CN114790591B - Polyimide/polyaniline composite conductive fiber membrane material and preparation method thereof - Google Patents
Polyimide/polyaniline composite conductive fiber membrane material and preparation method thereof Download PDFInfo
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- CN114790591B CN114790591B CN202210362854.9A CN202210362854A CN114790591B CN 114790591 B CN114790591 B CN 114790591B CN 202210362854 A CN202210362854 A CN 202210362854A CN 114790591 B CN114790591 B CN 114790591B
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 161
- 239000004642 Polyimide Substances 0.000 title claims abstract description 91
- 229920001721 polyimide Polymers 0.000 title claims abstract description 91
- 239000000835 fiber Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 89
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 46
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
- 239000010410 layer Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000012792 core layer Substances 0.000 claims abstract description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 114
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 50
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 40
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 7
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000009471 action Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
Abstract
The invention discloses a polyimide/polyaniline composite conductive fiber membrane material which is of a coaxial fiber structure; the core layer is a polyimide layer, and the shell layer is a polyaniline layer. The invention also provides a preparation method of the composite conductive fiber membrane material, which comprises the following steps: (1) Aniline is used as a raw material, protonic acid doped polyaniline is prepared by emulsion polymerization, undoped polyaniline is prepared by dedoping, and polyaniline spinning solution is prepared by secondary doping; (2) Taking soluble polyimide as a raw material, and dissolving the soluble polyimide in an organic solvent to prepare polyimide spinning solution; (3) The polyimide/polyaniline composite conductive fiber membrane material is prepared by taking polyaniline spinning solution as a shell spinning solution and polyimide spinning solution as a core spinning solution and adopting coaxial electrostatic spinning. The polyimide/polyaniline composite conductive fiber membrane material prepared by the invention has unique pore structure, better flexibility and conductivity, simple preparation steps, short period and low cost.
Description
Technical Field
The invention relates to the technical field of conductive composite materials, in particular to a polyimide/polyaniline composite conductive fiber membrane material and a preparation method thereof.
Background
In recent years, with the light and thin electronic devices and the intelligent wearable devices, flexible electronic technology has become the technological leading edge and hot research field nowadays, and various portable and wearable electronic devices have also grown. The advent of these new electronic devices has also placed higher demands on the flexibility of various devices while enriching the lives of people. The flexible conductive material is used as an important component of the flexible electronic device, and the performance quality of the flexible conductive material becomes a bottleneck problem for restricting the further development of the flexible electrode technology in various directions, so that the development of the high-performance flexible conductive material has important significance for the development of the flexible electronic field.
Polyaniline is a common conductive polymer, and has great application advantages in many fields because of low cost, easily available raw materials, simple synthesis process, excellent physical and chemical characteristics, diversified structural design, specific doping modes and good environmental stability, and has been widely studied. As a current mature method for simply and efficiently preparing the superfine fiber film, the high-voltage electrostatic spinning achieves the aim of controlling the shape and the porosity of the nanofiber by changing a high-molecular precursor, adding various filling particles and changing process parameters, and obtains wide attention of various nationists. The polyimide fiber prepared by the technology can obtain the fiber membrane material with small fiber diameter, uniform distribution, high specific surface area, high porosity, narrow pore size distribution and excellent corrosion resistance. However, because polyaniline molecular chains have stronger rigidity and poorer dissolution and processing properties, the research of combining and applying an electrostatic spinning technology and conductive polyaniline is mainly focused on two aspects, on one hand, polyaniline is directly subjected to electrostatic spinning, but because of the characteristic that polyaniline is difficult to process, a spinning aid (such as polyethylene oxide) is usually adopted to slightly dissolve or disperse polyaniline to prepare spinning solution with higher viscosity and more stable properties for spinning at present, however, because the spinning aid is usually an insulating high polymer material, and the amount of the polyaniline which can be dissolved or dispersed in the solution is less, generally only accounting for 0.5-3 wt% of the total mass of the solution, the conductivity of the prepared fiber membrane is poorer; or strong acid (such as concentrated sulfuric acid) is adopted as a solvent to be dissolved for spinning so as to obtain spinning solution with higher concentration, but strong acid such as concentrated sulfuric acid has stronger corrosiveness, and has more severe requirements on spinning equipment and personnel operation, and the strength of the prepared fiber is also poorer; on the other hand, the acid doped polyaniline with conductive property is coated on the surface of the prepared electrospun fiber membrane matrix material by utilizing an in-situ growth technology, and most of the matrix materials are carbon fiber membrane materials prepared by electrospinning high-molecular solution and carbonizing at high temperature, so that the preparation process is complicated, the mass production of the materials is not facilitated, and the requirements on the process are very strict. In the in-situ polymerization process, the polymerization of polyaniline on the fiber surface is generally random, and is difficult to uniformly coat all the fiber surfaces, so that the unique pore structure of the fiber membrane is easily damaged, and the application performance of the fiber membrane is affected. Therefore, how to prepare a high-concentration stable polyaniline solution, so that polyaniline is directly introduced into fibers or the surfaces of the fibers during high-voltage electrostatic spinning, and the flexible polyaniline-based fiber film with good pore structure and excellent conductive function is obtained by adjusting process parameters, so that the high-concentration stable polyaniline-based fiber film has important significance.
