CN110790967A - Aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material and preparation method thereof - Google Patents
Aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material and preparation method thereof Download PDFInfo
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 97
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 97
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 87
- 239000002121 nanofiber Substances 0.000 title claims abstract description 87
- 239000004760 aramid Substances 0.000 title claims abstract description 85
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 54
- 239000010931 gold Substances 0.000 title claims abstract description 54
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 49
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 34
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 108010025899 gelatin film Proteins 0.000 claims description 16
- 238000003828 vacuum filtration Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000002052 molecular layer Substances 0.000 claims description 3
- 238000006136 alcoholysis reaction Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims 1
- 238000004070 electrodeposition Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000010408 film Substances 0.000 description 56
- 239000000178 monomer Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000271 Kevlar® Polymers 0.000 description 5
- 239000004761 kevlar Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920006231 aramid fiber Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
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Abstract
The invention discloses an aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material and a preparation method thereof. The invention adopts polyvinyl alcohol to reinforce the aramid nano-fiber film to prepare the aramid nano-fiber/polyvinyl alcohol hybrid film matrix with high tensile strength and high toughness, and then the matrix is subjected to suction filtration technologyAssembling gold nano conductive layer on the surface, and finally adopting electrochemical deposition technology to compound polyaniline pseudocapacitance active layer. The composite film material of the aramid nano-fiber/polyvinyl alcohol/gold/conductive polyaniline has the advantages that the mass specific capacitance can reach 703F/g, the mechanical strength of a film electrode reaches 315MPa, and the toughness reaches 39MJ/cm under the charge-discharge current density of 1A/g3Has high mechanical strength and high toughness, and can be used as a flexible self-supporting electrode.
Description
Technical Field
The invention belongs to the technical field of polymer composite material preparation, and relates to an aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material and a preparation method thereof.
Background
Electrochemical deposition is a high-efficiency, safe and simple material preparation technology, and is widely applied to the field of preparation of electrode materials of energy devices such as super capacitors, lithium batteries and solar batteries. An important prerequisite for the realization of electrochemical deposition reactions is the preparation of highly conductive, chemically inert electrode substrate materials. At present, most electrode substrates are made of noble metal materials such as gold or platinum. However, the inherent high density and rigidity of the conventional metal electrode substrate cannot meet the requirements of flexibility, convenience and wearability of the novel electronic device on the energy storage device. Moreover, because of lack of certain flexibility, the adhesion between the traditional metal electrode substrate and the electrochemical active material is often poor, and the active component coating is cracked after being bent for several times, so that the active component coating falls off from the electrode, and the electrochemical performance of the supercapacitor is deteriorated. More importantly, the electrode material prepared by the electrochemical deposition technology is difficult to use in practical operation environments such as bending, folding and stretching, and therefore, the preparation of the flexible electrode substrate material with high mechanical strength and high toughness still faces huge challenges.
Poly (p-phenylene terephthalamide) (PPTA) is a high-performance para-aramid fiber, and the basic repeating unit is- [ -CO-C6H4-CONH-C6H4NH- ] -. The aramid fiber yarn has the advantages of high strength, high modulus, high temperature resistance, chemical corrosion resistance, strong flame retardance, fatigue resistance, strong stability and the like. The para-aramid fiber is dissolved in dimethyl sulfoxide to obtain the aramid nanofiber (ACS nano,2011,5(9): 6945-. The film material compounded and assembled by the aramid nano-fiber and other polymer components has excellent mechanical properties. For example, aramid nanofibers are compounded with polyvinyl alcohol (PVA) by liquid phase blending, and can be assembled into flexible film materials by using a casting film technique (Composites Science and technology,2017,144: 193-. Although the mechanical strength of the composite film can be improved by introducing the aramid nano-fibers, the reinforcing effect of single performance is achieved at the cost of sacrificing the toughness of the material, and the tensile strength of the composite material is still low and is not more than 100MPa due to the limitation of the lower content of the aramid nano-fibers.
