CN110164704B - Light-enhanced flexible supercapacitor and preparation method thereof - Google Patents
Light-enhanced flexible supercapacitor and preparation method thereof Download PDFInfo
- Publication number
- CN110164704B CN110164704B CN201910362218.4A CN201910362218A CN110164704B CN 110164704 B CN110164704 B CN 110164704B CN 201910362218 A CN201910362218 A CN 201910362218A CN 110164704 B CN110164704 B CN 110164704B
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyvinyl alcohol
- electrode plates
- light
- polyaniline
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 268
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 151
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 111
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 111
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 229920000767 polyaniline Polymers 0.000 claims abstract description 51
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 47
- 239000003990 capacitor Substances 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 24
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 17
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 16
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 16
- 239000000017 hydrogel Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 36
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000006260 foam Substances 0.000 claims description 31
- 229910052786 argon Inorganic materials 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000499 gel Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims 2
- 238000007906 compression Methods 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004146 energy storage Methods 0.000 abstract description 7
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 description 16
- 238000002484 cyclic voltammetry Methods 0.000 description 11
- 239000011245 gel electrolyte Substances 0.000 description 10
- 238000005452 bending Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005566 electron beam evaporation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001566 impedance spectroscopy Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
-
- 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- H01G11/66—Current collectors
- H01G11/68—Current collectors 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a light-enhanced flexible supercapacitor and a preparation method thereof, wherein the supercapacitor comprises two electrode plates and electrolyte positioned between the two electrode plates, the electrode plates are flexible electrode plates, the flexible electrode plates comprise polydimethylsiloxane substrates and graphene/carbon nano tube/polyaniline composite materials covering one side of the polydimethylsiloxane substrates, and the electrolyte is polyvinyl alcohol/phosphoric acid hydrogel and is coated on the flexible electrode plates. Compared with the prior art, the super capacitor constructed by the invention has an obvious photo-enhancement effect on the energy storage performance of the super capacitor by utilizing the excellent photo-conductivity of the covalently connected graphene/carbon nano tube, and meanwhile, the super capacitor prepared by the invention has excellent mechanical performance and good electrochemical energy storage performance, and is expected to be used in the fields of wearable electronic devices, photosensitive flexible integrated devices and the like.
Description
Technical Field
The invention relates to the technical field of flexible energy storage devices, in particular to a light-enhanced flexible supercapacitor and a preparation method thereof.
Background
With the development of society and the advancement of technology, people have higher demands on electronic devices. Supercapacitors, common energy storage electronics; graphene, the most common material for flexible electronic devices — however, graphene-based supercapacitors generally have the problems of low capacity, poor flexibility and stretchability, and the like, so that there is an urgent need to develop a graphene-based supercapacitor with high specific capacity and good flexibility for application to flexible electronic devices. According to investigation, in 2015, the market of domestic super capacitors is 73 hundred million yuan, the composite speed increasing rate is 47.82% every 2012-2015, a large number of manufacturers engaged in research and development of the super capacitors are provided, but a few manufacturers capable of realizing batch production and achieving a practical level are provided, and the number of flexible super capacitors is reduced, so that the flexible super capacitors have a wide commercial prospect in addition to the rapid development of flexible electronic equipment and wearable devices in recent years.
Due to large specific surface area, excellent electrochemical performance and good mechanical stability, graphene and carbon nanotubes are widely used as electrode materials of supercapacitors, especially in flexible devices. However, due to the strong pi-pi interaction between the graphenes, between the carbon nanotubes or between the graphenes and the carbon nanotubes, the aggregation is very easy to occur in the solution or in the process of preparing the electrode material, thereby significantly reducing the effective electrochemical area of the macroscopic electrode material, and causing the performance of the developed flexible super capacitor to be not ideal. Researches show that the carbon nano tube with a three-dimensional structure is grown on the graphene sheet or between the graphene sheets, so that the aggregation effect of the graphene and the carbon nano tube can be effectively prevented, and the flexible super capacitor with higher energy storage performance is obtained. In addition, both carbon nanotubes and graphene have excellent photoconductive properties, that is, under the condition of illumination, the conductivity of graphene, carbon nanotubes or a composite material thereof is remarkably enhanced, but at present, few studies on the light-enhanced flexible supercapacitor based on the materials are reported. Therefore, the development of high-performance light-enhanced flexible super capacitors is of great significance to flexible and wearable electronic devices or integrated devices.
Disclosure of Invention
The invention aims to solve the problems and provide a light-enhanced flexible supercapacitor and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the utility model provides a flexible ultracapacitor system of light enhancement mode, this ultracapacitor system includes two electrode slices and is located the electrolyte layer between two electrode slices, the electrode slice is flexible electrode slice, and flexible electrode slice includes the polydimethylsiloxane base and covers the graphite alkene/carbon nanotube/polyaniline combined material in polydimethylsiloxane base one side, the electrolyte layer is polyvinyl alcohol/phosphoric acid aquogel, coats on flexible electrode slice.
Preferably, the graphene/carbon nanotube/polyaniline composite material is in covalent connection, and the mass percentage of polyaniline in the composite material is 0-30%.
Preferably, the mass ratio of the polyvinyl alcohol to the phosphoric acid in the polyvinyl alcohol/phosphoric acid hydrogel is 1: 1, the total thickness of the applied gel is 5 to 10 μm.
