CN111276335A - Aramid nanofiber/graphene/conductive polymer flexible composite electrode and preparation method thereof - Google Patents
Aramid nanofiber/graphene/conductive polymer flexible composite electrode and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 83
- 239000002121 nanofiber Substances 0.000 title claims abstract description 74
- 239000004760 aramid Substances 0.000 title claims abstract description 71
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 23
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 31
- 229920000767 polyaniline Polymers 0.000 claims description 26
- 229920006231 aramid fiber Polymers 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000128 polypyrrole Polymers 0.000 claims description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920001197 polyacetylene Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 13
- 238000004070 electrodeposition Methods 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 27
- 239000007772 electrode material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000835 fiber Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002238 carbon nanotube film Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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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
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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
- 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
- H01G11/22—Electrodes
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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
- 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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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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
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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Abstract
The invention discloses an aramid nanofiber/graphene/conductive polymer flexible composite electrode and a preparation method thereof. The method comprises the steps of preparing an aramid nano-fiber/graphene oxide composite film by adopting a blending and vacuum induction suction filtration method, reducing graphene oxide into graphene by reducing hydroiodic acid, preparing the aramid nano-fiber/graphene composite film, and depositing a conductive polymer on the surface of the graphene by electrodeposition to obtain the aramid nano-fiber/graphene/conductive polymer flexible composite electrode. The tensile strength of the flexible composite electrode of the present invention was 83.29 MPa; the toughness is 1.38MJ/m3(ii) a At a current density of 1mA/cm2The specific area volume is 487.67mF/cm2(ii) a At a current density of 5mA/cm2The specific area volume is 390.05mF/cm2(ii) a At 2mA/cm2The capacitor has the capacity retention rate of 86 percent after being charged and discharged for 3000 times under the current density, and has higher mechanical strength, high electrochemical performance and high cycle stability.
Description
Technical Field
The invention belongs to the technical field of preparation of flexible supercapacitor electrode materials, and relates to an aramid nanofiber/graphene/conductive polymer flexible composite electrode and a preparation method thereof.
Background
With the commercial development of portable electronic devices and hybrid electric vehicles, higher requirements are put on electrode materials of supercapacitors, and the materials need to have not only excellent electrochemical properties, but also relatively high mechanical strength. At present, most of electrode materials adopt a traditional coating process, namely, electrochemical active components, a polymer binder, a conductive agent and a dispersing solvent are uniformly mixed in proportion and coated on a metal current collector. However, the inherent high density and rigidity of the metal current collector cannot meet the requirements of the novel electronic device on flexibility, convenience and wearability of the energy storage device. Moreover, the adhesion between the electrode material and the metal current collector is poor, and the electrode material is cracked after being bent for several times, so that the electrode material falls off from the current collector, and the electrochemical performance of the supercapacitor is reduced. More importantly, this class of electrode materials is difficult to use in practical operating environments such as bending, folding, stretching, etc. Therefore, the self-supporting flexible electrode material with high mechanical strength, high electrochemical performance and high cycling stability becomes a research hotspot in the field of new energy at present.
Graphene (RGO), as a unique carbon nanomaterial, has the advantages of high specific surface area, good conductivity, and the like, and has been widely used in flexible electrode materials. The document Nano lett,2008,8(10): 3498-. However, the inherent brittleness of graphene cannot adapt to the deformation states of bending, folding, twisting and the like which may occur in practical application, and meanwhile, the compatibility of high mechanical property and high electrochemical property of the electrode cannot be realized.
The conductive polymer, such as Polyaniline (PANI), polypyrrole and the like, has unique electrical properties and extremely high specific capacitance, and meanwhile, the conductive polymer is easy to obtain raw materials, low in price and simple in synthesis conditions, and becomes a hot material for preparing the flexible supercapacitor. The document 'Energy & Environmental science,2012,5(9): 4983-4988' deposits polyaniline on a self-supporting carbon nanotube film, and finds that the specific capacitance of the carbon nanotube film electrode after loading the polyaniline is improved from 23.5F/g to 236F/g. But it is still brittle and cannot adapt to the deformation states of bending, folding, twisting and the like which may occur in practical application.
Poly-p-phenylene terephthamide (PPTA) is a high-performance para-aramid fiber with a basic repeating unit of- [ -CO-C6H4-CONH-C6H4NH-]-. The macroscopic 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 aramid nanofiber ACS nano,2011,5(9): 6945-.
