CN109637821B - Flexible asymmetric supercapacitor and preparation method thereof - Google Patents
Flexible asymmetric supercapacitor and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 177
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 107
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 71
- 239000004744 fabric Substances 0.000 claims abstract description 69
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920000767 polyaniline Polymers 0.000 claims abstract description 54
- 239000007774 positive electrode material Substances 0.000 claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000010410 layer Substances 0.000 claims description 211
- 238000000151 deposition Methods 0.000 claims description 113
- 230000008021 deposition Effects 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 53
- 239000002356 single layer Substances 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 238000002484 cyclic voltammetry Methods 0.000 claims description 34
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000003990 capacitor Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
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- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229910018106 Ni—C Inorganic materials 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- 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
- H01G11/32—Carbon-based
-
- 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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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a flexible asymmetric supercapacitor, which comprises a collector electrode, a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises carbon cloth and a positive electrode material layer loaded on the carbon cloth; the positive electrode material layer comprises polyaniline layers and reduced graphene oxide layers which are alternately stacked; the negative electrode comprises carbon cloth and a negative electrode material layer loaded on the carbon cloth; the negative electrode material layer comprises a poly 3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer which are alternately stacked. According to the invention, the positive electrode and the negative electrode are subjected to synergistic effect through matching of the positive electrode material layer and the negative electrode material layer, so that the potential window of the flexible asymmetric supercapacitor is enlarged, and the electrochemical performance of the supercapacitor is improved.
Description
Technical Field
The invention relates to the technical field of supercapacitors, in particular to a flexible asymmetric supercapacitor and a preparation method thereof.
Background
Supercapacitors are energy storage elements capable of providing higher power densities than batteries. The positive electrode and the negative electrode of the super capacitor are made of the same electrode material, the non-symmetrical super capacitor is a novel capacitor which is obtained by improving the symmetrical super capacitor, and the non-symmetrical super capacitor is formed by respectively taking the electrode materials in two different working voltage ranges as positive and negative electrodes, so that the working voltage of the super capacitor is increased.
At present, a metal oxide/hydroxide is usually selected as a positive electrode material of the asymmetric supercapacitor, a carbon material is used as a negative electrode, and an electrolyte is water-washing electrolyte. Asymmetric supercapacitors using Ac-Ni (OH) 2 as the positive electrode material are currently commercialized and can be applied to electric vehicle power systems. The super capacitor bus of Shanghai Aowei company adopts an electrode structure of Ni-C, and the energy density of the super capacitor bus is 4-5 times higher than that of a C-C super capacitor bus.
At present, the specific capacitance of the asymmetric supercapacitor is generally within 100F/g, the energy density is about 20 Wh.kg -1, but the types of the asymmetric supercapacitor are few at present, the novel asymmetric supercapacitor is researched, and the problem that the electrochemical performance of the asymmetric supercapacitor is further improved still needs to be solved.
Disclosure of Invention
In view of the above, the present invention aims to provide a flexible asymmetric supercapacitor and a preparation method thereof. The flexible asymmetric supercapacitor provided by the invention has the advantages of high energy density, high power density and good cycling stability.
In order to achieve the above object, the present invention provides the following technical solutions:
The flexible asymmetric supercapacitor comprises a collector electrode, a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the positive electrode comprises carbon cloth and a positive electrode material layer loaded on the carbon cloth; the positive electrode material layer comprises polyaniline layers and reduced graphene oxide layers which are alternately stacked; the polyaniline layer is in direct contact with the carbon cloth, and the surface layer is a reduced graphene oxide layer;
the negative electrode comprises carbon cloth and a negative electrode material layer loaded on the carbon cloth; the negative electrode material layer comprises a poly 3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer which are alternately laminated; the poly 3, 4-ethylenedioxythiophene layer is in direct contact with the carbon cloth, and the surface layer is a reduced graphene oxide layer.
Preferably, the number of polyaniline layers in the positive electrode material layer is 8-24; the number of the reduced graphene oxide layers in the positive electrode material layer is the same as that of the polyaniline layers;
the amount of the single-layer polyaniline in the positive electrode material layer is 0.5-10 mg/cm 2;
the amount of the monolayer reduced graphene oxide in the positive electrode material layer is 0.5-2 mg/cm 2.
Preferably, the number of the poly 3, 4-ethylenedioxythiophene layers in the anode material layer is 10-30 independently; the number of the reduced graphene oxide layers in the negative electrode material layer is the same as that of the poly 3, 4-ethylenedioxythiophene layers;
The amount of the single-layer poly 3, 4-ethylenedioxythiophene layer in the negative electrode material layer is 0.5-8 mg/cm 2;
The amount of the monolayer reduced graphene oxide in the negative electrode material layer is 0.5-2 mg/cm 2.
Preferably, the membrane is a Nafion proton exchange membrane or a polyvinyl alcohol membrane; the electrolyte is sulfuric acid solution.