Disclosure of Invention
The invention aims to provide an aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material with high mechanical strength and high toughness and a preparation method thereof. According to the invention, on the basis of preparing the aramid nano-fiber/polyvinyl alcohol hybrid film with high tensile strength and high toughness, the gold nano-conductive layer is assembled, and the polyaniline pseudocapacitance active layer is compounded by adopting a simple electrochemical deposition technology, so that the electrode material with high mechanical strength and high toughness is prepared and can be used as a flexible self-supporting electrode.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material comprises the following specific steps:
(1) dissolving PPTA spinning fibers by adopting a dimethyl sulfoxide (DMSO)/KOH system to prepare an aramid fiber nano fiber solution;
(2) dissolving PVA in a high-temperature DMSO system to prepare a PVA solution;
(3) adding a PVA solution into the aramid nano-fiber solution, and uniformly stirring;
(4) adding water into the mixed solution obtained in the step (3), stirring at room temperature, and aging and defoaming the obtained mixed gel system;
(5) assembling the mixed system obtained in the step (4) into an aramid nanofiber/polyvinyl alcohol composite gel film by adopting a vacuum filtration method according to the content of PVA being 5-40 wt% of PPTA;
(6) adding a nanogold solution according to the content of the nanogold which is 2.5-10 wt% of the PPTA, and assembling a gold nano layer on the composite gel film obtained in the step (5) by adopting a vacuum filtration method to obtain an aramid nanofiber/polyvinyl alcohol/gold composite film;
(7) washing the aramid nanofiber/polyvinyl alcohol/gold composite film to remove redundant ions, and then drying;
(8) soaking a dry aramid nanofiber/polyvinyl alcohol/gold composite film serving as a working electrode in a sulfuric acid solution of aniline, carrying out constant potential anodic oxidation polymerization, setting the potential constant to be 0.8V, maintaining for 5-16 min to carry out polyaniline polymerization reaction, washing and drying to obtain the aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material.
Further, in the step (1), the concentration of the aramid nanofiber solution is 2-10 mg/mL, the dissolving time is two weeks, the dissolving temperature is room temperature, and the average size of the aramid nanofiber is as follows: the diameter is 30-40 nm and the length is 5-10 μm.
Further, in the step (2), the concentration of the PVA solution is 1-5 mg/mL, the dissolving time is two days, the dissolving temperature is 80 ℃, the molecular weight distribution of the PVA is 145000-195000, and the alcoholysis degree is 99.8%.
In the step (3), the content of PVA is 5-40 wt% of PPTA, and when the content of PVA is too high, the obtained mixed solution can be subjected to phase separation, so that the film is prepared unevenly.
Further, in the step (4), 125-200 mL of water is added into every 100mL of aramid nano-fiber solution; stirring for 2-4 h at room temperature; the aging time at room temperature is more than 2 h.
Further, in the steps (5) and (6), a sand core funnel is adopted by the suction filtration device to prepare a microporous filter membrane with the diameter of 47mm, and the vacuum suction filtration pressure is-0.1 MPa;
further, in the step (7), the washing method comprises the steps of dripping 100-200 mL of water on the surface of the aramid nano-fiber/polyvinyl alcohol/gold composite film, and then carrying out vacuum filtration to remove redundant ions; the drying procedure is drying at room temperature for 24-48 h, and then vacuum drying at 50-60 ℃ for 20-24 h.
Further, in the step (8), the size of the aramid nano-fiber/polyvinyl alcohol/gold composite film electrode is 1 multiplied by 1cm2(ii) a The concentration of the sulfuric acid solution is 1M, and the concentration of the aniline is 0.05M; the counter electrode is a platinum sheet, and the reference electrode is Ag/AgCl.
Compared with the prior art, the invention has the following remarkable advantages:
(1) polyvinyl alcohol is used as a toughness component and compounded with rigid aramid nano-fibers, the polyvinyl alcohol improves the toughness of the composite film and simultaneously enhances the tensile strength of the composite film, and the composite film with high tensile strength and high toughness is prepared.
