CN112582187A - Flexible electrode, preparation method thereof and application of flexible electrode in preparation of flexible all-solid-state supercapacitor - Google Patents
Flexible electrode, preparation method thereof and application of flexible electrode in preparation of flexible all-solid-state supercapacitor Download PDFInfo
- Publication number
- CN112582187A CN112582187A CN202011331921.8A CN202011331921A CN112582187A CN 112582187 A CN112582187 A CN 112582187A CN 202011331921 A CN202011331921 A CN 202011331921A CN 112582187 A CN112582187 A CN 112582187A
- Authority
- CN
- China
- Prior art keywords
- flexible
- preparation
- flexible electrode
- solid
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 67
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 64
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 64
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 239000006185 dispersion Substances 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 30
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000012528 membrane Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000007605 air drying Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000006136 alcoholysis reaction Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- 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
Abstract
The invention discloses a flexible electrode, a preparation method thereof and application of the flexible electrode in preparation of a flexible all-solid-state supercapacitor. The preparation method of the flexible electrode comprises the following steps: preparing a redox graphene/carbon nanotube composite dispersion liquid; and preparing the redox graphene/carbon nanotube electrode. The preparation method of the capacitor comprises the following steps: preparing a potassium hydroxide (KOH) gel electrolyte; and (4) preparing the electric double layer flexible supercapacitor. Compared with the traditional preparation method of the porous carbon material, the preparation method provided by the invention has the advantages of simple synthesis method, easiness in control and high reproducibility. The flexible all-solid-state supercapacitor has good electrochemical performance, omits a diaphragm, has simple process flow, and is convenient for realizing commercial application.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a flexible electrode, a preparation method of the flexible electrode and application of the flexible electrode in preparation of a flexible all-solid-state supercapacitor.
Background
The use of clean energy is becoming more and more important due to the consumption of fossil fuels and environmental pollution. However, since energy sources such as solar energy and wind energy are affected by geographical and seasonal factors, the development of energy storage technology is very important. The super capacitor has the advantages of high energy density, high charging speed, long cycle life, light weight and the like. They are of interest because of their ability to balance the high energy density requirements of batteries with the rapid powering of capacitors. With the development of foldable mobile phones and displays, flexible energy storage devices are receiving more and more attention. Conventional commercial supercapacitors are composed primarily of rigid electrodes and cannot be bent or twisted. This requires that the electrodes possess good flexibility and mechanical strength as well as excellent electrochemical properties.
At present, much research is carried out on electrode materials of supercapacitors, but research on preparing flexible all-solid-state supercapacitors directly from the materials is less, and the research is mainly influenced by the mechanical properties of the electrode materials (Zhang, l.l., et al, Chemical Society Reviews,2009,38(9), 2520-. Graphene and carbon nanotubes are used as materials of super capacitors with wide application, have characteristics of very large theoretical specific surface area, excellent electron mobility and the like, and are ideal choices of super capacitor electrode materials (Trist n-L Lopez, F., et al., ACS nano,2013,7(12), 10788-10798.). Xi et al developed a graphene-carbon nanotube supercapacitor, but both carbon nanotubes and graphene were prone to agglomeration during the electrode preparation process, resulting in the electrochemical performance of the prepared supercapacitor being far lower than expected. The preparation of flexible super capacitors with both mechanical and energy storage characteristics still faces a great challenge.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a flexible electrode, a preparation method thereof and application thereof in preparing a flexible all-solid-state supercapacitor.
The invention provides a flexible electrode and a flexible all-solid-state supercapacitor to solve the problems.
The invention provides a preparation method of a redox graphene-carbon nanotube flexible electrode and assembly of an all-solid-state symmetrical supercapacitor of the redox graphene-carbon nanotube flexible electrode.
The purpose of the invention is realized by at least one of the following technical solutions.
The preparation method of the flexible electrode provided by the invention comprises the following steps:
(1) preparing a dispersion solution: adding the carbon nano tube into deionized water, and uniformly dispersing to obtain a carbon nano tube dispersion liquid; adding graphene oxide into water, and uniformly dispersing to obtain a graphene oxide dispersion liquid;
(2) preparing a flexible composite film: mixing the carbon nanotube dispersion liquid and the graphene oxide dispersion liquid obtained in the step (1), and performing ultrasonic dispersion uniformly to obtain a mixed liquid; performing suction filtration on the mixed solution by using a filter membrane, removing filtrate, and drying to obtain a flexible composite film;
(3) preparing a flexible electrode: and (3) heating the flexible composite film obtained in the step (2) under a protective atmosphere to perform a reduction reaction (calcination treatment), so as to obtain the flexible electrode.