The invention provides a preparation method of the flexible asymmetric supercapacitor, which comprises the following steps:
(1) Sequentially alternately depositing an polyaniline layer and a reduced graphene oxide layer on the surface of the carbon cloth by using a cyclic voltammetry to obtain a positive electrode;
(2) Depositing a3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer on the surface of the carbon cloth alternately by using a cyclic voltammetry to obtain a negative electrode;
(3) Assembling the collector electrode, the positive electrode, the negative electrode, the diaphragm and the electrolyte to obtain a flexible asymmetric supercapacitor;
the steps (1) and (2) are not limited in time sequence.
Preferably, the deposition voltage for depositing the polyaniline layer in the step (1) is-0.4-1.3V, the scanning speed is 0.005-0.2V/s, and the deposition time of a single layer is 5-10 min; the single-layer scanning turns are 2-10 turns;
The deposition solution for depositing the polyaniline layer is a mixed solution of aniline monomer and sulfuric acid; the concentration of the aniline monomer in the deposition solution is 0.05-2 mol/L, and the concentration of sulfuric acid is 0.05-2 mol/L.
Preferably, the deposition voltage of depositing the reduced graphene oxide layer in the step (1) is-1.4-0.9V, the scanning speed is 0.005-0.2V/s, the monolayer deposition time is 5-10 min, and the monolayer scanning circle number is 2-10 circles;
the deposition solution for depositing the reduced graphene oxide layer is graphene oxide dispersion liquid; the concentration of the graphene oxide dispersion liquid is 2-4 g/L.
Preferably, the deposition voltage of the poly 3, 4-ethylenedioxythiophene layer deposited in the step (2) is-0.4-1.3V, the scanning rate is 0.005-0.2V/s, and the deposition time of a single layer is 5-10 min; the single-layer scanning turns are 4-20.
Preferably, the deposition solution for depositing the poly 3, 4-ethylenedioxythiophene layer comprises 3, 4-ethylenedioxythiophene, an anionic surfactant and sulfuric acid; the concentration of the 3, 4-ethylenedioxythiophene in the deposition solution is 4-6 mmol/L, the concentration of the anionic surfactant is 4-6 mmol/L, and the concentration of sulfuric acid is 0.05-6 mol/L.
Preferably, the deposition voltage of depositing the reduced graphene oxide layer in the step (2) is-1.2-0.9V, the scanning speed is 0.005-0.2V/s, the monolayer deposition time is 5-10 min, and the monolayer scanning circle number is 2-10.
The invention provides a flexible asymmetric supercapacitor, which comprises a collector electrode, a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode comprises carbon cloth and a positive electrode material layer loaded on the carbon cloth; the positive electrode material layer comprises polyaniline layers and reduced graphene oxide layers which are alternately stacked; the negative electrode comprises carbon cloth and a negative electrode material layer loaded on the carbon cloth; the negative electrode material layer comprises a poly 3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer which are alternately stacked. According to the invention, the polyaniline layers and the reduced graphene oxide layers which are alternately laminated are used as the positive electrode material, and the poly-3, 4-ethylenedioxythiophene layers and the reduced graphene oxide layers which are alternately laminated are used as the negative electrode material, so that the positive electrode and the negative electrode perform synergistic action, the potential window of the flexible asymmetric supercapacitor is enlarged, and the electrochemical performance of the supercapacitor is improved. The example results show that the potential window of the flexible asymmetric supercapacitor provided by the invention is 0-1.6V, the energy density can reach 36.35 Wh.kg -1, the corresponding power density is 422.15 W.kg -1, and the asymmetric supercapacitor provided by the invention has excellent cycling stability, and the capacitor retention rate is still 101% after 5000 times of cycling.
The invention provides a preparation method of the asymmetric supercapacitor. The preparation method provided by the invention has simple steps and is easy to operate.
Drawings
FIG. 1 is a schematic structural diagram of a flexible asymmetric supercapacitor of the present invention;
in FIG. 1, 1-positive electrode, 2-negative electrode, 3-collector, 4-electrolyte-impregnated separator;
FIG. 2 is a cyclic voltammogram of a flexible supercapacitor prepared in example 1 of the present invention at different scan speeds;
FIG. 3 is cyclic voltammograms of the flexible asymmetric supercapacitor prepared in example 1 of the present invention at different potentials;
FIG. 4 is a constant current charge-discharge curve of the flexible asymmetric supercapacitor prepared in example 1 of the present invention;
FIG. 5 is a graph showing the cycle performance test of the flexible asymmetric supercapacitor prepared in example 1 of the present invention;
FIG. 6 is a constant current charge-discharge curve of the flexible asymmetric supercapacitor prepared in example 1 of the present invention at a current density of 1 mA/g;
fig. 7 is a cyclic voltammogram of the flexible asymmetric supercapacitor prepared in example 1 of the present invention under the condition that the bending angle is 0 ° to 180 °.
Detailed Description
The invention provides a flexible asymmetric supercapacitor, which comprises a collector electrode, a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the structure of the flexible asymmetric supercapacitor is shown in figure 1.
