CN111719212B - Preparation method of flexible graphene conductive yarn capable of being woven - Google Patents
Preparation method of flexible graphene conductive yarn capable of being woven Download PDFInfo
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- CN111719212B CN111719212B CN202010032663.7A CN202010032663A CN111719212B CN 111719212 B CN111719212 B CN 111719212B CN 202010032663 A CN202010032663 A CN 202010032663A CN 111719212 B CN111719212 B CN 111719212B
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties
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- 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
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0046—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by coagulation, i.e. wet electro-spinning
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
Abstract
The invention provides a preparation method of flexible braided graphene conductive yarns, which is characterized in that a polymer spinning solution is prepared from a graphene oxide dispersion liquid with DMF (dimethyl formamide) and the like as solvents, and the graphene oxide dispersion liquid is used as a receiving and coagulating bath through a wet electrostatic spinning method. And (3) drawing and twisting the nanofibers deposited in the coagulating bath to form graphene oxide layer coated nanofiber yarns, and further reducing the graphene oxide layer coated nanofiber yarns by hydrazine hydrate to obtain the conductive graphene/nanofiber yarns. The average diameter of the nano-fiber is about 150nm, the diameter of the nano-fiber yarn is about 250 mu m, the porosity is high, the comparative area is large, and the mechanical property is good. The conductivity is about 80S/cm, and the conductive material has good conductive capability. The yarn has flexibility, overcomes the defect that a film material cannot be directly used in a fabric, and provides an excellent electrode material for the flexibility and the wearability of an electronic device.
Description
Technical Field
The invention belongs to the field of conductive fiber materials, relates to a preparation method of flexible braided graphene conductive yarns, and particularly relates to continuous twisted graphene/nanofiber conductive yarns obtained by combining wet electrostatic spinning and hydrazine hydrate reduction, which can be used as electrode materials of electronic devices and applied to flexible wearable equipment.
Background
In recent years, the demand of society for energy is higher and higher due to rapid development, and among a plurality of energy sources, electric energy cannot cause any pollution in the using process. Along with the gradual increase of the demand of electric energy, the power generation device and the electric storage device are increased day by day, and the electrode material with high stability and high performance has great market demand. The graphene has excellent optical, electrical and mechanical properties, and has good application prospects in the field of electric heating. In addition, with the development of society and the pursuit of human beings for convenient intelligent wearable, the application of the electronic device flexibility to wearable equipment has attracted extensive attention.
In the prior research, most of the prepared two-dimensional thin-film electrode materials are difficult to be combined in fabrics or clothes. In contrast to two-dimensional planar materials, fibers or yarns may be woven and knitted as part of a fabric. The nanofiber has many applications in the aspect of energy storage due to the characteristics of small size, large specific surface area, high porosity and the like. The yarn twisted by adopting the nano-fiber not only retains the excellent characteristics of the fiber, but also has good mechanical property and knittability.
Disclosure of Invention
Aiming at the limitation of application of a wearable device made of a two-dimensional planar electrode material, the invention provides a preparation method of a flexible braided graphene conductive yarn, which overcomes the defects that a film cannot be produced in batch and cannot be directly used in a fabric. The continuous graphene conductive yarn has the advantages that fibers in the continuous graphene conductive yarn are oriented along a yarn axis, and graphene is wrapped from the inner layer to the outer layer, so that the continuous graphene conductive yarn has good electrical, thermal and acoustic conductivity, and can be widely applied to the fields of nano cables, electronic devices and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of flexible braided graphene conductive yarns comprises the following steps: carrying out wet electrostatic spinning on a polymer spinning solution to obtain continuous twisted graphene oxide/nanofiber composite yarns, collecting the graphene oxide/nanofiber yarns by using a graphene oxide aqueous solution as a receiving coagulation bath and adopting a twisting winding device, and carrying out thermal reduction on the prepared yarns by using a hydrazine hydrate solution to obtain flexible braided graphene/nanofiber conductive yarns; the method comprises the following specific steps:
(1) adding graphene oxide powder into an organic solvent, and performing ultrasonic dispersion for 6-48h to obtain a graphene oxide dispersion liquid;
(2) adding graphene oxide powder into deionized water, and performing ultrasonic dispersion for 10-48h to obtain a coagulation bath for wet electrostatic spinning;
(3) adding the dried high polymer powder into the graphene oxide dispersion liquid obtained in the step (1), stirring for 6-24h on a magnetic stirrer, heating at 50-95 ℃ in the stirring process, and preparing high polymer spinning solution with the mass fraction of 8% -25%;
(4) performing wet electrostatic spinning by using the high polymer spinning solution obtained in the step (3), wherein spinning equipment mainly comprises a liquid accumulator, a liquid supply pump, a receiving device, a twisting and winding device and a high-pressure power sending device, the receiving device adopts a groove-shaped receiving plate for receiving, the length of the groove-shaped receiving plate is 10-70cm, the width of the groove-shaped receiving plate is 5-30cm, the obtained nano fibers are deposited in a graphene oxide coagulation bath, and graphene oxide/nano fiber yarns are obtained after twisting;
(5) and reducing the graphene oxide/nanofiber yarns in a hydrazine hydrate steam environment to obtain the graphene/nanofiber conductive yarns.