Disclosure of Invention
The invention aims to provide an aramid nanofiber/graphene/conductive polymer flexible composite electrode and a preparation method thereof. According to the invention, on the basis of high conductivity of graphene, aramid nano-fiber with high mechanical strength and high flexibility is used as a reinforcing material, the mechanical property and flexibility of graphene are improved, and then a conductive polymer is deposited on the surface of the graphene through electrodeposition, so that the flexible self-supporting electrode material with high mechanical strength, high electrochemical performance and high cycling stability is prepared.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the aramid nanofiber/graphene/conductive polymer flexible composite electrode comprises the following steps:
step 1, dissolving aramid fibers by adopting a dimethyl sulfoxide (DMSO)/KOH system to prepare an aramid nanofiber solution;
step 3, placing the aramid fiber nanofiber/graphene oxide composite film in hydroiodic acid, carrying out reduction reaction, soaking and cleaning with ethanol to remove hydroiodic acid after the reaction is finished, and drying to obtain the aramid fiber nanofiber/graphene oxide composite film;
step 4, soaking the aramid fiber nanofiber/graphene composite film serving as a working electrode in a sulfuric acid solution of a conductive polymer monomer by adopting a three-electrode system, electrochemically depositing the conductive polymer on the surface of the aramid fiber nanofiber/graphene film, maintaining the constant potential at 0.8V for 0.5-1 min to perform a nucleation reaction of the conductive polymer, and then maintaining the constant current density at 0.25-1.98 mA/cm2Maintaining for 10-20 min for polymerization reaction, and washing and drying to obtain an aramid nanofiber/graphene/conductive polymer flexible composite electrode; the flexible composite electrode comprises 11-25 parts by weight of aramid nano-fiber, 100 parts by weight of graphene and 0.8-1.8 parts by weight of conductive polymer.
Further, in the step 1, the concentration of the aramid nano-fiber solution is 2-10 mg/mL.
Further, in the step 2, the concentration of the graphene oxide in the dimethyl sulfoxide dispersion liquid of the graphene oxide is 2 mg/mL.
Further, in step 3, the soaking time of the hydroiodic acid is more than 10 hours, and the soaking time of the ethanol is 72 hours.
Further, in step 4, the conductive polymer monomer is a monomer conventionally used in the art, and may be aniline, pyrrole, thiophene, acetylene, and the like; the conductive polymer is a conductive polymer conventionally used in the art, and may be polyaniline, polypyrrole, polythiophene, polyacetylene, and the like.
Preferably, in the step 4, the flexible composite electrode comprises 11-18 parts by weight of aramid nanofiber, 100 parts by weight of graphene and 1.4-1.8 parts by weight of conductive polymer.
Compared with the prior art, the invention has the following advantages:
according to the invention, the graphene oxide is enhanced and modified by para-aramid fibers, the mechanical property and toughness of the graphene oxide film are improved, the graphene oxide is reduced by hydroiodic acid, the aramid nano fiber/graphene film with mechanical strength and electrical conductivity is prepared, and finally, a conductive polymer is deposited on the surface of the film through electrodeposition, so that the electrochemical performance of the composite electrode is improved. Meanwhile, the content of each component in the aramid nano-fiber/graphene/conductive polymer flexible composite electrode is controlled, so that the flexible composite electrode with high mechanical strength, high electrochemical performance and high cycling stability is prepared. The tensile strength of the composite electrode material prepared by the invention is 83.29 MPa; the toughness is 1.38MJ/m3(ii) a At a current density of 1mA/cm2The specific area volume is 487.67mF/cm2(ii) a At a current density of 5mA/cm2The specific area volume is 390.05mF/cm2(ii) a At 2mA/cm2The capacity retention rate is 86 percent when the charge and the discharge are cycled for 3000 times under the current density of (1).
Drawings
Fig. 1 is a schematic flow chart of a preparation method of an aramid nanofiber/graphene/conductive polymer flexible composite electrode.
FIG. 2 is a schematic representation of the electrochemical deposition of a conductive polymer according to the invention.
Fig. 3 is a charge-discharge curve of the aramid nanofiber/graphene/polyaniline flexible composite electrode of example 1 under different current densities.
Fig. 4 is a specific capacitance-current density curve of the aramid nanofiber/graphene/polyaniline flexible composite electrode of example 1.
Fig. 5 is a stress-strain curve of the aramid nanofiber/graphene/polyaniline flexible composite electrode of example 1.
Detailed Description
The invention is further illustrated by the following examples and figures.
The schematic diagram of the preparation process of the aramid nanofiber/graphene/conductive polymer flexible composite electrode is shown in fig. 1.