A preparation method of a light-enhanced flexible supercapacitor specifically comprises the following steps: growing graphene on the surface of a foamed nickel substrate by adopting a primary chemical vapor deposition method, etching to remove the foamed nickel substrate to obtain graphene foam, loading a catalyst for growing a carbon nano tube on the graphene foam by utilizing a polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate, growing the carbon nano tube on a graphene sheet layer in situ by adopting secondary chemical vapor deposition, then growing polyaniline in situ by polymerization, transferring and pressing the obtained graphene/carbon nano tube/polyaniline composite material to one side surface of a polydimethylsiloxane film serving as a substrate to obtain a flexible electrode sheet, coating polyvinyl alcohol/phosphoric acid hydrogel on the two electrode sheets, and crimping to obtain the light-enhanced flexible supercapacitor. The graphene/carbon nanotube composite material in covalent connection is an electrode material of a supercapacitor with photoresponse; the graphene/carbon nano tube/polyaniline composite material is an electrode material of a high-specific-capacity flexible stretchable supercapacitor.
Preferably, the graphene grown by the primary chemical vapor deposition method takes methane as a carbon source and takes a mixed gas of argon and hydrogen as a carrier gas;
the volume ratio of the argon to the hydrogen is 10: (2-3), the volume ratio of argon to methane is 40: (5-7) and the reaction temperature is 950-1000 ℃. The thickness of the obtained graphene foam is 1-1.2 mm.
Preferably, the etching foamed nickel substrate adopts a mixed solution of ferric chloride and hydrochloric acid, and the molar concentration ratio of the ferric chloride to the hydrochloric acid is 1: (1-3).
Preferably, the loading of the catalyst is specifically: soaking the graphene foam in a polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate for 5-10min, taking out and drying at 50-60 ℃;
the concentration of polyvinyl alcohol in the polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate is 0.003-0.006g mL < -1 >, the concentration of ferric nitrate is 200-300mM and the concentration of aluminum nitrate is 200-300mM, more specifically, 0.003g of polyvinyl alcohol is added into 10mL of deionized water, the mixture is heated and stirred for 2-3h after being swelled at normal temperature for 12-14 h, 1.212g of ferric nitrate and 1.125g of aluminum nitrate are added, and the mixture is stirred and mixed uniformly to obtain a catalyst precursor, namely the polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate.
Preferably, the carbon nanotube grows on the graphene foam coated with the catalyst by the secondary chemical vapor deposition method, ethylene is used as a carbon source, and a mixed gas of argon and hydrogen is used as a carrier gas, and the growth is carried out in a tube furnace to obtain the graphene/carbon nanotube composite material, wherein the length of the obtained carbon nanotube is 10-15 μm;
the volume ratio of the argon to the hydrogen is 4: 1, the volume ratio of argon to methane is 40: 1, the reaction temperature is 740 to 760 ℃, and the growth time is 5 to 20 min.
Preferably, the method for growing polyaniline specifically comprises: adding aniline with the volume of 105-110 mu L into 20mL of 1M perchloric acid, stirring for 8-10 minutes, then adding 29-31mg of ammonium persulfate, and stirring for 1-2 minutes to prepare a pre-polymerization solution;
and soaking the graphene/carbon nano tube composite material in a pre-polymerization solution, wherein the reaction temperature is 3-5 ℃, the reaction time is 18-24 hours, and after the growth is finished, washing with deionized water to obtain the graphene/carbon nano tube/polyaniline composite material.
Preferably, the polyvinyl alcohol/phosphoric acid hydrogel is prepared by the following method: dissolving polyvinyl alcohol in deionized water, wherein the mass ratio of the polyvinyl alcohol to the water is 1: (9-11), stirring for 18-24h at the temperature of 80-90 ℃, then adding phosphoric acid with the same mass as the polyvinyl alcohol, and uniformly stirring until the mixture is clear to obtain the polyvinyl alcohol/phosphoric acid hydrogel.
Preferably, the flexible electrode sheet is prepared by the following steps: and pressing and transferring the graphene/carbon nanotube (/ polyaniline) composite material onto a polydimethylsiloxane film (with the thickness of 0.5-1.5mm), dripping ethanol to soak the electrode material, pressing the electrode material into a film by using a glass slide, and connecting one end of the electrode with a copper wire by using conductive silver colloid to obtain the flexible electrode plate.
Preferably, the flexible supercapacitor is assembled by: and (3) placing the flexible electrode slice into a low-temperature plasma treatment instrument for treatment for 3-10min, coating polyvinyl alcohol/phosphoric acid hydrogel electrolyte on the electrode slice in a scraping mode, and vacuumizing for 1 h. After the electrolyte is completely permeated, a layer of polyvinyl alcohol/phosphoric acid hydrogel electrolyte is coated on the electrode plates in a scraping mode again, and the two flexible electrode plates are pressed together to obtain the flexible super container.