Further, the mass percent concentration of the carbon nanotube dispersion liquid in the step (1) is 0.5-1.5mg/mL, and the mass percent concentration of the graphene oxide dispersion liquid is 0.5-1.5 mg/mL.
Further, the mass ratio range of the carbon nanotube dispersion liquid and the graphene oxide dispersion liquid in the step (2) is 3: 1-1: 3.
preferably, in the mixed solution in the step (2), the mass ratio of the carbon nanotubes to the graphene oxide is 1: 1.
preferably, the suction filtration in the step (2) is vacuum filtration.
Preferably, the temperature for drying in step (2) is 30 ℃.
Preferably, the drying in step (2) is natural air drying.
Further, the filter membrane in the step (2) is polyether sulfone, and the pore size of the filter membrane is 0.2 mu m.
Preferably, the time of the ultrasound in the step (2) is 1 h.
Further, the temperature of the reduction reaction in the step (3) is 300-400 ℃, and the time of the reduction reaction is 2-6 h.
Preferably, the protective atmosphere in step (3) is a nitrogen atmosphere.
Preferably, the temperature of the reduction reaction in the step (3) is 350 ℃, and the time of the reduction reaction is 4 h.
The invention provides a flexible electrode prepared by the preparation method.
The application of the flexible electrode in preparing the flexible all-solid-state supercapacitor provided by the invention comprises the following steps:
(1) preparation of KOH gel electrolyte: dissolving polyvinyl alcohol in deionized water to obtain a polyvinyl alcohol solution, and then adding a KOH solution to obtain a KOH gel electrolyte;
(2) and (2) soaking the flexible electrode in the KOH gel electrolyte in the step (1), air-drying to obtain pole pieces, assembling the two pole pieces into a capacitor (and assembling a current collector into a capacitor), and obtaining the flexible all-solid-state supercapacitor.
Further, the alcoholysis degree of the polyvinyl alcohol in the step (1) is 96-98%, the concentration of the polyvinyl alcohol solution is 0.08-0.16g/mL, and the concentration of the KOH solution is 0.4-0.8 g/mL; the volume ratio of the polyvinyl alcohol solution to the KOH solution is 4:1-6: 1.
preferably, in the application of the flexible electrode in the preparation of a flexible all-solid-state supercapacitor, the alcoholysis degree of the polyvinyl alcohol in the step (1) is 96-98%, the mass concentration of the polyvinyl alcohol solution is 0.12g/mL, and the mass concentration of the KOH solution is 0.6 g/mL; the volume ratio of the polyvinyl alcohol solution to the KOH solution is 5: 1.
Preferably, in the application of the flexible electrode in preparing a flexible all-solid-state supercapacitor, in the step (1), the dissolution temperature of the polyvinyl alcohol is 90 ℃, and the dissolution time is 5 h.
Further, the air drying time of the air drying in the step (2) is 24-48 h.
Preferably, in the application of the flexible electrode in the preparation of a flexible all-solid-state supercapacitor, the air drying time in the step (2) is 24 hours.
The invention provides a flexible all-solid-state supercapacitor (redox graphene-carbon nanotube all-solid-state symmetrical flexible supercapacitor) prepared by applying the flexible electrode to the preparation of the flexible all-solid-state supercapacitor.
The invention provides a flexible electrode and a flexible all-solid-state supercapacitor.
Compared with the traditional preparation method of the porous carbon material, the preparation method provided by the invention has the advantages of simple synthesis method, easiness in control and high reproducibility. The flexible all-solid-state supercapacitor has good electrochemical performance, omits a diaphragm, has simple process flow, and is convenient for realizing commercial application.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) in the preparation method of the flexible electrode provided by the invention, as shown in fig. 2, the carbon nanotubes are effectively inserted between graphene sheet layers, so that not only are the distance and the specific surface area between graphene sheets increased, but also the carbon nanotubes can make up for the defects generated in the oxidation process of graphene, and are beneficial to electron transmission, so that the unit capacitance of the flexible electrode is improved, and as shown in fig. 1, a three-electrode test method is adopted, 2M KOH is used as an electrolyte, and the redox graphene-carbon nanotube composite film shows excellent specific capacitance.