(2) The gold nanolayers are assembled on the surface of the composite film by a simple suction filtration method, and the film is endowed with excellent conductivity on the premise of not damaging the mechanical property of the composite film.
(3) The flexible electrode material with excellent mechanical property and electrochemical property is prepared by adjusting the use amounts of the polyvinyl alcohol and the aramid nano-fiber and controlling the structure of the aramid nano-fiber/polyvinyl alcohol/gold/polyaniline film. For example, when the polyvinyl alcohol content is 5 wt% of the aramid nano-fiber and the aniline polymerization time is 13min, the mass specific capacitance of the obtained film electrode material can reach 703F/g under the charge-discharge current density of 1A/g, the mechanical strength of the film electrode is 315MPa, and the toughness is 39MJ/cm3And the comprehensive performance is excellent.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a composite film material of aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline;
FIG. 2 is a stress-strain curve of a composite film material of aramid nanofibers/polyvinyl alcohol/gold/conductive polyaniline;
FIG. 3 is the cyclic voltammetry curve (scan rate 100mV/s) of the composite film material of aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline in sulfuric acid electrolyte.
Detailed Description
The invention is further illustrated by the following examples and figures.
The schematic diagram of the preparation process of the composite film material of aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline is shown in fig. 1.
The poly (p-phenylene terephthalamide) (PPTA) used in the examples below was a commercially available kevlar spun fiber.
Example 1
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain a 2mg/mL aramid nanofiber solution.
Weighing polyvinyl alcohol, adding DMSO, stirring until the polyvinyl alcohol is uniformly mixed, and stirring in a water bath at 80 ℃ for two days to obtain a polyvinyl alcohol solution of 1 mg/mL.
And uniformly mixing the polyvinyl alcohol solution and the aramid nano-fiber solution, adding 50mL of deionized water, and stirring at room temperature for more than 2 hours to obtain the aramid nano-fiber/polyvinyl alcohol mixed solution. Aging the mixed solution for 2h under the condition of 0.01MPa of air pressure, removing bubbles, and performing vacuum filtration treatment to obtain the aramid nano-fiber/polyvinyl alcohol composite gel film.
And slowly dripping 200mL of gold nano solution into a filter cup, completely covering the gel film, and performing vacuum filtration to obtain the aramid nano fiber/polyvinyl alcohol/gold gel film. The system comprises the following components in percentage by mass: 100 parts of aramid nano-fiber, 5 parts of polyvinyl alcohol and 5 parts of nanogold. And (3) drying the composite film at room temperature for more than 24 hours, and then carrying out vacuum drying at 60 ℃ for 24 hours to obtain the aramid nano-fiber/polyvinyl alcohol/gold composite film.
And transferring the aniline monomer to dissolve in 45mL of 1M sulfuric acid solution, and stirring for more than 1h until the aniline monomer and the sulfuric acid solution are uniformly mixed to obtain the polymer electrolyte with the aniline concentration of 0.05M. The electrochemical deposition of polyaniline adopts a three-electrode system, and the aramid nano-fiber/polyvinyl alcohol/gold composite film is cut into 1 in1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is polymerized for 13min under the anode voltage of 0.8V to obtain the aramid nano-fiber/polyvinyl alcohol/gold/conductive polyaniline composite film electrode. The tensile strength of the composite film electrode prepared by the embodiment is 315MPa, and the toughness is 39MJ/cm3And the mass specific capacitance can reach 703F/g under the charge-discharge current density of 1A/g.
Example 2
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain 4mg/mL of aramid nano-fiber solution.
Weighing polyvinyl alcohol, adding DMSO, stirring until the polyvinyl alcohol is uniformly mixed, and stirring for two days in a water bath at 80 ℃ to obtain a polyvinyl alcohol solution of 2 mg/mL.
And uniformly mixing the polyvinyl alcohol solution and the aramid nano-fiber solution, adding 50mL of deionized water, and stirring at room temperature for more than 2 hours to obtain the aramid nano-fiber/polyvinyl alcohol mixed solution. Aging the mixed solution for 2h under the condition of 0.01MPa of air pressure, removing bubbles, and performing vacuum filtration treatment to obtain the aramid nano-fiber/polyvinyl alcohol composite gel film.
