CN115029866A - Preparation method of flexible electronic sensor composite material - Google Patents

Preparation method of flexible electronic sensor composite material Download PDF

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Publication number
CN115029866A
CN115029866A CN202210964826.4A CN202210964826A CN115029866A CN 115029866 A CN115029866 A CN 115029866A CN 202210964826 A CN202210964826 A CN 202210964826A CN 115029866 A CN115029866 A CN 115029866A
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composite material
spinning
layer
polyethylene
spinning solution
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CN115029866B (en
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岳甜甜
刘宇清
郑松明
关晋平
王丽丽
周文龙
寇婉婷
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Jiangsu Hengli Chemical Fiber Co Ltd
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Jiangsu Hengli Chemical Fiber Co Ltd
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D11/00—Other features of manufacture
    • D01D11/06—Coating with spinning solutions or melts
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43828—Composite fibres sheath-core
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838—Ultrafine fibres, e.g. microfibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/593—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives to layered webs
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/22—Polymers or copolymers of halogenated mono-olefins

Abstract

The invention relates to a preparation method of a flexible electronic sensor composite material, which comprises the steps of firstly forming a three-layer composite fiber filament through microfluidic spinning, then coating a polyethylene melt with the temperature of 85-110 ℃ on the surface of the three-layer composite fiber filament, spraying a nanofiber formed by electrostatic spinning on the three-layer composite fiber filament coated with the polyethylene melt in a double-needle opposite spraying manner when the temperature of the polyethylene melt is reduced to 50-60 ℃ to form a multilayer composite material containing the nanofiber, and finally spraying MXene conductive ink on the multilayer composite material containing the nanofiber to obtain the flexible electronic sensor composite material. According to the invention, a multilayer composite structure is formed by microfluidics, electrostatic spinning and spraying, and the flexible electronic sensor composite material finally prepared has good conductivity by mutual matching of layers, reduces the risk of electrode short circuit, and has certain stretchability, high sensitivity and stability.

Description

Preparation method of flexible electronic sensor composite material
Technical Field
The invention belongs to the technical field of textile composite materials, and relates to a preparation method of a flexible electronic sensor composite material.
Background
The micro-fluidic technology is characterized in that a principle that mutually insoluble fluids in a micro-fluidic multi-phase fluid can be mutually sheared is utilized to form multi-phase micro-nanofibers, and the requirements of high-performance textile preparation are met by mutual matching of structures among layers of the multi-phase micro-nanofibers besides the common characteristics of the nanofibers such as high specific surface area and easily fixed structure; electrospinning is one of the most efficient and versatile methods currently used to produce nanofibers by which nanofiber materials can be prepared with simple processes and excellent properties.
In recent years, a great deal of research on polymer nanocomposite-based flexible electronic sensors focuses on improving various performances of a single polymer nanocomposite-based flexible electronic sensor through conductive network construction and microstructure design, and although multifunctional and multi-signal monitoring can be achieved, the preparation process is complex and the production cost is high, so that the difficulty of the process and the requirement on the precision of equipment are increased. The invention has the patent application number of CN112225942A, and discloses a preparation method of a strain-temperature dual-response flexible electronic sensor composite material and an obtained electronic sensor and the composite material, wherein the main process comprises the steps of mixing solutions, carrying out ultrasonic treatment, carrying out freeze drying, preparing aerogel, injecting the mixed solution into the aerogel, and curing to obtain the electronic sensor composite material, and the preparation method has the advantages of complex operation process and high production cost; patent application No. CN113491509A, a method for preparing a flexible electronic sensor, comprises forming a self-supporting polypyrrole/silver film on a gas-liquid interface, and then using a patterned polydimethylsiloxane film as a flexible substrate and an encapsulation layer to construct a flexible sensor with a microstructure on the surface, wherein the flexible sensor is easy to cause a short circuit phenomenon in an electric sensing process; the patent application number is CN112710223A, a preparation method of a flexible strain sensor based on silver-coated copper powder composite gelatin hydrogel, which is a flexible strain sensor with a sandwich structure constructed based on silver-coated copper powder composite gelatin hydrogel, and the high conductivity and the sensitivity of an electronic sensor of the flexible strain sensor are still to be improved; patent application No. CN113201802A, "method for preparing tension sensing fiber, yarn, fabric and tension sensing fiber," describes the conductive material for sensor in detail, but does not describe the specific preparation device and process; patent application No. CN109341902B, a flexible pressure sensor using graphene as electrode material and a preparation method thereof, which comprises two outer flexible film layers, two electrode layers and a dielectric layer, and can not reach an ideal conductive state for interlayer recombination.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a flexible electronic sensor composite material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a flexible electronic sensor composite material comprises forming three layers of composite fiber yarns by microfluidic spinning, then coating a polyethylene melt with the temperature of 85-110 ℃ on the surface of the three-layer composite fiber (the coating quality of the polyethylene melt is 25% of that of the three-layer composite fiber), and spraying nanofiber formed by electrostatic spinning on the three-layer composite fiber coated with the polyethylene melt in a double-needle opposite spraying mode when the temperature of the polyethylene melt is reduced to 50-60 ℃ (the high temperature can influence the spinning effect and cannot achieve an ideal effect, and the polyethylene melt is arranged at 50-60 ℃ to ensure the spinning effect and realize bonding), so as to realize the compounding of the three-layer composite fiber and the nanofiber, form a multilayer composite material containing the nanofiber, and finally spraying MXene conductive ink on the multilayer composite material containing the nanofiber, so as to prepare the flexible electronic sensor composite material;
in the three-layer composite fiber yarn formed by microfluidic spinning, the core layer is made of graphene, the middle layer is made of PVDF (polyvinylidene fluoride) nano fiber or Carbon Nano Tube (CNT), and the shell layer is made of Polyurethane (PU) or graphene;
the nanofiber formed by electrostatic spinning is silk fibroin nanofiber.