The graphene oxide is in a single-layer sheet shape, the thickness is 0.2-2.0nm, the sheet diameter is 0.2-10.0 mu m, and the specific surface area is 500-2000m2/g。
Further, the organic solvent in the step (1) comprises N-N dimethylformamide, tetrahydrofuran or acetone.
Further, the mass ratio of the graphene oxide to the organic solvent in the step (1) is (1.0-10.0): (20.0-200.0).
Further, the mass ratio of the graphene oxide to the deionized water in the step (2) is (1.0-20.0): (500.0-2000.0).
Further, the high polymer in the step (2) is a high polymer comprehensively suitable for an electrostatic spinning method, and the molecular weight of the high polymer is 10000-1000000; the solvent may be polyacrylonitrile, polyurethane, polyvinylidene fluoride, polyimide, etc., and is selected according to the kind of the polymer.
Further, when the electrostatic spinning device in the step (4) works, the voltage of the high-voltage generator is 0-50 KV; the transverse distance from the nozzle to the groove-shaped receiving plate is 5-20cm, and the longitudinal distance is 10-20 cm; the nanofiber bundle at one end is led out in the spinning process and drawn through a twisting device, and twisted yarns are wound on a rotary collecting roller. The diameter of the nano-fiber is 100-300nm, and the diameter of the yarn is 50-1000 μm.
Further, the mass concentration of the hydrazine hydrate solution in the step (5) is 30-60%, and the heating temperature is 60-100 ℃.
The conductivity of the flexible braided graphene conductive yarn prepared by the preparation method is 5-150S/cm, the tensile breaking strength is 5-100MPa, and the flexible braided graphene conductive yarn can be used as a flexible electrode material of an electronic device and applied to flexible wearable equipment.
Compared with the existing preparation method of the conductive yarn, the preparation method has the following advantages:
(1) the graphene is used as a main substrate material, has excellent optical, electrical and mechanical properties, can effectively improve the migration of electrons and the output of electric energy, and can obtain good comprehensive properties when being used as a conductive material. The conductive yarn has good flexibility, a large amount of graphene is doped, the breaking strength is increased, the conductive yarn can be used as an electrode material of an electronic device, is used for wearable electronic equipment, and has a wide application prospect.
(2) The conductive polymer yarns with different high polymer materials and different structural properties can be obtained by the wet electrostatic spinning continuous nanofiber yarn. The graphene is large in doping amount, the yarn resistance is small, the resistance change is small under the action of stress, and the graphene can be used as an electrode material; the graphene is less in doping amount, and the resistance change is large under the action of stress, so that the graphene can be applied to a sensor component.
(3) The graphene composite yarn can be continuously prepared by the method, and provides possibility for the industrial process of the conductive yarn.
(4) According to the preparation method, the graphene oxide dispersion liquid is used as the coagulating bath, and the uniformly doped graphene nanofiber yarn can be directly and continuously prepared. The preparation process is simple, the doping degree of the graphene is high, and the graphene is uniformly doped in the yarn. Compared with the method for preparing the graphene/nanofiber composite yarn in the soaking mode, the method can effectively avoid the problem that the graphene cannot be uniformly soaked into the yarn.
Drawings
Fig. 1 shows the surface morphology of the graphene/nanofiber conductive yarn prepared by the present invention.
Fig. 2 is a cross-sectional view of the graphene/nanofiber conductive yarn prepared by the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
In this embodiment, the flexible graphene conductive yarn capable of being woven is prepared by using a wet electrostatic spinning nanofiber continuous yarn forming device, and the steps are as follows:
1) weighing a certain amount of graphene oxide powder, ultrasonically dispersing in N-N Dimethylformamide (DMF), and ultrasonically dispersing for 10h to obtain a graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the DMF is 1.0:50.0, and the graphene oxide dispersion liquid is used for preparing a polymer spinning solution.
