CN111020882A - Flexible conductive fiber membrane material and preparation method thereof - Google Patents
Flexible conductive fiber membrane material and preparation method thereof Download PDFInfo
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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
- D04H1/70—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
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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
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- 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
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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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
- D04H1/42—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
- D04H1/4326—Condensation or reaction polymers
- D04H1/4334—Polyamides
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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Abstract
The invention discloses a flexible conductive fiber membrane material and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving a fiber base material, a conductive nano material and a surfactant in an organic solvent to prepare a spinning solution; preparing the spinning solution into a nanofiber membrane through an electrostatic spinning process; in-situ polymerizing a conductive polymer on the nanofiber membrane to prepare and obtain the flexible conductive fiber membrane material; the nanofiber membrane has a structure of primary main fibers and secondary spider web fibers which are connected with each other, the conductive polymer is formed on the primary main fibers and the secondary spider web fibers in an in-situ polymerization mode, and due to the presence of the spider web fibers, the specific surface area of the fibers in a sample is improved, so that more binding sites can be provided for the attachment of the conductive polymer during the in-situ polymerization reaction, and the conductivity of the conductive fiber membrane material is greatly improved.
Description
Technical Field
The invention belongs to the technical field of conductive materials, and particularly relates to a flexible conductive fiber membrane material and a preparation method thereof.
Background
Conventionally, metals or metal oxides are often used as conductors to realize conductive interconnection of electronic components, such as Indium Tin Oxide (ITO) thin films, which have good conductivity and high transmittance, and thus are widely used in solar cells, displays, solid-state lighting, and other components. However, indium is a rare metal, the global storage capacity is low, the ITO preparation process is complex, the cost is high, cracks can be generated under low strain, and the like, and the defects are difficult to meet the manufacturing requirements of modern flexible electronic devices.
In recent years, inorganic conductive materials and doped composite materials thereof have attracted more and more researchers' attention in the field of flexible electronic device preparation. The Liu Tianxi subject group of Donghua university utilizes a hydrogel method to prepare a porous self-supporting nitrogen-doped graphene film for a super capacitor, a macroporous structure is favorable for rapid ion adsorption, and a nitrogen-doped structure ensures that the film has sufficient pseudocapacitance and conductivity, but the graphene is high in cost and is not favorable for large-scale industrial production, and the method is disclosed in the following documents: "Jin, Y., et al," Free-standing macro-gene mutated gene file for high specificity supercapacitor. electrochimica Acta,2019.318: p.865-874 ". The zheng national strong topic group of zhengzhou university adopts a method of three-layer film blowing-multilayer hot pressing to prepare an anisotropic conductive composite material of polypropylene/multi-wall carbon nano-tube with an alternate microstructure, the conductivity of the anisotropic conductive composite material in the x direction is as high as 1s/m, and is higher than that in the z direction by about 16 orders of magnitude, but the inorganic nano-material has the problem of difficult dispersion, which is shown in the literature: "ZHao, K., et al, marked and isolated conductive MWCNTs/multipropylene nanocomposites with alternating microorganisms. chemical Engineering Journal,2019.358: p.924-935".
In recent years, the conductive properties of polymers have been found, and a large number of conductive polymers such as polypyrrole, polythiophene, polyaniline, and the like have been successively developed. The conductive polymer has the advantages of the polymer, and has the excellent conductivity and electrochemistry of metal. The conductive polymer is compounded with other macromolecules to obtain the conductive composite material with better flexibility. For example, the trailjun group at Qingdao university polymerizes polyaniline in situ on a polyurethane nanofiber membrane obtained by electrostatic spinning to form a conductive composite membrane, but the fiber size in the fiber membrane is single, the polymerization site of the aniline is limited, and more polyaniline cannot be loaded, so that the conductive performance cannot be further improved, see the literature: "the university of Qingdao Master academic thesis" polyaniline/polyurethane electrospun nanofiber membrane preparation and flexible stress strain sensor assembly ", Wangyoujiao".
Disclosure of Invention
In view of the defects in the prior art, the invention provides a flexible conductive fiber membrane material and a preparation method thereof, so as to improve the conductivity of the conductive fiber membrane material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a flexible conductive fiber membrane material comprises the following steps:
dissolving a fiber base material, a conductive nano material and a surfactant in an organic solvent to prepare a spinning solution;
preparing the spinning solution into a nanofiber membrane through an electrostatic spinning process;
and polymerizing a conductive polymer on the nanofiber membrane in situ to prepare the flexible conductive fiber membrane material.
