CN111485298A - Conductive fiber based on cellulose-dopamine/carbon nanotube and preparation method and application thereof - Google Patents
Conductive fiber based on cellulose-dopamine/carbon nanotube and preparation method and application thereof Download PDFInfo
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- CN111485298A CN111485298A CN202010320653.3A CN202010320653A CN111485298A CN 111485298 A CN111485298 A CN 111485298A CN 202010320653 A CN202010320653 A CN 202010320653A CN 111485298 A CN111485298 A CN 111485298A
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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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
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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
- D01D5/06—Wet spinning methods
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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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- G—PHYSICS
- G01—MEASURING; TESTING
- G01G—WEIGHING
- G01G3/00—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances
- G01G3/12—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing
- G01G3/14—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing measuring variations of electrical resistance
Abstract
The invention discloses a cellulose-dopamine/carbon nanotube-based conductive fiber, and a preparation method and application thereof. The flexible sensor assembled by the conductive fibers has the characteristics of high flexibility, high mechanical property, high conductivity and strain sensitivity, and is expected to serve as novel wearable electronic equipment to serve as future robots, prosthesis users and human body real-time motion detection equipment. The invention has the advantages of rich raw material sources, low cost, simple preparation process and strong feasibility, and has great potential in the application in the fields of wearable electronic devices, flexible energy devices and the like.
Description
Technical Field
The invention belongs to the field of flexible high-molecular conductive materials, and particularly relates to a cellulose-dopamine/carbon nanotube-based conductive fiber, and a preparation method and application thereof.
Background
By 2022, the usage of electronic products for textile use in the world is expected to exceed one trillion pieces per year, and the rapid development of the internet of things has led to great attention and higher requirements of people on electronic sensing technology. Carbon Nanotubes (CNTs), a tubular carbon material with high axial strength and high electrical conductivity, have been the focus of research on flexible conductive materials, but their inherent difficulty in uniform dispersion has influenced the commercialization progress of CNTs. At the same time, increasing environmental concerns have increased the use and exploitation of clean energy. Carboxymethyl cellulose (CMC), a polyanionic polysaccharide obtained by reacting natural cellulose with alkali and chloroacetic acid, is widely used in the fields of biology, medicine, food, and the like. Recently, the property of negative charge on the surface of CMC is utilized as a template for synthesizing conductive polymers, so that the electrochemical performance of the electric polymers can be improved. Research shows that CMC is used as surfactant to disperse CNT as conducting matter, so that CNT may exist stably in CMC solution via electrostatic interaction or pi-pi interaction. Meanwhile, the previous researches show that the mechanical strength and the water stability of CMC in a wet state can be obviously improved by grafting mussel biomimetic protein Dopamine (DA) onto a CMC molecular chain, and the DA can further improve the dispersion performance of CNT.
Disclosure of Invention
The purpose of the invention is as follows: cellulose resources with homology and biocompatibility are used as raw materials to prepare a cellulose-dopamine/carbon nanotube-based conductive fiber, and further prepare a flexible sensor to develop application research of the flexible sensor in wearable electronic devices and flexible energy devices.
The technical scheme is as follows:
a kind ofBased on cellulose-dopamine/carbon nanotube conductive fibers, the conductive fiber has the characteristics of high flexibility, high mechanical property, high conductivity and strain sensitivity, and has the tensile strength of 62.27-399.42 MPa, the elongation at break of 7.67-23.99 percent and the volume resistivity of 6.97 × 10-4～2.29×10-2ohm m, conductivity of 43.72-1.43 × 103S m-1。
The invention further provides a preparation method of the cellulose-dopamine/carbon nanotube-based conductive fiber, which comprises the following steps:
(1) preparing a dopamine modified cellulose aqueous solution;
(2) adding carbon nano tubes into the dopamine modified cellulose aqueous solution obtained in the step (1), and performing ultrasonic blending to obtain a cellulose-dopamine/carbon nano tube spinning solution;
(3) and obtaining the cellulose-dopamine/carbon nano tube conductive fiber by adopting a wet spinning process.