2) Weighing a certain amount of graphene oxide powder, ultrasonically dispersing in deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 1.0:1000.0, and ultrasonically dispersing for 24 hours to obtain a coagulating bath for wet electrostatic spinning.
3) Adding a proper amount of dried polyacrylonitrile powder into the graphene oxide dispersion liquid obtained in the step 1) to prepare a high polymer spinning solution with the mass fraction of 10%. The solution was stirred for 10h on a magnetic stirrer with heating at 50 ℃ during stirring.
4) And (3) carrying out wet electrostatic spinning by using the polymer solution obtained in the step 3), wherein the spinning equipment mainly comprises a liquid accumulator, a liquid supply pump, a receiving device, a twisting and winding device and a high-voltage power sending device. And (3) receiving by using a groove-shaped receiving plate, wherein the length of the groove-shaped receiving plate is 20cm, the width of the groove-shaped receiving plate is 6cm, and the coagulation bath in the groove is the graphene oxide dispersion liquid obtained in the step 2).
5) When the electrostatic spinning device in the step 4) works, the voltage of the high-voltage generator is 15 KV; the lateral distance from the nozzle to the trough-shaped receiving plate was 10 cm. The longitudinal direction was 15 cm.
6) Depositing the nano-fiber obtained in the step 5) in a graphene oxide coagulation bath, leading out a nano-fiber bundle at one end in the spinning process, drawing the nano-fiber bundle through a twisting device, and winding the twisted yarn on a rotary collecting roller. The diameter of the nano-fiber is 180nm, and the diameter of the yarn is 300 μm.
7) And 6) reducing the graphene oxide/nanofiber yarns in the step 6) in a hydrazine hydrate steam environment to obtain the graphene/nanofiber conductive yarns. The concentration of the hydrazine hydrate solution is 50%, and the heating temperature is 80 ℃.
And (3) testing the electrical and mechanical properties of the conductive yarn obtained in the step 7), wherein the conductivity is 40S/cm, and the tensile breaking strength is 7 MPa.
Example 2
In this embodiment, the flexible graphene conductive yarn capable of being woven is prepared by using a wet electrostatic spinning nanofiber continuous yarn forming device, and the steps are as follows:
1) weighing a certain amount of graphene oxide powder, ultrasonically dispersing in N-N Dimethylformamide (DMF), and ultrasonically dispersing for 11h to obtain a graphene oxide dispersion liquid, wherein the mass ratio of graphene oxide to DMF is 1.0:100.0, and the graphene oxide dispersion liquid is used for preparing a polymer spinning solution.
2) Weighing a certain amount of graphene oxide powder, ultrasonically dispersing the graphene oxide powder in deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 2.0:1000.0, and ultrasonically dispersing the graphene oxide powder for 15 hours to obtain a coagulating bath for wet electrostatic spinning.
3) Adding a proper amount of dried polyacrylonitrile powder into the graphene oxide dispersion liquid obtained in the step 1) to prepare a polyacrylonitrile spinning solution with the mass fraction of 12%. The solution was stirred for 8h on a magnetic stirrer with heating at 55 ℃ during stirring.
4) And (3) carrying out wet electrostatic spinning by using the polymer solution obtained in the step 3), wherein the spinning equipment mainly comprises a liquid accumulator, a liquid supply pump, a receiving device, a twisting and winding device and a high-voltage power sending device. And (3) receiving by using a groove-shaped receiving plate, wherein the length of the groove-shaped receiving plate is 20cm, the width of the groove-shaped receiving plate is 5cm, and the coagulation bath in the groove is the graphene oxide dispersion liquid obtained in the step 2).
5) When the wet electrostatic spinning device works in the step 4), the voltage of the high-voltage generator is 20 KV; the lateral distance from the nozzle to the trough-shaped receiving plate was 5 cm. The longitudinal direction was 10 cm.
6) Depositing the nano-fiber obtained in the step 5) in a graphene oxide coagulation bath, leading out a nano-fiber bundle at one end in the spinning process, drawing the nano-fiber bundle through a twisting device, and winding the twisted yarn on a rotary collecting roller. The diameter of the nanofiber is 150nm, and the diameter of the yarn is 200 μm.
7) And 6) reducing the graphene oxide/nanofiber yarns in the step 6) in a hydrazine hydrate steam environment to obtain the graphene/nanofiber conductive yarns. The concentration of the hydrazine hydrate solution is 35%, and the heating temperature is 85 ℃.
8) And (3) testing the electrical and mechanical properties of the conductive yarn obtained in the step 7), wherein the conductivity is 80S/cm, and the tensile breaking strength is 10 MPa.
Example 3
In this embodiment, the flexible graphene conductive yarn capable of being woven is prepared by using a wet electrostatic spinning nanofiber continuous yarn forming device, and the steps are as follows:
1) weighing a certain amount of graphene oxide powder, ultrasonically dispersing in N-N Dimethylformamide (DMF), and ultrasonically dispersing for 12h to obtain a graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the DMF is 1.00:60.0, and the graphene oxide dispersion liquid is used for preparing a polymer spinning solution.
2) Weighing a certain amount of graphene oxide powder, ultrasonically dispersing in deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 3.0:1000.0, and ultrasonically dispersing for 24 hours to obtain a coagulating bath for wet electrostatic spinning.
3) Adding a proper amount of dried polyurethane particles into the graphene oxide dispersion liquid obtained in the step 1) to prepare a high polymer spinning solution, wherein the mass fraction of the high polymer spinning solution is 15%. The solution was stirred for 10h on a magnetic stirrer with heating at 75 ℃ during stirring.
4) And (3) carrying out wet electrostatic spinning by using the polymer solution obtained in the step 3), wherein the spinning equipment mainly comprises a liquid accumulator, a liquid supply pump, a receiving device, a twisting and winding device and a high-voltage power sending device. And (3) receiving by using a groove-shaped receiving plate, wherein the length of the groove-shaped receiving plate is 25cm, the width of the groove-shaped receiving plate is 10cm, and the coagulation bath in the groove is the graphene oxide dispersion liquid obtained in the step 2).
5) When the electrostatic spinning device in the step 4) works, the voltage of the high-voltage generator is 25 KV; the lateral distance from the nozzle to the trough-shaped receiving plate was 5 cm. The longitudinal direction was 10 cm.
6) Depositing the nano-fiber obtained in the step 5) in a graphene oxide coagulation bath, leading out a nano-fiber bundle at one end in the spinning process, drawing the nano-fiber bundle through a twisting device, and winding the twisted yarn on a rotary collecting roller. The diameter of the nanofiber was 130nm and the yarn diameter was 250 μm.
7) And 6) reducing the graphene oxide/nanofiber yarns in the step 6) in a hydrazine hydrate steam environment to obtain the graphene/nanofiber conductive yarns. The concentration of the hydrazine hydrate solution is 40%, and the heating temperature is 90 ℃.
8) And (3) testing the electrical and mechanical properties of the conductive yarn obtained in the step 7), wherein the conductivity is 100S/cm, and the tensile breaking strength is 30 MPa.
Example 4
In this embodiment, the flexible graphene conductive yarn capable of being woven is prepared by using a wet electrostatic spinning nanofiber continuous yarn forming device, and the steps are as follows:
1) weighing a certain amount of graphene oxide powder, ultrasonically dispersing in N-N Dimethylformamide (DMF), and ultrasonically dispersing for 20h to obtain a graphene oxide dispersion liquid, wherein the mass ratio of graphene oxide to DMF is 1.0:30.0, and the graphene oxide dispersion liquid is used for preparing a polymer spinning solution.
2) Weighing a certain amount of graphene oxide powder, ultrasonically dispersing in deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 6.0:1000.0, and ultrasonically dispersing for 22 hours to obtain a coagulating bath for wet electrostatic spinning.
3) Adding a proper amount of dried high polymer powder into the graphene oxide dispersion liquid obtained in the step 1) to prepare a high polymer spinning solution with the mass fraction of 18%. The solution was stirred for 20h on a magnetic stirrer with heating at 75 ℃ during stirring.
4) And (3) carrying out wet electrostatic spinning by using the polymer solution obtained in the step 3), wherein the spinning equipment mainly comprises a liquid accumulator, a liquid supply pump, a receiving device, a twisting and winding device and a high-voltage power sending device. And the receiving device adopts a groove-shaped receiving plate for receiving, the length of the groove-shaped receiving plate is 35cm, the width of the groove-shaped receiving plate is 15cm, and the coagulation bath in the groove is the graphene oxide dispersion liquid obtained in the step 2).