(2) The flexible electrode provided by the invention is applied to the preparation of a flexible all-solid-state supercapacitor, the electrode is placed in a KOH gel electrolyte, and the gel electrolyte has the function of a diaphragm, so that the diaphragm is omitted, and the preparation of the supercapacitor is simpler and more efficient.
Drawings
Fig. 1 is a specific capacity display diagram of a redox graphene/carbon nanotube based composite electrode prepared in example 1.
Fig. 2 is a scanning electron microscope image and a transmission electron microscope image of the redox graphene/carbon nanotube-based composite electrode prepared in example 1.
Fig. 3 is a specific capacity display diagram of an all-solid-state supercapacitor based on a redox graphene/carbon nanotube composite electrode prepared in example 1.
Fig. 4 is a specific capacity display diagram of the redox graphene/carbon nanotube based composite electrode prepared in example 2.
Fig. 5 is an SEM image of the redox graphene/carbon nanotube based composite electrode prepared in example 2.
Fig. 6 is a specific capacity display diagram of a redox graphene/carbon nanotube based composite electrode prepared in example 3.
Fig. 7 is an SEM image of the redox graphene/carbon nanotube based composite electrode prepared in example 3.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of a flexible electrode comprises the following steps:
(1) adding the carbon nano tube into water, and uniformly dispersing to obtain a carbon nano tube dispersion liquid; the mass concentration of the carbon nano tube dispersion liquid is 1 mg/mL; adding graphene oxide into water, and uniformly dispersing to obtain a graphene oxide dispersion liquid; the mass concentration of the graphene oxide dispersion liquid is 1 mg/mL;
(2) respectively taking 12mg of the dispersion liquid of the carbon nano tube and the dispersion liquid of the graphene oxide, mixing the mixture in a beaker, performing ultrasonic treatment for 1 hour, performing ultrasonic dispersion uniformly to obtain a mixed liquid, performing vacuum filtration on a filter membrane, wherein the filter membrane is made of polyether sulfone, the aperture size of the filter membrane is 0.2 mu m, and drying or naturally air-drying the filter membrane at 30 ℃ to obtain a flexible composite film;
(3) and (3) preserving the heat of the flexible composite film obtained in the step (2) for 4 hours at 350 ℃ in a nitrogen atmosphere by using a tubular furnace to reduce the graphene oxide to obtain a flexible electrode (based on the redox graphene/carbon nanotube composite electrode), and testing by using the electrode as a working electrode, a platinum mesh as a counter electrode and mercury oxide as a reference electrode and using a three-electrode testing system and 2M KOH as electrolyte. The performance is shown in fig. 1, the redox graphene/carbon nanotube based composite electrode shows excellent specific capacitance, and the SEM and TEM are shown in fig. 2. Parts a-c in fig. 2 are SEM images of the redox graphene/carbon nanotube composite electrode-based example 1, wherein parts a and b are plan views, and part c is a sectional view; sections d-f are TEM images of example 1 based on redox graphene/carbon nanotube composite electrodes. As shown in fig. 2, the carbon nanotubes are effectively inserted between the graphene sheet layers, so that not only are the distance and the specific surface area between the graphene sheets increased, but also the carbon nanotubes can make up for the defects generated in the oxidation process of graphene, thereby facilitating electron transmission and improving the unit capacitance of the flexible electrode.
A preparation method of a flexible all-solid-state supercapacitor based on a redox graphene/carbon nanotube composite electrode specifically comprises the following steps:
dissolving 3g of polyvinyl alcohol in 25mL of deionized water, stirring for 5h at 90 ℃, cooling to 60 ℃ after the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution, dissolving 3g of KOH in 5mL of deionized water, and adding the dissolved KOH solution into the polyvinyl alcohol solution to prepare a KOH gel electrolyte;
and (3) connecting the obtained 1 cm-2 cm flexible electrode small piece and a silver wire serving as a current collector with a silver paste, placing the prepared pole piece in a 10mL small beaker, adding a KOH gel electrolyte, soaking the pole piece in the KOH gel electrolyte, naturally drying for 24h to wait for gel to tend to solidify, superposing the two pole pieces from top to bottom, and wrapping the two pole pieces with a polyethylene film to prepare the flexible all-solid-state supercapacitor, wherein mass ratio capacitance data of the flexible all-solid-state supercapacitor is shown in figure 3. The flexible all-solid-state supercapacitor has good electrochemical performance.