The fiber base material comprises, by mass, 5% -25% of a fiber base material, 0.01% -0.1% of a surfactant and 2% -20% of a conductive nano material.
The conductive nano material is selected from any one of carbon nano tubes, graphene or nano metal particles, the surfactant is selected from any one of sodium dodecyl sulfate, dodecyl trimethyl ammonium bromide, linear alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether ammonium sulfate and polyoxyethylene fatty alcohol ether, the organic solvent is selected from any one of formic acid, hexafluoroisopropanol and m-cresol, and the conductive polymer is polyaniline, polypyrrole or polythiophene.
Specifically, the fiber base material is nylon 6, the conductive nano material is a carbon nano tube, the surfactant is sodium dodecyl sulfate, and the conductive polymer is polyaniline.
In the electrostatic spinning process, the spinning voltage is 10kV to 30kV, the receiving distance is 10cm to 30cm, the ambient temperature for receiving the nanofiber membrane is 15 ℃ to 40 ℃, and the humidity is 40 RH percent to 70RH percent.
Wherein the step of in-situ polymerizing the conductive polymer on the nanofiber membrane specifically comprises:
soaking the nanofiber membrane in a monomer solution for forming a conductive polymer;
placing the soaked nanofiber membrane in an acid solution of an oxidant to perform in-situ polymerization reaction, and performing in-situ polymerization on the nanofiber membrane to form a conductive polymer;
and washing and drying the nanofiber membrane after the in-situ polymerization to form the conductive polymer to prepare the flexible conductive fiber membrane material.
In the monomer solution for forming the conductive polymer, the mass concentration of the monomer is 5-30%, and the soaking time is 0.5-3 hours.
Wherein, in the acid solution of the oxidant, the concentration of the oxidant is 10 g/L-40 g/L, the concentration of the acid is 0.1 mol/L-2 mol/L, and the polymerization time is 1-3 hours.
Wherein the monomer for forming the conductive polymer is an aniline monomer, a pyrrole monomer or a thiophene monomer; in the monomer solution, the solvent is selected from any one of ethanol, diethyl ether and acetone.
Wherein, when the monomer is aniline monomer, the oxidant is ammonium persulfate; when the monomer is a pyrrole monomer or a thiophene monomer, the oxidant is ferric trichloride; the acid is selected from any one of hydrochloric acid, sulfuric acid and phosphoric acid.
The invention also provides a flexible conductive fiber membrane material prepared by the preparation method, wherein the nanofiber membrane has a structure of primary main fibers and secondary spider web fibers which are connected with each other, and the conductive polymer is formed on the primary main fibers and the secondary spider web fibers in an in-situ polymerization manner.
Wherein the diameter of the primary main fiber is 100 nm-200 nm, and the diameter of the secondary spider web fiber is 5 nm-15 nm.
According to the preparation method of the flexible conductive fiber membrane material provided by the embodiment of the invention, the spinning solution contains the conductive nano material and the surfactant, so that the nanofiber membrane prepared by the spinning process has the structure of the primary main fiber and the secondary spider web fiber which are mutually connected, and when in-situ polymerization reaction is carried out, the conductive polymer is formed on the primary main fiber and the secondary spider web fiber in an in-situ polymerization manner, so that more binding sites can be provided for the attachment of the conductive polymer, and the conductivity of the conductive fiber membrane material is greatly improved.
Drawings
FIG. 1 is a process flow diagram of a method of making a flexible conductive fibrous membrane material according to an embodiment of the present invention;
FIG. 2 is an SEM image of a nanofiber membrane sample PA6@ CNT in accordance with an embodiment of the present invention;
FIG. 3 is an SEM image of a nanofiber membrane sample PA6 in an example of the invention;
FIG. 4 is an SEM image of a conductive fiber film sample PA6@ CNT @ PANI in accordance with an embodiment of the present invention;
FIG. 5 is an SEM image of a sample of a conductive fiber film of PA6@ PANI in an example of the present invention;
FIG. 6 is an exemplary graphical representation of a flexibility test conducted on a conductive fiber film sample PA6@ PANI in an embodiment of the present invention;
FIG. 7 is an exemplary graphical representation of a flexibility test conducted on the conductive fiber film sample PA6@ CNT @ PANI in an embodiment of the present disclosure;
FIG. 8 is a graph of infrared spectroscopy measurements taken on a sample of a fiber membrane before and after in situ polymerization in an example of the invention;
FIG. 9 is a graph of thermogravimetric analysis testing of a sample of a fiber membrane before and after in situ polymerization in an example of the present invention;
FIG. 10 is a graph of tensile property tests conducted on fiber film samples before and after in situ polymerization in accordance with an example of the present invention;
fig. 11 and 12 are graphs of conductivity tests performed on fiber film samples before and after in situ polymerization in accordance with an example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a preparation method of a flexible conductive fiber membrane material, as shown in fig. 1, the preparation method comprises the following steps.