As a preferable technical scheme:
according to the preparation method of the flexible electronic sensor composite material, the MXene conductive ink is sprayed on the multilayer composite material containing the nano fibers in a snare clamping mode, the MXene conductive ink can be comprehensively covered on the fibers by the aid of the method, high sensitivity is achieved, and meanwhile production cost can be saved.
According to the preparation method of the flexible electronic sensor composite material, the adopted preparation device comprises a microfluidic preparation and collection device, an electrostatic spinning device and a snare clamping and spraying device;
the microfluidic preparation and collection device comprises a coagulation bath, and a solution collection device is arranged in the coagulation bath; three microfluidic spinning needle heads which are arranged in parallel are arranged on one side of two opposite sides above the coagulating bath, and the other side of the two microfluidic spinning needle heads sequentially comprises a first transmission roller, a drying box and a second transmission roller;
the electrostatic spinning device is positioned below the second transmission roller and sequentially comprises a polyethylene collecting box, a heating box, an electrostatic spinning opposite-spraying double-needle head and a cooling collecting roller from top to bottom, wherein the polyethylene collecting box is provided with a feeding hole, and the heating box is provided with a fiber collecting hole;
the snare clamping and spraying device is positioned below the electrostatic spinning opposite-spraying double needle head and sequentially comprises an MXene ink ejector and a winding and collecting device, the MXene ink ejector and the winding and collecting device are positioned in the direction that the cooling and collecting roller is inclined at forty-five degrees downwards, the MXene ink ejector comprises a collecting and spraying pipe and a snare device, the collecting and spraying pipe is provided with a spraying needle head and a feed inlet, the snare device is provided with a porous structure and a switch joint, and the collecting and spraying pipe is connected with the snare device through the spraying needle head.
The device comprises a micro-fluidic technology, a micro-fluidic technology and a micro-fluidic technology, wherein three needles are controlled to spray nanofiber solution, and three layers of composite fiber filaments are spun under the action of a coagulating bath and a solution collecting device; then the fiber is conveyed under the action of a first conveying roller and a second conveying roller, and the fiber is processed under the action of a drying box; then the polyethylene adhesive is processed by a polyethylene collecting box and a heating box to be combined with the composite fiber yarns formed by the microfluidic spinning; then carrying out electrostatic spinning treatment on the fiber yarns in an electrostatic spinning device, and cooling the fiber yarns by a cooling collecting roller after the electrostatic spinning treatment; and finally, spraying the MXene ink in the MXene ink sprayer on the composite fiber yarns, and realizing winding and collection of the final finished product under the action of a winding and collecting device.
The preparation method of the flexible electronic sensor composite material comprises the following specific steps:
(1) respectively preparing a core layer spinning solution, a middle layer spinning solution and a shell layer spinning solution, adding the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain three-layer composite fiber filaments;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 85-110 ℃;
(3) the three-layer composite fiber obtained in the step (1) is dried by a drying box and then is transmitted to a polyethylene collecting box, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber in a melt form;
(4) when the temperature of a polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 50-60 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using an electrostatic spinning double-needle head, wherein the double-needle head is arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
(5) and (5) spraying the MXene ink in the MXene ink sprayer on the multilayer composite material containing the nano fibers formed in the step (4), and winding and collecting the formed finished product under the action of a winding and collecting device to obtain the flexible electronic sensor composite material.
According to the preparation method of the flexible electronic sensor composite material, in the step (1), the concentration of the core layer spinning solution is 1.1-2.6 wt%, the concentration of the middle layer spinning solution is 1.8-3.5 wt%, and the concentration of the shell layer spinning solution is 2.3-4.7 wt%. The core layer and the shell layer of the microfluidic spinning form electrodes, the middle layer of the material is used as a dielectric material, and the concentration of the spinning solution of the three layers is distributed in a gradient manner by changing the concentration of the spinning solution of each layer during preparation, so that the optimal matching state among the three layers is realized. Microfluidic spinning requires appropriate concentration ratios between the different layers. The shell layer is generally required to have a sufficient concentration, i.e., viscosity, to create viscous friction with the inner layer to form fibers. The concentration of the inner layer cannot be too high, otherwise the viscous friction of the shell layer is not sufficient to cause the inner layer to form fibres, and the concentration of the inner layer cannot be too low, otherwise unstable jet streams are formed.
In the preparation method of the flexible electronic sensor composite material, in the step (1), the extrusion speeds of the needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are 1.3 mL/min, 1.1 mL/min and 1.2 mL/min respectively (1)On one hand, the influence of the solution concentration is considered, so that different extrusion speeds are required to be set for the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution; on the other hand, the extrusion speed of the spinning solution of the middle layer is minimum, so that the spinning solution can form high orientation with the solution between the electrode layer as the dielectric layer, the extrusion speed of the core layer and the shell layer as the electrode layer is relatively higher, so that the stretchability of the fiber can be ensured), and the coagulating bath is 5wt% of CaCl 2 The volume ratio of the ethanol to the water is 5:1, and the flow rate in the solution collection device is set to be 100-500 muL/h.