Example 2
A preparation method of a flexible electrode comprises the following steps:
(1) adding the carbon nano tube into water, and uniformly dispersing to obtain a carbon nano tube dispersion liquid; the mass concentration of the carbon nano tube dispersion liquid is 1 mg/mL; adding graphene oxide into water, and uniformly dispersing to obtain a graphene oxide dispersion liquid; the mass concentration of the graphene oxide dispersion liquid is 1 mg/mL.
(2) Respectively taking 6mg and 18mg from the dispersion liquid of the carbon nano tube and the graphene oxide, mixing the mixture in a beaker, performing ultrasonic treatment for 1 hour, performing ultrasonic dispersion uniformly to obtain a mixed liquid, performing vacuum filtration on a filter membrane, wherein the filter membrane is made of polyether sulfone, the aperture size of the filter membrane is 0.2 mu m, and drying or naturally air-drying the filter membrane at 30 ℃ to obtain the flexible composite film.
(3) And (3) preserving the heat of the flexible composite film obtained in the step (2) for 4 hours at 350 ℃ in a nitrogen atmosphere by using a tubular furnace to reduce the graphene oxide to obtain a flexible electrode (based on the redox graphene/carbon nanotube composite electrode), and testing by using the electrode as a working electrode, a platinum mesh as a counter electrode and mercury oxide as a reference electrode and using a three-electrode testing system and 2M KOH as electrolyte. The performance is shown in fig. 4, the redox graphene/carbon nanotube based composite electrode shows excellent specific capacitance, and the SEM is shown in fig. 5. As shown in fig. 5, the carbon nanotubes are effectively inserted between the graphene sheet layers, so that the distance and the specific surface area between the graphene sheets are increased, the carbon nanotubes can make up for the defects generated in the oxidation process of graphene, and are beneficial to electron transmission, thereby improving the unit capacitance of the flexible electrode.
A preparation method of a flexible all-solid-state supercapacitor based on a redox graphene/carbon nanotube composite electrode specifically comprises the following steps:
dissolving 3g of polyvinyl alcohol in 25mL of deionized water, stirring for 5h at 90 ℃, cooling to 60 ℃ after the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution, dissolving 3g of KOH in 5mL of deionized water, and adding the dissolved KOH solution into the polyvinyl alcohol solution to prepare a KOH gel electrolyte;
and (3) connecting the obtained 1 cm-2 cm flexible electrode piece and a silver wire serving as a current collector by using silver paste, placing the prepared pole piece in a 10mL small beaker, adding KOH gel electrolyte, soaking the pole piece in the KOH gel electrolyte, naturally airing for 24 hours to wait for gel to tend to solidify, superposing the two pole pieces from top to bottom, and wrapping the two pole pieces by using a polyethylene film to prepare the flexible all-solid-state supercapacitor.
Example 3
A preparation method of a flexible electrode comprises the following steps:
(1) adding the carbon nano tube into water, and uniformly dispersing to obtain a carbon nano tube dispersion liquid; the mass concentration of the carbon nano tube dispersion liquid is 1mg/mL, graphene oxide is added into water and uniformly dispersed, and the graphene oxide dispersion liquid is obtained; the mass concentration of the graphene oxide dispersion liquid is 1 mg/mL;
(2) respectively taking 18mg and 6mg from the dispersion liquid of the carbon nano tube and the graphene oxide, mixing the mixture in a beaker, performing ultrasonic treatment for 1 hour, performing ultrasonic dispersion uniformly to obtain a mixed liquid, performing vacuum filtration on a filter membrane, wherein the filter membrane is made of polyether sulfone, the aperture size of the filter membrane is 0.2 mu m, and drying or naturally air-drying the filter membrane at 30 ℃ to obtain the flexible composite film.
(3) And (3) preserving the heat of the flexible composite film obtained in the step (2) for 4 hours at 350 ℃ in a nitrogen atmosphere by using a tubular furnace to reduce the graphene oxide to obtain a flexible electrode (based on the redox graphene/carbon nanotube composite electrode), and testing by using the electrode as a working electrode, a platinum mesh as a counter electrode and mercury oxide as a reference electrode and using a three-electrode testing system and 2M KOH as electrolyte. The performance is shown in fig. 6, the redox graphene/carbon nanotube based composite electrode shows excellent specific capacitance, and the SEM is shown in fig. 7. As shown in fig. 7, the carbon nanotubes are effectively inserted between the graphene sheet layers, so that not only are the distance and the specific surface area between the graphene sheets increased, but also the carbon nanotubes can make up for the defects generated in the oxidation process of graphene, thereby facilitating electron transmission and improving the unit capacitance of the flexible electrode.
A preparation method of a flexible all-solid-state supercapacitor based on a redox graphene/carbon nanotube composite electrode specifically comprises the following steps:
dissolving 3g of polyvinyl alcohol in 25mL of deionized water, stirring for 5h at 90 ℃, cooling to 60 ℃ after the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution, dissolving 3g of KOH in 5mL of deionized water, and adding the dissolved KOH solution into the polyvinyl alcohol solution to prepare a KOH gel electrolyte;
and (3) connecting the obtained 1 cm-2 cm flexible electrode piece and a silver wire serving as a current collector by using silver paste, placing the prepared pole piece in a 10mL small beaker, adding KOH gel electrolyte, soaking the pole piece in the KOH gel electrolyte, naturally airing for 24 hours to wait for gel to tend to solidify, superposing the two pole pieces from top to bottom, and wrapping the two pole pieces by using a polyethylene film to prepare the flexible all-solid-state supercapacitor.
Example 4
A preparation method of a flexible electrode comprises the following steps:
(1) adding the carbon nano tube into water, and uniformly dispersing to obtain a carbon nano tube dispersion liquid; the mass concentration of the carbon nano tube dispersion liquid is 1.5 mg/mL; adding graphene oxide into water, and uniformly dispersing to obtain a graphene oxide dispersion liquid; the mass concentration of the graphene oxide dispersion liquid is 1.5 mg/mL;
(2) respectively taking 12mg of the dispersion liquid of the carbon nano tube and the dispersion liquid of the graphene oxide, mixing the mixture in a beaker, performing ultrasonic treatment for 1 hour, performing ultrasonic dispersion uniformly to obtain a mixed liquid, performing vacuum filtration on a filter membrane, wherein the filter membrane is made of polyether sulfone, the aperture size of the filter membrane is 0.2 mu m, and drying or naturally air-drying the filter membrane at 30 ℃ to obtain a flexible composite film;
(3) and (3) preserving the heat of the flexible composite film obtained in the step (2) for 2 hours at 400 ℃ in a nitrogen atmosphere by using a tubular furnace to reduce the graphene oxide to obtain a flexible electrode (based on the redox graphene/carbon nanotube composite electrode), and testing by using the electrode as a working electrode, a platinum mesh as a counter electrode and mercury oxide as a reference electrode and using a three-electrode testing system and 2M KOH as electrolyte.
A preparation method of a flexible all-solid-state supercapacitor based on a redox graphene/carbon nanotube composite electrode specifically comprises the following steps:
dissolving 2g of polyvinyl alcohol in 25mL of deionized water, stirring for 5h at 90 ℃ until the polyvinyl alcohol is completely dissolved, cooling to 60 ℃ to obtain a polyvinyl alcohol solution, dissolving 2g of KOH in 5mL of deionized water, and adding the dissolved KOH solution into the polyvinyl alcohol solution to prepare a KOH gel electrolyte;
and (3) connecting the obtained 1 cm-2 cm flexible electrode small piece and a silver wire serving as a current collector with a silver paste, placing the prepared pole piece in a 10mL small beaker, adding a KOH gel electrolyte, soaking the pole piece in the KOH gel electrolyte, naturally drying for 48h to wait for gel to tend to solidify, superposing the two pole pieces from top to bottom, and wrapping the two pole pieces with a polyethylene film to prepare the flexible all-solid-state supercapacitor.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a flexible electrode is characterized by comprising the following steps:
(1) adding the carbon nano tube into water, and uniformly dispersing to obtain a carbon nano tube dispersion liquid; adding graphene oxide into water, and uniformly dispersing to obtain a graphene oxide dispersion liquid;
(2) mixing the carbon nanotube dispersion liquid and the graphene oxide dispersion liquid obtained in the step (1), and performing ultrasonic dispersion uniformly to obtain a mixed liquid; performing suction filtration on the mixed solution by using a filter membrane, removing filtrate, and drying to obtain a flexible composite film;
(3) and (3) heating the flexible composite film obtained in the step (2) under a protective atmosphere to carry out reduction reaction, so as to obtain the flexible electrode.
2. The method for preparing a flexible electrode according to claim 1, wherein the concentration of the carbon nanotube dispersion in the step (1) is 0.5-1.5mg/mL, and the concentration of the graphene oxide dispersion is 0.5-1.5 mg/mL.
3. The method for preparing a flexible electrode according to claim 1, wherein the mass ratio of the carbon nanotube dispersion liquid to the graphene oxide dispersion liquid in the step (2) is 3: 1-1: 3.
4. the method for preparing the flexible electrode according to claim 1, wherein the filter membrane in the step (2) is made of polyether sulfone, and the pore size of the filter membrane is 0.2 μm.
5. The method for preparing a flexible electrode according to claim 1, wherein the temperature of the reduction reaction in the step (3) is 300 ℃ to 400 ℃, and the time of the reduction reaction is 2h to 6 h.
6. A flexible electrode produced by the production method according to any one of claims 1 to 5.
7. The application of the flexible electrode in preparing a flexible all-solid-state supercapacitor, which is characterized by comprising the following steps:
(1) dissolving polyvinyl alcohol in water to obtain a polyvinyl alcohol solution, and then adding a KOH solution to obtain a KOH gel electrolyte;
(2) and (2) soaking the flexible electrode in the KOH gel electrolyte in the step (1), air-drying to obtain pole pieces, and assembling the two pole pieces into a capacitor to obtain the flexible all-solid-state supercapacitor.
8. The use of the flexible electrode in the preparation of a flexible all-solid-state supercapacitor according to claim 7, wherein the alcoholysis degree of the polyvinyl alcohol in the step (1) is 96% -98%, the mass percentage concentration of the polyvinyl alcohol solution is 0.08-0.16g/mL, and the mass percentage concentration of the KOH solution is 0.4-0.8 g/mL; the volume ratio of the polyvinyl alcohol solution to the KOH solution is 4:1-6: 1.
9. The use of the flexible electrode according to claim 7 in the preparation of a flexible all-solid-state supercapacitor, wherein the air drying time in step (2) is 24-48 h.
10. A flexible all-solid-state supercapacitor made from the use of the flexible electrode of any one of claims 7-9 in the manufacture of a flexible all-solid-state supercapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011331921.8A CN112582187A (en) | 2020-11-24 | 2020-11-24 | Flexible electrode, preparation method thereof and application of flexible electrode in preparation of flexible all-solid-state supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011331921.8A CN112582187A (en) | 2020-11-24 | 2020-11-24 | Flexible electrode, preparation method thereof and application of flexible electrode in preparation of flexible all-solid-state supercapacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112582187A true CN112582187A (en) | 2021-03-30 |
Family
ID=75124192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011331921.8A Pending CN112582187A (en) | 2020-11-24 | 2020-11-24 | Flexible electrode, preparation method thereof and application of flexible electrode in preparation of flexible all-solid-state supercapacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112582187A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117430832A (en) * | 2023-12-19 | 2024-01-23 | 北京科技大学 | Multilayer potassium ion gel electrolyte and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078248A (en) * | 2014-06-10 | 2014-10-01 | 北京大学深圳研究生院 | Flexible electrode and preparation method thereof |
| CN105513832A (en) * | 2015-12-16 | 2016-04-20 | 华南理工大学 | Graphene/porous carbon composite hydrogel, graphene/porous carbon composite aerogel, and preparation methods and applications thereof |
| CN107221454A (en) * | 2017-06-08 | 2017-09-29 | 陕西师范大学 | A kind of all-solid-state flexible ultracapacitor based on porous carbon fiber cloth and preparation method thereof |
| CN107622875A (en) * | 2017-09-04 | 2018-01-23 | 吉林大学 | A kind of preparation method of the wearable device of the self-powered of electromagnetic shielding |
| CN110767470A (en) * | 2019-10-25 | 2020-02-07 | 华南理工大学 | Super capacitor based on anti-freezing hydrogel electrolyte and preparation method thereof |
| CN111243870A (en) * | 2020-01-14 | 2020-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Flexible self-supporting hollow activated carbon micro-tube-based composite film electrode, preparation method and application |
-
2020
- 2020-11-24 CN CN202011331921.8A patent/CN112582187A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078248A (en) * | 2014-06-10 | 2014-10-01 | 北京大学深圳研究生院 | Flexible electrode and preparation method thereof |
| CN105513832A (en) * | 2015-12-16 | 2016-04-20 | 华南理工大学 | Graphene/porous carbon composite hydrogel, graphene/porous carbon composite aerogel, and preparation methods and applications thereof |
| CN107221454A (en) * | 2017-06-08 | 2017-09-29 | 陕西师范大学 | A kind of all-solid-state flexible ultracapacitor based on porous carbon fiber cloth and preparation method thereof |
| CN107622875A (en) * | 2017-09-04 | 2018-01-23 | 吉林大学 | A kind of preparation method of the wearable device of the self-powered of electromagnetic shielding |
| CN110767470A (en) * | 2019-10-25 | 2020-02-07 | 华南理工大学 | Super capacitor based on anti-freezing hydrogel electrolyte and preparation method thereof |
| CN111243870A (en) * | 2020-01-14 | 2020-06-05 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Flexible self-supporting hollow activated carbon micro-tube-based composite film electrode, preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117430832A (en) * | 2023-12-19 | 2024-01-23 | 北京科技大学 | Multilayer potassium ion gel electrolyte and preparation method thereof |
| CN117430832B (en) * | 2023-12-19 | 2024-03-05 | 北京科技大学 | Multilayer potassium ion gel electrolyte and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ye et al. | Coordination derived stable Ni–Co MOFs for foldable all-solid-state supercapacitors with high specific energy | |
| CN102923698B (en) | Preparation method for three-dimensional porous graphene for supercapacitor | |
| CN105869911B (en) | A kind of porous sulfide/graphene combination electrode material and preparation method thereof for ultracapacitor | |
| CN106783203B (en) | A kind of preparation method, product and the application of manganese dioxide/ultramicropore flexibility carbon cloth | |
| CN102107909B (en) | Method for preparing mesoporous nano manganese dioxide | |
| CN103708450B (en) | A kind of preparation method of graphene nanobelt paper | |
| EP3022785A1 (en) | Microtubes made of carbon nanotubes | |
| CN102832050B (en) | Method for preparing graphene/carbon nanotube hybrid in hierarchical structure | |
| CN110467182A (en) | A kind of multi-stage porous carbon sill and its preparation method and application based on reaction template | |
| CN107934955A (en) | A kind of method of activation process commercialization carbon cloth | |
| CN106449136B (en) | Alpha-nickel hydroxide cobalt electrode material and the preparation method and application thereof | |
| CN111799462A (en) | Preparation method of metal manganese oxide/graphene composite electrode material | |
| CN108808021A (en) | Mo2C/C nanocomposites and preparation method thereof and lithium carbon dioxide anode and preparation method thereof comprising the material | |
| CN112582187A (en) | Flexible electrode, preparation method thereof and application of flexible electrode in preparation of flexible all-solid-state supercapacitor | |
| CN114005683B (en) | CoZn-MOF/NiCo 2 O 4 Preparation method of @ CNTs/rGO composite electrode material | |
| CN113470981A (en) | Preparation method of porous carbon fiber/metal oxide composite material and graphene-based conductive ink and application of porous carbon fiber/metal oxide composite material and graphene-based conductive ink in supercapacitor | |
| CN109585176A (en) | The method for preparing three-dimensional grapheme-transition metal oxide gel and its electrode material | |
| CN106887610A (en) | A kind of load Ir nano composite materials and its application in lithium air battery positive electrode in situ of nickel foam | |
| CN107154498A (en) | Vegetable material prepares the preparation method and applications of microporous carbon structure electrode material | |
| CN111017908A (en) | Method for preparing biomass-based membrane by using strip-shaped graphene oxide as binder | |
| CN111740080A (en) | Electrochemical sodium storage electrode made of composite nano material and preparation method thereof | |
| CN106653388A (en) | Three-dimensional pure graphene hydrogel material with high conductivity and preparation method thereof | |
| CN110739462A (en) | flexible carbon film substrate materials and preparation method and application thereof | |
| CN107331529B (en) | Graphene oxide slurry, miniature Graphene electrodes and preparation method thereof | |
| US20220044879A1 (en) | Large-Area Continuous Flexible Free-Standing Electrode And Preparation Method And Use Thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210330 |
|
| RJ01 | Rejection of invention patent application after publication |