And slowly dripping 100mL of gold nano solution into a filter cup, completely covering the gel film, and performing vacuum filtration to obtain the aramid nano fiber/polyvinyl alcohol/gold gel film. The system comprises the following components in percentage by mass: 100 parts of aramid nano-fiber, 10 parts of polyvinyl alcohol and 2.5 parts of nanogold. And (3) drying the composite film at room temperature for more than 24 hours, and then carrying out vacuum drying at 60 ℃ for 24 hours to obtain the aramid nano-fiber/polyvinyl alcohol/gold composite film.
And transferring the aniline monomer to dissolve in 45mL of 1M sulfuric acid solution, and stirring for more than 1h until the aniline monomer and the sulfuric acid solution are uniformly mixed to obtain the polymer electrolyte with the aniline concentration of 0.05M. The electrochemical deposition of polyaniline adopts a three-electrode system to cut the aramid nano-fiber/polyvinyl alcohol/gold composite film into 1 multiplied by 1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is polymerized for 5min under the anode voltage of 0.8V to obtain the aramid nano-fiber/polyvinyl alcohol/gold/conductive polyaniline composite film electrode. This example systemThe tensile strength of the obtained composite film electrode is 292MPa, and the toughness is 34MJ/cm3And the mass specific capacitance can reach 587F/g under the charge-discharge current density of 1A/g.
Example 3
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain a 6mg/mL aramid nanofiber solution.
Weighing polyvinyl alcohol, adding DMSO, stirring until the polyvinyl alcohol is uniformly mixed, and stirring for two days in a water bath at 80 ℃ to obtain a polyvinyl alcohol solution of 3 mg/mL.
And uniformly mixing the polyvinyl alcohol solution and the aramid nano-fiber solution, adding 50mL of deionized water, and stirring at room temperature for more than 2 hours to obtain the aramid nano-fiber/polyvinyl alcohol mixed solution. Aging the mixed solution for 2h under the condition of 0.01MPa of air pressure, removing bubbles, and performing vacuum filtration treatment to obtain the aramid nano-fiber/polyvinyl alcohol composite gel film.
And slowly dripping 300mL of gold nano solution into a filter cup, completely covering the gel film, and performing vacuum filtration to obtain the aramid nano fiber/polyvinyl alcohol/gold gel film. The system comprises the following components in percentage by mass: 100 parts of aramid nano-fiber, 20 parts of polyvinyl alcohol and 7.5 parts of nanogold. And (3) drying the composite film at room temperature for more than 24 hours, and then carrying out vacuum drying at 60 ℃ for 24 hours to obtain the aramid nano-fiber/polyvinyl alcohol/gold composite film.
And transferring the aniline monomer to dissolve in 45mL of 1M sulfuric acid solution, and stirring for more than 1h until the aniline monomer and the sulfuric acid solution are uniformly mixed to obtain the polymer electrolyte with the aniline concentration of 0.05M. The electrochemical deposition of polyaniline adopts a three-electrode system to cut the aramid nano-fiber/polyvinyl alcohol/gold composite film into 1 multiplied by 1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is polymerized for 10min under the anode voltage of 0.8V to obtain the aramid nano-fiber/polyvinyl alcohol/gold/conductive polyaniline composite film electrode. The tensile strength of the composite film electrode prepared by the embodiment is 242MPa, and the toughness is 33MJ/cm3And the mass specific capacitance can reach 656F/g under the charge-discharge current density of 1A/g.
Example 4
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain a 2mg/mL aramid nanofiber solution.
Weighing polyvinyl alcohol, adding DMSO, stirring until the polyvinyl alcohol is uniformly mixed, and stirring for two days in a water bath at 80 ℃ to obtain a polyvinyl alcohol solution of 5 mg/mL.