5) When the electrostatic spinning device in the step 4) works, the voltage of the high-voltage generator is 30 KV; the lateral distance from the nozzle to the trough-shaped receiving plate was 5 cm. The longitudinal direction was 15 cm.
6) Depositing the nano-fiber obtained in the step 5) in a graphene oxide coagulation bath, leading out a nano-fiber bundle at one end in the spinning process, drawing the nano-fiber bundle through a twisting device, and winding the twisted yarn on a rotary collecting roller. The diameter of the nano-fiber is 120nm, and the diameter of the yarn is 190 μm.
7) And 6) reducing the graphene oxide/nanofiber yarns in the step 6) in a hydrazine hydrate steam environment to obtain the graphene/nanofiber conductive yarns. The concentration of the hydrazine hydrate solution is 30%, and the heating temperature is 90 ℃.
And (3) testing the electrical and mechanical properties of the conductive yarn obtained in the step 7), wherein the conductivity is 100S/cm, and the tensile breaking strength is 35 MPa.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A preparation method of flexible graphene conductive yarns capable of being woven is characterized by comprising the following steps: carrying out wet electrostatic spinning on a polymer spinning solution to obtain continuous twisted graphene oxide/nanofiber composite yarns, collecting the graphene oxide/nanofiber yarns by using a graphene oxide aqueous solution as a receiving coagulation bath and adopting a twisting winding device, and carrying out thermal reduction on the prepared yarns by using a hydrazine hydrate solution to obtain flexible braided graphene/nanofiber conductive yarns; the method specifically comprises the following steps:
(1) adding graphene oxide powder into an organic solvent, and performing ultrasonic dispersion for 6-48h to obtain a graphene oxide dispersion liquid;
(2) adding graphene oxide powder into deionized water, and performing ultrasonic dispersion for 10-48h to obtain a coagulation bath for wet electrostatic spinning;
(3) adding the dried high polymer powder into the graphene oxide dispersion liquid obtained in the step (1), stirring for 6-24h on a magnetic stirrer, heating at 50-95 ℃ in the stirring process, and preparing high polymer spinning solution with the mass fraction of 8% -25%;
(4) performing wet electrostatic spinning by using the high polymer spinning solution obtained in the step (3), depositing the obtained nano fibers in a graphene oxide coagulation bath, and twisting to obtain graphene oxide/nano fiber yarns;
(5) reducing the graphene oxide/nanofiber yarns in a hydrazine hydrate steam environment to obtain graphene/nanofiber conductive yarns;
the graphene oxide is in a single-layer sheet shape, the thickness is 0.2-2.0nm, the sheet diameter is 0.2-10.0 mu m, and the specific surface area is 500-2000m2/g；
The conductivity of the flexible braided graphene conductive yarn is 5-150S/cm, and the tensile breaking strength is 5-100 MPa.
2. The preparation method of the flexible braided graphene conductive yarn according to claim 1, characterized in that: the organic solvent in the step (1) comprises N-N dimethylformamide, tetrahydrofuran or acetone.
3. The preparation method of the flexible braided graphene conductive yarn according to claim 1, characterized in that: in the step (1), the mass ratio of the graphene oxide to the organic solvent is (1.0-10.0) to (20.0-200.0).
4. The preparation method of the flexible braided graphene conductive yarn according to claim 1, characterized in that: in the step (2), the mass ratio of the graphene oxide to the deionized water is (1.0-20.0) to (500.0-2000.0).
5. The method as claimed in claim 1, wherein the polymer in step (3) comprises polyacrylonitrile, polyurethane, polyvinylidene fluoride or polyimide, and the molecular weight of the polymer is 10000-1000000.
6. The preparation method of the flexible braided graphene conductive yarn according to claim 1, characterized in that: when the electrostatic spinning device adopted in the wet electrostatic spinning in the step (4) works, the voltage of the high-voltage generator is 0-50 KV; the transverse distance from the nozzle to the groove-shaped receiving plate is 5-20cm, and the longitudinal distance is 10-20 cm; drawing the nanofiber bundle at one end of the nanofiber bundle through a twisting device in the spinning process, and winding the twisted yarn on a rotary collecting roller; the diameter of the nano-fiber is 100-300nm, and the diameter of the yarn is 50-1000 μm.
7. The preparation method of the flexible braided graphene conductive yarn according to claim 1, characterized in that: in the step (5), hydrazine hydrate steam is provided by hydrazine hydrate solution, wherein the mass concentration of the hydrazine hydrate solution is 30-60%, and the heating temperature is 60-100 ℃.
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