The aramid fiber is poly-p-phenylene terephthalamide (PPTA), and the aramid fiber adopted in the following embodiment is commercially available Kevlar spinning fiber.
Example 1
Adding 1g of aramid fiber yarn and 1.5g of potassium hydroxide into 500mL of dimethyl sulfoxide, and stirring at 25 ℃ for 7 days to obtain an aramid nanofiber solution.
Adding 50mL of dimethyl sulfoxide into 100mL of graphene oxide aqueous dispersion, carrying out ultrasonic treatment for 2 hours, and removing water in the mixed solution by rotary evaporation to obtain 2mg/mL of graphene oxide dimethyl sulfoxide dispersion.
1.67mL of the aramid nanofiber solution (2mg/mL) was added to 15mL of the graphene oxide dimethyl sulfoxide dispersion (2mg/mL), and after stirring at 800rpm for 1 hour, 40mL of deionized water was added, followed by further stirring at 80 ℃ for 2 hours and then at 300rpm for 1 hour to remove air bubbles. And (3) performing vacuum filtration on the aramid nano-fiber/graphene oxide/dimethyl sulfoxide mixture on a nylon filter to form a membrane. And then washing the composite film for 3 times by using deionized water, drying the composite film in air, stripping the composite film, and drying the composite film for 3 days in vacuum at the temperature of 80 ℃ to obtain the aramid nano-fiber/graphene oxide composite film.
Soaking the aramid nano-fiber/graphene oxide composite film in 20mL of hydroiodic acid for 10h, cleaning with ethanol to remove surface hydroiodic acid, soaking in ethanol for 72 h until no color is separated out, and completely removing hydroiodic acid to obtain the aramid nano-fiber/graphene composite film.
1.27mL of aniline monomer was dissolved in 45mL of 1M sulfuric acid solution and stirred for more than 1 hour until uniformly mixed to obtain a polymer electrolyte. The electrochemical deposition of polyaniline adopts a three-electrode system to cut into 1 × 1.5cm2The bulk film aramid fiber nanofiber/graphene composite film is used as a working electrode, a platinum sheet is used as an electrode, and Ag/AgCI is used as a reference electrode. The system is prepolymerized for 1min under the anode voltage of 0.8V to ensure that polyaniline nucleates between graphene sheets and aramid nanofibers, and then 0.25mA/cm is switched2And carrying out constant current polymerization, and carrying out reaction for 20min to obtain the aramid nano-fiber/graphene/conductive polymer flexible composite electrode. The prepared flexible composite electrode comprises 11 parts of aramid nano-fiber, 100 parts of graphene and 1.8 parts of polyaniline in parts by weight. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 487.67mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 390.05mF/cm2(ii) a The tensile strength is 83.29 MPa; the toughness is 1.38MJ/m3(ii) a At 2mA/cm2The capacity retention rate is still 86 percent after 3000 times of charge and discharge cycles under the current density.
Example 2
The same procedure as in example 1 was followed, except that the composite film contained 25 parts of aramid nanofibers, 100 parts of graphene, and 1.8 parts of polyaniline deposit. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 429.42mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 312.09mF/cm2(ii) a The tensile strength is 90.43 MPa; the toughness is 1.78MJ/m3(ii) a At 2mA/cm2The capacity retention rate is still 84 percent after 3000 times of charge and discharge cycles under the current density.
Example 3
According to the same method as in example 1, 0.67mL of aramid nanofiber solution (5mg/mL) was added to 15mL of a dimethyl sulfoxide dispersion of graphene oxide (2mg/mL), but the system was prepolymerized at 0.8V anode voltage for 0.5min to allow polyaniline to react with graphene sheets and aramid nanofibersNucleation between fibers and subsequent switching to 1.98mA/cm2Constant current polymerization, the reaction was carried out for 10 min. In the prepared flexible composite electrode, 11 parts of aramid nano-fiber, 100 parts of graphene and 0.8 part of polyaniline are deposited according to parts by weight. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 465.33mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 304.12mF/cm2(ii) a Tensile strength of 79.29 MP; the toughness is 1.35MJ/m3(ii) a At 2mA/cm2The capacity retention rate is still 85 percent after 3000 times of charge and discharge cycles under the current density.
Example 4
Following the same procedure as in example 1, but with 18 parts of aramid nanofibers in the composite film, the system was prepolymerized at 0.8V anode voltage for 0.8min to nucleate polyaniline between graphene sheets and aramid nanofibers, followed by 1.5mA/cm switching2Constant current polymerization, the reaction was carried out for 15 min. In the prepared flexible composite electrode, by weight, 18 parts of aramid nanofiber, 100 parts of graphene and 1.4 parts of polyaniline are deposited. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 481.52mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 353.17mF/cm2(ii) a The tensile strength is 82.34 MPa; the toughness is 1.53MJ/m3(ii) a At 2mA/cm2The capacity retention rate is still 86 percent after 3000 times of charge and discharge cycles under the current density.
Example 5
In the same manner as in example 2, 0.33mL of an aramid nanofiber solution (10mg/mL) was added to 15mL of a dimethyl sulfoxide dispersion of graphene oxide (2mg/mL), but the electrodeposited conductive polymer was changed to polypyrrole, and the prepared composite film was immersed in hydroiodic acid for 24 hours for reduction. In the prepared flexible composite electrode, 11 parts of aramid nano-fiber, 100 parts of graphene and 0.8 part of polypyrrole are deposited in parts by weight. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 497.32mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 377.51mF/cm2(ii) a The tensile strength is 78.30 MPa; the toughness is 1.21MJ/m3(ii) a At 2mA/cm2The capacity retention rate is still 84 percent after 3000 times of charge and discharge cycles under the current density.
Example 6
The same procedure as in example 2 was followed, except that the electrodeposited conductive polymer was replaced with polythiophene. In the prepared flexible composite electrode, 11 parts of aramid nano-fiber, 100 parts of graphene and 0.8 part of polythiophene are deposited in parts by weight. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 472.09mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 359.37mF/cm2(ii) a The tensile strength is 76.32 MPa; the toughness is 1.18MJ/m3(ii) a At 2mA/cm2The capacity retention rate is still 83 percent after 3000 times of charge and discharge cycles under the current density of (1).
Example 7
The same procedure as in example 2 was followed, except that the electrodeposited conductive polymer was changed to polyacetylene. In the prepared flexible composite electrode, 11 parts of aramid nano-fiber, 100 parts of graphene and 0.8 part of polyacetylene are deposited according to parts by weight. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 488.23mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 356.49mF/cm2(ii) a The tensile strength is 77.14 MPa; the toughness is 1.27MJ/m3(ii) a At 2mA/cm2The capacity retention rate is still 84 percent after 3000 times of charge and discharge cycles under the current density.
Comparative example 1
The same procedure as in example 1 was followed except that the aramid nanofibers were not added.
The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 480.05mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 347.58mF/cm2(ii) a The tensile strength is 35.29 MPa; the toughness is 0.63MJ/m3(ii) a At 2mA/cm2The capacity retention rate is 76 percent when the charge and the discharge are cycled for 3000 times under the current density of (1).
Comparative example 2
The same procedure as in example 1 was followed, except that polyaniline was not deposited.
The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 190.55mF/cm2(ii) a Current density 5mA/cm2Lower, area specific capacity 98.62mF/cm2(ii) a Tensile strength of 77.55 MPa; the toughness is 1.34MJ/m3(ii) a At 2mA/cm2The capacity retention rate is 73 percent when the charge and the discharge are cycled for 3000 times under the current density of (1).
Comparative example 3
The same procedure as in example 1 was followed except that the aramid nanofibers in the composite film were 42.8 parts.
The electrode can not electrodeposit conductive polymers and has no electrochemical performance; but a tensile strength of 120.71 MPa; the toughness is 2.08MJ/m3。
Comparative example 4
The same procedure as in example 1 was followed, except that the electrodeposition time was increased to 30 min.
Polyaniline on the surface of the composite membrane is easy to fall off in electrolyte and is difficult to form a complete thin film.
Comparative example 5
The same procedure as in example 1 was followed, except that the system was prepolymerized at 0.8V anode voltage for 0.1min, followed by switching to 0.1mA/cm2Constant current polymerization, the reaction was carried out for 15 min. The electrode was operated at a current density of 1mA/cm2Lower, area specific capacity 195mF/cm2(ii) a Current density 5mA/cm2Lower, specific area capacity 99.62mF/cm2(ii) a Tensile strength of 77.55 MPa; the toughness is 1.34MJ/m3(ii) a At 2mA/cm2The capacity retention rate is 74 percent when the charge and the discharge are cycled for 3000 times under the current density of (1).