Disclosure of Invention
The present invention aims to solve the above technical problems existing in the prior art. The invention provides a polyimide/polyaniline composite conductive fiber membrane material and a preparation method thereof, and the prepared polyimide/polyaniline composite conductive fiber membrane material has unique pore structure, better flexibility and conductivity, simple preparation steps, short period and low cost.
In order to solve the technical problems, the embodiment of the invention discloses a polyimide/polyaniline composite conductive fiber membrane material which is of a coaxial fiber structure;
the core layer of the coaxial fiber structure is a polyimide layer, and the shell layer is a polyaniline layer.
The embodiment of the invention also discloses a preparation method of the polyimide/polyaniline composite conductive fiber membrane material, which comprises the following steps:
(1) Preparing proton acid doped polyaniline by using aniline as a raw material through emulsion polymerization, wherein the proton acid doped polyaniline is dedoped to prepare dedoped polyaniline, and the dedoped polyaniline is secondarily doped to prepare polyaniline spinning solution;
(2) Taking soluble polyimide as a raw material, and dissolving the soluble polyimide in an organic solvent to prepare polyimide spinning solution;
(3) And taking the polyaniline spinning solution as a shell spinning solution, taking the polyimide spinning solution as a core spinning solution, and preparing coaxial composite fibers by adopting coaxial electrostatic spinning to obtain the polyimide/polyaniline composite conductive fiber membrane material.
Further, the organic solvent is any one or the combination of two of N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
Further, the shielding gas is one of nitrogen and argon.
Further, the mass fraction of polyaniline in the polyaniline spinning solution is 7.5-16 wt%, and the mass fraction of polyimide in the polyimide spinning solution is 15-25 wt%.
Further, in the step (1), the proton acid doped polyaniline is prepared by the following steps:
respectively dissolving protonic acid and Ammonium Persulfate (APS) into deionized water at normal temperature and normal pressure to prepare protonic acid aqueous solution and ammonium persulfate aqueous solution, adding Aniline (AN) into the protonic acid aqueous solution under the atmosphere of protective gas, magnetically stirring and reacting for 30-60 min, then dropwise adding the ammonium persulfate aqueous solution into the mixed solution of aniline and protonic acid, controlling the reaction temperature to be 0-5 ℃, continuously magnetically stirring and reacting for 2-10 h, filtering, washing to be neutral, and vacuum drying at 50-70 ℃ for 12-48 h to obtain protonic acid doped polyaniline;
wherein the mass ratio of the aniline to the protonic acid is 1:0.5-2.5, and the mass ratio of the aniline to the ammonium persulfate is 1:0.5-2.5.
Further, in step (1), the dedoping includes the steps of:
according to the volume ratio of the mass of the protonic acid doped polyaniline to the ammonia water of 1-1 g:100-500 mL, dispersing the protonic acid doped polyaniline in the ammonia water with the concentration of 1mol/L, magnetically stirring and reacting for 10-24 h, filtering, washing to neutrality, and vacuum drying at 50-70 ℃ for 12-48 h to obtain the dedoping polyaniline.
Further, in step (1), the secondary doping includes the steps of: mixing the dedoping polyaniline, morpholine and an organic solvent according to the mass ratio of 1:6-15:6-15, magnetically stirring at 80 ℃ for 10-20 min to completely dissolve the polyaniline, heating the solution to 130 ℃, evaporating morpholine and redundant organic solvent, cooling to room temperature after the total mass of the polyaniline solution is reduced by 50% -75%, adding protonic acid into the polyaniline solution, and changing the solution from blue to dark green after the polyaniline solution is completely dissolved to obtain the polyaniline spinning solution;
in the secondary doping, the mass ratio of the dedoping polyaniline to the protonic acid is 1:0.2-2.