According to the preparation method of the flexible electronic sensor composite material, the spinning solution adopted by electrostatic spinning in the step (4) is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 10-15 wt%.
According to the preparation method of the flexible electronic sensor composite material, the electrostatic spinning process parameters in the step (4) are as follows: the spinning voltage is 12kV, and the feeding speed is 0.6-1.5 ml/h.
According to the preparation method of the flexible electronic sensor composite material, MXene ink in the step (5) is prepared by compounding the sheet layer MXene under the action of deionized water, and the jet speed of the ink jet device is 2-5 m/min.
According to the preparation method of the flexible electronic sensor composite material, the highest sensitivity of the flexible electronic sensor composite material is 0.87-0.96 KPa -1 The maximum cyclic fluctuation value is 1.47-2.32M omega, and the relative resistance variation is 13.5-14.8%.
The principle of the invention is as follows:
the invention relates to a flexible electronic sensor, belonging to a capacitance type pressure sensor, which uses capacitance as a sensitive element to convert the measured pressure into the pressure sensor with the capacitance value changed, and mainly comprises an electrode and a dielectric layer. The method has the characteristics of low input energy, high dynamic response, small natural effect and good environmental adaptability. The capacitance type pressure sensor generally adopts a circular metal film or a metal-plated film (namely, the composite fiber material designed by the invention) as one electrode of a capacitor, and when the film is deformed by sensing pressure, the capacitance formed between the film and a fixed electrode is changed.
The invention mainly combines the micro-fluidic technology, electrostatic spinning and spraying, realizes high stability, high sensitivity and high stretchability through the interlayer composite relationship, and meets the requirement of the biocompatibility of the flexible electronic sensor. The fiber prepared by micro-fluidic is a three-layer composite structure fiber with high orientation degree prepared by in-situ assembly by utilizing an interface complexation effect, and the orientation degree of the fiber is improved while the special structure is satisfied, so that the mechanical property of the fiber is enhanced, and the practical performance of the flexible electronic sensor is improved. The core layer graphene of the three-layer composite fiber yarn formed by microfluidic spinning is used as a base material, the conductivity is good, the PVDF nanofiber or the Carbon Nanotube (CNT) in the middle layer can achieve a good dielectric effect, and the polyurethane or the graphene in the shell layer can provide certain tensile property, so that a stable and reliable conductive network can be formed under the cooperation of the layers; the silk fibroin nanofiber is selected in the electrostatic spinning process, so that the sensor has biocompatibility and degradability, appropriate reaction is caused at a specific part of an organism, and the application requirement of the flexible electronic sensor is met; the two-dimensional transition metal carbonitride MXene has the advantages of large specific surface area, high conductivity, good electrochemical performance and the like, and can ensure high sensitivity in the sensing process.
Polyethylene adhesive is added in the process of compounding three-layer composite fiber yarns formed by microfluidic spinning and nano-fibers formed by electrostatic spinning, so that efficient compounding is realized, short circuit of a circuit is avoided, and orderly transmission of the circuit is ensured; and MXene is sprayed on the surface of the composite fiber, so that the sensitivity can be improved.
The heating temperature of the adhesive polyethylene is 85-110 ℃, and the adhesive polyethylene is bonded with the nanofiber formed by electrostatic spinning after being cooled to 50-60 ℃, so that the performance of the nanofiber cannot be influenced, and the double-adhesion effect is achieved. On one hand, the polyethylene hot-melt powder is firstly bonded with the three layers of composite fibers through high-temperature melting, and then bonded with the nano fibers in the cooling process to serve as a bonding substance of the middle layer; on the other hand, the electrostatic theory suggests that the adhesion is caused by the presence of an electric double layer in the interface between the adhesive and the adherend, and that the electrostatic attraction between the conductive fibers used in the micro-fluidic technology and the electrospun nanofibers is caused, thereby forming an electrostatic force.
Has the advantages that:
compared with the prior art, the invention has the beneficial effects that:
on one hand, a multilayer composite structure is formed by microfluidics, electrostatic spinning and spraying, and finally the flexible sensor has good conductivity through mutual matching of layers, so that the risk of short circuit of electrodes is reduced, and the flexible sensor has certain stretchability, high sensitivity and stability.
The flexible electronic sensor is generally formed by combining a conductive material and an elastomer polymer or other flexible/stretchable substrates, in the microfluidic technology, core layer graphene has good conductivity, a PVDF nanofiber or a Carbon Nanotube (CNT) in the middle layer can achieve the function of good circuit transmission, and Polyurethane (PU) or graphene in the shell layer can provide certain stretchable performance, so that a stable and reliable conductive network can be formed under the cooperation of three layers;
selecting silk fibroin nanofiber in the electrostatic spinning process can enable the sensor to have biocompatibility and degradability, so that appropriate reaction is caused at a specific part of an organism, and application requirements are met;
and the two-dimensional transition metal carbonitride MXene has the advantages of large specific surface area, high conductivity, good electrochemical performance and the like, and can ensure high sensitivity in the sensing process.
On the other hand, the addition of the adhesive polyethylene is beneficial to the effective bonding between fiber layers in a high-temperature molten state, and the circuit transmission effect is ensured.