Comparative example 6
Blending a solution containing 11 parts of aramid nano-fiber, 100 parts of graphene oxide and 1.8 parts of polyaniline, performing suction filtration to form a film according to the method in the embodiment 1 to obtain an aramid nano-fiber/graphene oxide/polyaniline film, and reducing the aramid nano-fiber/graphene oxide/polyaniline film by hydroiodic acid to obtain the aramid nano-fiber/graphene/polyaniline film. The electrode was operated at a current density of 1mA/cm2Lower, specific area capacity 134.74mF/cm2(ii) a Current density 5A/cm2Lower, specific area capacity 87.93mF/cm2(ii) a The tensile strength is 33.79 MPa; toughness of 0.44MJ/m3(ii) a At 2mA/cm2Electricity (D) fromThe capacitor is circularly charged and discharged 3000 times under the current density, and the capacity retention rate is 68 percent.
Comparative example 7
The same procedure as in example 1 was followed except that the aramid nanofibers were replaced with polyethylene terephthalate (PET). After the polyaniline is deposited, the polyaniline is found to be easy to fall off, and a complete aramid nanofiber/graphene/polyaniline film is difficult to obtain.
Comparative example 8
The same procedure was followed as in example 1, except that the hydriodic acid reduction time was 4 hours. The electrode was operated at a current density of 1mA/cm2Lower, area specific capacity 94.32mF/cm2(ii) a Current density 5mA/cm2Lower, area specific capacity 32.24mF/cm2(ii) a The tensile strength is 68.34 MPa; the toughness is 1.41MJ/m3。
The method adopts simple blending and a vacuum induction suction filtration method to prepare the aramid nano-fiber/graphene oxide film, improves the toughness and mechanical strength of the graphene oxide/graphene by using the aramid nano-fiber, improves the conductivity of the aramid nano-fiber/graphene by reducing hydroiodic acid, deposits a conductive polymer on the surface of a graphene sheet by electrodeposition, and greatly improves the specific capacitance of a composite electrode by using the high specific capacitance of the conductive polymer.
Claims (7)
1. The preparation method of the aramid nanofiber/graphene/conductive polymer flexible composite electrode is characterized by comprising the following steps of:
step 1, dissolving aramid fibers by using a DMSO/KOH system to prepare an aramid nanofiber solution;
step 2, uniformly mixing the aramid nano-fiber solution and the dimethyl sulfoxide dispersion liquid of the graphene oxide, and preparing the aramid nano-fiber/graphene oxide composite film by adopting a vacuum-assisted suction filtration method;
step 3, placing the aramid fiber nanofiber/graphene oxide composite film in hydroiodic acid, carrying out reduction reaction, soaking and cleaning with ethanol to remove hydroiodic acid after the reaction is finished, and drying to obtain the aramid fiber nanofiber/graphene oxide composite film;
step 4, adopting a three-electrode bodyThe method comprises the steps of taking an aramid nano-fiber/graphene composite film as a working electrode, soaking the aramid nano-fiber/graphene composite film in a sulfuric acid solution of a conductive polymer monomer, electrochemically depositing the conductive polymer on the surface of the aramid nano-fiber/graphene film, maintaining the constant potential at 0.8V for 0.5-1 min to perform a nucleation reaction of the conductive polymer, and then keeping the constant current density at 0.25-1.98 mA/cm2Maintaining for 10-20 min for polymerization reaction, and washing and drying to obtain an aramid nanofiber/graphene/conductive polymer flexible composite electrode; the flexible composite electrode comprises 11-25 parts by weight of aramid nano-fiber, 100 parts by weight of graphene and 0.8-1.8 parts by weight of conductive polymer.
2. The preparation method of claim 1, wherein in the step 1, the concentration of the aramid nanofiber solution is 2-10 mg/mL.
3. The method according to claim 1, wherein in the step 2, the concentration of the graphene oxide in the dimethylsulfoxide dispersion liquid of the graphene oxide is 2 mg/mL.
4. The method according to claim 1, wherein the hydriodic acid is soaked for 10 hours or more and the ethanol is soaked for 72 hours in step 3.
5. The method according to claim 1, wherein in step 4, the conductive polymer monomer is aniline, pyrrole, thiophene or acetylene; the conductive polymer is polyaniline, polypyrrole, polythiophene or polyacetylene.
6. The preparation method of the flexible composite electrode according to claim 1, wherein in the step 4, the flexible composite electrode comprises 11-18 parts by weight of aramid nanofiber, 100 parts by weight of graphene and 1.4-1.8 parts by weight of conductive polymer.
7. The aramid nanofiber/graphene/conductive polymer flexible composite electrode prepared by the preparation method according to any one of claims 1 to 6.
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