And step S10, dissolving the fiber matrix material, the conductive nano material and the surfactant in an organic solvent to prepare the spinning solution.
The fiber base material comprises, by mass, 5% -25% of a fiber base material, 0.01% -0.1% of a surfactant and 2% -20% of a conductive nano material. In a preferred scheme, the mass fraction of the conductive nano material is 2-10%.
The conductive nano material is selected from any one of carbon nano tubes, graphene or nano metal particles, the surfactant is selected from any one of sodium dodecyl sulfate, dodecyl trimethyl ammonium bromide, linear alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether ammonium sulfate and polyoxyethylene fatty alcohol ether, the organic solvent is selected from any one of formic acid, hexafluoroisopropanol and m-cresol, and the conductive polymer is polyaniline, polypyrrole or polythiophene.
Among them, the fiber base material is preferably polyamide, such as nylon 6, nylon 66, and the like.
In the specific embodiment of the invention, the fiber base material is selected to be nylon 6, the conductive nano material is selected to be a carbon nano tube, the surfactant is selected to be sodium dodecyl sulfate, and the conductive polymer is selected to be polyaniline, which are explained in detail. Specifically, in step S10, the nylon 6 pellets are mixed with formic acid, carbon nanotubes and sodium dodecyl sulfate, and stirred at 15-40 ℃ for 3-6 hours until the solute is uniformly dispersed, so as to form a uniform spinning solution. In this example, in the spinning solution, the mass fraction of nylon 6 was 20%, the mass fraction of sodium dodecylsulfate was 0.05%, and the mass fraction of carbon nanotubes was 8%.
And step S20, preparing the spinning solution to form a nanofiber membrane through an electrostatic spinning process.
Specifically, in carrying out this example, the voltage was set to 20kV, the receiving distance was set to 15cm, the ambient temperature for receiving the nanofiber membrane was set to 25 ℃ and the humidity was set to 50 RH% in the electrospinning process. It should be noted that, in some other embodiments, the spinning voltage may be selected to be in the range of 10 to 30kV, the receiving distance may be selected to be in the range of 10 to 30cm, the ambient temperature for receiving the nanofiber membrane may be selected to be in the range of 15 to 40 ℃, and the humidity may be selected to be in the range of 40 to 70 RH%.
Step S20 prepared the resulting nanofiber film, hereinafter denoted as sample PA6@ CNT. FIG. 2 is an SEM image of a sample PA6@ CNT, and referring to FIG. 2, a nanofiber membrane PA6@ CNT prepared by an embodiment of the invention has a structure of a primary fiber and a secondary spider-web fiber which are connected with each other, and the fibers are in a multi-level distribution state, wherein the fibers comprise the primary fibers with larger sizes (100-200 nm) and the spider-web secondary fibers with smaller sizes (5-15 nm).
For comparison, the spinning solution was prepared in the above step S10 without adding carbon nanotubes (conductive nanomaterial) and sodium dodecyl sulfate (surfactant), and the rest was completely referred to the processes of the above steps S10 and S20 to prepare a nanofiber membrane of a comparative sample, hereinafter referred to as sample PA 6. Fig. 3 is an SEM image of sample PA6, and referring to fig. 3, nanofiber membrane sample PA6, which has substantially only one size of fibers, corresponding to the primary fibers in the present example, due to the absence of conductive nanomaterials and surfactants added to the spinning solution.