The innovation of the invention is mainly embodied in the following three aspects: 1) the catalyst for growing the carbon nano tube is loaded by using a solution method, so that the process is simpler and more energy-saving than the traditional process using an electron beam evaporation technology; 2) the graphene and the carbon nano tube are in covalent connection, so that collapse of the graphene can be effectively avoided, charge transmission between the graphene and the carbon nano tube can be effectively enhanced, and a higher-performance energy storage device can be obtained; 3) in the invention, the performance of the super capacitor has obvious light enhancement effect, and the super capacitor is benefited from the excellent photoconductive effect of the covalently-connected graphene/carbon nanotube composite material, which is difficult to realize by using other electrode materials.
According to the invention, the three-dimensional graphene foam synthesized by the chemical vapor deposition method extends the excellent optical, electrical and mechanical properties of graphene from the original two-dimensional to the three-dimensional space. The three-dimensional continuous network can effectively avoid excessive stacking of graphene; the porous structure of the graphene electrode material can be used as a functional platform to load other active substances, and is favorable for permeation of gel electrolyte, so that transmission of charges or ions between the graphene electrode material and the gel electrolyte is effectively promoted. The invention uses the solution method to load the catalyst for growing the carbon nano tube, does not need to use the electron beam evaporation technology with high energy consumption, and has simple preparation process; according to the three-dimensional graphene/carbon nanotube hybrid material prepared by the invention, the graphene and the carbon nanotube are in covalent connection, so that the electrolyte permeation and charge transmission are facilitated, and the aggregation of graphene sheets and the carbon nanotube can be effectively avoided.
Hair brushThe chemically connected graphene/carbon nano tube and the composite material thereof are used as the electrode, and the introduction of the carbon nano tube greatly improves the mechanical property of the electrode, so that the flexible supercapacitor with higher performance is obtained. According to the invention, by utilizing the synergistic photoconductive effect of graphene and carbon nano tubes, the specific capacity of the developed super capacitor can be effectively improved under the sunlight, and the specific capacity of the capacitor under the sunlight is increased by 2.86 times compared with that of the capacitor without the sunlight; meanwhile, the super capacitor has good responsiveness to different light intensities. By introducing a material (such as polyaniline) with a high pseudocapacitance effect, the pseudocapacitance material can generate reversible redox reaction in the charging and discharging process, and can store more electric energy, so that higher specific capacity is obtained. The results show that the specific capacity of the capacitor based on graphene/carbon nanotube electrodes is about 50mF cm-2After polyaniline is introduced, the specific capacity of the capacitor based on the graphene/carbon nano tube/polyaniline composite material is improved by 3.4 times and reaches 219.2mF cm-2. In addition, the super capacitor developed by taking polydimethylsiloxane as the flexible substrate can normally work under large bending radian (0-180 degrees) and tensile deformation (0-240 percent), and keeps good electrochemical energy storage performance.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
(1) according to the flexible super capacitor constructed by the invention, due to the synergistic photoconductive effect of the graphene and the carbon nano tube, the energy storage performance of the capacitor shows an obvious enhancement effect (2.86 times) under illumination, and the capacitor has obvious response to different illumination intensities.
(2) According to the chemically-connected graphene/carbon nanotube composite material with the compact structure, the toughening mechanism of the carbon nanotube on the graphene enables the graphene/carbon nanotube and the composite material thereof to be effectively prevented from being damaged in the bending and stretching processes, the developed electrode material and the supercapacitor still keep good electrochemical energy storage performance when the electrode material and the supercapacitor are bent 6000 times or stretched 240%, and compared with the 'flexible stretchable supercapacitor based on the graphene composite film' (the bending cycle is 500 times and the stretching is 60%) disclosed by the patent CN 106803462A, the bending cycle stability and the stretching performance are both greatly improved.
(3) Compared with the supercapacitor based on the graphene/carbon nanotube composite fabric electrode disclosed in patent CN 109216041A, the catalyst is loaded by adopting an electron beam evaporation method, and the method for loading the catalyst by adopting the solution method is simpler in process, lower in cost, more green and environment-friendly and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a graphene foam grown by chemical vapor deposition;
FIGS. 2-4 are scanning electron micrographs of the top low power, top high power and side of graphene/carbon nanotubes, respectively;
FIG. 5 is a transmission electron micrograph of a chemical junction between graphene and carbon nanotubes;
FIG. 6 is a Raman spectrum of graphene, graphene/nickel foam, and graphene/carbon nanotubes;
fig. 7 and 8 are scanning electron micrographs of graphene/carbon nanotube/polyaniline at low power and high power, respectively;
FIG. 9 is a Raman spectrum of graphene/carbon nanotube/polyaniline;
FIGS. 10-13 show the scan rates of 10mV s for supercapacitors based on graphene, graphene/carbon nanotubes, and graphene/carbon nanotube/polyaniline electrodes, respectively-1A cyclic voltammetry curve, a charge-discharge curve under the condition that the constant current is 1.0mA, a Nyquist diagram and a change curve of area specific capacity along with the discharge current are obtained;
fig. 14 to 17 are a cyclic voltammetry curve, a constant current charging and discharging curve, a resistance change curve, and a change curve of resistance and specific capacitance of a supercapacitor based on a graphene/carbon nanotube composite electrode under different illumination intensities, respectively;
fig. 18 to 21 are a cyclic voltammetry curve, a constant current charging and discharging curve, a resistance change curve, and a change curve of a capacity retention rate with bending times of a supercapacitor based on a graphene/carbon nanotube/polyaniline composite electrode at different bending angles, respectively;
fig. 22 to 24 are a cyclic voltammetry curve, a constant current charge-discharge curve, and a resistance change curve of the supercapacitor based on the graphene/carbon nanotube/polyaniline composite electrode in different tensile states, respectively.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The light-enhanced flexible supercapacitor comprises two electrode plates and electrolyte positioned between the two electrode plates, wherein the electrode plates are flexible electrode plates, the flexible electrode plates comprise polydimethylsiloxane substrates and graphene/carbon nano tube/polyaniline composite materials covering one sides of the polydimethylsiloxane substrates, and the electrolyte is polyvinyl alcohol/phosphoric acid hydrogel and is coated on the flexible electrode plates. The graphene/carbon nano tube/polyaniline composite material is in covalent connection, and the mass percentage of polyaniline in the composite film is 0-30%. The mass ratio of polyvinyl alcohol to phosphoric acid in the polyvinyl alcohol/phosphoric acid hydrogel is 1: 1, the thickness of the coated gel is 5-10 μm.
