CN112376282B - Polyaniline/thermoplastic polymer conductive nanofiber membrane and preparation method thereof - Google Patents
Polyaniline/thermoplastic polymer conductive nanofiber membrane and preparation method thereof Download PDFInfo
- Publication number
- CN112376282B CN112376282B CN202011271860.0A CN202011271860A CN112376282B CN 112376282 B CN112376282 B CN 112376282B CN 202011271860 A CN202011271860 A CN 202011271860A CN 112376282 B CN112376282 B CN 112376282B
- Authority
- CN
- China
- Prior art keywords
- thermoplastic polymer
- polyaniline
- nanofiber membrane
- aniline
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- 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
- D04H1/4282—Addition polymers
- D04H1/4291—Olefin series
-
- 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
-
- 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
- D04H1/435—Polyesters
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/007—Addition polymers
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
- D04H3/009—Condensation or reaction polymers
- D04H3/011—Polyesters
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
- D06M2101/08—Esters or ethers of cellulose
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The invention relates to a polyaniline/thermoplastic polymer conductive nanofiber membrane and a preparation method thereof, wherein the preparation method comprises the following steps: adding an oxidant solution into a mixture of the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, the acidic solution II and aniline (the volume ratio of the acidic solution II to the aniline is 48: 0.1-0.9) to obtain a reaction system, and applying an electric field with a certain voltage (1-4 kV) to the reaction system to react for a certain time to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane. The finally prepared polyaniline/thermoplastic polymer conductive nanofiber membrane consists of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers (the average length is 300-800 nm); the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure. The preparation method is simple, and the conductivity of the prepared polyaniline/thermoplastic polymer conductive nanofiber membrane is 11.4-26.3 mS/cm.
Description
Technical Field
The invention belongs to the technical field of conductive nanofiber membranes, and relates to a polyaniline/thermoplastic polymer conductive nanofiber membrane and a preparation method thereof.
Background
Polyaniline has excellent performances of high conductivity, good stability, fast response speed, low working voltage and the like, is one of the most promising conductive polymer materials, and has been applied to a plurality of new fields, such as exchange electrodes, secondary batteries, gas sensitive materials, electrochromic displays, electronic equipment, sensors, electromagnetic shielding, antistatic, metal corrosion prevention and the like.
At present, the methods for synthesizing polyaniline mainly include electrochemical polymerization, chemical oxidative polymerization, and the like. The electrochemical method is only suitable for synthesizing small batches of polyaniline, the synthesis speed is low, and meanwhile, the product is generated on an electrode and is difficult to strip, so that the application of the product is limited. The structure and performance of polyaniline polymerized by chemical oxidative polymerization vary with the variety and concentration of doping acid, the variety and concentration of oxidant, monomer concentration, reaction temperature, reaction time and other factors.
In recent years, nanomaterial preparation technology has been widely applied to the preparation and synthesis of conductive polymers. Due to the size effect, the surface effect and the like of the nano material, the functional characteristics of the conductive polymer material are greatly expanded. The forms of the nano-structured polyaniline are various, such as nanoparticles, nanowires, nanotubes, nanospheres, nanosheets, nanofibers, and the like. Polyaniline nanofibers, nanotubes, nanorods, etc. have the same main chain structure as the irregular particle polyaniline prepared by a common method, but have different properties. Polyaniline nano-fiber, nano-tube, nano-rod and the like have higher conductivity due to more regular molecular structure, more ordered arrangement, larger specific surface area and the like.