It should be explained that:
the electrostatic spinning technology is a method for preparing nano-fibers by drawing spinning solution at high speed by using a strong electric field formed by high-voltage static electricity. Melt electrospinning and solution electrospinning can be classified according to the state of the spinning solution system. Under the action of electric field force, the internal ions are gathered to the electrode with the opposite charge property, and finally a large amount of charges are accumulated on the surface of the spinning solution near the electrode, and at the moment, surface tension pointing to the inside of the spinning solution and the opposite electric field force exist at the tail end of a spinning nozzle. Along with the gradual increase of the electric field force, when the electric field force applied to the tail end of the spinning nozzle exceeds the surface tension of the spinning solution, liquid drops are ejected to form jet flow to form a Taylor cone, continuous nano fibers are formed through electric field stretching, solvent volatilization or melt solidification and are deposited on a collecting device, and finally a nano fiber film is formed.
As described above, in the electrostatic spinning process, surface tension directed to the spinning solution and electric field force directed to the receiving plate exist at the needle (spinning nozzle) of the injector, and in the technical scheme provided by the invention, after the conductive nano material (such as carbon nano tube) and the surfactant (such as sodium dodecyl sulfate) are added into the spinning solution, the conductivity of the spinning solution is increased and the surface tension thereof is reduced, so that droplets at the needle are in an unstable state under stress, and charged droplets are generated while jet flow is generated, and the charged droplets are subjected to stretching and solvent volatilization in the electric field to finally form a nano spider web, and are deposited on the receiving plate together with the main fiber formed by the jet flow, so that the prepared nano fiber membrane has a structure with a primary main fiber and a secondary spider web fiber.
Thus, the presence of nano-spider web fibers in the PA6@ CNTs of the inventive examples increased the specific surface area of the fibers in the samples compared to the comparative sample PA6, thereby providing more binding sites for polymer attachment during subsequent in situ polymerization reactions.
And step S30, polymerizing a conductive polymer on the nanofiber membrane in situ to prepare the flexible conductive fiber membrane material. The method specifically comprises the following steps:
s31, soaking the nanofiber membrane in a monomer solution for forming a conductive polymer.
Wherein the monomer for forming the conductive polymer is an aniline monomer, a pyrrole monomer or a thiophene monomer; in the monomer solution, the solvent is selected from any one of ethanol, diethyl ether and acetone. In the monomer solution for forming the conductive polymer, the mass concentration of the monomer can be 5-30%, and the soaking time in the step can be 0.5-3 hours.
In the embodiment of the present invention, the conductive polymer is polyaniline, and thus the monomer for forming the conductive polymer is aniline monomer. Step S31 specifically includes: soaking the nanofiber membrane in an ethanol solution of an aniline monomer; in the ethanol solution of the aniline monomer, the mass concentration of the aniline monomer is 20%, and the soaking time is 2 hours.
And S32, placing the soaked nanofiber membrane in an acid solution of an oxidant for in-situ polymerization reaction, and carrying out in-situ polymerization on the nanofiber membrane to form a conductive polymer.
Wherein in the acid solution of the oxidant, the concentration of the oxidant is 10-40 g/L, the concentration of the acid is 0.1-2 mol/L, and the polymerization time is 1-3 hours; the acid is selected from any one of hydrochloric acid, sulfuric acid and phosphoric acid.
Wherein, when the monomer is aniline monomer, the oxidant is ammonium persulfate; when the monomer is a pyrrole monomer or a thiophene monomer, the oxidant is ferric trichloride; the acid is selected from any one of hydrochloric acid, sulfuric acid and phosphoric acid.
In a specific embodiment of the invention, the monomer used to form the conductive polymer is an aniline monomer, and thus the oxidant is selected to be ammonium persulfate. Step S31 specifically includes: and (3) placing the soaked nanofiber membrane in a hydrochloric acid solution of ammonium persulfate to carry out in-situ polymerization reaction, and carrying out in-situ polymerization on the nanofiber membrane to form polyaniline. In the hydrochloric acid solution of the ammonium persulfate, the concentration of the ammonium persulfate is 30g/L, the concentration of the hydrochloric acid is 0.5mol/L, and the polymerization time is 2 hours.
S33, washing and drying the nanofiber membrane after the conductive polymer is formed by in-situ polymerization, and preparing the flexible conductive fiber membrane material. Specifically, the fiber membrane after in-situ polymerization is washed with distilled water and dried at 15-40 ℃ until the sample membrane is completely dried.
In this example, a part of the sample PA6@ CNT prepared in step S20 was subjected to in situ polyaniline polymerization according to step S30 (the other part was left for use), and the sample of the conductive fiber film prepared was designated as PA6@ CNT @ PANI. FIG. 4 is an SEM image of sample PA6@ CNT @ PANI with reference to FIG. 4, sample PA6@ CNT @ PANI in which polyaniline is uniformly polymerized in situ on the primary and secondary spider fibers.