The bonding principle is as follows: the first stage is that polyethylene diffuses to the surface of the fiber to be bonded by means of Brownian motion to make polar groups or chain links of two interfaces approach each other, and in the process, the temperature rise is favorable for strengthening Brownian motion. When the distance between the polyethylene and the adherend molecules reaches a certain value, the interface molecules generate mutual attraction, so that the distance between the molecules is further shortened to be in the maximum stable state.
The bonding principle is combined, so that the bonded micro-fluidic spinning fiber and electrostatic spinning nanofiber can be tightly bonded, an electrode can be fully chemically reduced under the condition of not damaging a fiber structure, a good contact interface is formed, the risk of short circuit is avoided, a continuous conductive process is formed, the tensile strength is favorably improved, and the effect achieved by using the adhesive is not found in the prior patent.
Drawings
FIG. 1 is an apparatus and process for preparing a flexible electronic sensor composite;
FIG. 2 is a diagram of a finished product for making a flexible electronic sensor composite;
FIG. 3 is a schematic view of a microfluidic device;
FIG. 4 is an enlarged schematic view of the MXene ink jetting process;
wherein, 1, a microfluidic spinning needle head; 2. a coagulation bath; 3. a solution collection device; 4. a first transfer roller; 5. a drying oven; 6. a second transfer roller; 7. a polyethylene collection box; 8. a heating box; 9. electrostatic spinning opposite-spraying double needles; 10. cooling the collection roller; 11. MXene ink jet; 12. a winding and collecting device; 101. a microfluidic core structure; 102. a microfluidic interlayer structure; 103. a microfluidic shell structure; 110. MXene printing ink; 701. a polyethylene binder; 901. electrostatic nanofibrous filaments.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
A preparation device of a flexible electronic sensor composite material is shown in figure 1 and comprises a microfluidic preparation and collection device, an electrostatic spinning device and a snare clamping and spraying device;
the microfluidic preparation collecting device comprises a coagulation bath 2, a solution collecting device 3 is arranged in the coagulation bath 2, three microfluidic spinning needle heads 1 which are arranged in parallel are arranged on one side of two opposite sides above the coagulation bath 2, the distance between every two adjacent microfluidic spinning needle heads 1 is 5cm, and the other side of the microfluidic preparation collecting device sequentially comprises a first transmission roller 4, a drying box 5 and a second transmission roller 6;
the electrostatic spinning device is positioned below the second transmission roller 6 and sequentially comprises a polyethylene collecting box 7, a heating box 8, an electrostatic spinning opposite-spraying double-needle head 9 and a cooling collecting roller 10 from top to bottom, wherein the polyethylene collecting box 7 is provided with a feeding hole, and the heating box 8 is provided with a fiber collecting hole;
the snare clamping and spraying device is located below the electrostatic spinning double-needle 9 and sequentially comprises an MXene ink ejector 11 and a winding and collecting device 12, the MXene ink ejector 11 and the winding and collecting device 12 are located in the cooling and collecting roller 10 in the direction inclined by forty-five degrees downwards, as shown in the figure 4, the MXene ink ejector 11 comprises a collecting and spraying tube and a snare device, the collecting and spraying tube is provided with a spraying needle head and a feeding hole, the snare device is provided with a porous structure and a switch joint, and the collecting and spraying tube is connected with the snare device through the spraying needle head.
The specific process flow for preparing the flexible electronic sensor composite material by adopting the device comprises the following steps: controlling three microfluidic spinning needles 1 to spray nanofiber solutions by a microfluidic technology, and spinning to obtain three-layer composite fiber filaments under the action of a coagulating bath 2 and a solution collecting device 3, wherein specifically, as shown in fig. 3, the microfluidic spinning needles 1 are transversely transmitted by a transmission pipe and then vertically connected with the solution collecting device downwards, the solution collecting device comprises three equidistant solution collecting holes which are positioned in the same plane, the nanofiber solutions sprayed by the microfluidic spinning needles 1 respectively enter the three solution collecting holes, and three-layer convergence is realized at a bell mouth, and due to different concentrations and different flow rates of spinning solutions corresponding to different needles, interlayer differences are caused, and the three-layer composite fiber filaments as shown in fig. 2 are finally formed; then the fiber is conveyed under the action of a first conveying roller 4 and a second conveying roller 6, and the fiber is processed under the action of a drying box 5 in the conveying process; then the polyethylene adhesive is processed by a polyethylene collecting box 7 and a heating box 8, so that the polyethylene adhesive is combined with three layers of composite fiber yarns formed by microfluidic spinning; then electrostatic spinning treatment is carried out on the fiber yarns in an electrostatic spinning device, and the fiber yarns are cooled by a cooling collecting roller 10 after the electrostatic spinning treatment; and finally, spraying the MXene ink in the MXene ink sprayer 11 on the multilayer composite fiber yarn, and realizing winding and collection of the final finished product under the action of a winding and collecting device 12.
The MXene ink adopted by the invention has the brand number of BK2020032601-01, and is produced by Suzhou Kai Sen New Material science and technology Co.