Further, in the step (2), the polyimide spinning solution is prepared by the following steps:
adding a certain amount of soluble polyimide into a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone at normal temperature and normal pressure, and stirring and reacting for 2-10 hours at 60-80 ℃ to obtain the polyimide spinning solution;
wherein the mass ratio of the N, N-dimethylformamide to the N-methylpyrrolidone is 1:1-7.
In the step (3), a coaxial stainless steel needle is adopted in the electrostatic spinning process, high-voltage electrostatic spinning is carried out under the action of a high-voltage electric field with the voltage of 10-30 kV at the flow rate ratio of 1:0.1-5 of the spinning solution of the core layer to the spinning solution of the shell layer, the spinning time is 2-10 h, a roller with a certain rotating speed is used as a receiving end for collection, and then the material is soaked in water to be demoulded and dried in vacuum at 50-70 ℃ for 12-48 h, so that the polyimide/polyaniline composite conductive fiber membrane material is prepared. Wherein, the type of the coaxial stainless steel needle head is any one of 15G/20G, 17G/22G and 18G/25G.
Further, the soluble polyimide is one of polyetherimide or fluorine-containing polyimide.
Further, the proton acid is any one of camphorsulfonic acid (CSA), dodecylbenzenesulfonic acid (DBSA), 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS).
Compared with the prior art, the invention has the following technical effects:
the invention prepares polyaniline doped with protonic acid by emulsion polymerization method, and dissolves in corresponding solvent after dedoping under the action of ammonia water, and prepares polyaniline spinning solution by adopting protonic acid for secondary doping; and then preparing the coaxial electrospun polyimide/polyaniline composite conductive fiber membrane material by taking the soluble polyimide spinning solution as a core layer and the polyaniline spinning solution as a shell layer through a coaxial high-voltage electrostatic spinning technology. The composite conductive fiber membrane material with the core-shell structure is prepared by taking polyimide with excellent mechanical properties as a core layer supporting material and taking conductive polyaniline doped with proton acid as a shell layer conductive material, and has the characteristics of light weight, good flexibility, unique fiber and pore structure, controllable preparation size and thickness and the like on the basis of better conductive performance, and has good application prospect in the field of flexible electronic devices, and particularly has obvious advantages in the field of multifunctional integrated requirements such as flexible energy storage, sensing and the like.
Drawings
Fig. 1 shows SEM images of the polyimide/polyaniline composite conductive fiber film material of example 1 of the present invention at different magnifications ((a) 2000-fold; (b) 5000-fold; (c) 10000-fold);
fig. 2 shows SEM images of the polyimide/polyaniline composite conductive fiber membrane material of example 2 of the present invention at different magnifications ((a) 2000-fold; (b) 5000-fold; (c) 10000-fold);
fig. 3 shows SEM images of the polyimide/polyaniline composite conductive fiber film material of example 3 of the present invention at different magnifications ((a) 2000-fold; (b) 5000-fold; (c) 10000-fold);
fig. 4 shows a shape change chart of the polyimide/polyaniline composite conductive fiber film materials of examples 1 to 4 of the present invention in a natural state, a twisted state, and a bent state in order: (a) example 1; (b) example 2; (c) example 3; (d) example 4.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present specification, by describing the embodiments of the present invention with specific examples. While the description of the invention will be described in connection with the preferred embodiments, it is not intended to limit the inventive features to the implementation. Rather, the purpose of the invention described in connection with the embodiments is to cover other alternatives or modifications, which may be extended by the claims based on the invention. The following description contains many specific details for the purpose of providing a thorough understanding of the present invention. The invention may be practiced without these specific details. Furthermore, some specific details are omitted from the description in order to avoid obscuring the invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Example 1
(1) Preparing polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) and 10 g Ammonium Persulfate (APS) in 80 mL and 40 mL deionized water at normal temperature and normal pressure, adding aniline into an aqueous solution of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) according to the mass ratio of aniline to protonic acid of 1:2.5 under a protective gas atmosphere, magnetically stirring for 30-60 min, dropwise adding an aqueous solution of ammonium persulfate into a mixed solution of aniline and protonic acid according to the mass ratio of aniline to ammonium persulfate of 1:1.5, continuously magnetically stirring at the reaction temperature of 0-5 ℃, reacting for 8 h under continuous magnetic stirring, filtering, washing to neutrality, and vacuum drying at the temperature of 60 ℃ for 24 h to obtain AMPS doped polyaniline;
according to the volume ratio of the AMPS doped polyaniline to the ammonia water of 1g of 300 mL, dispersing 5g of the AMPS doped polyaniline in the ammonia water with the concentration of 1M, magnetically stirring for reacting 12 h, filtering again, washing to be neutral, and vacuum drying at 50 ℃ for 24 h;
dissolving 0.6 g of dried dedoped polyaniline in morpholine and N, N-dimethylformamide according to the mass ratio of the dedoped polyaniline to the morpholine to the organic solvent of 1:7:7, magnetically stirring the solution at 80 ℃ for 10 min to completely dissolve the polyaniline, heating the solution to 130 ℃, evaporating the morpholine and the redundant N, N-dimethylformamide, cooling the solution to room temperature after the total mass of the solution is reduced to 44.4%, and adding 0.6 g of AMPS into the polyaniline solution according to the mass ratio of the dedoped polyaniline to the AMPS of 1:1, and obtaining polyaniline spinning solution with the mass fraction of 15 wt% from blue to dark green after the polyaniline is completely dissolved;
(2) Preparing polyimide spinning solution: adding 6.0. 6.0 g of polyetherimide into 6.68 mL of mixed solvent of N, N-dimethylformamide and 12.32 mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 h at 60-80 ℃ to prepare polyimide spinning solution with polyimide mass fraction of 24-wt%;
(3) Preparing a polyimide/polyaniline composite conductive fiber membrane material: taking polyimide spinning solution as core spinning solution and polyaniline spinning solution as shell spinning solution, adopting a coaxial stainless steel needle with an inner/outer needle model of 17G/22G, taking the flow rate of the core solution as 0.1 mL/h and the flow rate of the shell solution as 0.1 mL/h, carrying out high-voltage electrostatic spinning under the action of a high-voltage electric field with the voltage of 10 kV, collecting with a roller with a certain rotating speed as a receiving end, spinning for 6 h, soaking in water to demould, and obtaining the polyimide/polyaniline composite conductive fiber film material, wherein the conductivity of the obtained composite conductive fiber film is 0.33S/cm.
Example 2
(1) Preparing polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) and 10 g Ammonium Persulfate (APS) in 80 mL and 40 mL deionized water at normal temperature and normal pressure, adding aniline into an aqueous solution of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) according to the mass ratio of aniline to protonic acid of 1:2.5 under a protective gas atmosphere, magnetically stirring for 30-60 min, dropwise adding an aqueous solution of ammonium persulfate into a mixed solution of aniline and protonic acid according to the mass ratio of aniline to ammonium persulfate of 1:1.5, continuously magnetically stirring at the reaction temperature of 0-5 ℃, reacting for 8 h under continuous magnetic stirring, filtering, washing to neutrality, and vacuum drying at the temperature of 60 ℃ for 24 h to obtain AMPS doped polyaniline;
according to the volume ratio of the AMPS doped polyaniline to the ammonia water of 1g of 300 mL, dispersing 5g of the AMPS doped polyaniline in the ammonia water with the concentration of 1M, magnetically stirring for reacting 12 h, filtering again, washing to be neutral, and vacuum drying at 50 ℃ for 24 h;
dissolving 0.6 g of dried dedoped polyaniline in morpholine and N, N-dimethylformamide according to the mass ratio of the dedoped polyaniline to the morpholine to the organic solvent of 1:7:7, magnetically stirring the solution at 80 ℃ for 10 min to completely dissolve the polyaniline, heating the solution to 130 ℃, evaporating the morpholine and the redundant N, N-dimethylformamide, cooling the solution to room temperature after the total mass of the solution is reduced to 44.4%, and adding 0.6 g of AMPS into the polyaniline solution according to the mass ratio of the dedoped polyaniline to the AMPS of 1:1, and obtaining polyaniline spinning solution with the mass fraction of 15 wt% from blue to dark green after the polyaniline is completely dissolved;
(2) Preparing polyimide spinning solution: adding 6.0. 6.0 g of polyetherimide into 6.68 mL of mixed solvent of N, N-dimethylformamide and 12.32 mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 h at 60-80 ℃ to prepare polyimide spinning solution with polyimide mass fraction of 24-wt%;
(3) Preparing a polyimide/polyaniline composite conductive fiber membrane material: taking polyimide spinning solution as core spinning solution and polyaniline spinning solution as shell spinning solution, adopting a coaxial stainless steel needle with an inner/outer needle model of 17G/22G, taking the flow rate of the core solution as 0.1 mL/h and the flow rate of the shell solution as 0.3 mL/h, carrying out high-voltage electrostatic spinning under the action of a high-voltage electric field with the voltage of 10 kV, collecting with a roller with a certain rotating speed as a receiving end, spinning for 6 h, soaking in water to demould, and obtaining the polyimide/polyaniline composite conductive fiber film material, wherein the conductivity of the obtained composite conductive fiber film is 0.25S/cm.
Example 3
(1) Preparing polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) and 10 g Ammonium Persulfate (APS) in 80 mL and 40 mL deionized water at normal temperature and normal pressure, adding aniline into an aqueous solution of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) according to the mass ratio of aniline to protonic acid of 1:2.5 under a protective gas atmosphere, magnetically stirring for 30-60 min, dropwise adding an aqueous solution of ammonium persulfate into a mixed solution of aniline and protonic acid according to the mass ratio of aniline to ammonium persulfate of 1:1.5, continuously magnetically stirring at the reaction temperature of 0-5 ℃, reacting for 8 h under continuous magnetic stirring, filtering, washing to neutrality, and vacuum drying at the temperature of 60 ℃ for 24 h to obtain AMPS doped polyaniline;
according to the volume ratio of the AMPS doped polyaniline to the ammonia water of 1g of 300 mL, dispersing 5g of the AMPS doped polyaniline in the ammonia water with the concentration of 1M, magnetically stirring for reacting 12 h, filtering again, washing to be neutral, and vacuum drying at 50 ℃ for 24 h;
dissolving 0.6 g of dried dedoped polyaniline in morpholine and N, N-dimethylformamide according to the mass ratio of the dedoped polyaniline to the morpholine to the organic solvent of 1:7:7, heating the solution to 130 ℃ after the solution is completely dissolved by magnetic stirring for 10 min at 80 ℃, evaporating morpholine and redundant N, N-dimethylformamide, cooling to room temperature after the total mass of the solution is reduced to 44.4%, and adding 0.6 g of AMPS into the polyaniline solution according to the mass ratio of the dedoped polyaniline to the AMPS of 1:1, and obtaining the polyaniline spinning solution with the mass fraction of 15 wt% of polyaniline from blue to dark green after the solution is completely dissolved;
(2) Preparing polyimide spinning solution: adding 6.0. 6.0 g of polyetherimide into 6.68 mL of mixed solvent of N, N-dimethylformamide and 12.32 mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 h at 60-80 ℃ to prepare polyimide spinning solution with polyimide mass fraction of 24-wt%;
(3) Preparing a polyimide/polyaniline composite conductive fiber membrane material: taking polyimide spinning solution as core spinning solution and polyaniline spinning solution as shell spinning solution, adopting a coaxial stainless steel needle with an inner/outer needle model of 17G/22G, taking the flow rate of the core solution as 0.3 mL/h and the flow rate of the shell solution as 0.1 mL/h, carrying out high-voltage electrostatic spinning under the action of a high-voltage electric field with the voltage of 10 kV, collecting with a roller with a certain rotating speed as a receiving end, spinning for 6 h, soaking in water to demould, and obtaining the polyimide/polyaniline composite conductive fiber film material, wherein the conductivity of the obtained composite conductive fiber film is 0.76S/cm.
Example 4
(1) Preparing polyaniline spinning solution: respectively dissolving 20g of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) and 10 g Ammonium Persulfate (APS) in 80 mL and 40 mL deionized water at normal temperature and normal pressure, adding aniline into an aqueous solution of 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS) according to the mass ratio of aniline to protonic acid of 1:2.5 under a protective gas atmosphere, magnetically stirring for 30-60 min, dropwise adding an aqueous solution of ammonium persulfate into a mixed solution of aniline and protonic acid according to the mass ratio of aniline to ammonium persulfate of 1:1.5, continuously magnetically stirring at the reaction temperature of 0-5 ℃, reacting for 8 h under continuous magnetic stirring, filtering, washing to neutrality, and vacuum drying at the temperature of 60 ℃ for 24 h to obtain AMPS doped polyaniline;
according to the volume ratio of the AMPS doped polyaniline to the ammonia water of 1g of 300 mL, dispersing 5g of the AMPS doped polyaniline in the ammonia water with the concentration of 1M, magnetically stirring for reacting 12 h, filtering again, washing to be neutral, and vacuum drying at 50 ℃ for 24 h;
dissolving 0.6 g g of dried dedoping polyaniline in morpholine and N, N-dimethylformamide according to the mass ratio of the dedoping polyaniline to the morpholine to the organic solvent of 1:7:7, magnetically stirring for 10 min at 80 ℃ to completely dissolve the polyaniline, heating the solution to 130 ℃, evaporating out morpholine and redundant N, N-dimethylformamide, cooling to room temperature after the total mass of the solution is reduced to 44.4%, and adding 0.3 g AMPS into the polyaniline solution according to the mass ratio of the dedoping polyaniline to the AMPS of 1:0.5, and changing the solution from blue to dark green after the polyaniline is completely dissolved to prepare polyaniline spinning solution with the mass fraction of 15 wt%;
(2) Preparing polyimide spinning solution: adding 6.0. 6.0 g of polyetherimide into 6.68 mL of mixed solvent of N, N-dimethylformamide and 12.32 mL of N-methylpyrrolidone at normal temperature and normal pressure, and stirring for 5 h at 60-80 ℃ to prepare polyimide spinning solution with polyimide mass fraction of 24-wt%;
(3) Preparing a polyimide/polyaniline composite conductive fiber membrane material: taking polyimide spinning solution as core spinning solution and polyaniline spinning solution as shell spinning solution, adopting a coaxial stainless steel needle with an inner/outer needle model of 17G/22G, taking the flow rate of the core solution as 0.3 mL/h and the flow rate of the shell solution as 0.1 mL/h, carrying out high-voltage electrostatic spinning under the action of a high-voltage electric field with the voltage of 10 kV, collecting with a roller with a certain rotating speed as a receiving end, spinning for 6 h, soaking in water to demould, and obtaining the polyimide/polyaniline composite conductive fiber film material, wherein the conductivity of the obtained composite conductive fiber film is 0.18S/cm.
The invention provides a preparation method of a coaxial electrospun polyimide/polyaniline composite conductive fiber membrane material. Firstly, preparing proton acid doped polyaniline by an emulsion polymerization method, and dissolving the polyaniline in a corresponding solvent after being dedoping under the action of ammonia water, and preparing polyaniline spinning solution by adopting proton acid for secondary doping; and then, taking the soluble polyimide spinning solution as a core layer and the polyaniline spinning solution as a shell layer, and preparing the coaxial electrospun polyimide/polyaniline composite conductive fiber membrane material by a coaxial high-voltage electrostatic spinning technology, thereby solving the problem of polyaniline agglomeration in an in-situ polymerization preparation process. The prepared polyimide/polyaniline composite conductive fiber membrane material has stable chemical property, higher specific surface area, unique pore structure and better flexibility. The preparation method of the coaxial electrospun polyimide/polyaniline composite conductive fiber membrane material has the advantages of simple preparation steps, short period, low cost and the like, and provides a new idea for preparing the multifunctional three-dimensional porous flexible conductive polymer membrane material with good flexibility, excellent mechanical property, good conductive property and the like.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a further detailed description of the invention with reference to specific embodiments, and it is not intended to limit the practice of the invention to those descriptions. Various changes in form and detail may be made therein by those skilled in the art, including a few simple inferences or alternatives, without departing from the spirit and scope of the present invention.
Claims (6)
1. The polyimide/polyaniline composite conductive fiber membrane material is characterized in that the composite conductive fiber membrane material has a coaxial fiber structure;
the core layer of the coaxial fiber structure is a polyimide layer, and the shell layer is a polyaniline layer;
the polyimide/polyaniline composite conductive fiber membrane material is prepared by the following method:
(1) Preparing proton acid doped polyaniline by using aniline as a raw material through emulsion polymerization, wherein the proton acid doped polyaniline is dedoped to prepare dedoped polyaniline, and the dedoped polyaniline is secondarily doped to prepare polyaniline spinning solution;
(2) Taking soluble polyimide as a raw material, and dissolving the soluble polyimide in an organic solvent to prepare polyimide spinning solution;
(3) Taking the polyaniline spinning solution as a shell spinning solution, taking the polyimide spinning solution as a core spinning solution, and preparing coaxial composite fibers by adopting coaxial electrostatic spinning to obtain the polyimide/polyaniline composite conductive fiber membrane material;
wherein, in the step (1), the secondary doping comprises the following steps: mixing the dedoping polyaniline, morpholine and an organic solvent according to a mass ratio of 1:6-15:6-15, stirring until the polyaniline is completely dissolved to form a polyaniline solution, heating the polyaniline solution to 130 ℃, cooling to room temperature after the total mass of the polyaniline solution is reduced by 50% -75%, adding protonic acid into the polyaniline solution, and changing the solution from blue to dark green after the polyaniline solution is completely dissolved to obtain the polyaniline spinning solution;
in the secondary doping, the mass ratio of the dedoping polyaniline to the protonic acid is 1:0.2-2;
wherein the mass fraction of polyaniline in the polyaniline spinning solution is 7.5-16 wt%, and the mass fraction of polyimide in the polyimide spinning solution is 15-25 wt%;
the organic solvent is any one or the combination of two of N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone;
the proton acid is any one of camphorsulfonic acid (CSA), dodecylbenzene sulfonic acid (DBSA) and 2-acrylamido-2-methyl-1-propane sulfonic Acid (AMPS);
in the step (3), in the electrostatic spinning process, the flow rate ratio of the core layer spinning solution to the shell layer spinning solution is 1:0.1-5, the control voltage is 10-30 kV, and the spinning time is 2-10 h.
2. A method for preparing the polyimide/polyaniline composite conductive fiber membrane material according to claim 1, comprising the steps of:
(1) Preparing proton acid doped polyaniline by using aniline as a raw material through emulsion polymerization, wherein the proton acid doped polyaniline is dedoped to prepare dedoped polyaniline, and the dedoped polyaniline is secondarily doped to prepare polyaniline spinning solution;
(2) Taking soluble polyimide as a raw material, and dissolving the soluble polyimide in an organic solvent to prepare polyimide spinning solution;
(3) And taking the polyaniline spinning solution as a shell spinning solution, taking the polyimide spinning solution as a core spinning solution, and preparing coaxial composite fibers by adopting coaxial electrostatic spinning to obtain the polyimide/polyaniline composite conductive fiber membrane material.
3. The method for preparing a polyimide/polyaniline composite conductive fiber membrane material according to claim 2, wherein in step (1), the protonic acid doped polyaniline is prepared by the following steps:
respectively dissolving protonic acid and ammonium persulfate to prepare protonic acid aqueous solution and ammonium persulfate aqueous solution, adding aniline into the protonic acid aqueous solution under the atmosphere of protective gas, reacting for 30-60 min, then dropwise adding the ammonium persulfate aqueous solution into the mixed solution of aniline and protonic acid, controlling the reaction temperature to be 0-5 ℃, reacting for 2-10 h, filtering, washing to be neutral, and vacuum drying to obtain protonic acid doped polyaniline;
wherein the mass ratio of the aniline to the protonic acid is 1:0.5-2.5, and the mass ratio of the aniline to the ammonium persulfate is 1:0.5-2.5.
4. The method for preparing a polyimide/polyaniline composite conductive fiber film material according to claim 2, wherein in step (1), the undoped comprises the steps of:
dispersing the proton acid doped polyaniline in ammonia water, reacting for 10-15 h, filtering, washing to neutrality, and vacuum drying to obtain the undoped polyaniline.
5. The method for preparing the polyimide/polyaniline composite conductive fiber membrane material according to claim 2, wherein in the step (2), the polyimide spinning solution is prepared by the following steps:
adding soluble polyimide into a mixed solvent of N, N-dimethylformamide and N-methylpyrrolidone, and stirring and reacting for 2-10 hours to obtain polyimide spinning solution;
wherein the mass ratio of the N, N-dimethylformamide to the N-methylpyrrolidone is 1:1-7.
6. The method for preparing a polyimide/polyaniline composite conductive fiber film material according to any one of claims 2 to 5, wherein the soluble polyimide is one of polyetherimide or fluorine-containing polyimide.
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