In addition, for comparison, a portion of the comparative sample PA6 was also subjected to in situ polymerization of polyaniline according to step S30 (the other portion was left for use), and the conductive fiber film sample obtained was designated as PA6@ PANI. FIG. 5 is an SEM image of sample PA6@ PANI, with reference to FIG. 5, sample PA6@ PANI in which polyaniline is polymerized in situ on the fibers.
Fig. 6 is an exemplary illustration of a flexibility test of the conductive fiber film material PA6@ PANI of the comparative example sample. Specifically, sample PA6@ PANI was cut into square pieces (FIG. 6-a), then folded into the shape of a "fish" (FIG. 6-a'), and finally unfolded to restore the square shape (FIG. 6-a ").
FIG. 7 is an exemplary illustration of a flexibility test of a conductive fiber film material PA6@ CNT @ PANI prepared according to an embodiment of the present invention. Specifically, sample PA6@ CNT @ PANI was cut into square pieces (FIG. 7-b), then folded into the shape of a "fish" (FIG. 7-b'), and finally unfolded to restore the square shape (FIG. 7-a ").
As can be seen from fig. 6 and 7, the fiber membrane obtained by electrospinning has good flexibility, and the in-situ polymerization reaction does not lose the flexibility of the fiber membrane, and the shape of the fiber membrane can be arbitrarily changed and can be restored to the original shape. In addition, as shown in fig. 7, the sample of the technical solution of the present invention further includes carbon nanotubes without losing the flexibility of the fiber film, which indicates that the flexible conductive multi-layer fiber film provided by the present invention provides a possibility for application in fields such as flexible wearable devices.
The embodiment of the invention also performs infrared spectrum test on the sample before and after in-situ polymerization. Specifically, infrared spectroscopy was performed on each of the four samples PA6, PA6@ CNT, PA6@ PANI, and PA6@ CNT @ PANI to determine whether the in situ polymerization reaction successfully coated polyaniline on the surface of the fiber, and the results are shown in FIG. 8.
As can be seen in FIG. 8, the samples PA6@ PANI and PA6@ CNT @ PANI after in situ polymerization are 807cm wave number compared to the samples PA6 and PA6@ CNT before polymerization-1Has an absorption peak of C-H bending vibration on the benzene ring at a wave number of 1505cm-1The position (2) has an absorption peak of stretching vibration of the benzene ring C ═ C. These absorption peaks belong to the characteristic peaks of polyaniline, so that the polyaniline can be successfully coated on the surface of the fiber by in-situ polymerization.
The embodiment of the invention also performs thermogravimetric analysis test on the sample before and after in-situ polymerization. Specifically, thermogravimetric analysis tests were performed on four samples, PA6, PA6@ CNT, PA6@ PANI and PA6@ CNT @ PANI, respectively, to determine the change in thermal properties of the polyaniline-coated composite material by in situ polymerization, and the test results are shown in fig. 9.
As can be seen from fig. 9, samples PA6 and PA6@ PANI were substantially completely thermally decomposed after the end of the test, while samples PA6@ CNT and PA6@ CNT @ PANI remained residual amounts of 7.08% and 4.46%, respectively, because the carbon nanotubes could not be destroyed by high temperature, so the residual amount was the actual content of carbon nanotubes in the sample. And because the carbon nanotubes cannot be uniformly dispersed on a microscopic scale, the content of the carbon nanotubes in samples at different parts is slightly different. As can be seen from the figure, the initial decomposition temperature of the sample after in situ polymerization was reduced, which indicates that the addition of polyaniline decreased the thermal stability of the fibrous membrane.
The embodiment of the invention also performs tensile property test on the sample before and after in-situ polymerization. Specifically, the tensile property test was carried out on four samples, PA6, PA6@ CNT, PA6@ PANI and PA6@ CNT @ PANI, respectively, according to the following steps: (1) cutting each fiber membrane sample into strips of 3 multiplied by 1 cm; (2) respectively sticking sand paper on two ends of the strip-shaped sample obtained in the step (1) so as to increase the friction force between the sample and the clamp; (3) and (3) carrying out a tensile test on the sample obtained in the step (2) by using a universal testing machine, wherein the test result is shown in FIG. 10.