A light-enhanced flexible supercapacitor and a preparation method thereof comprise the following specific steps:
(1) taking methane as a carbon source and a mixed gas of argon and hydrogen as a carrier gas; wherein the volume ratio of argon to hydrogen in the carrier gas is 10: 2, and the volume ratio of argon to methane is 40: 6, growing graphene on a foamed nickel substrate by vapor deposition at the reaction temperature of 1000 ℃;
(2) the concentration ratio of 1: 2, etching off nickel foam by using a mixed solution of ferric trichloride and hydrochloric acid to obtain graphene foam with the thickness of 1.2 mm;
(3) 0.003g of polyvinyl alcohol is added into 10mL of deionized water, the mixture is swelled for 12 hours at normal temperature, heated and stirred for 2 hours, and after the solution is cooled, 1.212g of ferric nitrate and 1.125g of aluminum nitrate are added and stirred until the solution is completely dissolved. Completely soaking the graphene foam in the catalyst solution, taking out the graphene foam, and drying the graphene foam in an oven at 60 ℃. Putting the graphene foam coated with the catalyst into a tubular furnace, and growing a carbon nano tube by taking ethylene as a carbon source and taking a mixed gas of argon and hydrogen as a carrier gas; wherein the volume ratio of argon to hydrogen is 4: 1, the volume ratio of argon to ethylene is 40: 1, the reaction temperature is 750 ℃, and the growth time is 5min, so that the chemically connected graphene/carbon nano tube is obtained.
(4) mu.L of aniline was added to 20mL of 1M perchloric acid and stirred for 10 minutes, followed by addition of 30mg of ammonium persulfate and stirring for 2 minutes, all over the course of an ice-water bath. And soaking the graphene/carbon nano tube in the prepared pre-polymerization solution, and reacting for 24 hours at 3 ℃ to obtain the graphene/carbon nano tube/polyaniline composite material.
(5) Pressing the composite materials obtained in the steps (3) and (4) and transferring the composite materials to a polydimethylsiloxane substrate to obtain a compact graphene composite material; coating polyvinyl alcohol/phosphoric acid gel electrolyte by a pressure difference method to prepare an electrode material which uniformly permeates the gel electrolyte;
(6) and assembling the two composite electrode materials permeated with the gel electrolyte into the light-enhanced flexible supercapacitor.
The polyvinyl alcohol/phosphoric acid gel electrolyte of the present example was prepared by the following method: dissolving polyvinyl alcohol in water, wherein the mass ratio of the polyvinyl alcohol to the water is 1: 10, stirring for 24 hours at 83 ℃, then adding phosphoric acid with the same mass as polyvinyl alcohol, and uniformly stirring until the mixture is clear.
Graphene and carbon nanotubes are prepared by chemical vapor deposition. Fig. 1 is a scanning electron microscope photograph of the graphene foam after the nickel substrate is removed by etching, and it is seen that the graphene foam is in a three-dimensional porous self-supporting structure. Fig. 2 is a scanning electron micrograph of graphene/carbon nanotubes at low magnification, which shows that dense carbon nanotubes grow on the surface of graphene. Fig. 3 is a top scanning electron micrograph of graphene/carbon nanotubes, illustrating that the carbon nanotubes are uniformly grown and have an orientation. FIG. 4 is a side scanning electron micrograph of graphene/carbon nanotubes, which shows that the carbon nanotubes are aligned perpendicular to the graphene sheets, and the length of the obtained carbon nanotubes is 10-15%And mu m. Fig. 5 is a transmission electron micrograph of the connecting portion of graphene and carbon nanotubes, which shows that graphene and carbon nanotubes are well fused. FIG. 6 is a Raman spectrum of graphene (G), graphene/nickel foam (G/Ni) and graphene/carbon nanotube (G/CNT), wherein the Raman characteristic peak of graphene appears at 1360cm-1And 1586cm-1Here, corresponding to the D and G peaks, respectively.
For a supercapacitor with higher specific capacity, polyaniline is polymerized in situ on graphene/carbon nanotubes, the carbon nanotubes can also maintain a better array (as shown in fig. 7), and a layer of polyaniline particles can be uniformly grown around the carbon nanotubes after the carbon nanotubes are amplified to 100nm (as shown in fig. 8), so that the capacitor is ensured to have good pseudo-capacitance behavior. Raman spectroscopy (fig. 9) further indicates the presence of polyaniline in the graphene/carbon nanotube/polyaniline (G/CNT/PANI) composite.
The electrochemical performance of the super capacitor is mainly characterized by Cyclic Voltammetry (CV), constant current charge-discharge (GCD) and impedance spectroscopy (EIS), and key performance indexes comprise specific capacity, energy density, power density and rate capability. The specific capacity is the most important parameter for representing the energy storage capacity of the super capacitor.
FIG. 10 shows the scan rate of 10mV s for a supercapacitor based on graphene, graphene/carbon nanotubes, and graphene/carbon nanotube/polyaniline electrodes-1Cyclic voltammogram. CV curves of graphene and graphene/carbon nanotubes all show nearly rectangular characteristics, which shows that the super capacitor provided by the invention has excellent double-layer capacitance behavior; the CV curve after depositing the polyaniline has very obvious oxidation reduction peak, which proves that the super capacitor of the invention has good pseudocapacitance effect and effectively improves the specific capacity of the super capacitor. Fig. 11 is a GCD curve of a supercapacitor based on graphene, graphene/carbon nanotubes, and graphene/carbon nanotubes/polyaniline electrodes at a constant current of 1.0mA, wherein the voltage window is 0-0.8V. It can be known that the GCD curves of the graphene and the graphene/carbon nanotube both maintain symmetrical triangular characteristics, and show approximately ideal capacitance performance, while the supercapacitor based on the graphene/carbon nanotube/polyaniline electrodeThe device has a large redox platform, creating an ideal pseudocapacitance. According to the GCD curve, the area specific capacity of the super capacitor can be calculated by the following formula:
CA＝IΔt/SΔV
where I, S, Δ V and Δ t are the discharge current, the area of the electrode, the voltage window and the discharge time, respectively. The area specific capacity (C) of the supercapacitor based on the graphene/carbon nano tube/polyaniline can be calculated by the formulaA) Is 219.2mF cm-2And C of the supercapacitor of pure grapheneAOnly 0.26mF cm-2. Fig. 12 is a Nyquist plot for a supercapacitor based on graphene, graphene/carbon nanotubes, and graphene/carbon nanotube/polyaniline electrodes. Fig. 13 is a curve of the change of the specific area capacity of the supercapacitor based on graphene, graphene/carbon nanotubes and graphene/carbon nanotubes/polyaniline electrodes with the discharge current, which shows that the supercapacitor has good rate capability.
The energy density (E) and the power density (P) of the supercapacitor are calculated by the following formulas:
E＝CAΔV2/2
P＝CAΔV2/2Δt
wherein C isAΔ V and Δ t are the area specific capacity, voltage window and discharge time, respectively. The highest values of the energy density and the power density of the super capacitor based on the graphene/carbon nano tube/polyaniline composite material are respectively 19.5 mu Wh cm-3And 88.97. mu.W.cm-3。
Due to the fact that the graphene/carbon nano tube has excellent photoconductivity, the resistance of the graphene/carbon nano tube composite material is reduced under illumination, the transmission rate of charges is accelerated, and the specific capacity of the super capacitor is increased. FIGS. 14 to 16 are a CV curve, a GCD curve and an electrochemical impedance spectrum of a supercapacitor under different light intensities, respectively, and it can be seen that the series resistance of the supercapacitor decreases with the increase of the solar light intensity, thereby resulting in the increase of the specific area capacity of the supercapacitor (FIG. 17) when the solar power density is 1kW/m2In this case, the specific area capacity of the supercapacitor can be increased by 2.86 times.
Example 2
A light-enhanced flexible supercapacitor and a preparation method thereof comprise the following specific steps:
(1) taking methane as a carbon source and a mixed gas of argon and hydrogen as a carrier gas; wherein the volume ratio of argon to hydrogen in the carrier gas is 10: 2, and the volume ratio of argon to methane is 40: 5, growing graphene on a foamed nickel substrate by vapor deposition at the reaction temperature of 980 ℃;
(2) the concentration ratio of 1: 1, etching off nickel foam by using a mixed solution of ferric trichloride and hydrochloric acid to obtain graphene foam with the thickness of 1.0 mm;
(3) 0.003g of polyvinyl alcohol is added into 10mL of deionized water, the mixture is swelled for 12 hours at normal temperature, heated and stirred for 2 hours, and after the solution is cooled, 1.212g of ferric nitrate and 1.125g of aluminum nitrate are added and stirred until the solution is completely dissolved. Completely soaking the graphene foam in the catalyst solution, taking out the graphene foam, and drying the graphene foam in an oven at 60 ℃. Putting the graphene foam coated with the catalyst into a tubular furnace, and growing a carbon nano tube by taking ethylene as a carbon source and taking a mixed gas of argon and hydrogen as a carrier gas; wherein the volume ratio of argon to hydrogen is 4: 1, the volume ratio of argon to ethylene is 40: 1, the reaction temperature is 760 ℃, the growth time is 10min, and the chemically connected graphene/carbon nano tube is obtained.
(4) mu.L of aniline was added to 20mL of 1M perchloric acid and stirred for 10 minutes, followed by addition of 30mg of ammonium persulfate and stirring for 2 minutes, all through an ice-water bath. And soaking the graphene/carbon nano tube in the prepared pre-polymerization solution, and reacting for 18 hours at 3 ℃ to obtain the graphene/carbon nano tube/polyaniline composite material.
(5) Pressing the composite materials obtained in the steps (3) and (4) and transferring the composite materials to a polydimethylsiloxane substrate to obtain a compact graphene composite material; coating polyvinyl alcohol/phosphoric acid gel electrolyte by a pressure difference method to prepare an electrode material which uniformly permeates the gel electrolyte;
(6) and assembling the two composite electrode materials permeated with the gel electrolyte into the light-enhanced flexible supercapacitor.
The all-solid-state supercapacitor disclosed by the invention shows excellent flexibility and tensile properties under the comprehensive action of an elastic polydimethylsiloxane substrate, a compact graphene/carbon nanotube/polyaniline composite membrane and polymer molecule constraint in a gel electrolyte. Fig. 18 and 19 are CV curves and GCD curves of a supercapacitor constructed based on a graphene/carbon nanotube/polyaniline composite material at different bending degrees, respectively. As can be seen from the graph, in the case of large-amplitude bending, the specific capacity of the supercapacitor was almost maintained, showing excellent flexibility; and even bending to 180 deg., the resistance of the supercapacitor does not increase significantly (fig. 20). The relation between the change of the specific capacity and the cycle number of the supercapacitor constructed on the basis of the graphene/carbon nanotube/polyaniline composite material in the process of being bent 6000 times in a circulating manner is shown in fig. 21, and the result shows that the capacity retention rate of the supercapacitor is 91%, so that the good flexibility of the supercapacitor is further explained. Fig. 22 and 23 are CV curves and GCD curves of a supercapacitor constructed based on a graphene/carbon nanotube/polyaniline composite material in different tensile states, respectively. As can be seen from the figure, the specific capacity of the supercapacitor can be maintained at 80% or more in the process of being stretched to 240% from the initial state, and the supercapacitor shows good tensile stability. As shown in fig. 24, when stretched 240%, the resistance of the supercapacitor increased only 3 times, because at higher tensile strain, the graphene frameworks were relatively moved or slightly broken, but the carbon nanotubes were still connected between the slightly broken graphene layers, the interior was still in good contact, and therefore the internal resistance was slightly increased.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A light-enhanced flexible supercapacitor comprises two electrode plates and an electrolyte layer positioned between the two electrode plates, and is characterized in that the electrode plates are flexible electrode plates, the flexible electrode plates comprise polydimethylsiloxane substrates and graphene/carbon nano tube/polyaniline composite materials covering one sides of the polydimethylsiloxane substrates, and the electrolyte layer is polyvinyl alcohol/phosphoric acid hydrogel and is coated on the flexible electrode plates;
the preparation method of the super capacitor comprises the following steps:
growing graphene on the surface of a foamed nickel substrate by adopting a primary chemical vapor deposition method, etching to remove the foamed nickel substrate to obtain graphene foam, loading a catalyst for growing a carbon nano tube on the graphene foam by utilizing a polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate, growing the carbon nano tube on the graphene foam in situ by adopting secondary chemical vapor deposition, and then growing polyaniline by in situ polymerization;
transferring and pressing the obtained graphene/carbon nanotube/polyaniline composite material to one side surface of a polydimethylsiloxane film serving as a substrate to obtain flexible electrode plates, coating polyvinyl alcohol/phosphoric acid hydrogel on the two electrode plates, and performing compression joint to obtain a light-enhanced flexible supercapacitor;
the load of the catalyst is specifically as follows: soaking the graphene foam in a polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate for 5-10min, taking out and drying at 50-60 ℃;
the concentration of the polyvinyl alcohol in the polyvinyl alcohol aqueous solution of the ferric nitrate and the aluminum nitrate is 0.003 to 0.006g mL-1The concentration of ferric nitrate is 200-300mM and the concentration of aluminum nitrate is 200-300 mM;
the method for growing polyaniline specifically comprises the following steps: adding 105-110 mu L aniline into 20mL 1M perchloric acid, stirring for 8-10 minutes, adding 29-31mg ammonium persulfate, and stirring for 1-2 minutes to prepare a pre-polymerization solution;
soaking the graphene/carbon nanotube composite material in a pre-polymerization solution, wherein the reaction temperature is 3-5 ℃, the reaction time is 18-24 hours, and after the graphene/carbon nanotube composite material grows and is cleaned, obtaining the graphene/carbon nanotube/polyaniline composite material;
the graphene is covalently connected with the carbon nano tube.
2. The light-enhanced flexible supercapacitor according to claim 1, wherein the graphene/carbon nanotube/polyaniline composite material is covalently connected, and the mass percentage of polyaniline in the composite material is 0-30%.
3. The light-enhanced flexible supercapacitor according to claim 1, wherein the mass ratio of the polyvinyl alcohol to the phosphoric acid in the polyvinyl alcohol/phosphoric acid hydrogel is 1: 1, the total thickness of the applied gel is 5 to 10 μm.
4. The method for preparing a light-enhanced flexible supercapacitor according to any one of claims 1 to 3, wherein the method comprises: growing graphene on the surface of a foamed nickel substrate by adopting a primary chemical vapor deposition method, etching to remove the foamed nickel substrate to obtain graphene foam, loading a catalyst for growing carbon nanotubes on the graphene foam by utilizing a polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate, growing the carbon nanotubes on the graphene foam in situ by adopting secondary chemical vapor deposition, then polymerizing in situ to grow polyaniline,
transferring and pressing the obtained graphene/carbon nano tube/polyaniline composite material to one side surface of a polydimethylsiloxane film serving as a substrate to obtain flexible electrode plates, coating polyvinyl alcohol/phosphoric acid hydrogel on the two electrode plates, and performing compression joint to obtain the light-enhanced flexible supercapacitor.
5. The method for preparing the light-enhanced flexible supercapacitor according to claim 4, wherein the graphene grown by the one-time chemical vapor deposition method uses methane as a carbon source and uses a mixed gas of argon and hydrogen as a carrier gas;
the volume ratio of the argon to the hydrogen is 10: (2-3), the volume ratio of argon to methane is 40: (5-7) and the reaction temperature is 950-1000 ℃.
6. The method for preparing the light-enhanced flexible supercapacitor according to claim 4, wherein the step of removing the foamed nickel substrate by etching adopts a mixed solution of ferric chloride and hydrochloric acid, and the molar concentration ratio of the ferric chloride to the hydrochloric acid is 1: (1-3).
7. The method for preparing the light-enhanced flexible supercapacitor according to claim 4, wherein the catalyst is specifically loaded as follows: soaking the graphene foam in a polyvinyl alcohol aqueous solution of ferric nitrate and aluminum nitrate for 5-10min, taking out and drying at 50-60 ℃;
the concentration of the polyvinyl alcohol in the polyvinyl alcohol aqueous solution of the ferric nitrate and the aluminum nitrate is 0.003 to 0.006g mL-1The concentration of ferric nitrate is 200-300mM and the concentration of aluminum nitrate is 200-300 mM.
8. The method for preparing the light-enhanced flexible supercapacitor according to claim 4, wherein the carbon nanotubes grown by the secondary chemical vapor deposition method use ethylene as a carbon source and a mixed gas of argon and hydrogen as a carrier gas;
the volume ratio of the argon to the hydrogen is 4: 1, the volume ratio of argon to ethylene is 40: 1, the reaction temperature is 740 to 760 ℃, and the growth time is 5 to 20 min.
9. The method for preparing the light-enhanced flexible supercapacitor according to claim 4, wherein the method for growing polyaniline specifically comprises: adding 105-110 mu L aniline into 20mL 1M perchloric acid, stirring for 8-10 minutes, adding 29-31mg ammonium persulfate, and stirring for 1-2 minutes to prepare a pre-polymerization solution;
and soaking the graphene/carbon nano tube composite material in a pre-polymerization solution, wherein the reaction temperature is 3-5 ℃, the reaction time is 18-24 hours, and after the growth is finished and the graphene/carbon nano tube/polyaniline composite material is obtained after cleaning.
10. The method for preparing a light-enhanced flexible supercapacitor according to claim 4, wherein the polyvinyl alcohol/phosphoric acid hydrogel is prepared by the following steps: dissolving polyvinyl alcohol in deionized water, wherein the mass ratio of the polyvinyl alcohol to the water is 1 g: (9-11) mL, stirring for 18-24h at the temperature of 80-90 ℃, then adding phosphoric acid with the mass equal to that of polyvinyl alcohol, and uniformly stirring until the mixture is clear, thus obtaining the polyvinyl alcohol/phosphoric acid hydrogel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910362218.4A CN110164704B (en) | 2019-04-30 | 2019-04-30 | Light-enhanced flexible supercapacitor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910362218.4A CN110164704B (en) | 2019-04-30 | 2019-04-30 | Light-enhanced flexible supercapacitor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110164704A CN110164704A (en) | 2019-08-23 |
| CN110164704B true CN110164704B (en) | 2021-02-02 |
Family
ID=67633110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910362218.4A Active CN110164704B (en) | 2019-04-30 | 2019-04-30 | Light-enhanced flexible supercapacitor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110164704B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024072226A1 (en) * | 2022-09-30 | 2024-04-04 | Nanocaps As | Fabricating an electrode for a lithium-ion capacitor |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111524718B (en) * | 2020-04-11 | 2021-07-13 | 中南民族大学 | Method for preparing asymmetric supercapacitor by using hydrophilic carbon nanotube film and hyperbranched polymer as double templates |
| KR20230085189A (en) * | 2020-11-03 | 2023-06-13 | 지 닝 룽 뎬 (베이징) 테크놀로지 컴퍼니 리미티드 | Flexible variable capacitor and manufacturing method thereof |
| CN112420400B (en) * | 2020-11-11 | 2021-12-10 | 华北电力大学（保定） | Preparation method of super-hydrophobic self-repairing flexible supercapacitor |
| CN113517145B (en) * | 2021-03-22 | 2023-05-16 | 西湖大学 | Polar plate of super capacitor, super capacitor and manufacturing method of polar plate |
| CN114605674B (en) * | 2022-04-22 | 2023-06-16 | 福州大学 | Polyaniline composite flexible conductive hydrogel with high specific capacitance and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011105021A1 (en) * | 2010-02-24 | 2011-09-01 | パナソニック株式会社 | Substrate for forming carbon nanotubes, carbon nanotube composite, energy device, method for producing same, and device incorporating same |
| CN102745679A (en) * | 2012-07-19 | 2012-10-24 | 南京邮电大学 | Method for preparing three-dimensional graphene-carbon nitrogen nanotube composite |
| US20150318120A1 (en) * | 2013-01-30 | 2015-11-05 | Empire Technology Development Llc. | Carbon nanotube-graphene composite |
| CN103903870B (en) * | 2014-03-09 | 2017-12-26 | 宁国市龙晟柔性储能材料科技有限公司 | A kind of changeable colour and stretchable ultracapacitor and preparation method thereof |
| CN104952630A (en) * | 2015-07-23 | 2015-09-30 | 武汉理工大学 | Mini-sized supercapacitor with high flexibility and high transparency and large-scale preparation method of mini-sized supercapacitor |
| CN205069395U (en) * | 2015-10-30 | 2016-03-02 | 梧州三和新材料科技有限公司 | Porous electrode material that graphite alkene and carbon nanotube are compound |
| CN106449135B (en) * | 2016-07-11 | 2018-10-26 | 同济大学 | It is a kind of based on the stretchable capacitor of ordered carbon nanotube composite membrane and its preparation |
| CN109216041B (en) * | 2018-08-17 | 2021-02-02 | 同济大学 | Supercapacitor based on graphene/carbon nanotube composite fabric electrode and preparation method thereof |
-
2019
- 2019-04-30 CN CN201910362218.4A patent/CN110164704B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024072226A1 (en) * | 2022-09-30 | 2024-04-04 | Nanocaps As | Fabricating an electrode for a lithium-ion capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110164704A (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110164704B (en) | Light-enhanced flexible supercapacitor and preparation method thereof | |
| Sardana et al. | Conducting polymer hydrogel based electrode materials for supercapacitor applications | |
| He et al. | All-solid state symmetric supercapacitors based on compressible and flexible free-standing 3D carbon nanotubes (CNTs)/poly (3, 4-ethylenedioxythiophene)(PEDOT) sponge electrodes | |
| Rajesh et al. | A high performance PEDOT/PEDOT symmetric supercapacitor by facile in-situ hydrothermal polymerization of PEDOT nanostructures on flexible carbon fibre cloth electrodes | |
| Wu et al. | Enhanced electrochemical performances of organ-like Ti3C2 MXenes/polypyrrole composites as supercapacitors electrode materials | |
| Wu et al. | Highly flexible, foldable and stretchable Ni–Co layered double hydroxide/polyaniline/bacterial cellulose electrodes for high-performance all-solid-state supercapacitors | |
| Xu et al. | Pseudocapacitive anthraquinone modified with reduced graphene oxide for flexible symmetric all-solid-state supercapacitors | |
| Alexandre et al. | A highly adhesive PIL/IL gel polymer electrolyte for use in flexible solid state supercapacitors | |
| Zhang et al. | Polypyrrole film based flexible supercapacitor: mechanistic insight into influence of acid dopants on electrochemical performance | |
| Niu et al. | Coral-like PEDOT nanotube arrays on carbon fibers as high-rate flexible supercapacitor electrodes | |
| Li et al. | Facile synthesis and super capacitive behavior of SWNT/MnO2 hybrid films | |
| Jin et al. | Long-life flexible supercapacitors based on nitrogen-doped porous graphene@ π-conjugated polymer film electrodes and porous quasi-solid-state polymer electrolyte | |
| CN112038114B (en) | Preparation method of carbon fiber-based graphene/nano polyaniline composite material | |
| CN107161979B (en) | Carbon-based nanobelt porous material, and preparation method and application thereof | |
| Zhu et al. | Carbon cloth supported graphitic carbon nitride nanosheets as advanced binder-free electrodes for supercapacitors | |
| Chen et al. | Polyaniline electropolymerized within template of vertically ordered polyvinyl alcohol as electrodes of flexible supercapacitors with long cycle life | |
| Feng et al. | Sponge integrated highly compressible all-solid-state supercapacitor with superior performance | |
| Wang et al. | Electrochemical polymerization of polypyrrole on carbon cloth@ ZIF67 using alizarin red S as redox dopant for flexible supercapacitors | |
| CN110790277A (en) | Preparation method and application of HHK-CC @ MXenes composite flexible electrode material | |
| Wu et al. | A novel and facile step-by-step hydrothermal fabrication of peony-like Ni0. 4Co0. 6 (OH) 2 supported on carbon fiber cloth as flexible electrodes for advanced electrochemical energy storage | |
| Chen et al. | High-performance all-solid-state flexible asymmetric supercapacitors composed of PPy@ Ti3C2Tx/CC and Ti3C2Tx/CC electrodes | |
| Tseng et al. | Electropolymerized poly (3, 4-ethylenedioxythiophene)/screen-printed reduced graphene oxide–chitosan bilayer electrodes for flexible supercapacitors | |
| CN112038108A (en) | Preparation method and application of self-supporting flexible polyaniline supercapacitor material | |
| CN110739162A (en) | Preparation method of flexible supercapacitor positive electrode materials | |
| Ren et al. | REN et al. |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |