1) the tension device arranged on the hot table can regulate and control the surface tension of the fabric in real time, and prevent uneven tension caused by stress relaxation of the fabric in the surface polymerization process; (2) the tension device can realize that the surface of the polymerized fabric fiber has microscopic wrinkles, thereby being beneficial to the sensing performance of the fabric; (3) the real-time monitoring and controller tension adjusting device can make the surface tension of the fabric uniform and realize the uniform polymerization of the surface of the conductive polymer fabric.
The step 2) is specifically as follows: dipping the fabric treated in the step 1) in MXene dispersion liquid, adding a photoinitiator, and heating and reacting under an infrared light source to obtain the multifunctional fabric.
In the step 2), the photoinitiator is benzophenone; the concentration of the photoinitiator in MXene dispersion liquid is 0.001-0.01 mmol/L.
Adding the photoinitiator in a manner of benzophenone ethanol solution. Preferably, the addition amount of the benzophenone ethanol solution is 200-400 mu L.
The preparation method of the benzophenone ethanol solution comprises the following steps: dissolving a certain amount of benzophenone in absolute ethyl alcohol to prepare a 50-100mmol/L benzophenone ethyl alcohol solution.
In the step 2), the power of the infrared light source is 100-1000W; the heating reaction is carried out at the temperature of 50-70 ℃ for 5-60 minutes.
In the step 2), the concentration of the MXene dispersion liquid is 0.5-20 mg/mL;
the bath ratio of the fabric treated in the step 1) in the step 2) to the MXene dispersion liquid is 1: 10-50.
Heating in the step 2), taking out the fabric, and drying at 50-80 ℃ for 5-30 minutes.
In the step 2), under the action of a photoinitiator, functional groups such as oxygen, fluorine, hydroxyl and the like on the surface of MXene can react with epoxy disulfide bonds, amino and the like in the conductive polymer, so that the conductive polymer and MXene are combined through covalent bonds and hydrogen bonds; in addition, MXene can also react with a hydroxyl group in the molecular structure of cellulose fiber, a glucose residue group, or a disulfide bond, an amino group, a carboxyl group, an amide bond, etc. in the molecular structure of protein fiber, and two-dimensional MXene nanosheets are bonded to the fiber surface through a covalent bond such as a hydrogen bond, an ester bond, or an ether bond. Therefore, the combination of the oxidative chemical vapor deposition technology and the photoinitiated grafting technology has excellent synergistic effect, and the fiber-conductive polymer-MXene is firmly combined through covalent bonds to form a continuous MXene/conductive polymer film with high combination fastness on the surface of the fabric. Ultimately imparting excellent conductivity and wash fastness to the fabric.
Further, in the step 2), the preparation method of the MXene dispersion liquid comprises the following steps: adding the precursor of the transition metal carbide and the metal fluoride into a hydrochloric acid solution, uniformly stirring, carrying out hydrothermal reaction, washing, carrying out ultrasonic treatment, and centrifuging to obtain the MXene dispersion liquid.
The transition metal carbide precursor is selected from Ti3AlC2、Nb2AlC、V2AlC、Mo2Ga2C、Zr3Al3C5Or Mo2TiAlC2(ii) a Preferably ultra-large sheets of Ti3AlC2And the size range is 50-200 mu m.
The fluoride is preferably lithium fluoride or sodium fluoride;
further, the mass ratio of the transition metal carbide precursor to the metal fluoride is 1: 1-10;
the concentration of the precursor of the transition metal carbide in the hydrochloric acid solution is 5-200g/L, and the concentration of the metal fluoride in the hydrochloric acid solution is 5-2000 g/L.
The concentration of the hydrochloric acid solution is 1-12 mol/L.
The hydrothermal reaction refers to hydrothermal reaction at 60-180 ℃ for 18-48 hours.
The washing refers to fully washing the mixed solution after the hydrothermal reaction;
the ultrasonic treatment refers to ultrasonic stripping for 5-120 minutes under the power of 50-750W;
the centrifugation parameters were as follows: 8000-10000RPM centrifugation for 5-20 minutes, dispersing the lower layer sediment into water, further 4000-6000RPM centrifugation for 5-20 minutes, collecting the sediment and dispersing into water, further 2000-4000RPM centrifugation for 5-20 minutes.
And after centrifugation, taking the precipitate and dispersing the precipitate into water to obtain the MXene dispersion liquid with the oversized size.
Compared with the existing MXene preparation method, the method for preparing the oversized MXene dispersion liquid mainly adopts the high-temperature high-pressure hydrothermal reaction and the gradient centrifugation method to prepare the oversized MXene, and has the remarkable advantages compared with the existing MXene preparation method: the MXene prepared by the method has a better stripping and layering effect and a high single-chip rate, has rich functional groups and has more excellent stability and dispersibility; the MXene prepared by the method has larger sheet diameter.
The multifunctional fabric provided by the invention is prepared by adopting the method.
The invention provides application of a multifunctional fabric, which is used for manufacturing electrode materials of a super capacitor, electrothermal materials, strain sensors, electromagnetic shielding materials or antibacterial textiles.
According to the invention, the conductive polymer film is deposited on the surface of the fabric by an oxidative chemical vapor deposition method, and the conductive polymer/MXene composite film is constructed on the surface of the fiber in the fabric by MXene surface modification to form a continuous conductive network, so that the fabric is endowed with excellent conductivity, electrothermal property, sensing property and electrochemical property. In addition, as MXene can generate active oxygen, lipid peroxidation of bacterial cell membranes and damage of intracellular proteins or genes are caused, the finally prepared conductive polymer/MXene modified fabric has excellent antibacterial performance.
The invention develops a multifunctional fabric based on oxidation chemical vapor deposition and infrared grafting modification technology and by constructing a conductive polymer and MXene composite membrane on the surface of a fiber in the fabric, and the multifunctional fabric has the following advantages:
1) and the technical popularization is strong: through reasonable matching of the monomer and the oxidant, a plurality of conductive polymers such as polyaniline, polypyrrole, poly-3 hexylthiophene, poly-3 methylthiophene, poly-3, 4-ethylenedioxythiophene (PEDOT) and the like can be polymerized on the surface of the fabric; the fabric can be cotton fabric, hemp fabric, wool fabric, silk fabric, chemical fiber fabric, blended fabric, carbon fiber fabric and the like.
2) The continuous conductive polymer film can be deposited on the surface of the fabric by an OCVD (optical vapor deposition) technology, the thickness of the conductive polymer film is adjustable and controllable, the conductive polymer film can be adjusted by changing the flow of the conductive polymer monomer and the oxidant and the polymerization time, and the prepared conductive polymer modified fabric has better conductivity.
3) The fabric is oxidized by chemical vapor deposition of the conductive polymer under tension, so that the specific surface area of the fabric can be improved, the uniform conductive polymer film with microcosmic folds can be formed more favorably, and the sensing performance of the conductive polymer film as a flexible strain sensor can be improved.
4) The invention adopts ultra-large sheets of Ti3AlC2MXene prepared by taking the raw material as a raw material and carrying out high-temperature high-pressure hydrothermal reaction has larger transverse dimension and ultra-large Ti3AlC2Can strip large-size MXene, and is helpful for improving the conductivity of the modified fabric.
5) The OCVD technology combined with infrared grafting modification can construct a compact conductive polymer/MXene composite membrane on the surface of the fiber, and can further improve the conductivity of the fabric.
6) The infrared light initiated grafting process is simple, the MXene loading capacity can be adjusted and controlled, and the MXene loading capacity can be adjusted and controlled by the photoinitiated grafting time. And MXene and poly 3, 4-ethylenedioxythiophene are combined through hydrogen bonds and covalent bonds, so that the bonding force is good, and the prepared poly 3, 4-ethylenedioxythiophene/MXene modified fabric has good washing fastness.
7) The poly 3, 4-ethylenedioxythiophene/MXene modified fabric prepared by the OCVD technology and the infrared grafting technology has multiple functions, and can be used as a supercapacitor electrode material, an electrothermal material, a strain sensor, an electromagnetic shielding material and an antibacterial textile.
Drawings
FIG. 1 is a schematic flow chart of the preparation of a modified fabric of the present invention;
FIG. 2 is a scanning electron microscope image of the multifunctional fabric prepared in example 2 and comparative example 2; in the figure, a and b are scanning electron micrographs of comparative example 2, and c and d are scanning electron micrographs of example 2;
FIG. 3 is a comparison of the square resistance of cotton fabrics of each example and comparative example;
FIG. 4 shows the sheet resistance of the fabric before and after washing in accordance with the examples;
FIG. 5 is an application of the multifunctional fabric of the present invention, wherein a is used for manufacturing an all-solid-state supercapacitor, b is used for manufacturing an electrothermal textile, c is used for manufacturing an antibacterial textile, d is used for manufacturing an electromagnetic shielding textile, and e is used for manufacturing a flexible strain sensor;
FIG. 6 is a scanning electron microscope image of the surface of the multifunctional fabric prepared in example 1 and example 5; wherein a is the multifunctional fabric prepared in example 1 and b is the multifunctional fabric prepared in example 5.
Detailed Description
Example 1
A preparation method of the multifunctional fabric comprises the following steps:
1) fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: fixing cotton fabric on hot table of oxidation chemical vapor deposition reactor with pre-tension of 5cN, and preparing gaseous poly (3, 4-ethylenedioxythiophene) and vanadium oxytrichloride (VOCl)3) The oxidant is respectively delivered into the reactor at certain flow rate and temperature, and polymerized on the surface of the fabric for 60 minutes at 80 ℃ to prepare the fabric modified by the poly 3, 4-ethylenedioxythiophene. Wherein, the temperature of the poly 3, 4-ethylenedioxythiophene and the temperature of the vanadium oxytrichloride delivery pipeline are respectively maintained at 160 ℃ and 60 ℃; the flow rates of gaseous poly-3, 4-ethylenedioxythiophene and oxidant were 9 and 12 standard ml/min, respectively, and the pressure throughout the reactor was maintained at 1 Torr.
2) Hydrothermal preparation of oversized MXene dispersion: ti of 10-200 μm in size3AlC2And adding lithium fluoride into a 9mol/L hydrochloric acid solution according to the mass ratio of 1:1, wherein the concentration of the lithium fluoride in the hydrochloric acid solution is 10g/L, uniformly stirring, transferring to a polytetrafluoroethylene-lined high-temperature high-pressure reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 36 hours. And (3) fully washing the reacted mixed solution with water, ultrasonically stripping for 10 minutes under 750W power, and centrifuging: centrifuging at 10000RPM for 10 minutes, dispersing the lower layer precipitate into water, further centrifuging at 4000RPM for 15 minutes, collecting the precipitate, dispersing the precipitate into water, further centrifuging at 3000RPM for 15 minutes, and dispersing the precipitate into water to obtain an MXene dispersion liquid with an oversized size.
3) Infrared grafting MXene: dipping the poly 3, 4-ethylenedioxythiophene modified cotton fabric prepared in the step 1) into the MXene dispersion liquid prepared in the step 2) according to a bath ratio of 1:10, wherein the concentration of the MXene dispersion liquid is 10mg/mL, adding 200 mu L of 50mmol/L photoinitiator benzophenone ethanol solution into the solution, and the concentration of the photoinitiator in the MXene dispersion liquid is 0.01 mmol/L; and (3) reacting for 30 minutes at the temperature of 60 ℃ under an infrared light source of 1000W, taking out the fabric, and drying for 10 minutes at the temperature of 60 ℃ to obtain the multifunctional fabric.
Example 2
A preparation method of the multifunctional fabric comprises the following steps:
1) fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: same as in example 1, step 1), except that the polymerization time was 120 minutes.
2) Hydrothermal preparation of oversized MXene dispersion: same as in step 2) of example 1.
3) Infrared grafting MXene: same as in example 1, step 3), except that the reaction time was 60 minutes.
Example 3
A preparation method of the multifunctional fabric comprises the following steps:
1) fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: same as example 1, step 1), except that vanadium oxytrichloride was replaced with iron p-toluenesulfonate.
2) Hydrothermal preparation of oversized MXene dispersion: same as in step 2) of example 1.
3) Infrared grafting MXene: same as in step 3) of example 1.
Example 4
A preparation method of the multifunctional fabric comprises the following steps:
1) fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: same as in step 1) of example 1, except that vanadium oxytrichloride was changed to ferric trichloride.
2) Hydrothermal preparation of oversized MXene dispersion: same as in step 2) of example 1.
3) Infrared grafting MXene: same as in step 3) of example 1.
Example 5
A preparation method of the multifunctional fabric comprises the following steps:
1) fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: same as in step 1) of example 1.
2) Hydrothermal preparation of oversized MXene dispersion: same as in step 2) of example 1.
3) Infrared grafting MXene: same as in example 1, step 3), except that the infrared grafting time was changed to 60 minutes.
As can be seen in fig. 6, example 5 (ir-grafted for 60 minutes) had a cleaner fabric surface, significantly reduced hairiness, and was covered by a large number of MXene sheets compared to example 1 (ir-grafted for 30 minutes). The method shows that the loading of MXene on the surface of the fabric can be obviously improved by increasing the infrared grafting time, and the longer the grafting time is, the more the loading of MXene is.
Comparative example 1
A preparation method of the multifunctional fabric comprises the following steps:
fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: fixing cotton fabric on hot table of oxidation chemical vapor deposition reactor with pre-tension of 5cN, gaseous 3, 4-ethylenedioxythiophene and vanadium oxychloride (VOCl)3) The oxidant is respectively delivered into the reactor at certain flow rate and temperature, and polymerized on the surface of the fabric for 60 minutes at 80 ℃ to prepare the fabric modified by the poly 3, 4-ethylenedioxythiophene. Wherein, the temperature of the 3, 4-ethylenedioxythiophene and the iron p-toluenesulfonate transfer pipeline is respectively maintained at 160 ℃ and 60 ℃. The flow rates of the monomer and the oxidizing agent were 9 and 12 ml/min, respectively, and the pressure of the entire reactor was maintained at 1 Torr.
Comparative example 2
A preparation method of the multifunctional fabric comprises the following steps:
fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: same as comparative example 1, step 1), except that the polymerization time was 120 minutes.
Comparative example 3
A preparation method of the multifunctional fabric comprises the following steps:
fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: same as comparative example 1, step 1), except that vanadium oxytrichloride was replaced with iron p-toluenesulfonate.
Comparative example 4
A preparation method of the multifunctional fabric comprises the following steps:
fabric oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene: same as in step 1) of comparative example 1 except that vanadium oxytrichloride was changed to iron trichloride.
Scanning electron microscope images of the multifunctional fabrics prepared in example 2 and comparative example 2 are shown in fig. 2, and it can be seen from fig. 2 that the PEDOT film with dendritic texture structure and wrinkle structure is formed on the surface of the fiber after the comparative example 2 is subjected to oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene, and the fiber surface is wrapped by an MXene sheet layer after the example 2 is subjected to oxidation chemical vapor deposition of 3, 4-ethylenedioxythiophene and infrared grafting MXene modification, so that a poly 3, 4-ethylenedioxythiophene/MXene composite film is formed.
The multifunctional fabrics prepared in examples 1-4 and comparative examples 1-4 were subjected to the sheet resistance test in a manner consistent with the AATCC76-2005 test standard, the results of which are shown in fig. 3.
It can be seen from fig. 3 that the sheet resistance of the fabric of the example is significantly lower than that of the comparative example, because the cotton fabric forms a PEDOT/MXene composite film on the surface of the fiber after infrared grafting of MXene, forming a more continuous conductive path. In addition, the fabric of example 2 had the lowest sheet resistance and the fabric of example 4 had the highest sheet resistance. This is mainly because vanadium oxychloride has lower evaporation temperature relative to ferric p-toluenesulfonate and ferric trichloride, and is easier to carry out polymerization reaction on the surface of the fabric, and compared with example 1, the time of oxidative chemical polymerization is longer, the time of infrared grafting MXene on the fabric is longer, and the loading amount of poly 3, 4-ethylenedioxythiophene and MXene is higher in example 2.
The multifunctional fabrics prepared in examples 1-4 were washed with water, and the square resistances of the fabrics before and after washing were compared. Washing method the fabrics were washed according to the method described in AATCC61-2007 and their resistance to washing was examined.
From fig. 4, it can be seen that the fabric sheet resistance of the multifunctional fabrics prepared in the above examples 1to 4 is not significantly improved after 20 times of water washing, which is mainly because after infrared grafting, epoxy groups and disulfide bonds in-OH and poly 3, 4-ethylenedioxythiophene in MXene form strong hydrogen bonds and covalent bonds, so that the multifunctional fabrics have high binding fastness and good washing fastness.
Example 6
The multifunctional fabric is used as electrode material of super capacitor, electrothermal material, strain sensor, electromagnetic shielding material or antibiotic fabric.
The method specifically comprises the following steps:
manufacturing a super capacitor electrode material: example 2 preparation of a fabric sample using H2SO4the/PVA colloidal electrolyte was assembled into an all solid state supercapacitor, as shown in figure 5 a,
manufacturing an electric heating material: the size of the fabric is 1cm x 3cm, the fabric is connected with a direct current power supply, the electric heating performance is represented by an infrared imager, as shown in b in figure 5,
manufacturing an antibacterial textile: the characteristics of the antibacterial performance of the fabric refer to the third part of the evaluation of the antibacterial performance of the textile in GB/T20944.3-2008: an oscillation method for testing;
electromagnetic shielding material: the electromagnetic shielding frequency test range of the fabric is 8.2-12.4 GHz;
a strain sensor: the fabric is closely attached to the surface of the wrist, and two ends of the fabric are connected with a universal meter for carrying out sensing performance characterization.
As can be seen from fig. 5, the poly 3, 4-ethylenedioxythiophene/MXene modified cotton fabric can simultaneously have multiple functions, for example, can be used for all-solid-state supercapacitor electrodes, has a high energy density, and can be used as a flexible wearable energy source to easily light 3 LED lamps (a in fig. 5); can be used as a flexible electric heating device, and the surface temperature of the fabric can reach 193.1 ℃ under the application of 12V voltage (b in figure 5); can be used as an antibacterial textile, the bacteriostasis rate can reach as high as 99.5 percent, as shown in c in figure 5; the fabric can be used as an efficient electromagnetic shielding fabric, and the average shielding effectiveness can be as high as 36.62dB (d in figure 5) in an X wave band; can also be used as a flexible strain sensor for monitoring the movement of the human body and has better stability (e in figure 5).

Claims (10)

1. A preparation method of multifunctional fabric is characterized by comprising the following steps:
1) conducting polymer is deposited by chemical vapor deposition of fabric oxidation;
2) infrared grafting of MXene.
2. The method according to claim 1, wherein the conductive polymer in step 1) includes, but is not limited to, polyaniline, polypyrrole, poly-3 hexylthiophene, poly-3 methylthiophene, or poly-3, 4-ethylenedioxythiophene.
3. The preparation method according to claim 1 or 2, wherein the deposition conditions of the fabric oxidation chemical vapor deposition conductive polymer in the step 1) are as follows: reacting at 60-160 deg.c for 10-300 min.
4. The method of claim 1, wherein in step 1), the fabric is fixed at a pre-tension of 0.1 to 20cN before the conductive polymer is deposited by oxidative chemical vapor deposition of the fabric.
5. The preparation method according to claim 1, wherein the step 2) is specifically: the step 2) is specifically as follows: dipping the fabric treated in the step 1) in MXene dispersion liquid, adding a photoinitiator, and heating and reacting under an infrared light source to obtain the multifunctional fabric.
6. The preparation method according to claim 5, wherein the concentration of the MXene dispersion in the step 2) is 0.5 to 20 mg/mL.
7. The preparation method according to claim 5 or 6, wherein the MXene dispersion liquid in the step 2) is prepared by: adding the precursor of the transition metal carbide and the metal fluoride into a hydrochloric acid solution, uniformly stirring, carrying out hydrothermal reaction, washing, carrying out ultrasonic treatment, and centrifuging to obtain the MXene dispersion liquid.
8. The preparation method according to claim 7, wherein the hydrothermal reaction is carried out at 60-180 ℃ for 18-48 hours.
9. A multifunctional fabric prepared by the preparation method of any one of claims 1to 8.
10. The application of the multifunctional fabric prepared by the preparation method of any one of claims 1to 8, which is used for manufacturing electrode materials of supercapacitors, electrothermal materials, strain sensors, electromagnetic shielding materials or antibacterial textiles.
CN202011203965.2A 2020-11-02 2020-11-02 Multifunctional fabric and preparation method and application thereof Pending CN112323498A (en)

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CN113411918A (en) * 2021-06-08 2021-09-17 合肥工业大学 High-temperature-resistant Ti in air3C2Composite film heater
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CN114717722A (en) * 2022-02-25 2022-07-08 浙江理工大学 Preparation method of conductive hydrogel composite three-dimensional spaced hollow woven fabric sensor
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