As can be seen from fig. 10, the tensile strengths of samples PA6 and PA6@ CNT were 5.55MPa and 4.09MPa, respectively, and the elongations at break were 0.08 and 0.12, respectively, which indicates that the addition of carbon nanotubes reduced the tensile strength of the samples. The carbon nanotubes are not uniformly dispersed in the sample, and the agglomerates thereof correspond to stress concentration points in the sample, thereby causing a decrease in the tensile strength of the sample. The samples PA6@ PANI and PA6@ CNT @ PANI after in-situ polymerization of polyaniline have tensile strengths of 13.39MPa and 4.37MPa respectively and breaking elongations of 0.37 and 0.40 respectively, and the strength and toughness of the samples are improved. In addition, the conductive fiber film sample PA6@ CNT @ PANI prepared by the technical scheme of the invention has the maximum elongation at break, mainly the nanofiber film has the structure of primary main fibers and secondary spider fibers, and polyaniline polymerized in situ is more uniformly coated on the surfaces of the fibers.
The embodiment of the invention also performs conductivity tests on the samples before and after in-situ polymerization. Specifically, conductivity tests were performed on four samples, PA6, PA6@ CNT, PA6@ PANI, and PA6@ CNT @ PANI, respectively, as follows: (1) cutting each fiber membrane sample into strips of 3 multiplied by 1cm, and coating a layer of conductive silver adhesive on two ends of each strip sample; (2) respectively sticking conductive copper adhesive tapes on two ends of the strip-shaped sample obtained in the step (1); (3) and (3) testing the sample obtained in the step (2) by using an electrochemical workstation, wherein the test results are shown in fig. 11 and 12, fig. 11 is an I-V curve chart of four fiber membrane samples, and fig. 12 is a conductivity parameter chart of the four fiber membrane samples obtained according to fig. 11. In FIG. 11, the curves for samples PA6, PA6@ CNT and PA6@ PANI in the large graph are almost completely coincident and indistinguishable, therefore, the overlapping portions are magnified to the smaller graph, and the curves for PA6 and PA6@ CNT are also almost completely coincident and the curve for PA6@ PANI is distinguishable.
As can be seen in FIG. 11, the resistances of samples PA6 and PA6@ CNT are not very different, and after in situ polymerization, the resistances of samples PA6@ PANI and PA6@ CNT @ PANI are greatly reduced, and the resistance of samples PA6@ CNT @ PANI is reduced by a larger amount. As can be seen in FIG. 12, the conductivity of sample PA6 was 1.75X 10-9S/m, sample PA6@ CNT after addition of carbon nanotubes has a conductivity of 8.24X 10-10S/m, the conductivity was hardly improved because the carbon nanotubes were not uniformly dispersed and no conductive path was formed, thus not contributing to the conductivity of the fiber film sample. The conductivity of the sample PA6@ PANI after in-situ polymerization of polyaniline is 1.52 multiplied by 10-5S/m, compared with a sample without polymerized polyaniline, the conductivity is improved by 4 orders of magnitude, and the conductivity of the sample is greatly improved by the polyaniline uniformly coated on the surface of the fiber. The conductivity of the conductive fiber film sample PA6@ CNT @ PANI prepared by the technical scheme is 9.18 multiplied by 10-3S/m, the conductivity of the polyaniline-doped nano-fiber is improved by 7 orders of magnitude compared with that of a sample of unpolymerized polyaniline, and the conductivity of the polyaniline-doped nano-fiber is also improved by 2 orders of magnitude compared with that of a sample PA6@ PANI without the carbon nano-tube. This indicates that the presence of the nano spider web in the nanofiber membrane provides more binding sites for the coating of polyaniline, and thusThe conductivity can be greatly improved.
It should be noted that, in the above specific implementation, only the sample prepared by selecting the fiber base material as nylon 6, the conductive nano material as carbon nanotube, the surfactant as sodium dodecyl sulfate, and the conductive polymer as polyaniline is subjected to the relevant tests as specific description, based on the concept of the present invention, "after the conductive nano material and the surfactant are added into the spinning solution, the conductivity of the spinning solution is increased and the surface tension thereof is reduced, so that the prepared nanofiber membrane has the structure of the primary main fiber and the secondary spider web fiber, and can provide more binding sites for the attachment of the polymer, thereby greatly improving the conductivity of the conductive fiber membrane material", those skilled in the art can easily know that, when the fiber base material, the conductive nano material, the surfactant, and the conductive polymer are selected as other specific materials listed in the present invention, similar effects can be obtained.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (12)
1. A preparation method of a flexible conductive fiber membrane material is characterized by comprising the following steps:
dissolving a fiber base material, a conductive nano material and a surfactant in an organic solvent to prepare a spinning solution;
preparing the spinning solution into a nanofiber membrane through an electrostatic spinning process;
and polymerizing a conductive polymer on the nanofiber membrane in situ to prepare the flexible conductive fiber membrane material.
2. The preparation method of the flexible conductive fiber membrane material as claimed in claim 1, wherein in the spinning solution, the mass fraction of the fiber base material is 5-25%, the mass fraction of the surfactant is 0.01-0.1%, and the mass fraction of the conductive nano material is 2-20%.
3. The method for preparing the flexible conductive fiber membrane material as claimed in claim 1, wherein the fiber base material is selected from any one of polyamide, polyacrylic acid, polyurethane, chitosan or silk fibroin, the conductive nanomaterial is selected from any one of carbon nanotubes, graphene or metal nanoparticles, the surfactant is selected from any one of sodium dodecyl sulfonate, dodecyl trimethyl ammonium bromide, linear alkyl benzene sulfonate, fatty alcohol polyoxyethylene ether ammonium sulfate and polyoxyethylene fatty alcohol ether, the organic solvent is selected from any one of formic acid, hexafluoroisopropanol and m-cresol, and the conductive polymer is polyaniline, polypyrrole or polythiophene.
4. The preparation method of the flexible conductive fiber membrane material according to claim 3, wherein the fiber base material is nylon 6, the conductive nano material is carbon nano tube, the surfactant is sodium dodecyl sulfate, and the conductive polymer is polyaniline.
5. The preparation method of the flexible conductive fiber membrane material as claimed in claim 1, wherein in the electrostatic spinning process, the spinning voltage is 10kV to 30kV, the receiving distance is 10cm to 30cm, the ambient temperature for receiving the nanofiber membrane is 15 ℃ to 40 ℃, and the humidity is 40 RH% to 70 RH%.
6. The preparation method of the flexible conductive fiber membrane material according to any one of claims 1 to 5, wherein the step of polymerizing the conductive polymer in situ on the nanofiber membrane specifically comprises:
soaking the nanofiber membrane in a monomer solution for forming a conductive polymer;
placing the soaked nanofiber membrane in an acid solution of an oxidant to perform in-situ polymerization reaction, and performing in-situ polymerization on the nanofiber membrane to form a conductive polymer;
and washing and drying the nanofiber membrane after the in-situ polymerization to form the conductive polymer to prepare the flexible conductive fiber membrane material.
7. The preparation method of the flexible conductive fiber membrane material as claimed in claim 6, wherein in the monomer solution for forming the conductive polymer, the mass concentration of the monomer is 5-30%, and the soaking time is 0.5-3 hours.
8. The preparation method of the flexible conductive fiber membrane material as claimed in claim 6, wherein in the acid solution of the oxidant, the concentration of the oxidant is 10 g/L-40 g/L, the concentration of the acid is 0.1 mol/L-2 mol/L, and the polymerization time is 1-3 hours.
9. The preparation method of the flexible conductive fiber membrane material according to claims 6-8, wherein the monomer for forming the conductive polymer is aniline monomer, pyrrole monomer or thiophene monomer; in the monomer solution, the solvent is selected from any one of ethanol, diethyl ether and acetone.
10. The method for preparing the flexible conductive fiber membrane material according to claim 9, wherein when the monomer is aniline monomer, the oxidant is ammonium persulfate; when the monomer is a pyrrole monomer or a thiophene monomer, the oxidant is ferric trichloride; the acid is selected from any one of hydrochloric acid, sulfuric acid and phosphoric acid.
11. A flexible conductive fibrous membrane material obtained by the production method according to any one of claims 1 to 10, wherein the nanofiber membrane has a structure of primary and secondary spider web fibers connected to each other, and the conductive polymer is polymerized in situ on the primary and secondary spider web fibers.
12. The flexible conductive fibrous membrane material of claim 11, wherein the primary fibers have a diameter of 100nm to 200nm and the secondary spider web fibers have a diameter of 5nm to 15 nm.
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| PCT/CN2019/125900 WO2021114321A1 (en) | 2019-12-13 | 2019-12-17 | Flexible conductive fiber membrane material and preparation method therefor |
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