Due to its good chemical stability, mechanical strength, versatility and continuity, thermoplastic polymer nanofiber membranes can be extensively derivatized while being used to make stable and robust supports, matrices or scaffold assemblies of functional materials. The huge specific surface area of the thermoplastic polymer nanofiber membrane provides a stable solid matrix for the in-situ chemical oxidative polymerization of polyaniline, so that a composite material with good performance is obtained. The material can combine the electrical property of polyaniline and the unique property of a thermoplastic polymer nanofiber membrane, has small density and low cost, can be produced in a large scale, and can be applied to the fields of adsorption filtration, friction nano-generators, flexible wearable sensors, energy storage devices and the like. However, most polyaniline is only loaded on the surface of the thermoplastic polymer nanofiber membrane in the form of a coating or a thin film, the conductivity is low, and only a small amount of polyaniline can grow on the surface of the thermoplastic polymer nanofiber membrane in the form of fibers. In the literature (High Sensitivity ammonium Sensor Using a High purity Polyaniline/Poly (ethylene-co-glycidyl methacrylate. Nanofibrous Composite Membrane J. ACS appl. Mater. interfaces 2013,5,6473-6477.) a three-dimensional network nanofiber Composite Membrane with a layered structure is prepared by in-situ growth of uniform Polyaniline on the surface of Poly (ethylene-co-glycidyl methacrylate) (PE-co-GMA) nanofibers, the method solves the problem that the polyaniline is difficult to grow on the surface of the thermoplastic polymer nanofiber membrane, has the defects that the polyaniline is in the form of nanorods, has shorter length (about 100nm) and can not penetrate through the pores of the nanofiber membrane, so that the polyaniline nanorods on the whole nanofiber membrane are connected, the conductivity is further improved, the order of the polyaniline nano-rods is reduced along with the increase of the reaction time, and more nano-rods are randomly stacked on the surface of the fiber membrane.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polyaniline/thermoplastic polymer conductive nanofiber membrane and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the steps of firstly preparing a mixture of thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, acidic solution II and aniline; adding oxidant solution into the mixture to obtain a reaction system, and applying an electric field with certain voltage to the reaction system to react for a certain time to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane;
the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing the aniline is prepared by sequentially soaking the thermoplastic polymer nanofiber membrane in an acid solution I and the aniline; the thermoplastic polymer nanofiber membrane is simple to prepare and environment-friendly, and can be produced in a large scale; the acid solution I is soaked to perform hydrophilic treatment on the thermoplastic polymer nanofiber membrane, so that aniline can be better adsorbed by the thermoplastic polymer nanofiber membrane; the aniline is infiltrated to provide nucleation points for in-situ growth of the aniline;
the volume ratio of the acid solution II to the aniline in the mixture is 48: 0.1-0.9, the dosage of the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing the aniline is not limited, and the thermoplastic polymer nanofiber membrane can be completely immersed in the acid solution II and the aniline;
the acid solution I and the acid solution II are both aqueous solutions of acid doping agents;
the certain voltage is 1-4 kV.
In the process of forming polyaniline nanofibers and nanorods, if concentrated aniline and an oxidant are used in an in-situ polymerization system, aniline is induced to form polyaniline in a bulk solution at a high speed, and the polyaniline is deposited on the surface of a solid matrix slowly, on the contrary, if diluted aniline and an oxidant are used in the in-situ polymerization system, heterogeneous nucleation reaction of aniline firstly occurs on the surface of the solid matrix, and then aniline grows from an active nucleation center, so that polyaniline nanorods are formed. The method applies an electric field with a certain voltage to a reaction system, and oxidized aniline cation free radicals are oriented along the direction of the electric field under the action of the electric field, so that the secondary growth of the polyaniline is inhibited.
As a preferred technical scheme:
in the preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane, the acidic doping agents in the acidic solution I and the acidic solution II are the same and are hydrochloric acid, citric acid or sulfuric acid; the concentration of the acid solution I and the acid solution II is 0.05-1 mol/L.
In the preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane, the thermoplastic polymer nanofiber membrane is prepared by adopting an electrostatic spinning method, a sea-island spinning method, a dry spinning method or a wet spinning method, and the thermoplastic polymer is polyester polymer (PET, PBT, PTT), polyamide polymerization degree (PA6, PA66, PA1010) or polyolefin copolymer (PVA-co-PE, PE-co-GMA).
According to the preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane, when the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline is prepared, the time of soaking in the acid solution I is 5-10 min, ultrasonic treatment is accompanied during soaking, and the frequency of ultrasonic treatment is 35-53 Hz;
soaking in aniline for 2-5 min, and standing during soaking;
soaking in aniline and then in ethanol or deionized water for 1-3 s, and quickly taking out after soaking; the ethanol or deionized water is soaked to ensure that the aniline in the thermoplastic polymer nanofiber membrane is uniformly distributed and remove the redundant aniline;
in the soaking process, the solid-to-liquid ratio of the thermoplastic polymer nanofiber membrane to the acidic solution I, aniline, ethanol or deionized water is not limited as long as the thermoplastic polymer nanofiber membrane can be completely immersed in the acidic solution I, aniline, ethanol or deionized water.
The preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the following steps: firstly, mixing the acid solution II and aniline, stirring for 10-15 min at a stirring speed of 50-300 r/min, then adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring for 10-15 min at a stirring speed of 50-300 r/min.
According to the preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane, the oxidant solution is a mixed solution of an oxidant and an acidic solution III, the content of the oxidant is 0.01-0.05 mol/L, the oxidant is ammonium persulfate or potassium dichromate, the acidic solution III is an aqueous solution of an acidic dopant, the acidic dopants in the acidic solution III and the acidic solution I are the same, and the concentration of the acidic solution III is 0.05-1 mol/L.