Specifically, in the step (1), the dopamine modified cellulose aqueous solution is prepared by the following steps:
s1: adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into a carboxymethyl cellulose aqueous solution, mechanically stirring, and after uniform dispersion, dropwise adding a dilute hydrochloric acid solution to adjust the pH value of the system to 3.5-6;
s2: sequentially adding N-hydroxysuccinimide and dopamine hydrochloride, reacting for 6-24 hours under the protection of inert gas, dialyzing after reaction, washing, and concentrating to obtain the dopamine modified cellulose aqueous solution.
Preferably, the carboxymethyl cellulose aqueous solution is prepared by carboxymethyl cellulose salt, the mass concentration is 0.5-3%, and the molecular weight range of the carboxymethyl cellulose salt is 9-1000 kDa; the reaction mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the carboxymethyl cellulose salt, the N-hydroxysuccinimide and the dopamine hydrochloride is (0.96-1.92): (100-200): (0.58-1.16): (0.95-1.90).
In step S2, the dialysis is performed by ultrafiltration membrane interception with deionized water, the intercepted molecular weight of the ultrafiltration membrane is 1.5 kDa-10 kDa, and the dialysis time is more than 12 h.
Specifically, in the step (2), the mixing mass ratio of the carbon nano tube to the dopamine-modified cellulose aqueous solution is (0.5-2): (8-9.5). The dispersion of the carbon nano tube can be improved by steric hindrance and electrostatic repulsion generated by the carboxymethyl cellulose (CMC) modified by Dopamine (DA), so that favorable guarantee is provided for the spinnability of the spinning solution and the mechanical property of the conductive fiber.
Preferably, stable conductive compound suspension is formed after ultrasonic blending, and defoaming treatment is carried out; in the obtained cellulose-dopamine/carbon nano tube spinning solution, the mass fraction of the dopamine-modified cellulose is 0.5-2%, and the mass fraction of the carbon nano tube is 0.1-0.5%.
Specifically, in the step (3), the wet spinning process includes:
passing the obtained cellulose-dopamine/carbon nano tube spinning solution through a precision injection pump for 2-8 m L min-1And injecting the mixture into a coagulating bath for coagulation, standing for 30-60 s, fishing out the fibers, and washing in a water bath at 25-40 ℃ to obtain the cellulose-dopamine/carbon nanotube conductive fiber.
Preferably, the capacity of the precision injection pump is 3-10 m L, the inner diameter of the needle is 0.2-1 mm, the outer diameter of the needle is 0.2-1.4 mm, the ambient temperature of spinning is 25-35 ℃, and the humidity is 30-50%.
Further, the fiber may be further drawn while passing through the coagulation bath.
Preferably, the coagulating bath adopts an aqueous solution of ethanol, acetone, acetic acid or ferric trichloride; wherein, the volume concentration of the water solution of ethanol, acetone and acetic acid is 20-75%, and the mass concentration of the water solution of ferric trichloride is 0.5-5%.
The cellulose-dopamine/carbon nanotube-based conductive fiber prepared by the preparation method is also within the protection scope of the invention.
Further, the invention claims the application of the prepared cellulose-dopamine/carbon nanotube-based conductive fiber in the preparation of flexible sensors.
Has the advantages that:
the invention utilizes a wet spinning method, adopts CMC modified by DA as a fiber framework and CNT as a conductive filling material to prepare the conductive fiber based on the cellulose-dopamine/carbon nano tube, and further prepares the conductive fiber into a flexible sensor. The invention has the advantages of rich raw material sources, low cost, simple preparation process and strong feasibility of implementation. The flexible sensor assembled by the conductive fibers has the characteristics of high flexibility, high mechanical property, high conductivity and strain sensitivity, is expected to serve as novel wearable electronic equipment to serve as real-time motion detection equipment of future robots, prosthesis users and human bodies, and has great potential in the fields of wearable electronic devices, flexible energy devices and the like.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is an optical microscope photograph of the DACMC/CNT conductive fiber prepared in example 1.
Fig. 2 is a stress-strain curve of the DACMC/CNT conductive fiber prepared in example 2 repeatedly stretched 100 times and the resistivity monitored in real time.
FIG. 3 is a schematic representation of a flexible sensor of the DACMC/CNT conductive fibers prepared in example 2 and a real-time resistivity profile at different pressures.
FIG. 4 is a graph of tensile strength and elastic modulus of the DACMC/CNT and CMC/CNT conductive fibers prepared in examples 1-3 at different CNT loading levels and at different humidities.
FIG. 5 shows the volume resistivity and conductivity of the DACMC/CNT conductive fibers prepared in examples 1-3.
Detailed Description
The present invention will be further specifically described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
(1) Preparation of dopamine-modified aqueous cellulose solution
Weighing 100g sodium carboxymethyl cellulose (with a molecular weight of 700kDa, takingSubstitution degree 0.9), 0.5 wt% carboxymethyl cellulose aqueous solution was prepared, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride was added to the above aqueous solution and mechanically stirred for 1h, using 0.1mol L-1Adjusting the pH value of the solution to 4.5-5 by using dilute hydrochloric acid, and continuously adding 0.58g N-hydroxysuccinimide and 0.95g of dopamine hydrochloride into the solution in the presence of N2Mechanically stirring for 24h under the environment with the rotating speed of 1000rad min-1. Dialysis was performed at room temperature for 5d using a dialysis bag with a molecular weight cut-off of 3kDa, with distilled water being replaced every 12 h. A2% by weight DACMC pale yellow transparent solution was subsequently obtained by suction filtration and stored at 4 ℃ in a refrigerator.
(2) Preparation of cellulose-dopamine/carbon nanotube spinning solution
Adding 0.005g of single-walled carbon nanotube into 4.75g of 2 wt% DACMC aqueous solution, and mechanically stirring for 1h at room temperature; and (3) taking the mixture, carrying out ultrasonic crushing for 15min to form a stable conductive compound suspension, preparing the carbon nanotube DACMC/CNT spinning solution, and carrying out static defoaming treatment on the dispersion solution for later use. The mass fraction of the DACMC in the spinning solution is 2 percent; the mass fraction of CNTs was 0.1%.
(3) Preparation of cellulose-dopamine/carbon nanotube conductive fiber
The DACMC/CNT dope was transferred to an injector and spun using a spinning apparatus at 4.2m L min-1Injection rate the suspension was injected into an ethanol coagulation bath by a precision injection pump and left for 1 min. The gel fibers were then pulled out and washed with deionized water at room temperature. The gel fiber is dried at room temperature, so that the excessive shrinkage of the fiber is avoided, the structural defects of the composite fiber are reduced, and the mechanical property and the electric conductivity of the fiber are improved. Finally obtaining the DACMC/CNT conductive fiber.
FIG. 1 is an optical microscope photograph of the DACMC/CNT conductive fiber prepared in example 1. As can be seen from the figure, the surface of the conductive fiber obtained by wet spinning was very uniform, and the surface had good orientation in the axial direction of the fiber. This means that the wet spinning process provides a process of orienting the fibers so that the overall structure is denser.
Example 2
(1) Preparation of dopamine-modified aqueous cellulose solution
100g of sodium carboxymethyl cellulose (molecular weight 700kDa, degree of substitution 0.9) is weighed to prepare 0.5 wt% aqueous solution of carboxymethyl cellulose, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is added into the aqueous solution and mechanically stirred for 1h, 0.1mol of L is used-1Adjusting the pH value of the solution to 4.5-5 by using dilute hydrochloric acid, and continuously adding 0.58g N-hydroxysuccinimide and 0.95g of dopamine hydrochloride into the solution in the presence of N2Mechanically stirring for 24h under the environment with the rotating speed of 1000rad min-1. Dialysis was performed at room temperature for 5d using a dialysis bag with a molecular weight cut-off of 3kDa, with distilled water being replaced every 12 h. A2% by weight DACMC pale yellow transparent solution was subsequently obtained by suction filtration and stored at 4 ℃ in a refrigerator.
(2) Preparation of cellulose-dopamine/carbon nanotube spinning solution
Adding 0.01g of single-walled carbon nanotube into 4.5g of 2 wt% DACMC aqueous solution, and mechanically stirring for 1h at room temperature; and (3) taking the mixture, carrying out ultrasonic crushing for 15min to form a stable conductive compound suspension, preparing the carbon nanotube DACMC/CNT spinning solution, and carrying out static defoaming treatment on the dispersion solution for later use. The mass fraction of the DACMC in the spinning solution is 2 percent; the mass fraction of CNTs was 0.2%.
(3) Preparation of cellulose-dopamine/carbon nanotube conductive fiber
The DACMC/CNT dope was transferred to an injector and spun using a spinning apparatus at 4.2m L min-1Injection rate the suspension was injected into an ethanol coagulation bath by a precision injection pump and left for 1 min. The gel fibers were then pulled out and washed with deionized water at room temperature. The gel fiber is dried at room temperature, so that the excessive shrinkage of the fiber is avoided, the structural defects of the composite fiber are reduced, and the mechanical property and the electric conductivity of the fiber are improved. Finally obtaining the DACMC/CNT conductive fiber.
Fig. 2 is a stress-strain curve of the DACMC/CNT conductive fiber prepared in example 2 repeatedly stretched 100 times and the resistivity monitored in real time. As can be seen from the figure, in the 100 times of repeated stretching processes, the stretching distance is adjusted, the fiber elongation of the wire is kept at 5%, and the stretching speed is set at 10mm min-1Obtained byThe resistance rate decreases and then becomes stable. The cellulose substrate plays a role in bearing load in the stretching process, and large slippage is not generated inside a molecular chain; on the other hand, repeated stretching enhances orientation inside the fiber, increases effective contact of CNTs, and thus the resistivity decreases. In conclusion, the DACMC/CNT conductive fiber has excellent stretch resistance, cycle toughness and knittability.
FIG. 3 is a schematic representation of the DACMC/CNT sensor prepared in example 2 and the real-time resistivity profiles at different pressures. It can be seen that the resistivity of the sensor increases significantly with increasing mass. The resistivity was about 3.85% when the loading was 100 g. The loads with different masses are corresponding to the corresponding resistance values, so that the sensor can effectively monitor the mass change of the load. The resistivity is improved mainly because the load provides tensile stress for the DACMC/CNT fiber in the sensor, and the tensile stress does not exceed the yield stress of the fiber, so that the CNT in the fiber can generate certain oriented tension, the track for electron transportation is smoother, the resistance value is reduced, and the resistivity is improved. The sensor prepared from the DACMC/CNT conductive fiber has sensitive signal feedback, so that the sensor has important application prospects in the fields of bioelectronic medical sensing equipment, wearable electronic equipment and the like.
Example 3
(1) Preparation of dopamine-modified aqueous cellulose solution
100g of sodium carboxymethyl cellulose (molecular weight 700kDa, degree of substitution 0.9) is weighed to prepare 0.5 wt% aqueous solution of carboxymethyl cellulose, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is added into the aqueous solution and mechanically stirred for 1h, 0.1mol of L is used-1Adjusting the pH value of the solution to 4.5-5 by using dilute hydrochloric acid, and continuously adding 0.58g N-hydroxysuccinimide and 0.95g of dopamine hydrochloride into the solution in the presence of N2Mechanically stirring for 24h under the environment with the rotating speed of 1000rad min-1. Dialysis was performed at room temperature for 5d using a dialysis bag with a molecular weight cut-off of 3kDa, with distilled water being replaced every 12 h. A2% by weight DACMC pale yellow transparent solution was subsequently obtained by suction filtration and stored at 4 ℃ in a refrigerator.
(2) Preparation of cellulose-dopamine/carbon nanotube spinning solution
Adding 0.02g of single-walled carbon nanotube into 4g of 2 wt% DACMC aqueous solution, and mechanically stirring for 1h at room temperature; and (3) taking the mixture, carrying out ultrasonic crushing for 15min to form a stable conductive compound suspension, preparing the carbon nanotube DACMC/CNT spinning solution, and carrying out static defoaming treatment on the dispersion solution for later use. The mass fraction of the DACMC in the spinning solution is 2 percent; the mass fraction of CNTs was 0.5%.
(3) Preparation of cellulose-dopamine/carbon nanotube conductive fiber
The DACMC/CNT dope was transferred to an injector and spun using a spinning apparatus at 4.2m L min-1Injection rate the suspension was injected into an ethanol coagulation bath by a precision injection pump and left for 1 min. The gel fibers were then pulled out and washed with deionized water at room temperature. The gel fiber is dried at room temperature, so that the excessive shrinkage of the fiber is avoided, the structural defects of the composite fiber are reduced, and the mechanical property and the electric conductivity of the fiber are improved. Finally obtaining the DACMC/CNT conductive fiber.
(4) Flexible sensor based on cellulose-dopamine/carbon nanotube conductive fibers
Selecting five pieces of DACMC/CNT conductive fibers, assembling the five pieces of DACMC/CNT conductive fibers into yarns in a winding mode, and connecting two independent copper wires to two ends of the yarns to obtain the flexible sensor based on the cellulose-dopamine/carbon nanotube conductive fibers.
FIG. 4 is a graph of tensile strength and elastic modulus of the DACMC/CNT and CMC/CNT conductive fibers prepared in examples 1-3 at different CNT loading levels (5%, 10%, 20%) and at different humidity levels. The CMC/CNT not modified by dopamine is used as a control group, and the mass ratio of the CMC to the CNT is the same as that of the CMC/CNT in the examples 1-3. As can be seen from the graph, the tensile strength (399.42MPa) and the elastic modulus (6.02GPa) of the conductive fiber (DACMC/CNT) are obviously improved after the dopamine is modified under different humidities. The reason is that after the grafting reaction, the adhesive force of CMC and the stability of the system can be increased by the o-diphenyl functional group in the dopamine, so that the DACMC and the CNT are well dispersed, and the mechanical property is improved.
FIG. 5 shows the results of examples 1 to 3It can be seen from the figure that as the content of CNT in the DACMC/CNT is increased from 5 wt% to 20 wt%, the volume resistivity of the CMC/CNT and the DACMC/CNT conductive fiber is respectively increased from 2.47 × 10-2ohm m and 2.29 × 10-2ohm m dropped to 7.14 × 10-4ohm m and 6.97 × 10-4ohmm, conductivity of 28.86S m-1And 43.72S m-1Down to 1.40 × 103S m-1And 1.43 × 103S m-1. This demonstrates that the addition of carbon nanotubes and dopamine contributes to the improvement in the conductivity of the fiber, probably because the dopamine increases the directionality inside the fiber, thereby improving the electron transport efficiency.
Example 4
(1) Preparation of dopamine-modified aqueous cellulose solution
200g of sodium carboxymethyl cellulose (molecular weight 700kDa, degree of substitution 0.9) is weighed to prepare 0.5 wt% carboxymethyl cellulose aqueous solution, 1.92g of 1- (3-dimethylaminopropyl) -3-ethyl carbodiimide hydrochloride is added into the aqueous solution and mechanically stirred for 1h, 0.1mol of L is used-1Adjusting the pH value of the solution to 4.5-5 by using dilute hydrochloric acid, and continuously adding 1.16g N-hydroxysuccinimide and 1.90g of dopamine hydrochloride into the solution in the presence of N2Mechanically stirring for 24h under the environment with the rotating speed of 1000rad min-1. Dialysis was performed at room temperature for 5d using a dialysis bag with a molecular weight cut-off of 3kDa, with distilled water being replaced every 12 h. A2% by weight DACMC pale yellow transparent solution was subsequently obtained by suction filtration and stored at 4 ℃ in a refrigerator.
(2) Preparation of cellulose-dopamine/carbon nanotube spinning solution
Diluting 2 wt% DACMC aqueous solution to 0.5 wt% with deionized water, adding 0.005g single-walled carbon nanotube into 4g 0.5 wt% DACMC aqueous solution, and mechanically stirring at room temperature for 1 h; and (3) taking the mixture, carrying out ultrasonic crushing for 15min to form a stable conductive compound suspension, preparing the carbon nanotube DACMC/CNT spinning solution, and carrying out static defoaming treatment on the dispersion solution for later use. The mass fraction of the DACMC in the spinning solution is 0.5 percent; the mass fraction of CNTs was 0.1%.
(3) Preparation of cellulose-dopamine/carbon nanotube conductive fiber
The DACMC/CNT dope was transferred to an injector and spun using a spinning apparatus at 4.2m L min-1Injection rate the suspension was injected into an ethanol coagulation bath by a precision injection pump and left for 1 min. The gel fibers were then pulled out and washed with deionized water at room temperature. The gel fiber is dried at room temperature, so that the excessive shrinkage of the fiber is avoided, the structural defects of the composite fiber are reduced, and the mechanical property and the electric conductivity of the fiber are improved. Finally obtaining the DACMC/CNT conductive fiber.
(4) Flexible sensor based on cellulose-dopamine/carbon nanotube conductive fibers
Selecting five pieces of DACMC/CNT conductive fibers, assembling the five pieces of DACMC/CNT conductive fibers into yarns in a winding mode, and connecting two independent copper wires to two ends of the yarns to obtain the flexible sensor based on the cellulose-dopamine/carbon nanotube conductive fibers.
The invention provides a cellulose-dopamine/carbon nanotube-based conductive fiber, a preparation method and an application thereof, and a plurality of methods and ways for realizing the technical scheme, wherein the above description is only a preferred embodiment of the invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the invention, and the improvements and modifications should also be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. The conductive fiber based on the cellulose-dopamine/carbon nano tube is characterized by having the tensile strength of 62.27-399.42 MPa, the elongation at break of 7.67-23.99 percent and the volume resistivity of 6.97 × 10-4～2.29×10-2ohm m, conductivity of 43.72-1.43 × 103Sm-1。
2. The preparation method of the conductive fiber based on the cellulose-dopamine/carbon nano tube is characterized by comprising the following steps:
(1) preparing a dopamine modified cellulose aqueous solution;
(2) adding carbon nano tubes into the dopamine modified cellulose aqueous solution obtained in the step (1), and performing ultrasonic blending to obtain a cellulose-dopamine/carbon nano tube spinning solution;
(3) and obtaining the cellulose-dopamine/carbon nano tube conductive fiber by adopting a wet spinning process.
3. The preparation method of the cellulose-dopamine/carbon nanotube-based conductive fiber according to claim 1, wherein in the step (1), the dopamine-modified cellulose aqueous solution is prepared by the following steps:
s1: adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride into a carboxymethyl cellulose aqueous solution, mechanically stirring, and adjusting the pH of a system to 3.5-6 after uniform dispersion;
s2: sequentially adding N-hydroxysuccinimide and dopamine hydrochloride, reacting for 6-24 hours under the protection of inert gas, dialyzing after reaction, washing, and concentrating to obtain the dopamine modified cellulose aqueous solution.
4. The preparation method of the cellulose-dopamine/carbon nanotube-based conductive fiber according to claim 3, characterized in that the carboxymethyl cellulose aqueous solution is prepared by using carboxymethyl cellulose salt, the mass concentration is 0.5% -3%, and the molecular weight range of the carboxymethyl cellulose salt is 9-1000 kDa; the reaction mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the carboxymethyl cellulose salt, the N-hydroxysuccinimide and the dopamine hydrochloride is (0.96-1.92): (100-200): (0.58-1.16): (0.95-1.90).
5. The preparation method of the cellulose-dopamine/carbon nanotube-based conductive fiber according to claim 3, wherein in step S2, the dialysis is performed by ultrafiltration membrane interception with deionized water, the molecular weight of the ultrafiltration membrane interception is 1.5 kDa-10 kDa, and the dialysis time is 12h or longer.
6. The preparation method of the cellulose-dopamine/carbon nanotube-based conductive fiber according to claim 2, wherein in the step (2), the mixing mass ratio of the carbon nanotubes to the dopamine-modified cellulose aqueous solution is (0.5-2): (8-9.5).
7. The preparation method of the conductive fiber based on the cellulose-dopamine/carbon nano tube of claim 6, characterized in that, after ultrasonic blending, a stable conductive compound suspension is formed and is subjected to defoaming treatment; in the obtained cellulose-dopamine/carbon nano tube spinning solution, the mass fraction of the dopamine-modified cellulose is 0.5-2%, and the mass fraction of the carbon nano tube is 0.1-0.5%.
8. The method for preparing cellulose-dopamine/carbon nanotube-based conductive fibers according to claim 2, wherein in the step (3), the wet spinning process comprises:
passing the obtained cellulose-dopamine/carbon nano tube spinning solution through a precision injection pump for 2-8 m L min-1Injecting the mixture into a coagulating bath for coagulation, standing for 30-60 s, fishing out the fibers, and washing in a water bath at 25-40 ℃ to obtain cellulose-dopamine/carbon nanotube conductive fibers;
the capacity of the precise injection pump is 3-10 m L, the inner diameter of the needle is 0.2-1 mm, the ambient temperature of spinning is 25-35 ℃, and the humidity is 30-50%.
9. The preparation method of the cellulose-dopamine/carbon nanotube-based conductive fiber according to claim 8, wherein the coagulating bath is an aqueous solution of ethanol, acetone, acetic acid or ferric chloride; wherein, the volume concentration of the water solution of ethanol, acetone and acetic acid is 20-75%, and the mass concentration of the water solution of ferric trichloride is 0.5-5%.
10. Use of the cellulose-dopamine/carbon nanotube-based conductive fiber of claim 1 in a flexible sensor.
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| CN113355762A (en) * | 2021-05-27 | 2021-09-07 | 上海茂腾针织有限公司 | High-strength acetate fiber and preparation method thereof |
| CN114395159A (en) * | 2022-02-21 | 2022-04-26 | 浙江理工大学 | Preparation method of flexible porous conductive material |
| CN115637588A (en) * | 2022-11-11 | 2023-01-24 | 广东工业大学 | Photo-thermal driving self-sensing type multi-layer micro-nano fiber, preparation method and application |
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| CN112326743A (en) * | 2020-11-05 | 2021-02-05 | 重庆医科大学 | C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method of wearable wound monitoring sensor |
| CN112326743B (en) * | 2020-11-05 | 2024-01-16 | 重庆医科大学 | C-SF-FA flexible conductive film based on silk fibroin, wearable wound monitoring sensor and preparation method thereof |
| CN113355762A (en) * | 2021-05-27 | 2021-09-07 | 上海茂腾针织有限公司 | High-strength acetate fiber and preparation method thereof |
| CN114395159A (en) * | 2022-02-21 | 2022-04-26 | 浙江理工大学 | Preparation method of flexible porous conductive material |
| CN115637588A (en) * | 2022-11-11 | 2023-01-24 | 广东工业大学 | Photo-thermal driving self-sensing type multi-layer micro-nano fiber, preparation method and application |
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