In the invention, the positive electrode comprises carbon cloth and a positive electrode material layer loaded on the carbon cloth; the positive electrode material layer comprises polyaniline layers and reduced graphene oxide layers which are alternately stacked; the number of polyaniline layers in the positive electrode material layer is preferably 8-24, more preferably 10-20, and even more preferably 12; the number of the reduced graphene oxide layers in the positive electrode material layer is the same as that of the polyaniline layers; the polyaniline layer is directly contacted with the carbon cloth, and the surface layer is a reduced graphene oxide layer; in a specific embodiment of the present invention, it is preferable to alternately laminate the polyaniline layer/the reduced graphene oxide layer/… …/the polyaniline layer/the reduced graphene oxide layer in this order. In the present invention, the amount of the single-layer polyaniline in the positive electrode material layer is preferably 0.5 to 10mg/cm 2, more preferably 1mg/cm 2; the amount of the single-layer reduced graphene oxide in the positive electrode material layer is preferably 0.5 to 2mg/cm 2, more preferably 1 to 1.5mg/cm 2.
In the present invention, the negative electrode includes a carbon cloth and a negative electrode material layer supported on the carbon cloth; the negative electrode material layer comprises a poly 3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer which are alternately laminated; the number of the poly 3, 4-ethylenedioxythiophene layers in the negative electrode material layer is preferably 10-30, more preferably 15-25, and even more preferably 20; the number of the reduced graphene oxide layers in the negative electrode material layer is the same as that of the poly 3, 4-ethylenedioxythiophene layers; the carbon cloth is directly contacted with a poly 3, 4-ethylenedioxythiophene layer, and the surface layer is a reduced graphene oxide layer; in a specific embodiment of the present invention, it is preferable to arrange the poly 3, 4-ethylenedioxythiophene layer/reduced graphene oxide layer/… …/poly 3, 4-ethylenedioxythiophene layer/reduced graphene oxide layer in this order. In the present invention, the amount of the single layer poly 3, 4-ethylenedioxythiophene layer in the negative electrode material layer is preferably 0.5 to 8mg/cm 2, more preferably 1 to 6mg/cm 2; the amount of the single-layer reduced graphene oxide in the anode material layer is preferably 0.5 to 2mg/cm 2, more preferably 1 to 1.5mg/cm 2.
The carbon cloth is not particularly required, and carbon cloth well known to those skilled in the art can be used.
The positive electrode material layer comprises a polyaniline layer and a reduced graphene oxide layer, the polyaniline layer and the reduced graphene oxide layer form a polyaniline-graphene oxide composite material layer, the negative electrode material layer comprises a poly 3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer, the poly 3, 4-ethylenedioxythiophene-reduced graphene oxide composite material layer is formed by the polyaniline layer and the reduced graphene oxide layer, the potential window of the polyaniline is positive, and the potential window of the poly 3, 4-ethylenedioxythiophene is negative.
In the present invention, the membrane is preferably a Nafion proton exchange membrane or a polyvinyl alcohol membrane; the electrolyte is preferably a sulfuric acid solution; the collector is preferably copper foil. The thickness of the separator, the concentration of the electrolyte, the thickness of the collector, and the like are not required, and the separator, the electrolyte, and the collector, which are well known to those skilled in the art, may be used.
The invention provides a preparation method of the super capacitor, which comprises the following steps:
(1) Sequentially alternately depositing an polyaniline layer and a reduced graphene oxide layer on the surface of the carbon cloth by using a cyclic voltammetry to obtain a positive electrode;
(2) Depositing a3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer on the surface of the carbon cloth alternately by using a cyclic voltammetry to obtain a negative electrode;
(3) Assembling the collector electrode, the positive electrode, the negative electrode, the diaphragm and the electrolyte to obtain a flexible asymmetric supercapacitor;
the steps (1) and (2) are not limited in time sequence.
According to the invention, a cyclic voltammetry is used for alternately depositing an polyaniline layer and a reduced graphene oxide layer on the surface of carbon cloth in turn, so as to obtain the positive electrode. In the present invention, the deposition of the polyaniline layer is preferably specifically: and (3) immersing the carbon cloth serving as a working electrode in a deposition solution, and depositing an polyaniline layer on the surface of the carbon cloth by using a cyclic voltammetry.
The invention preferably uses a three-electrode system for cyclic voltammetry deposition, wherein a reference electrode in the three-electrode system is preferably a saturated calomel electrode, a counter electrode is preferably a platinum electrode, and a working electrode is carbon cloth.
The invention preferably pre-treats the carbon cloth prior to deposition, said pre-treatment preferably comprising the steps of: the carbon cloth is soaked in absolute ethyl alcohol, acetone and potassium permanganate solution in turn, and then washed until colorless. In the present invention, the soaking time in absolute ethanol, the soaking time in acetone and the soaking time in potassium permanganate solution are independently preferably 20 to 60min, more preferably 30 to 50min; the mass concentration of the potassium permanganate solution is preferably 5%; the water for washing is preferably distilled water; the present invention is not particularly limited to the water washing, and a water washing method well known to those skilled in the art may be used. According to the invention, the impurities on the surface of the carbon cloth are removed by pretreatment of the carbon cloth, and the oxygen-containing functional groups on the surface of the carbon cloth are increased, so that the subsequent deposition effect is improved.
After the pretreatment of the carbon cloth is completed, the pretreated carbon is preferably arranged in a deposition solution for deposition. In the invention, the deposition solution for depositing the polyaniline layer is preferably a mixed solution of aniline monomer and sulfuric acid; the concentration of the aniline monomer in the deposition solution is preferably 0.05 to 2mol/L, more preferably 0.1 to 1.5mol/L, and the concentration of sulfuric acid is preferably 0.05 to 2mol/L, more preferably 1mol/L.
In the invention, the deposition voltage of the polyaniline layer is preferably-0.4-1.3V, the scanning rate is preferably 0.005-0.2V/s, more preferably 0.02V/s, and the deposition time of a single layer is preferably 5-10 min, more preferably 8min; the number of single-layer scanning turns is preferably 2 to 10, more preferably 4 to 8.
After the polyaniline layer is deposited, the polyaniline layer is preferably washed with water to remove surface impurities and undeposited aniline monomers.
After the water washing is finished, the carbon cloth deposited with the polyaniline layer is used as a working electrode, soaked in the deposition solution, and the reduced graphene oxide layer is deposited on the surface of the polyaniline layer by using a cyclic voltammetry. In the present invention, the deposition solution for depositing the reduced graphene oxide layer is preferably a graphene oxide dispersion solution; the concentration of the graphene oxide dispersion liquid is preferably 2-4 g/L, more preferably 3g/L; the dispersion solvent of the graphene oxide dispersion liquid is preferably a phosphate buffer solution. In the present invention, the electrode system for depositing the reduced graphene oxide layer is preferably consistent with the above scheme, and will not be described herein.
In a specific embodiment of the present invention, the preparation method of the graphene oxide dispersion liquid preferably includes the following steps:
mixing NaH 2PO4 solution and Na 2HPO4 solution to obtain phosphate buffer solution;
And adjusting the pH value of the phosphate buffer solution to 8, and then adding the graphene oxide into the phosphate buffer solution, stirring and carrying out ultrasonic treatment to obtain graphene oxide dispersion liquid.
In the present invention, the concentration of the NaH 2PO4 solution is preferably 0.3M; the concentration of the Na 2HPO4 solution is preferably 0.2M; the volume ratio of the NaH 2PO4 solution to the Na 2HPO4 solution is preferably 10.6:189.4; the stirring time is preferably 30min; the time of the ultrasonic treatment is preferably 30min; the invention preferably alternately stirs-ultrasonic for 3 times to disperse the graphene oxide uniformly.
In the invention, the deposition voltage of the deposition reduction graphene oxide layer is preferably-1.4-0.9V, the scanning rate is preferably 0.005-0.2V/s, more preferably 0.05V/s, and the monolayer deposition time is preferably 5-10 min, more preferably 8min; the number of single-layer scanning turns is preferably 2-10. In the deposition process, graphene oxide is reduced and deposited on the surface of the polyaniline layer to form a reduced graphene oxide layer.
After the deposition is completed, the reduced graphene oxide layer is preferably washed with water to remove surface impurities and undeposited graphene oxide.
After water washing, the carbon cloth deposited with the reduced graphene oxide layer is preferably used as a working electrode, the polyaniline layer is deposited again, so that the polyaniline layer is formed on the surface of the reduced graphene oxide layer, after the polyaniline layer is deposited, the reduced graphene oxide layer is deposited on the surface of the polyaniline layer again, and the reduced graphene oxide layer is deposited alternately in sequence, so that a positive electrode material layer is formed on the surface of the carbon cloth; the conditions for each deposition are the same as those described above, and will not be described in detail here. After the alternate deposition, the invention preferably washes and dries the deposited part; the drying temperature is preferably 70 ℃, and the drying time is preferably 6h.
According to the invention, a cyclic voltammetry is used for alternately depositing a 3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer on the surface of carbon cloth in sequence to obtain the negative electrode. In the present invention, the deposition of the poly 3, 4-ethylenedioxythiophene layer is preferably specifically: and (3) immersing the carbon cloth serving as a working electrode in a deposition solution, and depositing a layer of accumulated 3, 4-ethylenedioxythiophene on the surface of the carbon cloth by using a cyclic voltammetry. In the invention, the electrode system for depositing the poly 3, 4-ethylenedioxythiophene layer is preferably consistent with the scheme, and is not repeated here; the carbon cloth is preferably pretreated before deposition; the pretreatment method is consistent with the above scheme, and will not be described herein.
In the invention, the deposition solution for depositing the poly 3, 4-ethylenedioxythiophene layer comprises 3, 4-ethylenedioxythiophene, an anionic surfactant and sulfuric acid; the concentration of 3, 4-ethylenedioxythiophene in the deposition solution is preferably 4-6 mmol/L, more preferably 5mmol/L, the concentration of the anionic surfactant is preferably 4-6 mmol/L, more preferably 5mmol/L, and the concentration of sulfuric acid is preferably 0.05-6 mol/L, more preferably 0.1mol/L; the anionic surfactant is preferably sodium dodecyl sulfate.
In the invention, the deposition voltage of the deposited poly 3, 4-ethylenedioxythiophene layer is preferably-0.4-1.3V, the scanning rate is preferably 0.005-0.2V/s, more preferably 0.02V/s, and the initial scanning direction is preferably anode; the sample interval is preferably 0.001V, and the rest time is preferably 2s; the deposition time of the monolayer is preferably 5 to 10min, more preferably 8min; the number of single-layer scanning turns is preferably 4 to 20, more preferably 12 to 18.
After the poly 3, 4-ethylenedioxythiophene layer is deposited, the polyaniline layer is preferably washed with water to remove surface impurities and undeposited 3, 4-ethylenedioxythiophene monomer.
After water washing is completed, the carbon cloth deposited with the poly 3, 4-ethylenedioxythiophene layer is used as a working electrode, soaked in deposition liquid, and a reduced epoxy graphene layer is deposited on the surface of the poly 3, 4-ethylenedioxythiophene layer by using a cyclic voltammetry. In the present invention, the electrode system for depositing the reduced graphene oxide layer and the deposition solution for depositing the reduced graphene oxide layer are preferably consistent with the above schemes, and will not be described herein. In the invention, the deposition voltage of the deposition reduction graphene oxide layer is preferably-1.2-0.9V, the scanning rate is preferably 0.005-0.2V/s, more preferably 0.05V/s, and the monolayer deposition time is preferably 5-10 min, more preferably 8min; the number of single-layer scanning turns is preferably 2 to 10, more preferably 3 to 8. In the deposition process, the graphene oxide is reduced and deposited on the surface of the poly 3, 4-ethylenedioxythiophene layer to form a reduced graphene oxide layer.
After the deposition of the reduced graphene oxide layer is completed, the carbon cloth deposited with the reduced graphene oxide layer is preferably used as a working electrode, and the deposition of the poly 3, 4-ethylenedioxythiophene layer is carried out again, so that the poly 3, 4-ethylenedioxythiophene layer is formed on the surface of the reduced graphene oxide layer, and after the deposition of the poly 3, 4-ethylenedioxythiophene layer is completed, the reduced graphene oxide layer is deposited on the surface of the poly 3, 4-ethylenedioxythiophene layer again, and the deposition is carried out alternately in turn, so that a negative electrode material layer is formed on the surface of the carbon cloth; the conditions for each deposition are the same as those described above, and will not be described in detail here. After the alternate deposition, the invention preferably washes and dries the deposited part; the drying temperature is preferably 70 ℃, and the drying time is preferably 6h.
After the positive electrode and the negative electrode are obtained, the collector, the positive electrode, the negative electrode, the diaphragm and the electrolyte are assembled to obtain the flexible asymmetric supercapacitor. The method of assembly is not particularly limited by the present invention, and can be carried out by methods well known to those skilled in the art.
The following describes a flexible asymmetric supercapacitor and a method for manufacturing the same in detail, but they should not be construed as limiting the scope of the invention.
Example 1
1. Positive electrode preparation:
(1) Preparing polyaniline deposition solution: a mixed solution of aniline monomer and sulfuric acid, wherein the concentration of the aniline monomer in the mixed solution is 0.05M, and the concentration of the sulfuric acid is 1M; ultrasonic stirring the mixed solution for 30min, magnetically stirring for 30min, repeating for three times respectively, and fully and uniformly mixing the solution;
(2) Preparing graphene oxide dispersion liquid: 15.6gNaH 2PO4 is weighed and dissolved in 500mL of water to obtain 0.3M NaH 2PO4 solution; 35.82g of Na 2HPO4 was weighed and dissolved in 500mL of water to give a 0.2M Na 2HPO4 solution; weighing 10.6mLNaH 2PO4 solution and 189.4mLNa 2HPO4 solution to prepare 200mL buffer solution, then titrating to 8.0 by using a pH meter, and then adding graphene oxide (controlling the concentration of the graphene oxide in the dispersion to be 3 mg/mL); then magnetically stirring the graphene oxide dispersion liquid for 30min, ultrasonically stripping for 30min, repeating for three times, and fully and uniformly mixing the solution;
(3) Pretreatment of carbon cloth: cutting the carbon cloth into strips with the width of 1 cm and the length of 3 cm, firstly soaking the strips in absolute ethyl alcohol for 20-60 minutes, then soaking the strips in acetone solution for 20-60 minutes, then soaking the strips in 5% potassium permanganate solution for 30-60 minutes, and finally repeatedly flushing the strips with distilled water until the strips are colorless.
(4) Growing a polyaniline layer by cyclic voltammetry: immersing the pretreated carbon cloth in polyaniline deposition solution for cyclic voltammetry deposition, using a three-electrode system, using a saturated calomel electrode as a reference electrode, using a platinum electrode as a counter electrode, using the carbon cloth as a working electrode, wherein the deposition time is 8min, the deposition voltage is-0.4-1.3V, the scanning rate is 20mV/s, and the deposition turns are 2 turns; then washing with a large amount of deionized water, thereby completing the preparation of a deposition cycle coating; the deposition amount of the polyaniline of the monolayer is 0.5mg/cm 2;
(5) And (3) growing a reduced graphene oxide layer by cyclic voltammetry: carrying out cyclic voltammetry deposition on the carbon cloth subjected to the step (4) in graphene oxide dispersion liquid, wherein the deposition voltage is-1.4-0.9V, the scanning speed is 50mV/s, the deposition time is 8min, and then washing with a large amount of deionized water; the deposition amount of the monolayer reduced graphene oxide is 1.0mg/cm 2;
(6) Repeating the steps (4) and (5) for 12 times, and forming 12 polyaniline layers and 12 reduced graphene oxide layers which are alternately laminated on the surface of the carbon cloth to obtain the positive electrode.
2. Negative electrode preparation
(1) Preparing a 3, 4-ethylenedioxythiophene solution: 3, 4-ethylenedioxythiophene, sodium dodecyl sulfate and H 2SO4 are dissolved in water at normal temperature, and stirred for about 1H to form a uniform solution, wherein the concentration of the 3, 4-ethylenedioxythiophene in the solution is 5mmol/L, the concentration of the sodium dodecyl sulfate is 5mmol/L and the concentration of the H 2SO4 is 0.1mol/L;
(2) Preparing graphene oxide solution: the preparation method of the graphene oxide solution is consistent with that in the first step.
(3) Pretreatment of carbon cloth: the pretreatment method of the carbon cloth is consistent with the pretreatment method in the first step;
(4) Growing a poly 3, 4-ethylenedioxythiophene layer by cyclic voltammetry: the pretreated carbon is arranged in 3, 4-ethylenedioxythiophene solution for cyclic voltammetry deposition, a three-electrode system is used, a saturated calomel electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, carbon cloth is used as a working electrode, the initial potential is-0.4V, the highest potential is 1.3V, the lowest potential is-0.4V, and the final potential is: -0.4V, initial scan direction: anode, scanning rate of 0.02V/s, number of scanning turns of 18, sample interval of 0.001V, and rest time of 2s; the deposition time is 8min, and then a large amount of deionized water is used for flushing, so that the preparation of a deposition periodic coating is completed; the deposition amount of the single-layer poly 3, 4-ethylenedioxythiophene is 0.5mg/cm 2;
(5) And (3) growing a reduced graphene oxide layer by cyclic voltammetry: and (3) carrying out cyclic voltammetry deposition on the carbon cloth subjected to the step (4) in graphene oxide dispersion liquid, wherein the initial potential is-1.2V, the highest potential is 0.9V, the lowest potential is-1.2V, and the final potential is as follows: -1.2V, initial scan direction: anode, scanning rate of 0.05V/s, number of scanning turns of 10, sample interval of 0.001V, and resting time of 2s; the deposition time is 8min, and a large amount of deionized water is used for flushing after the deposition is completed; the deposition amount of the monolayer reduced graphene oxide is 1.0mg/cm 2;
(6) And (3) repeating the steps (4) and (5) for 18 times, and forming 18 poly (3, 4-ethylenedioxythiophene) layers and 18 reduced graphene oxide layers which are alternately laminated on the surface of the carbon cloth to obtain the positive electrode.
3. Assembled super capacitor
And (3) using a Nafion117 proton exchange membrane as a diaphragm, immersing the diaphragm in a 1M H 2SO4 solution for 30 minutes, using copper foils as collecting electrodes on two sides, and assembling a positive electrode, a negative electrode, the copper foils and the diaphragm immersed with electrolyte to obtain the flexible asymmetric supercapacitor.
4. Electrochemical testing
(1) Cyclic voltammetry test (CV)
And (3) carrying out cyclic voltammetry test on the flexible asymmetric supercapacitor obtained in the step (III), wherein a test system is a Shanghai Chenhua CHI660D type electrochemical workstation, a two-electrode system is used, electrolyte is a sulfuric acid solution with the concentration of 1mol/L, the scanning voltage range is 0-1.6V, and the scanning speed is 5-100 mV/s.
The obtained cyclic voltammograms are shown in figures 2-3, and figure 2 is a cyclic voltammogram of the flexible asymmetric supercapacitor at different scanning speeds; according to the graph 2, an obvious oxidation-reduction peak appears in the cyclic voltammetry curve, and the area is larger, which indicates that the flexible asymmetric supercapacitor provided by the invention has larger specific capacitance, realizes the working potential of 1.6V, and the performance is obviously better than the result (about 1.2V) reported by the current symmetric capacitor of the related water system; fig. 3 is a cyclic voltammogram of the flexible asymmetric supercapacitor at different potentials, and according to fig. 3, it can be seen that the cyclic voltammogram maintains a similar shape at different potentials, which illustrates that the flexible asymmetric supercapacitor provided by the invention can work under a wider potential window.
(2) Constant current charge and discharge test (CD)
And (3) performing constant-current charge and discharge test on the flexible asymmetric supercapacitor obtained in the step (III), wherein a testing instrument is a Shanghai Chenhua CHI660D type electrochemical workstation, the charge and discharge voltage range is 0-1.6V, and the current density is 0.5 mA/g-10 mA/g. The supercapacitor specific capacitance can be calculated according to formula (1):
in the formula (1), C m is the specific capacitance of the capacitor, I is the current density of charge and discharge, t(s) is the discharge time, deltaV (V) is the working voltage interval, and m (mg) is the mass sum of active substances on the two electrodes.
The energy density E can be calculated from equation (2):
In formula (2): cs is the specific capacitance, and DeltaV (V) is the working voltage interval.
The power density P can be calculated from equation (3):
in formula (3): e is energy density and t is time.
The constant current charge-discharge curve is shown in figure 4; as calculated according to fig. 4, at current densities of 0.4,0.6,1,2ma/cm 2, the specific capacitances of the asymmetric supercapacitor provided by the present invention are 224, 143, 86 and 66F g -1, respectively; the coulomb efficiency is 98.3%,96.5%,83.5% and 79.0%, and the energy density reaches 36.35 Wh.kg -1 and the power density is 422.15 W.kg -1 at 2mA/cm 2.
(3) Cycle stability test
And (3) carrying out a cycle stability test on the flexible asymmetric supercapacitor obtained in the step (III), wherein the test instrument is a Wohan electric charge-discharge tester, a two-electrode system is used, a voltage window is 0-1.6V, the current density is 1mA/g, the cycle times are 5000 times, and the percentage of the capacitance value after 5000 times of cycles relative to the initial capacitance value, namely the capacitance retention rate, is used as an evaluation index of the cycle stability.
The obtained results are shown in figures 5-6, and figure 5 is a cycle performance test chart of the flexible asymmetric supercapacitor; according to the graph of fig. 5, the flexible asymmetric supercapacitor provided by the invention has excellent cycling stability, and the capacitance retention rate is still 101% after 5000 continuous constant current charge and discharge tests under the current density of 1 a.g -1.
Fig. 6 is a constant current charge-discharge curve of the flexible asymmetric supercapacitor at a current density of 1mA/g, and it can be seen from fig. 6 that the charge and discharge times of the flexible asymmetric supercapacitor are substantially equal.
(4) Flexible test
Carrying out cyclic voltammetry test on the asymmetric supercapacitor under different bending degrees, wherein the scanning rate is 20mV/s; the test results obtained are shown in FIG. 7; as can be seen from fig. 7, the electrochemical performance of the asymmetric supercapacitor is not reduced at the bending degree of 0 ° to 180 °, which indicates that the asymmetric supercapacitor has high flexibility.
Example 2
Other conditions were consistent with example 1, and the number of polyaniline layers and reduced graphene oxide layers in the positive electrode was changed to 15, and the number of poly-3, 4-ethylenedioxythiophene layers and reduced graphene oxide layers in the negative electrode was changed to 20;
Electrochemical test is carried out according to the method in the embodiment 1, the voltage window of the flexible asymmetric supercapacitor is 0-1.6V, the energy density under the current density of 1 A.g -1 reaches 32.23 Wh.kg -1, the power density is 478.18 W.kg -1, and the capacitor retention rate can reach 98% after 5000 times of circulation; the electrochemical performance is not reduced at the bending degree of 0-180 degrees.
Example 3
Other conditions are consistent with example 1, and the number of polyaniline layers and reduced graphene oxide layers in the positive electrode is changed to 20, and the number of poly-3, 4-ethylenedioxythiophene layers and reduced graphene oxide layers in the negative electrode is changed to 25;
Electrochemical test is carried out according to the method in the embodiment 1, the voltage window of the flexible asymmetric supercapacitor is 0-1.6V, the energy density under the current density of 1 A.g -1 reaches 30.02 Wh.kg -1, the power density is 500.26 W.kg -1, and the capacitor retention rate can reach 96% after 5000 times of circulation; the electrochemical performance is not reduced at the bending degree of 0-180 degrees.
The embodiment shows that the flexible asymmetric supercapacitor provided by the invention has the advantages of wide potential window, high energy density and power density, good cycling stability, simple preparation method and wide application prospect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The flexible asymmetric supercapacitor comprises a collector electrode, a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the positive electrode comprises carbon cloth and a positive electrode material layer loaded on the carbon cloth; the positive electrode material layer comprises polyaniline layers and reduced graphene oxide layers which are alternately stacked; the polyaniline layer is in direct contact with the carbon cloth, and the surface layer is a reduced graphene oxide layer; the negative electrode comprises carbon cloth and a negative electrode material layer loaded on the carbon cloth; the negative electrode material layer comprises a poly 3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer which are alternately laminated; the poly 3, 4-ethylenedioxythiophene layer is in direct contact with the carbon cloth, and the surface layer is a reduced graphene oxide layer;
the number of polyaniline layers in the positive electrode material layer is 12;
the number of the reduced graphene oxide layers in the positive electrode material layer is the same as that of the polyaniline layers;
The amount of the single-layer polyaniline in the positive electrode material layer is 1mg/cm 2;
The amount of the single-layer reduced graphene oxide in the positive electrode material layer is 1-1.5 mg/cm 2;
the number of the poly 3, 4-ethylenedioxythiophene layers in the negative electrode material layer is 20;
the number of the reduced graphene oxide layers in the negative electrode material layer is the same as that of the poly 3, 4-ethylenedioxythiophene layers;
The amount of the single-layer poly 3, 4-ethylenedioxythiophene layer in the anode material layer is 1-6 mg/cm 2;
the amount of the single-layer reduced graphene oxide in the negative electrode material layer is 1-1.5 mg/cm 2;
sequentially alternately depositing an polyaniline layer and a reduced graphene oxide layer on the surface of the carbon cloth by using a cyclic voltammetry to obtain a positive electrode;
Depositing a3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer on the surface of the carbon cloth alternately by using a cyclic voltammetry to obtain a negative electrode;
pretreating the carbon cloth before deposition, wherein the pretreatment comprises the following steps: the carbon cloth is soaked in absolute ethyl alcohol, acetone and potassium permanganate solution in turn, and then washed until colorless.
2. The flexible asymmetric supercapacitor according to claim 1, wherein the membrane is a Nafion proton exchange membrane or a polyvinyl alcohol membrane; the electrolyte is sulfuric acid solution.
3. The method for manufacturing the flexible asymmetric supercapacitor according to claim 1, comprising the steps of:
(1) Sequentially alternately depositing an polyaniline layer and a reduced graphene oxide layer on the surface of the carbon cloth by using a cyclic voltammetry to obtain a positive electrode;
(2) Depositing a3, 4-ethylenedioxythiophene layer and a reduced graphene oxide layer on the surface of the carbon cloth alternately by using a cyclic voltammetry to obtain a negative electrode;
(3) Assembling the collector electrode, the positive electrode, the negative electrode, the diaphragm and the electrolyte to obtain a flexible asymmetric supercapacitor;
the steps (1) and (2) are not limited in time sequence.
4. The method according to claim 3, wherein the deposition voltage for depositing the polyaniline layer in the step (1) is-0.4 to 1.3v, the scanning rate is 0.005 to 0.2v/s, and the deposition time of a single layer is 5 to 10min; the single-layer scanning turns are 2-10 turns;
The deposition solution for depositing the polyaniline layer is a mixed solution of aniline monomer and sulfuric acid; the concentration of the aniline monomer in the deposition solution is 0.05-2 mol/L, and the concentration of sulfuric acid is 0.05-2 mol/L.
5. The preparation method of claim 3, wherein the deposition voltage of the reduced graphene oxide layer deposited in the step (1) is-1.4-0.9 v, the scanning rate is 0.005-0.2 v/s, the monolayer deposition time is 5-10 min, and the monolayer scanning number of turns is 2-10 turns;
The deposition solution for depositing the reduced graphene oxide layer is graphene oxide dispersion liquid; the concentration of the graphene oxide dispersion liquid is 2-4 g/L.
6. The method according to claim 3, wherein the deposition voltage of the poly 3, 4-ethylenedioxythiophene layer deposited in the step (2) is-0.4 to 1.3v, the scanning rate is 0.005 to 0.2v/s, and the deposition time of the monolayer is 5 to 10min; the single-layer scanning turns are 4-20.
7. The method according to claim 3 or 6, wherein the deposition solution for depositing the poly 3, 4-ethylenedioxythiophene layer comprises 3, 4-ethylenedioxythiophene, an anionic surfactant, and sulfuric acid; the concentration of 3, 4-ethylenedioxythiophene in the deposition solution is 4-6 mmol/L, the concentration of the anionic surfactant is 4-6 mmol/L, and the concentration of sulfuric acid is 0.05-6 mol/L.
8. The method according to claim 3, wherein the deposition voltage of the reduced graphene oxide layer deposited in the step (2) is-1.2 to 0.9v, the scanning rate is 0.005 to 0.2v/s, the monolayer deposition time is 5 to 10min, and the monolayer scanning number of turns is 2 to 10.
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| CN104269281A (en) * | 2014-09-24 | 2015-01-07 | 吉林大学 | Method for manufacturing asymmetric super capacitor |
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| CN104269281A (en) * | 2014-09-24 | 2015-01-07 | 吉林大学 | Method for manufacturing asymmetric super capacitor |
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