According to the preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane, the molar ratio of the oxidant to the aniline in the mixture is 5: 1-1: 5.
The preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane has the advantages that the certain time is 12-24 hours; and washing and drying after reacting for a certain time, wherein the drying is vacuum drying and the temperature is 40-80 ℃.
The invention also provides the polyaniline/thermoplastic polymer conductive nanofiber membrane prepared by the preparation method, which consists of the thermoplastic polymer nanofiber membrane and polyaniline nanofibers; the average length of the polyaniline nano-fiber is 300-800 nm, and the average diameter is 70-150 nm; the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure.
As a preferred technical scheme:
the polyaniline/thermoplastic polymer conductive nanofiber membrane has the conductivity of 11.4-26.3 mS/cm; the polyaniline nanofibers in the polyaniline/thermoplastic polymer conductive nanofiber membrane are long, the average length is 300-800 nm, and the polyaniline nanofibers can penetrate through pores of the thermoplastic polymer nanofiber membrane (the pore diameter of the thermoplastic polymer nanofiber membrane is 20-600 nm), so that the polyaniline nanofibers on the whole thermoplastic polymer nanofiber membrane are connected, the conductivity of the membrane is effectively improved, and meanwhile, the polyaniline nanofibers in the polyaniline/thermoplastic polymer conductive nanofiber membrane are ordered in structure, more regular in molecular structure, more ordered in arrangement and higher in conductivity.
Has the advantages that:
(1) according to the invention, the polyaniline nanofiber grows on the surface and in the nanofiber membrane through voltage regulation for the first time, so that the length of polyaniline can be controlled, the conductivity of different application occasions can be adapted, and the accurate structural design of the nanofiber membrane can be realized in the aspect of microstructure;
(2) in the prior art, most of the prior art can only grow polyaniline films with different thicknesses or polyaniline nanofibers with fixed lengths on the surface and in the interior of the nanofiber membrane, and the problem that the polyaniline nanofibers with controllable lengths can not grow on the surface and in the interior of the nanofiber membrane is solved through voltage regulation, so that the requirement on the conductivity of the conductive nanofiber membrane on different occasions is met.
Drawings
FIG. 1 is an SEM image of a thermoplastic polymer nanofiber membrane;
FIG. 2 is an SEM image of a polyaniline/thermoplastic polymer conductive nanofiber membrane made in example 1;
FIG. 3 is an SEM image of a polyaniline/thermoplastic polymer conductive nanofiber membrane made in comparative example 1;
FIG. 4 is an SEM image of a polyaniline/thermoplastic polymer conductive nanofiber membrane made in example 4;
fig. 5 is a schematic diagram of a device for preparing the polyaniline/thermoplastic polymer conductive nanofiber membrane.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the following steps:
(1) soaking a thermoplastic polymer nanofiber membrane (shown in figure 1) prepared by adopting a sea-island spinning method in an acid solution I for 5min, wherein ultrasonic treatment is accompanied during soaking, the frequency of the ultrasonic treatment is 35Hz, then soaking in aniline for 2min, standing during soaking, soaking in ethanol for 1s again, and quickly taking out after soaking to obtain the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline; the thermoplastic polymer is PBT;
the sea-island spinning process comprises the following steps: uniformly mixing a thermoplastic polymer and CAB (cellulose acetate butyrate) according to a mass ratio of 2:8, performing melt blending extrusion by using a double-screw extruder, wherein the temperature of the double-screw extruder is 190-250 ℃, removing a matrix phase CAB by using acetone as a solvent at 80 ℃ to prepare a thermoplastic polymer nanofiber, uniformly dispersing 0.1g of the thermoplastic polymer nanofiber in an aqueous solution by using a high-speed dispersion machine to form a thermoplastic polymer nanofiber suspension, performing high-speed airflow deposition, collecting the thermoplastic polymer nanofiber suspension on the surface of a filter medium in a membrane form (specifically, a sand core filter device with the volume of 1000mL is adopted, the outer diameter of an upper opening is 60mm, the inner diameter of a lower opening is 40mm, filter paper is a PVDF filter membrane, the diameter is 60mm, and the pore diameter is 0.45 mu m), and naturally air-drying at room temperature to obtain a nanofiber membrane;
(2) mixing the acid solution II and aniline according to a volume ratio of 48:0.1, stirring for 11min at a stirring speed of 300r/min, adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring for 11min at a stirring speed of 300r/min to obtain a mixture;
(3) adding an oxidant solution into the mixture to obtain a reaction system, applying a 1kV electric field (the electrode spacing is 6cm) to the reaction system, reacting for 12h, washing and vacuum drying at 40 ℃ to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane; the oxidant solution is a mixed solution of ammonium persulfate and an acidic solution III, the content of the ammonium persulfate is 0.01mol/L, and the molar ratio of the ammonium persulfate to aniline in the mixture is 5: 1;
the acid solution I, the acid solution II and the acid solution III are all aqueous solutions of hydrochloric acid, and the concentration is 0.05 mol/L.