The electrochemical performance was measured using an electrochemical workstation model CHI660E, and the specific operation was as follows:
cutting different composite materials into equal weight, adhering the materials on a titanium sheet by using silver adhesive, and clamping the titanium sheet on an electrode clamp to be used as a working electrode; the platinum sheet is used as a counter electrode, the reference electrode is an Ag/AgCl electrode, and a simple flexible electronic sensor assembly is manufactured;
(1) the highest sensitivity is as follows: with 1 mol L -1 H 2 SO 4 The test method is characterized in that the test method is an electrolyte, the voltage window is 0V-0.8V, the frequency range is 0.01 Hz-100 KHz, the test amplitude of an electrochemical impedance spectrum is 5mV, and the highest sensitivity of the flexible electronic sensor composite material can be tested according to a sensitivity definition formula of a sensor:
Figure 236767DEST_PATH_IMAGE001
；
wherein the content of the first and second substances,Sindicating the sensitivity (kPa) -1 ），ΔCIn order to be the amount of change in capacitance,C 0 for the initial capacitance (pF) when no pressure is applied,Pindicates the applied pressure (kPa),ɛ e is the effective dielectric constant of the materialɛ e In order to change the effective dielectric constant by an amount,dthe relative distance between two polar platesdThe change of the relative distance of the two polar plates;
(2) maximum wave of circulationDynamic value: cyclic stability of coaxial fibrous supercapacitors measured by constant current charging and discharging (GCD) at 4 mA cm -2 The current density of the flexible electronic sensor composite material is evaluated for 10000 cycles, and the maximum cycle fluctuation value of the flexible electronic sensor composite material is obtained through testing;
(3) relative resistance change amount: fixing one end of the flexible electronic sensor, stretching the other end along the axial direction of the flexible strain sensor, and setting the strain to be 200%, thereby measuring the relative resistance variation (delta R/R) of the composite material of the flexible electronic sensor 0 ）。
Example 1
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing 1.6wt% graphene spinning solution (DMF as a solvent) as a core layer spinning solution, preparing 2.5wt% PVDF spinning solution (DMF as a solvent) as an intermediate layer spinning solution, preparing 3.6wt% graphene spinning solution (DMF as a solvent) as a shell layer spinning solution, respectively adding the core layer spinning solution, the intermediate layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain three-layer composite fiber filaments;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 The volume ratio of the ethanol to the water is 5:1, and the flow speed in the solution collecting device is set to be 300 mu L/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 95 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly transmitted to a drying box through a first transmission roller, is dried in the drying box and then is transmitted to a polyethylene collecting box under the action of a second transmission roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a fused mass mode;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber yarn;
(4) when the temperature of the polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 50 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using a dual-spraying needle by adopting electrostatic spinning, wherein the dual needles are arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 15 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 1.2 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a manner of snare clamping, and then winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet device is 2 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nanofibers and MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nanofibers; the multilayer composite material containing the nano-fiber comprises three layers of composite fiber filaments and electrostatic nano-fiber filaments 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell structure 103, wherein the microfluidic shell structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.87 KPa -1 Maximum fluctuation of 1.47 M.OMEGA.The resistance change amount was 13.7%.
Comparative example 1
The preparation method of the flexible electronic sensor composite material is basically the same as that in example 1, except that spinning solutions (with DMF as a solvent) of graphene with the concentration of 1.6wt% are added into three microfluidic spinning needle heads in the step (1).
The maximum sensitivity of the prepared flexible electronic sensor composite material is 0.64 KPa -1 The maximum fluctuation value of the cycle was 3.06 MOmega, and the relative resistance change amount was 15.2%.
Comparing comparative example 1 with example 1, it can be seen that the highest sensitivity of example 1 is significantly higher than that of comparative example 1, the maximum fluctuation value of the cycle is significantly lower than that of comparative example 1, and the relative resistance change of example 1 is lower than that of comparative example 1, because the PVDF used as the interlayer material in the microfluidic spinning process in example 1 generates a thin and highly wrinkled interface area, thereby facilitating circuit transmission, while the graphene material used in comparative example 1 has relatively poor circuit transmission.
Example 2
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing a graphene spinning solution (with a solvent of DMF) with a concentration of 2.3wt% as a core layer spinning solution, a carbon nanotube spinning solution (with a solvent of sodium dodecyl sulfate) with a concentration of 1.9wt% as an intermediate layer spinning solution, a polyurethane spinning solution (with a solvent of DMF) with a concentration of 4.5wt% as a shell layer spinning solution, respectively adding the core layer spinning solution, the intermediate layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain a three-layer composite fiber;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 Ethanol/water mixed solution (ethanol and water in a volume ratio of 5: 1), stream in the solution collecting meansSetting the speed to 200 muL/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 85 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly conveyed to a drying box through a first conveying roller, is dried in the drying box and then is conveyed to a polyethylene collecting box under the action of a second conveying roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a melt form;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber;
(4) when the temperature of the polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 50 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using a dual-spraying needle by adopting electrostatic spinning, wherein the dual needles are arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 15 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 1.5 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a manner of snare clamping, and then winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet device is 2 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nanofibers and MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nanofibers; the multilayer composite material containing the nano-fiber comprises three layers of composite fiber filaments and electrostatic nano-fiber filaments 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell layer structure 103, wherein the microfluidic shell layer structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.96 KPa -1 The maximum cycle fluctuation value was 2.32M Ω, and the relative resistance change amount was 13.5%.
Comparative example 2
A preparation method of a flexible electronic sensor composite material basically comprises the same steps as example 2, except that no polyethylene adhesive is added.
The maximum sensitivity of the prepared flexible electronic sensor composite material is 0.43KPa -1 The maximum fluctuation value of the cycle was 3.56M Ω, and the relative resistance change amount was 16.7%.
Comparing comparative example 2 with example 2, it can be seen that the highest sensitivity of example 2 is significantly higher than that of comparative example 2, and the maximum fluctuation value of the cycle and the relative resistance change amount are significantly lower than those of comparative example 2, because the polyethylene binder is added in example 2, so that the interlayer connection is more compact, thereby facilitating the electronic sensing response, and the response sensitivity is relatively higher and the cycle stability is better.
Example 3
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing 1.1wt% graphene spinning solution (DMF as a solvent) as a core layer spinning solution, 3.5wt% PVDF spinning solution (DMF as a solvent) as an intermediate layer spinning solution, 2.3wt% polyurethane spinning solution (DMF as a solvent) as a shell layer spinning solution, respectively adding the core layer spinning solution, the intermediate layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain three-layer composite fiber filaments;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 The volume ratio of the ethanol to the water is 5:1, and the flow rate in the solution collection device is set to be 100 muL/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 110 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly conveyed to a drying box through a first conveying roller, is dried in the drying box and then is conveyed to a polyethylene collecting box under the action of a second conveying roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a melt form;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber;
(4) when the temperature of the polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 50 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using a dual-spraying needle by adopting electrostatic spinning, wherein the dual needles are arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 10 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 0.6 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a snaring clamping mode, and winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet device is 5 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nano-fibers and an MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nano-fibers; the multilayer composite material containing the nano-fibers comprises three layers of composite fiber yarns and electrostatic nano-fiber yarns 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell layer structure 103, wherein the microfluidic shell layer structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.88 KPa -1 The maximum fluctuation value of the cycle was 1.48M Ω, and the relative resistance change amount was 13.6%.
Example 4
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing 2.6wt% graphene spinning solution (DMF as a solvent) as a core layer spinning solution, 1.8wt% PVDF spinning solution (DMF as a solvent) as a middle layer spinning solution, 4.7wt% polyurethane spinning solution (DMF as a solvent) as a shell layer spinning solution, respectively adding the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain three layers of composite fiber yarns;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 The volume ratio of the ethanol to the water is 5:1, and the flow rate in the solution collection device is set to be 200 muL/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 105 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly conveyed to a drying box through a first conveying roller, is dried in the drying box and then is conveyed to a polyethylene collecting box under the action of a second conveying roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a melt form;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber;
(4) when the temperature of the polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 60 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using a dual-spraying needle by adopting electrostatic spinning, wherein the dual needles are arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 12 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 1.2 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a snaring clamping mode, and winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet device is 5 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nano-fibers and an MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nano-fibers; the multilayer composite material containing the nano-fibers comprises three layers of composite fiber yarns and electrostatic nano-fiber yarns 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell structure 103, wherein the microfluidic shell structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.91 KPa -1 The maximum fluctuation value of the cycle was 1.52 M.OMEGA., and the relative resistance change amount was 14.8%.
Example 5
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing 1.8wt% graphene spinning solution (with a solvent of DMF) as a core layer spinning solution, preparing 2wt% carbon nanotube spinning solution (with a solvent of sodium dodecyl sulfate) as a middle layer spinning solution, preparing 4wt% graphene spinning solution (with a solvent of DMF) as a shell layer spinning solution, respectively adding the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain three-layer composite fiber filaments;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 The volume ratio of the ethanol to the water is 5:1, and the flow rate in the solution collection device is set to be 300 muL/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 100 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly transmitted to a drying box through a first transmission roller, is dried in the drying box and then is transmitted to a polyethylene collecting box under the action of a second transmission roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a fused mass mode;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber;
(4) when the temperature of the polyethylene melt coated on the surface of the three-layer composite filament is reduced to 55 ℃, carrying out electrostatic spinning treatment on the three-layer composite filament coated with the polyethylene melt by using double spraying needles by adopting electrostatic spinning, wherein the double needles are arranged oppositely in parallel, and then cooling the three-layer composite filament by using a cooling collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 15 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 1 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a snaring clamping mode, and winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet device is 3 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nano-fibers and an MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nano-fibers; the multilayer composite material containing the nano-fibers comprises three layers of composite fiber yarns and electrostatic nano-fiber yarns 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell structure 103, wherein the microfluidic shell structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.9 KPa -1 The maximum fluctuation value of the cycle was 1.55M Ω, and the relative resistance change amount was 14.3%.
Example 6
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing a graphene spinning solution (with a solvent of DMF) with a concentration of 2wt% as a core layer spinning solution, a carbon nano tube spinning solution (with a solvent of sodium dodecyl sulfate) with a concentration of 3wt% as a middle layer spinning solution, a graphene spinning solution (with a solvent of DMF) with a concentration of 3wt% as a shell layer spinning solution, respectively adding the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain three layers of composite fiber yarns;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 The volume ratio of the ethanol to the water is 5:1, and the flow rate in the solution collection device is set to be 400 mu L/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 95 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly conveyed to a drying box through a first conveying roller, is dried in the drying box and then is conveyed to a polyethylene collecting box under the action of a second conveying roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a melt form;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber;
(4) when the temperature of the polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 50 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using a dual-spraying needle by adopting electrostatic spinning, wherein the dual needles are arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 15 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 0.8 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a snaring clamping mode, and winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet device is 3 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nano-fibers and an MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nano-fibers; the multilayer composite material containing the nano-fibers comprises three layers of composite fiber yarns and electrostatic nano-fiber yarns 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell layer structure 103, wherein the microfluidic shell layer structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.89 KPa -1 The maximum cycle fluctuation value was 2.21 M.OMEGA.and the relative resistance change amount was 14.6%.
Example 7
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing a graphene spinning solution (with a solvent of DMF) with a concentration of 2wt% as a core layer spinning solution, a carbon nanotube spinning solution (with a solvent of sodium dodecyl sulfate) with a concentration of 2.2wt% as an intermediate layer spinning solution, a graphene spinning solution (with a solvent of DMF) with a concentration of 2.8wt% as a shell layer spinning solution, respectively adding the core layer spinning solution, the intermediate layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain a three-layer composite fiber yarn;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 The volume ratio of the ethanol to the water is 5:1, and the flow rate in the solution collection device is set to be 500 muL/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 90 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly conveyed to a drying box through a first conveying roller, is dried in the drying box and then is conveyed to a polyethylene collecting box under the action of a second conveying roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a melt form;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber yarn;
(5) when the temperature of the polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 60 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using a dual-spraying needle by adopting electrostatic spinning, wherein the dual needles are arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 12 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 1 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a snaring clamping mode, and winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet ejector is 4 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nano-fibers and an MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nano-fibers; the multilayer composite material containing the nano-fibers comprises three layers of composite fiber yarns and electrostatic nano-fiber yarns 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell layer structure 103, wherein the microfluidic shell layer structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.92 KPa -1 The maximum cycle fluctuation value was 2.27M Ω, and the relative resistance change amount was 13.9%.
Example 8
A preparation method of a flexible electronic sensor composite material adopts the preparation device of the flexible electronic sensor composite material, and comprises the following specific steps:
(1) preparing a graphene spinning solution (with a solvent of DMF) with a concentration of 2.3wt% as a core layer spinning solution, a carbon nanotube spinning solution (with a solvent of sodium dodecyl sulfate) with a concentration of 2.8wt% as an intermediate layer spinning solution, and a graphene spinning solution (with a solvent of DMF) with a concentration of 3.8wt% as a shell layer spinning solution, respectively adding the core layer spinning solution, the intermediate layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain a three-layer composite fiber;
wherein the extrusion speeds of needles corresponding to the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution are respectively 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, and the coagulating bath contains 5wt% of CaCl 2 The ethanol/water mixed solution (the volume ratio of ethanol to water is 5: 1) is collectedThe flow rate in the device was set to 300 μ L/h;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 85 ℃;
(3) the three-layer composite fiber yarn obtained in the step (1) is firstly conveyed to a drying box through a first conveying roller, is dried in the drying box and then is conveyed to a polyethylene collecting box under the action of a second conveying roller, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber yarn in a melt form;
wherein the coating mass of the polyethylene melt is 25% of that of the three-layer composite fiber yarn;
(4) when the temperature of the polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 55 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using a dual-spraying needle by adopting electrostatic spinning, wherein the dual needles are arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
wherein, the spinning solution adopted by electrostatic spinning is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water (the molar ratio of the calcium chloride to the formic acid to the water is 1:2:8) and magnetically stirring for 12 hours at room temperature, and the concentration of the silk fibroin in the spinning solution is 10 wt%; the electrostatic spinning process parameters are as follows: the spinning voltage is 12kV, and the feeding speed is 1.2 ml/h;
the ratio of the nano-fiber in the multi-layer composite material containing the nano-fiber is 30 wt%;
(5) spraying MXene ink in the MXene ink ejector on the multilayer composite material containing the nano fibers formed in the step (4) in a manner of snare clamping, and then winding and collecting under the action of a winding and collecting device to obtain a flexible electronic sensor composite material;
wherein the MXene ink is prepared by compounding a sheet layer MXene under the action of deionized water, and the jet speed of the ink jet ejector is 4 m/min;
as shown in fig. 2, the prepared flexible electronic sensor composite material comprises a multilayer composite material containing nano-fibers and an MXene ink 110 coated on the surface of the multilayer composite material, wherein the MXene ink accounts for 10wt% of the multilayer composite material containing nano-fibers; the multilayer composite material containing the nano-fibers comprises three layers of composite fiber yarns and electrostatic nano-fiber yarns 901; the three-layer composite fiber wire comprises a microfluidic core layer structure 101, a microfluidic middle layer structure 102 and a microfluidic shell layer structure 103, wherein the microfluidic shell layer structure 103 is bonded with the electrostatic nanofiber wire 901 through a polyethylene adhesive 701;
the maximum sensitivity of the prepared flexible electronic sensor composite material is 0.88 KPa -1 The maximum fluctuation value of the cycle was 1.95 M.OMEGA., and the relative resistance change amount was 14.1%.

Claims (10)

1. A preparation method of a flexible electronic sensor composite material is characterized by comprising the following steps: firstly, forming a three-layer composite fiber yarn through microfluidic spinning, then coating a polyethylene melt with the temperature of 85-110 ℃ on the surface of the three-layer composite fiber yarn, spraying a nanofiber formed through electrostatic spinning on the three-layer composite fiber yarn coated with the polyethylene melt in a double-needle opposite spraying mode when the temperature of the polyethylene melt is reduced to 50-60 ℃ to form a multilayer composite material containing the nanofiber, and finally spraying MXene conductive ink on the multilayer composite material containing the nanofiber to prepare the flexible electronic sensor composite material;
in the three-layer composite fiber yarn formed by microfluidic spinning, the core layer is made of graphene, the middle layer is made of PVDF (polyvinylidene fluoride) nano fibers or carbon nano tubes, and the shell layer is made of polyurethane or graphene;
the nanofiber formed by electrostatic spinning is silk fibroin nanofiber.
2. The method as claimed in claim 1, wherein MXene conductive ink is sprayed on the multilayered composite material containing nanofibers by means of snare clamping.
3. The method for preparing the flexible electronic sensor composite material according to claim 2, wherein the adopted preparation devices comprise a microfluidic preparation and collection device, an electrostatic spinning device and a snare clamping and spraying device;
the microfluidic preparation and collection device comprises a coagulation bath, and a solution collection device is arranged in the coagulation bath; three microfluidic spinning needle heads which are arranged in parallel are arranged on one side of two opposite sides above the coagulating bath, and the other side of the two microfluidic spinning needle heads sequentially comprises a first transmission roller, a drying box and a second transmission roller;
the electrostatic spinning device is positioned below the second transmission roller and sequentially comprises a polyethylene collecting box, a heating box, an electrostatic spinning opposite-spraying double-needle head and a cooling collecting roller from top to bottom, wherein the polyethylene collecting box is provided with a feeding hole, and the heating box is provided with a fiber collecting hole;
the snare clamping and spraying device is positioned below the electrostatic spinning opposite-spraying double needle head and sequentially comprises an MXene ink ejector and a winding and collecting device, the MXene ink ejector and the winding and collecting device are positioned in the direction that the cooling and collecting roller is inclined at forty-five degrees downwards, the MXene ink ejector comprises a collecting and spraying pipe and a snare device, the collecting and spraying pipe is provided with a spraying needle head and a feed inlet, the snare device is provided with a porous structure and a switch joint, and the collecting and spraying pipe is connected with the snare device through the spraying needle head.
4. The preparation method of the flexible electronic sensor composite material according to claim 3, characterized by comprising the following specific steps:
(1) respectively preparing a core layer spinning solution, a middle layer spinning solution and a shell layer spinning solution, adding the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution into three microfluidic spinning needles, spraying a composite spinning solution, and spinning under the action of a coagulating bath and a solution collecting device to obtain three-layer composite fiber filaments;
(2) adding polyethylene into a polyethylene collecting box, and heating the polyethylene in the polyethylene collecting box through a heating box at the heating temperature of 85-110 ℃;
(3) the three-layer composite fiber obtained in the step (1) is dried by a drying box and then is transmitted to a polyethylene collecting box, and polyethylene in the polyethylene collecting box is coated on the surface of the three-layer composite fiber in a melt form;
(4) when the temperature of a polyethylene melt coated on the surface of the three-layer composite fiber is reduced to 50-60 ℃, carrying out electrostatic spinning treatment on the three-layer composite fiber coated with the polyethylene melt by using an electrostatic spinning double-needle head, wherein the double-needle head is arranged oppositely in parallel, and then cooling the three-layer composite fiber by using a cooling and collecting roller to form a multi-layer composite material containing nano fibers;
(5) and (3) spraying the MXene ink in the MXene ink sprayer on the multilayer composite material containing the nanofibers formed in the step (4), and winding and collecting under the action of a winding and collecting device to obtain the flexible electronic sensor composite material.
5. The preparation method of the flexible electronic sensor composite material according to claim 4, wherein in the step (1), the concentration of the core layer spinning solution is 1.1-2.6 wt%, the concentration of the middle layer spinning solution is 1.8-3.5 wt%, and the concentration of the shell layer spinning solution is 2.3-4.7 wt%.
6. The method for preparing a flexible electronic sensor composite material as claimed in claim 4, wherein the core layer spinning solution, the middle layer spinning solution and the shell layer spinning solution in step (1) are extruded at a needle head extrusion speed of 1.3 mL/min, 1.1 mL/min and 1.2 mL/min, respectively, and the coagulation bath is 5wt% CaCl 2 The flow rate in the solution collection device is set to be 100-500 mu L/h.
7. The preparation method of the flexible electronic sensor composite material as claimed in claim 4, wherein the spinning solution adopted in the electrostatic spinning in the step (4) is prepared by dissolving silk fibroin in a mixed solution of calcium chloride, formic acid and water and magnetically stirring for 12h at room temperature, and the concentration of the silk fibroin in the spinning solution is 10-15 wt%.
8. The method for preparing the flexible electronic sensor composite material according to claim 4, wherein the electrostatic spinning in the step (4) comprises the following process parameters: the spinning voltage is 12kV, and the feeding speed is 0.6-1.5 ml/h.
9. The method as claimed in claim 4, wherein the MXene ink in step (5) is prepared by compounding MXene sheets under the action of deionized water, and the jet speed of the ink jet is 2-5 m/min.
10. The method of claim 1, wherein the maximum sensitivity of the flexible electronic sensor composite is 0.87 to 0.96 KPa -1 The maximum cyclic fluctuation value is 1.47-2.32 MOmega, and the relative resistance variation is 13.5-14.8%.
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