And uniformly mixing the polyvinyl alcohol solution and the aramid nano-fiber solution, adding 50mL of deionized water, and stirring at room temperature for more than 2 hours to obtain the aramid nano-fiber/polyvinyl alcohol mixed solution. Aging the mixed solution for 2h under the condition of 0.01MPa of air pressure, removing bubbles, and performing vacuum filtration treatment to obtain the aramid nano-fiber/polyvinyl alcohol composite gel film.
And slowly dripping 400mL of gold nano solution into a filter cup, completely covering the gel film, and performing vacuum filtration to obtain the aramid nano fiber/polyvinyl alcohol/gold gel film. The system comprises the following components in percentage by mass: 100 parts of aramid nano-fiber, 40 parts of polyvinyl alcohol and 10 parts of nanogold. And (3) drying the composite film at room temperature for more than 24 hours, and then carrying out vacuum drying at 60 ℃ for 24 hours to obtain the aramid nano-fiber/polyvinyl alcohol/gold composite film.
And transferring the aniline monomer to dissolve in 45mL of 1M sulfuric acid solution, and stirring for more than 1h until the aniline monomer and the sulfuric acid solution are uniformly mixed to obtain the polymer electrolyte with the aniline concentration of 0.05M. The electrochemical deposition of polyaniline adopts a three-electrode system to cut the aramid nano-fiber/polyvinyl alcohol/gold composite film into 1 multiplied by 1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is polymerized for 16min under the anode voltage of 0.8V to obtain the aramid nano-fiber/polyvinyl alcohol/gold/conductive polyaniline composite film electrode. The tensile strength of the composite film electrode prepared by the embodiment is 234MPa, and the toughness is 40MJ/cm3And the mass specific capacitance can reach 423F/g under the charge-discharge current density of 1A/g.
Comparative example 1
The method of example 1 was repeated with the specified amounts of the components, but with only aramid nanofibers in the material composition. The film has a tensile strength of 255MPa and a toughness of 30MJ/cm3No electrochemical behavior.
Comparative example 2
The procedure of example 1 is repeated with the specified contents of the components, but without polyvinyl alcohol in the material composition. The film had a tensile strength of 241MPa and a toughness of 28MJ/cm3The mass specific capacitance was 703F/g at a charge/discharge current density of 1A/g.
Comparative example 3
The procedure of example 1 was repeated with the specified contents of the components, but without the gold nanolayer in the material composition. The film had a tensile strength of 317MPa and a toughness of 39MJ/cm3And the polyaniline cannot be continuously deposited due to no conductive performance.
Comparative example 4
The method of example 1 was repeated with the specified contents of the respective components, but the deposition time of polyaniline was changed to 20 min. The film had a tensile strength of 301MPa and a toughness of 37MJ/cm3And the mass specific capacitance is 400F/g under the charge-discharge current density of 1A/g.
Comparative example 5
The method of example 1 was repeated with the specified amounts of the components, but the amount of nanogold was 12.5 wt.% of the aramid fiber. The film had a tensile strength of 262MPa and a toughness of 31MJ/cm3The mass specific capacitance was 703F/g at a charge/discharge current density of 1A/g. .
Table 1 shows the data of the performance tests of examples 1 to 5 and comparative examples 1 to 5.
TABLE 1
The invention adopts polyvinyl alcohol reinforced aramid fiber nano-fiber film to prepare a composite film matrix with high tensile strength and high toughness, and on the basis, the gold nano-conductive layer is assembled by a simple suction filtration technology and is compounded with the polyaniline pseudocapacitance active layer to prepare the self-supporting flexible electrode material with high mechanical strength and high toughness. The purpose of remarkably improving the compatibility degree of the mechanical property and the electrochemical property of the flexible electrode material is achieved.
Claims (10)
1. The preparation method of the aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material is characterized by comprising the following specific steps of:
(1) dissolving PPTA spinning fibers by adopting a DMSO/KOH system to prepare an aramid nano fiber solution;
(2) dissolving PVA in a high-temperature DMSO system to prepare a PVA solution;
(3) adding a PVA solution into the aramid nano-fiber solution, and uniformly stirring;
(4) adding water into the mixed solution obtained in the step (3), stirring at room temperature, and aging and defoaming the obtained mixed gel system;
(5) assembling the mixed system obtained in the step (4) into an aramid nanofiber/polyvinyl alcohol composite gel film by adopting a vacuum filtration method according to the content of PVA being 5-40 wt% of PPTA;
(6) adding a nanogold solution according to the content of the nanogold which is 2.5-10 wt% of the PPTA, and assembling a gold nano layer on the composite gel film obtained in the step (5) by adopting a vacuum filtration method to obtain an aramid nanofiber/polyvinyl alcohol/gold composite film;
(7) washing the aramid nanofiber/polyvinyl alcohol/gold composite film to remove redundant ions, and then drying;
(8) soaking a dry aramid nanofiber/polyvinyl alcohol/gold composite film serving as a working electrode in a sulfuric acid solution of aniline, carrying out constant potential anodic oxidation polymerization, setting the potential constant to be 0.8V, maintaining for 5-16 min to carry out polyaniline polymerization reaction, washing and drying to obtain the aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material.
2. The preparation method of claim 1, wherein in the step (1), the concentration of the aramid nanofiber solution is 2-10 mg/mL, the dissolving time is two weeks, the dissolving temperature is room temperature, and the average size of the aramid nanofibers is as follows: the diameter is 30-40 nm and the length is 5-10 μm.
3. The method according to claim 1, wherein in the step (2), the concentration of the PVA solution is 1-5 mg/mL, the dissolving time is two days, the dissolving temperature is 80 ℃, the molecular weight distribution of the PVA is 145000-195000, and the alcoholysis degree is 99.8%.
4. The preparation method of claim 1, wherein in the step (4), 125-200 mL of water is added to each 100mL of the aramid nanofiber solution.
5. The preparation method according to claim 1, wherein in the step (4), the stirring time at room temperature is 2-4 h; the aging time at room temperature is more than 2 h.
6. The preparation method according to claim 1, wherein in the steps (5) and (6), the suction filtration device adopts a sand core funnel to prepare the microfiltration membrane with the diameter of 47mm, and the vacuum filtration pressure is-0.1 MPa.
7. The preparation method of claim 1, wherein in the step (7), the washing method comprises the steps of dropwise adding 100-200 mL of water on the surface of the aramid nanofiber/polyvinyl alcohol/gold composite film, and then carrying out vacuum filtration to remove redundant ions.
8. The preparation method according to claim 1, wherein in the step (7), the drying process is carried out at room temperature for 24-48 h, and then vacuum drying is carried out at 50-60 ℃ for 20-24 h.
9. The preparation method according to claim 1, wherein in the step (8), the size of the aramid nanofiber/polyvinyl alcohol/gold composite film electrode is 1 x 1cm2(ii) a The concentration of the sulfuric acid solution is 1M, and the concentration of the aniline is 0.05M; the counter electrode is a platinum sheet, and the reference electrode is Ag/AgCl.
10. The aramid nanofiber/polyvinyl alcohol/gold/conductive polyaniline composite film material prepared by the preparation method according to any one of claims 1 to 9.
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| CN115570859A (en) * | 2022-09-14 | 2023-01-06 | 浙江大学 | Recyclable high-toughness composite hydrogel and preparation method and application thereof |
| CN116284894A (en) * | 2022-11-25 | 2023-06-23 | 四川大学 | Method for regulating and controlling electric heating performance of aramid fiber insulating paper by utilizing hydrogen bond donor molecules |
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| CN115570859A (en) * | 2022-09-14 | 2023-01-06 | 浙江大学 | Recyclable high-toughness composite hydrogel and preparation method and application thereof |
| CN116284894A (en) * | 2022-11-25 | 2023-06-23 | 四川大学 | Method for regulating and controlling electric heating performance of aramid fiber insulating paper by utilizing hydrogen bond donor molecules |
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