The polyaniline/thermoplastic polymer conductive nanofiber membrane finally prepared is composed of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers as shown in fig. 2; the average length of the polyaniline nano-fiber is 300nm (the length range is 200-350 nm), and the average diameter is 70nm (the diameter range is 50-80 nm); the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure; the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane was 11.4 mS/cm.
Comparative example 1
A preparation method of a polyaniline/thermoplastic polymer conductive nanofiber membrane, which is basically the same as that in example 1, except that in the step (3), an electric field of 1kV (with an electrode spacing of 6cm) is not applied to a reaction system for reaction for 12 hours, but aniline is directly subjected to chemical oxidative polymerization for 12 hours.
The finally prepared polyaniline/thermoplastic polymer conductive nanofiber membrane consists of a thermoplastic polymer nanofiber membrane and polyaniline nanoparticles, as shown in fig. 3; the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane was 1.8 mS/cm.
Comparing example 1 with comparative example 1, it can be seen that in comparative example 1, polyaniline grows on the surface of the thermoplastic polymer nanofiber in a granular form, and polyaniline nanofiber is not formed, so that the conductivity is low, and thus it is known that the electric field is a key element for ensuring the formation of polyaniline fiber.
Example 2
A preparation method of a polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the following steps:
(1) soaking the thermoplastic polymer nanofiber membrane prepared by the sea-island spinning method in an acidic solution I for 8min, carrying out ultrasonic treatment during soaking, wherein the frequency of the ultrasonic treatment is 35Hz, soaking in aniline for 3min, standing during soaking, soaking in ethanol for 1.2s again, and quickly taking out after soaking to obtain the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline; the thermoplastic polymer is PBT;
the sea-island spinning process comprises the following steps: uniformly mixing a thermoplastic polymer and CAB according to a mass ratio of 2:8, carrying out melt blending extrusion by using a double-screw extruder, wherein the temperature of the double-screw extruder is 190-250 ℃, removing a matrix phase CAB by using acetone as a solvent at 80 ℃ to prepare thermoplastic polymer nano fibers, uniformly dispersing 0.1g of thermoplastic polymer nano fibers in an aqueous solution by using a high-speed dispersion machine to form a thermoplastic polymer nano fiber suspension, carrying out high-speed airflow deposition, and collecting the thermoplastic polymer nano fibers on the surface of a filter medium in a membrane form (specifically, a sand core filter device with the volume of 1000mL is adopted, the outer diameter of an upper opening is 60mm, the inner diameter of a lower opening is 40mm, a filter paper is a PVDF filter membrane, the diameter is 60mm, and the pore diameter is 0.45 mu m), and carrying out natural air drying at room temperature to obtain a nano fiber membrane;
(2) mixing the acid solution II and aniline according to a volume ratio of 48:0.3, stirring for 13min at a stirring speed of 200r/min, adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring for 13min at a stirring speed of 200r/min to obtain a mixture;
(3) adding an oxidant solution into the mixture to obtain a reaction system, applying an electric field of 1.5kV (the electrode spacing is 7cm) to the reaction system, reacting for 15h, washing and vacuum drying at 45 ℃ to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane; the oxidant solution is a mixed solution of ammonium persulfate and an acidic solution III, the content of the ammonium persulfate is 0.02mol/L, and the molar ratio of the ammonium persulfate to aniline in the mixture is 1: 1;
the acid solution I, the acid solution II and the acid solution III are all aqueous solutions of hydrochloric acid, and the concentration is 0.16 mol/L.
The finally prepared polyaniline/thermoplastic polymer conductive nanofiber membrane consists of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers; the average length of the polyaniline nano-fiber is 420nm (the length range is 300-500 nm), and the average diameter is 90nm (the diameter range is 70-110 nm); the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure; the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane was 15.3 mS/cm.
Example 3
A preparation method of a polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the following steps:
(1) soaking the thermoplastic polymer nanofiber membrane prepared by the sea-island spinning method in an acidic solution I for 6min, wherein ultrasonic treatment is carried out during soaking, the frequency of the ultrasonic treatment is 35Hz, then the thermoplastic polymer nanofiber membrane is soaked in aniline for 4min, standing is carried out during soaking, the thermoplastic polymer nanofiber membrane is soaked in ethanol for 1.5s again, and the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline is obtained after soaking and then is taken out quickly; the thermoplastic polymer is EVOH;
the sea-island spinning process comprises the following steps: uniformly mixing a thermoplastic polymer and CAB according to a mass ratio of 2:8, carrying out melt blending extrusion by using a double-screw extruder, wherein the temperature of the double-screw extruder is 190-250 ℃, removing a matrix phase CAB by using acetone as a solvent at 80 ℃ to prepare thermoplastic polymer nano fibers, uniformly dispersing 0.1g of thermoplastic polymer nano fibers in an aqueous solution by using a high-speed dispersion machine to form a thermoplastic polymer nano fiber suspension, carrying out high-speed airflow deposition, and collecting the thermoplastic polymer nano fibers on the surface of a filter medium in a membrane form (specifically, a sand core filter device with the volume of 1000mL is adopted, the outer diameter of an upper opening is 60mm, the inner diameter of a lower opening is 40mm, a filter paper is a PVDF filter membrane, the diameter is 60mm, and the pore diameter is 0.45 mu m), and carrying out natural air drying at room temperature to obtain a nano fiber membrane;
(2) mixing the acid solution II and aniline according to a volume ratio of 48:0.5, stirring for 15min at a stirring speed of 50r/min, adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring for 15min at a stirring speed of 50r/min to obtain a mixture;
(3) adding an oxidant solution into the mixture to obtain a reaction system, applying a 2kV electric field (the electrode spacing is 8cm) to the reaction system, reacting for 18h, washing and drying at 50 ℃ in vacuum to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane; the oxidant solution is a mixed solution of ammonium persulfate and an acidic solution III, the content of the ammonium persulfate is 0.03mol/L, and the molar ratio of the ammonium persulfate to aniline in the mixture is 1: 2;
the acid solution I, the acid solution II and the acid solution III are all citric acid water solutions, and the concentration is 0.48 mol/L.
The finally prepared polyaniline/thermoplastic polymer conductive nanofiber membrane consists of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers; the average length of the polyaniline nano-fiber is 550nm (the length range is 500-600 nm), and the average diameter is 100nm (the diameter range is 90-120 nm); the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure; the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane was 19.5 mS/cm.
Example 4
A preparation method of a polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the following steps:
(1) soaking the thermoplastic polymer nanofiber membrane prepared by the sea-island spinning method in an acidic solution I for 7min, wherein ultrasonic treatment is carried out during the soaking, the frequency of the ultrasonic treatment is 53Hz, the thermoplastic polymer nanofiber membrane is soaked in aniline for 4.2min, standing is carried out during the soaking, the thermoplastic polymer nanofiber membrane is soaked in deionized water for 2.2s again, and the thermoplastic polymer nanofiber membrane with the aniline uniformly adsorbed on the surface is obtained after the soaking; the thermoplastic polymer is EVOH;
the sea-island spinning process comprises the following steps: uniformly mixing a thermoplastic polymer and CAB according to a mass ratio of 2:8, carrying out melt blending extrusion by using a double-screw extruder, wherein the temperature of the double-screw extruder is 190-250 ℃, removing a matrix phase CAB by using acetone as a solvent at 80 ℃ to prepare thermoplastic polymer nano fibers, uniformly dispersing 0.1g of thermoplastic polymer nano fibers in an aqueous solution by using a high-speed dispersion machine to form a thermoplastic polymer nano fiber suspension, carrying out high-speed airflow deposition, and collecting the thermoplastic polymer nano fibers on the surface of a filter medium in a membrane form (specifically, a sand core filter device with the volume of 1000mL is adopted, the outer diameter of an upper opening is 60mm, the inner diameter of a lower opening is 40mm, a filter paper is a PVDF filter membrane, the diameter is 60mm, and the pore diameter is 0.45 mu m), and carrying out natural air drying at room temperature to obtain a nano fiber membrane;
(2) mixing the acid solution II and aniline according to a volume ratio of 48:0.8, stirring for 10min at a stirring speed of 86r/min, adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring for 10min at a stirring speed of 86r/min to obtain a mixture;
(3) adding an oxidant solution into the mixture to obtain a reaction system, applying a 2.5kV electric field (the electrode spacing is 8cm) to the reaction system, reacting for 20h, washing, and vacuum drying at 68 ℃ to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane; the oxidant solution is a mixed solution of potassium dichromate and an acid solution III, the content of the potassium dichromate is 0.04mol/L, and the molar ratio of the potassium dichromate to aniline in the mixture is 1: 3;
the acid solution I, the acid solution II and the acid solution III are all citric acid water solutions, and the concentration is 0.61 mol/L.
The polyaniline/thermoplastic polymer conductive nanofiber membrane finally prepared is composed of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers as shown in fig. 4; the average length of the polyaniline nano-fiber is 600nm (the length range is 550-700 nm), and the average diameter is 110nm (the diameter range is 100-130 nm); the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure; the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane was 23.5 mS/cm.
Example 5
A preparation method of a polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the following steps:
(1) soaking the thermoplastic polymer nanofiber membrane prepared by the electrostatic spinning method in an acidic solution I for 10min, carrying out ultrasonic treatment during soaking, wherein the frequency of the ultrasonic treatment is 53Hz, soaking in aniline for 5min, standing during soaking, soaking in deionized water for 2.8s again, and quickly taking out after soaking to obtain the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline; the thermoplastic polymer is PA 6;
the preparation process parameters of the thermoplastic polymer nanofiber membrane are as follows: the concentration of the spinning solution is 12 wt%, the voltage is 20kV, the spinning speed is 0.2mL/h, the receiving distance is 15cm, and the spinning temperature is 25 ℃;
(2) mixing the acid solution II and aniline according to a volume ratio of 48:0.9, stirring at a stirring speed of 100r/min for 12min, adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring at a stirring speed of 100r/min for 12min to obtain a mixture;
(3) adding an oxidant solution into the mixture to obtain a reaction system, applying a 3kV electric field (the electrode spacing is 6cm) to the reaction system, reacting for 22h, washing, and vacuum drying at 72 ℃ to obtain a polyaniline/thermoplastic polymer conductive nanofiber membrane; the oxidant solution is a mixed solution of potassium dichromate and an acid solution III, the content of the potassium dichromate is 0.05mol/L, and the molar ratio of the potassium dichromate to aniline in the mixture is 1: 4;
the acid solution I, the acid solution II and the acid solution III are all aqueous solutions of sulfuric acid, and the concentration is 0.85 mol/L.
The finally prepared polyaniline/thermoplastic polymer conductive nanofiber membrane consists of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers; the average length of the polyaniline nano-fiber is 680nm (the length range is 650-750 nm), and the average diameter is 130nm (the diameter range is 120-150 nm); the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure; the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane was 25.1 mS/cm.
Example 6
A preparation method of a polyaniline/thermoplastic polymer conductive nanofiber membrane comprises the following steps:
(1) soaking the thermoplastic polymer nanofiber membrane prepared by the electrostatic spinning method in an acid solution I for 9min, carrying out ultrasonic treatment during soaking, wherein the frequency of the ultrasonic treatment is 53Hz, soaking in aniline for 3.5min, standing during soaking, soaking in deionized water for 3s again, and quickly taking out after soaking to obtain the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline; the thermoplastic polymer is PA 6;
the preparation process parameters of the thermoplastic polymer nanofiber membrane are as follows: the concentration of the spinning solution is 12 wt%, the voltage is 20kV, the spinning speed is 0.2mL/h, the receiving distance is 15cm, and the spinning temperature is 25 ℃;
(2) mixing the acid solution II and aniline according to a volume ratio of 48:0.5, stirring for 11min at a stirring speed of 150r/min, adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring for 11min at a stirring speed of 150r/min to obtain a mixture;
(3) adding an oxidant solution into the mixture to obtain a reaction system, applying a 4kV electric field (the electrode spacing is 7cm) to the reaction system, reacting for 24 hours, washing and vacuum drying at 80 ℃ to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane; the oxidant solution is a mixed solution of potassium dichromate and an acid solution III, the content of the potassium dichromate is 0.03mol/L, and the molar ratio of the potassium dichromate to aniline in the mixture is 1: 5;
the acid solution I, the acid solution II and the acid solution III are all aqueous solutions of sulfuric acid, and the concentration is 1 mol/L.
The finally prepared polyaniline/thermoplastic polymer conductive nanofiber membrane consists of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers; the average length of the polyaniline nano-fiber is 800nm (the length range is 750-900 nm), and the average diameter is 150nm (the diameter range is 130-180 nm); the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure; the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane was 26.3 mS/cm.
The apparatus used in examples 1-6 is shown in FIG. 5, in which the reaction system is placed between two electrodes (i.e., two metal wires in the figure, and the electrode distance is the distance between the ends of the two metal wires), and is not in contact with the electrodes.
Claims (9)
1. The preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane is characterized by firstly preparing a mixture; adding oxidant solution into the mixture to obtain a reaction system, and applying an electric field with certain voltage to the reaction system to react for a certain time to obtain the polyaniline/thermoplastic polymer conductive nanofiber membrane;
the preparation process of the mixture comprises the following steps: firstly, mixing the acid solution II with aniline, stirring for 10-15 min at a stirring speed of 50-300 r/min, adding a thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline, and stirring for 10-15 min at a stirring speed of 50-300 r/min;
the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing the aniline is prepared by sequentially soaking the thermoplastic polymer nanofiber membrane in an acid solution I and the aniline;
the volume ratio of the acid solution II to the aniline in the mixture is 48: 0.1-0.9;
the acid solution I and the acid solution II are both aqueous solutions of acid doping agents;
the certain voltage is 1-4 kV.
2. The method for preparing the polyaniline/thermoplastic polymer conductive nanofiber membrane as claimed in claim 1, wherein the acidic dopant in the acidic solution I is the same as that in the acidic solution II, and is hydrochloric acid, citric acid or sulfuric acid; the concentration of the acid solution I and the acid solution II is 0.05-1 mol/L.
3. The method for preparing polyaniline/thermoplastic polymer conductive nanofiber membrane as claimed in claim 1 or 2, wherein the thermoplastic polymer nanofiber membrane is nanofiber membrane prepared by electrospinning, sea-island spinning, dry spinning or wet spinning, and the thermoplastic polymer is polyester polymer, polyamide polymer or polyolefin copolymer.
4. The preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane as claimed in claim 1 or 2, wherein when the thermoplastic polymer nanofiber membrane with the surface uniformly adsorbing aniline is prepared, the soaking time in the acidic solution I is 5-10 min, the soaking is accompanied by ultrasonic treatment, and the ultrasonic treatment frequency is 35-53 Hz;
soaking in aniline for 2-5 min, and standing during soaking;
and soaking the mixture in aniline and then in ethanol or deionized water for 1-3 s.
5. The method for preparing the polyaniline/thermoplastic polymer conductive nanofiber membrane as claimed in claim 1 or 2, wherein the oxidant solution is a mixture of an oxidant and an acidic solution III, the content of the oxidant is 0.01-0.05 mol/L, the oxidant is ammonium persulfate or potassium dichromate, the acidic solution III is an aqueous solution of an acidic dopant, the acidic dopants in the acidic solution III and the acidic solution I are the same, and the concentration of the acidic solution III is 0.05-1 mol/L.
6. The method for preparing the polyaniline/thermoplastic polymer conductive nanofiber membrane as claimed in claim 1 or 2, wherein the molar ratio of oxidant to aniline in the mixture is 5: 1-1: 5.
7. The preparation method of the polyaniline/thermoplastic polymer conductive nanofiber membrane as claimed in claim 1 or 2, wherein the certain time is 12-24 hours; and washing and drying after reacting for a certain time, wherein the drying is vacuum drying and the temperature is 40-80 ℃.
8. The polyaniline/thermoplastic polymer conductive nanofiber membrane prepared by the preparation method according to any one of claims 1 to 7, which is characterized by consisting of a thermoplastic polymer nanofiber membrane and polyaniline nanofibers; the average length of the polyaniline nano-fiber is 300-800 nm, and the average diameter is 70-150 nm; the polyaniline nano-fiber is mainly rooted on the surface of the thermoplastic polymer nano-fiber, grows along the direction vertical to the thermoplastic polymer nano-fiber, and has an ordered structure.
9. The polyaniline/thermoplastic polymer conductive nanofiber membrane of claim 8, wherein the conductivity of the polyaniline/thermoplastic polymer conductive nanofiber membrane is 11.4-26.3 mS/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011271860.0A CN112376282B (en) | 2020-11-13 | 2020-11-13 | Polyaniline/thermoplastic polymer conductive nanofiber membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011271860.0A CN112376282B (en) | 2020-11-13 | 2020-11-13 | Polyaniline/thermoplastic polymer conductive nanofiber membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112376282A CN112376282A (en) | 2021-02-19 |
| CN112376282B true CN112376282B (en) | 2021-10-26 |
Family
ID=74583964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011271860.0A Active CN112376282B (en) | 2020-11-13 | 2020-11-13 | Polyaniline/thermoplastic polymer conductive nanofiber membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112376282B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113796866B (en) * | 2021-08-10 | 2023-06-20 | 中山大学 | Electrode and preparation method and application thereof |
| CN116536931B (en) * | 2023-05-05 | 2023-12-26 | 浙江佳康实业有限公司 | Shading and ultraviolet-resistant fabric and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255634A (en) * | 2013-05-23 | 2013-08-21 | 中原工学院 | Preparation method of polyacrylonitrile/polyaniline compound micro-nano conductive fiber |
| CN103290685A (en) * | 2012-02-22 | 2013-09-11 | 北京服装学院 | Method for preparing high-conductivity conductive fiber and fabric, prepared conductive fiber and fabric and applications thereof |
| CN103936984A (en) * | 2014-04-10 | 2014-07-23 | 东华大学 | Method for preparing polyaniline nanofiber by applying electric field regulation |
| CN109293918A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | A kind of polyaniline nano clump and preparation method thereof and device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7297305B2 (en) * | 2004-04-08 | 2007-11-20 | Research Triangle Institute | Electrospinning in a controlled gaseous environment |
-
2020
- 2020-11-13 CN CN202011271860.0A patent/CN112376282B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290685A (en) * | 2012-02-22 | 2013-09-11 | 北京服装学院 | Method for preparing high-conductivity conductive fiber and fabric, prepared conductive fiber and fabric and applications thereof |
| CN103255634A (en) * | 2013-05-23 | 2013-08-21 | 中原工学院 | Preparation method of polyacrylonitrile/polyaniline compound micro-nano conductive fiber |
| CN103936984A (en) * | 2014-04-10 | 2014-07-23 | 东华大学 | Method for preparing polyaniline nanofiber by applying electric field regulation |
| CN109293918A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | A kind of polyaniline nano clump and preparation method thereof and device |
Non-Patent Citations (1)
| Title |
|---|
| High sensitivity ammonia sensor using a hierarchical polyaniline/poly(ethylene-co-glycidyl methacrylate) nanofibrous composite membrane;Chen S et al.;《Acs Appl Mater Interfaces》;20130724;第5卷(第14期);6473-6477 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112376282A (en) | 2021-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Abdah et al. | Review of the use of transition-metal-oxide and conducting polymer-based fibres for high-performance supercapacitors | |
| Han et al. | Conducting polymers for flexible supercapacitors | |
| US10106420B2 (en) | Method for manufacturing graphene fiber | |
| Heme et al. | Recent progress in polyaniline composites for high capacity energy storage: A review | |
| Ahmed et al. | Preparation of PVDF-TrFE based electrospun nanofibers decorated with PEDOT-CNT/rGO composites for piezo-electric pressure sensor | |
| Yu et al. | All-solid-state flexible supercapacitors based on highly dispersed polypyrrole nanowire and reduced graphene oxide composites | |
| Nie et al. | Facile fabrication of flexible SiO2/PANI nanofibers for ammonia gas sensing at room temperature | |
| CN112376282B (en) | Polyaniline/thermoplastic polymer conductive nanofiber membrane and preparation method thereof | |
| Wang et al. | Flexible electrodes and electrolytes for energy storage | |
| Huang et al. | Fabrication of vanadium oxide, with different valences of vanadium,-embedded carbon fibers and their electrochemical performance for supercapacitor | |
| KR100564774B1 (en) | Nano-composite fiber its preparation and use | |
| Wu et al. | Graphene-based flexible all-solid-state supercapacitors | |
| CN104878590A (en) | Preparation method of conductive graphene nanofiber membrane | |
| CN111020882A (en) | Flexible conductive fiber membrane material and preparation method thereof | |
| Guan et al. | Hydrophilicity improvement of graphene fibers for high-performance flexible supercapacitor | |
| CN108831753B (en) | Aramid fiber electrode and preparation method thereof | |
| CN111739739B (en) | Flexible capacitor based on macroscopic high-conductivity MXene ribbon fiber and preparation method and application thereof | |
| Dawouda et al. | A brief overview of flexible CNT/PANI super capacitors | |
| Olad et al. | Study on the capacitive performance of polyaniline/activated carbon nanocomposite for supercapacitor application | |
| CN115295714B (en) | Flexible piezoelectric nanofiber net film and preparation method and application thereof | |
| Qiang et al. | Layer-by-layer self-assembled TEMPO-oxidized cellulose nanofiber/reduced graphene oxide/polypyrrole films for self-supporting flexible supercapacitor electrodes | |
| Ju et al. | Honeycomb-like polyaniline for flexible and folding all-solid-state supercapacitors | |
| CN110838412A (en) | Aramid fiber electrochemical capacitor | |
| KR101794440B1 (en) | Method of manufacturing coated porous material, coated porous material and electrode comprising the coated porous material | |
| KR101704246B1 (en) | Method for preparing conductive composite fiber based on graphene oxide and carbon nanotube, the conductive composite fiber prepared therefrom, and supercapacitor comprisng the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |