CN106653391A - Flexible supercapacitor and preparation method thereof - Google Patents
Flexible supercapacitor and preparation method thereof Download PDFInfo
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- CN106653391A CN106653391A CN201611260041.XA CN201611260041A CN106653391A CN 106653391 A CN106653391 A CN 106653391A CN 201611260041 A CN201611260041 A CN 201611260041A CN 106653391 A CN106653391 A CN 106653391A
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- manganese dioxide
- cnt
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- layer
- polyurethane
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- 238000002360 preparation method Methods 0.000 title claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 158
- 239000002131 composite material Substances 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 37
- 239000003990 capacitor Substances 0.000 claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 claims abstract description 30
- 239000004814 polyurethane Substances 0.000 claims abstract description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001548 drop coating Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920006264 polyurethane film Polymers 0.000 abstract description 13
- 239000000084 colloidal system Substances 0.000 abstract description 5
- 239000000470 constituent Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000005520 cutting process Methods 0.000 description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229940113088 dimethylacetamide Drugs 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000007970 homogeneous dispersion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- -1 carbon nano tube compound Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- ACOGMWBDRJJKNB-UHFFFAOYSA-N acetic acid;ethene Chemical group C=C.CC(O)=O ACOGMWBDRJJKNB-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- H01G11/30—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
- H01G11/26—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
- H01G11/46—Metal oxides
-
- 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
- H01G11/84—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a flexible supercapacitor. The flexible supercapacitor comprises a first electrode layer, a second electrode layer and a colloid electrolyte layer, wherein the colloid electrolyte layer is arranged between the first electrode layer and the second electrode layer, the first electrode layer is formed from a composite film layer of a carbon nanotube and manganese dioxide and a polyurethane film layer combined on the composite film layer, the second electrode layer is formed from a composite film layer of a carbon nanotube and manganese dioxide and a polyurethane film layer combined on the composite film layer, the collide electrolyte layer is formed from polyvinyl alcohol and an inorganic acid, and the composite film layers of the carbon nanotubes and the manganese dioxide are in contact with the collide electrolyte layer. The capacitor comprises electrolyte layers and a layered structure of the electrolyte layer; meanwhile, each electrolyte layer is formed from the composite film layer of the carbon nanotube and manganese dioxide and the polyurethane film layer combined on the composite film layer; and due to the carbon nanotubes, the manganese dioxide, polyurethane constituents and the structure, the flexible supercapacitor is controllable in shape and can be cut.
Description
Technical field
The present invention relates to technical field of new energies, more particularly, to a kind of flexible super capacitor and preparation method thereof.
Background technology
The controlled shapes such as solar cell, ultracapacitor, can cutting energy-storage travelling wave tube typically by flexible electrode and gel electricity
Solution matter is assembled by specific mode, in stretching, bending, is folded, and under the state such as cutting excellent electrochemistry is still kept
Energy.And become the focus of new energy field research.
Prior art yang cheng discloses ultracapacitor, by can the ethene of cutting, acetate ethylene copolymer be base
Bottom, Graphene assembles as electrode material, polyvinyl alcohol/sodium sulphate as gel electrolyte.But its disclosed super electricity
Container shapes are uncontrollable.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of flexible super capacitor, and the present invention is provided
Flexible super capacitor can cutting and controlled shape.
The invention provides a kind of flexible super capacitor, including：
First electrode layer, the second electrode lay and the colloid electrolysis being arranged between the first electrode layer and the second electrode lay
Matter layer；
The first electrode layer by CNT and manganese dioxide composite film and be compound on the composite film
Polyurethane film is formed；
The second electrode lay is by CNT and manganese dioxide composite film and is compound in poly- on the composite film
Urethane film layer is formed；
The colloidal electrolyte layer is formed by polyvinyl alcohol and inorganic acid；
The CNT and manganese dioxide composite film contact with colloidal electrolyte layer.
Preferably, the mol ratio of the CNT and manganese dioxide is (1～3)：(1～2).
Preferably, the mass ratio of the polyvinyl alcohol and inorganic acid is (1～10)：(1～10).
Preferably, the gross mass of the CNT and manganese dioxide and the mass ratio of polyurethane are (30～50)：(100
～150).
Preferably, one or more of the inorganic acid in sulfuric acid, phosphoric acid and hydrochloric acid.
The invention provides a kind of preparation method of the ultracapacitor as described in above-mentioned technical scheme, including：
By the compacting of first electrode layer, colloidal electrolyte layer and the second electrode lay, ultracapacitor is obtained；
The first electrode layer or the second electrode lay are prepared by the following method：
The composite film of CNT and manganese dioxide is prepared by the composite of CNT and manganese dioxide；
By polyurethane-coated on the composite film of the CNT and manganese dioxide.
Preferably, the CNT and manganese dioxide composite material are prepared by the following method：
Mix in acid condition with potassium permanganate after CNT pretreatment, it is ultrasonically treated, react under microwave condition, obtain
To CNT and manganese dioxide composite material.
Preferably, the power of the microwave is 600～800w；The pH value of the acid condition is 0.1～5；The ultrasound
Power be 1～100KHz；Time is 0.1～10h.
Preferably, the pressing pressure is 0.1～10Mpa；The pressing time is 1～60min.
Preferably, the polyurethane-coated is specially on the CNT and manganese dioxide composite film：
Polyurethane is dissolved in a solvent, heating stirring is coated on CNT and manganese dioxide composite film；It is described
Heating-up temperature is 10～150 DEG C；The mixing time is 0.1～10h；It is described to be applied to drop coating or be coated with.
Compared with prior art, the invention provides a kind of flexible super capacitor, including：It is first electrode layer, second electric
Pole layer and the colloidal electrolyte layer being arranged between the first electrode layer and the second electrode lay；The first electrode layer is received by carbon
The composite film of mitron and manganese dioxide and the polyurethane film being compound on the composite film are formed；The second electrode lay
Formed by CNT and manganese dioxide composite film and the polyurethane film being compound on the composite film；The colloid electricity
Solution matter layer is formed by polyvinyl alcohol and inorganic acid；The CNT and manganese dioxide composite film connect with colloidal electrolyte layer
Touch.The flexible super capacitor that the present invention is provided is by electrode layer and dielectric substrate stratiform structure composition；Meanwhile, electrode layer is received by carbon
The composite film of mitron and manganese dioxide and the polyurethane film being compound on the composite film are formed, just because of above-mentioned carbon
Nanotube, manganese dioxide and polyurethane component and said structure so that the flexible super capacitor that the present invention is prepared exists
External force and higher than can fold or twist into arbitrary shape under conditions of transition temperature, and withdraw from external force and temperature keep should
Shape；When temperature reaches transition temperature again, changing ultracapacitor can return to original shapes, and before and after cutting its
Area specific capacitance can keep constant.
Description of the drawings
Fig. 1 is the SEM figures of the functionalized carbon nano-tube that the embodiment of the present invention 1 is prepared；
Fig. 2 is the SEM figures of manganese dioxide/carbon nanotube composite material prepared by the embodiment of the present invention 1；
Fig. 3 is sweeping for manganese bioxide/carbon nano tube/shape memory polyurethane laminated film prepared by the embodiment of the present invention 1
Electron microscope；
Fig. 4 is cutting for manganese bioxide/carbon nano tube/shape memory polyurethane laminated film prepared by the embodiment of the present invention 1
Surface scan electron microscope；
Fig. 5 is cyclic voltammetry curve figure of the ultracapacitor of the preparation of the embodiment of the present invention 1 under differently curved angle；
Fig. 6 is circulation of the assembling ultracapacitor of the preparation of the embodiment of the present invention 1 before and after folding, sizing, shape are recovered
Volt-ampere curve figure；
Fig. 7 is ultracapacitor cutting Posterior circle volt-ampere curve figure prepared by the embodiment of the present invention 1.
Specific embodiment
The invention provides a kind of flexible super capacitor, including：
First electrode layer, the second electrode lay and the colloid electrolysis being arranged between the first electrode layer and the second electrode lay
Matter layer；
The first electrode layer by CNT and manganese dioxide composite film and be compound on the composite film
Polyurethane film is formed；
The second electrode lay is by CNT and manganese dioxide composite film and is compound in poly- on the composite film
Urethane film layer is formed；
The colloidal electrolyte layer is formed by polyvinyl alcohol and inorganic acid；
The CNT and manganese dioxide composite film contact with colloidal electrolyte layer.
The flexible super capacitor that the present invention is provided includes first electrode layer.The first electrode layer is by CNT and two
The composite film of manganese oxide and the polyurethane film being compound on the composite film are formed.
In the present invention, in the composite film of CNT and manganese dioxide, the CNT and manganese dioxide rub
You are than being preferably (1～3)：(1～2)；
The gross mass of the CNT and manganese dioxide is preferably (30～50) with the mass ratio of polyurethane：(100～
150)；More preferably (30～45)：(120～150).
The flexible super capacitor that the present invention is provided includes the second electrode lay.The second electrode lay is by CNT and two
The composite film of manganese oxide and the polyurethane film being compound on the composite film are formed.
In the present invention, in the composite film of CNT and manganese dioxide, the CNT and manganese dioxide rub
You are than being preferably (1～3)：(1～2)；
The gross mass of the CNT and manganese dioxide is preferably (30～50) with the mass ratio of polyurethane：(100～
150)；More preferably (30～45)：(120～150).
Polyurethane of the present invention is shape memory polyurethane, with reference to CNT and manganese dioxide, can be prepared
Ultracapacitor possess shape memory function.So that the flexible super capacitor for preparing of the present invention is in external force and higher than turning
Can fold or twist into arbitrary shape under conditions of temperature, and withdraw from external force and temperature keeps the shape；Work as temperature
When reaching transition temperature again, changing ultracapacitor can return to original shapes, and the present invention is relative to traditional flexible super
Capacitor；Controlled shape performance greatly reduces the problem for structural fatigue occur and rupturing after deformation, while solving capacitor
The deficiency that shape cannot be fixed in deformation process, increased the diversified actual demand of electronic functionalities.
First electrode layer of the present invention is preferably identical with the second electrode lay composition, as symmetrical structure.
The flexible super capacitor that the present invention is provided includes being arranged between the first electrode layer and the second electrode lay
Colloidal electrolyte layer；The colloidal electrolyte layer is formed by polyvinyl alcohol and inorganic acid；The CNT and manganese dioxide are multiple
Close film layer to contact with colloidal electrolyte layer.
In the present invention, the mass ratio of the polyvinyl alcohol and inorganic acid is preferably (1～10)：(1～10)；More preferably
(2～8)：(2～8)；Most preferably (3～6)：(3～6)；The inorganic acid is preferably selected from the one kind in sulfuric acid, phosphoric acid and hydrochloric acid
Or it is several；One or more more preferably in sulfuric acid and hydrochloric acid；Most preferably sulfuric acid.
Ultracapacitor of the present invention only includes electrode layer and colloidal electrolyte layer；Eliminate typical ultracapacitor
Encapsulated layer etc.；Structure is simpler.
The invention provides a kind of flexible super capacitor, including：First electrode layer, the second electrode lay and it is arranged at described
Colloidal electrolyte layer between first electrode layer and the second electrode lay；The first electrode layer is by CNT and manganese dioxide
Composite film and the polyurethane film being compound on the composite film are formed；The second electrode lay is by CNT and dioxy
The polyurethane film changed manganese composite film and be compound on the composite film is formed；The colloidal electrolyte layer is by polyvinyl alcohol
Formed with inorganic acid；The CNT and manganese dioxide composite film contact with colloidal electrolyte layer.What the present invention was provided
Flexible super capacitor is by electrode layer and dielectric substrate stratiform structure composition；Meanwhile, electrode layer is by CNT and manganese dioxide
Composite film and the polyurethane film that is compound on the composite film formed, just because of above-mentioned CNT, titanium dioxide
Manganese and polyurethane component and said structure so that the flexible super capacitor that the present invention is prepared is in external force and higher than transformation
Can fold or twist into arbitrary shape under conditions of temperature, and withdraw from external force and temperature keeps the shape；When temperature again
Secondary when reaching transition temperature, changing ultracapacitor can return to original shapes, and its area specific capacitance energy before and after cutting
Enough keep constant.
The invention provides a kind of preparation method of the ultracapacitor as described in above-mentioned technical scheme, including：
By the compacting of first electrode layer, colloidal electrolyte layer and the second electrode lay, ultracapacitor is obtained；
The first electrode layer or the second electrode lay are prepared by the following method：
The composite film of CNT and manganese dioxide is prepared by the composite of CNT and manganese dioxide；
By polyurethane-coated on the composite film of the CNT and manganese dioxide, obtain.
The compacting of first electrode layer, colloidal electrolyte layer and the second electrode lay is obtained ultracapacitor by the present invention.
The pressing pressure is preferably 0.1～10Mpa；More preferably 0.1～5Mpa；Most preferably 0.1～3Mpa；It is described
Pressing time is preferably 1～60min；More preferably 10～50min；Most preferably 20～40min.
The present invention is not defined for the instrument of the compacting, compacting instrument well known to those skilled in the art.
The first electrode layer or the second electrode lay are prepared by the following method：
The composite film of CNT and manganese dioxide is prepared by the composite of CNT and manganese dioxide；
By polyurethane-coated on the composite film of the CNT and manganese dioxide, obtain.
Specifically, the composite of CNT and manganese dioxide is prepared first.
The CNT and manganese dioxide composite material are prepared by the following method：
Mix in acid condition with potassium permanganate after CNT pretreatment, it is ultrasonically treated, react under microwave condition, obtain
To CNT and manganese dioxide composite material.
Wherein, CNT pretreatment is preferably specially：
By CNT and sour Hybrid Heating reaction, filter, wash, be dried to obtain functionalized carbon nano-tube.
The diameter of functionalized carbon nano-tube is preferably 20～30nm.
The acid is preferably one or more in the concentrated sulfuric acid and concentrated hydrochloric acid；The CNT is preferred with the weight ratio of acid
For (0.5～1)：(0.1～100)；More preferably (0.5～1)：(50～100).
The heating-up temperature is preferably 10～150 DEG C；More preferably 30～120 DEG C；Most preferably 50～100 DEG C；The most
Preferably 60～80 DEG C；The reaction time is preferably 0.1～100h；More preferably 1～20h；Most preferably 4～10h.
Described filtration is preferably suction filtration；The washing preferably washing is to neutrality；The drying is preferably vacuum dried；This
Invention is not defined for the concrete mode being filtered, washed and dried, well known to those skilled in the art above-mentioned concrete
Mode.
CNT pretreatment is obtained after functionalized carbon nano-tube, by functionalized carbon nano-tube and potassium permanganate in acidity
Under the conditions of mix, it is ultrasonically treated.
The functionalized carbon nano-tube is preferably (1～3) with the mol ratio of potassium permanganate：(1～2)；
The acid condition pH value is preferably 0.1～5；The acid is preferably the one kind or several in sulfuric acid, hydrochloric acid, nitric acid
Kind；The power of the ultrasound is preferably 1～100KHz；More preferably 10～90KHz；Most preferably 20～80KHz；The time
Preferably 0.1～10h；More preferably 1～8h；Most preferably 2～6h.
After ultrasonically treated, react under microwave condition, obtain CNT and manganese dioxide composite material.
The power of the microwave is preferably 600～800w；The reaction time is preferably 0.01～10min；More preferably 1
～8min；Most preferably 5～8min.
After microwave reaction, cooling is preferably included, the cooling is preferably and is cooled to room temperature, then microwave reaction one again
It is secondary.
It is preferably after microwave reaction and cleans, filters, washing, being dried to obtain CNT and manganese dioxide composite material.
Described filtration is preferably suction filtration；Washing preferably washing is to neutrality；The drying is preferably vacuum dried.The present invention
For the concrete mode being filtered, washed and dried is not defined, above-mentioned concrete mode well known to those skilled in the art
.
CNT and manganese dioxide composite material are obtained, by CNT and manganese dioxide composite material coating film forming,
CNT and manganese dioxide composite film is obtained.
It is preferred that being specially：
CNT and manganese dioxide composite material are distributed in solvent, dispersion liquid is obtained；Substrate surface is coated to, is treated
CNT and manganese dioxide composite film are obtained after solvent volatilization.
The solvent is preferably ethanol；The concentration of the dispersion liquid is preferably 0.1～100g/L；More preferably 1～10g/
L；Most preferably 2～8g/L.The base material is preferably plate glass.
In the present invention, after obtaining CNT and manganese dioxide composite film, by polyurethane-coated in the carbon nanometer
On the composite film of pipe and manganese dioxide, electrode layer is obtained.
It is preferred that being specially：
Polyurethane particles are dissolved in a solvent, heating stirring is coated on CNT and manganese dioxide composite film,
It is dried, obtains electrode layer.
The solvent is preferably dimethyl acetamide；The heating-up temperature is preferably 10～150 DEG C；More preferably 30～
130℃；Most preferably 50～85 DEG C；The mixing time is preferably 0.1～10h；More preferably 1～8h；Most preferably 2～
5h；It is described to be applied to drop coating or be coated with.
The drying is preferably vacuum dried；The temperature of the drying is preferably 50～200 DEG C；More preferably 60～150
℃；Most preferably 80～120 DEG C；The drying time is preferably 5～50h；More preferably 8～30h；Most preferably 10～20h；
The most it is preferably 12～18h.
In the present invention, colloidal electrolyte layer is sprawled by colloidal electrolyte, vapors away moisture and obtain final product.
The colloidal electrolyte is preferably adopted and prepared with the following method：
Polyvinyl alcohol, inorganic acid are mixed with water, heating stirring obtains colloidal electrolyte.
The inorganic acid is preferably selected from one or more in sulfuric acid, phosphoric acid and hydrochloric acid；More preferably selected from sulfuric acid and salt
One or more in acid；Most preferably sulfuric acid.
The mass ratio of the polyvinyl alcohol and inorganic acid is preferably (1～10)：(1～10)；More preferably (2～8)：(2～
8)；Most preferably (3～6)：(3～6)；The mass ratio of the polyvinyl alcohol, inorganic acid and distilled water is preferably (1～10)：(1
～10)：(10～100)；More preferably (2～8)：(2～8)：(20～80)；Most preferably (3～6)：(3～6)：(30～
60)；
The heating is preferably heating water bath；The heating-up temperature is preferably 85～100 DEG C；The heat time is preferably
1～5h；More preferably 2～4h.
Ultracapacitor that the present invention is prepared fold it is arbitrarily angled after not by external force in the case of still be able to protect
Hold folded state；Electric capacity is held essentially constant；And after certain size is cut into, area specific capacitance keeps substantially before and after cutting
It is constant.
Ultracapacitor of the present invention can be also used for the wearable field of intelligence.
Present invention preferably employs following manner is measured to capacitor performance：After ultracapacitor is completed, adopt
Under 0～0.8V potential windows, sweep speed is 10mVs to cyclic voltammetry-1Determine the chemical property of ultracapacitor.
In order to further illustrate the present invention, with reference to embodiments to the flexible super capacitor and its system of present invention offer
Preparation Method is described in detail.
Embodiment 1
80 DEG C are heated to after 1g CNTs, the 75mL concentrated sulfuric acids, 25mL red fuming nitric acid (RFNA)s are well mixed, are reacted 4 hours, to filter
Film suction filtration, cyclic washing to neutrality obtains functionalized carbon nano-tube after vacuum drying.Fig. 1 is prepared for the embodiment of the present invention 1
Functionalized carbon nano-tube SEM figure, as seen from Figure 1 carbon nanotube diameter is between 20～30nm.
By 80mg functionalized carbon nano-tubes, 0.25mmol potassium permanganate, the 5mL concentrated sulfuric acids be configured to 100mLpH values for 3 it is mixed
Solution is closed, is reacted mixed solution 5 minutes under 600W microwave actions after 50KHz is ultrasonically treated 2 hours, wash products, to filter
Film suction filtration, cyclic washing to neutrality obtains manganese dioxide/carbon nanotube composite material after vacuum drying.Fig. 2 is present invention enforcement
The SEM figures of manganese dioxide/carbon nanotube composite material prepared by example 1, as seen from Figure 2 manganese dioxide nano-rod is equably attached
On CNT tube wall.100mg manganese dioxide/carbon nanotube composite materials are distributed in 50mL ethanol, compound concentration
For 2mg/mL dispersion liquids.It is coated to surface of plate glass (2.5 × 7.5cm with taking 20mL homogeneous dispersions2), treat that ethanol steams completely
Uniform manganese bioxide/carbon nano tube composite membrane is obtained after sending out.
By in 10g shape memory polyurethanes grain dissolution to 100mL dimethylacetamide solvents, in 85 DEG C of water-baths fully
Stirring 5 hours, after particle is completely dissolved equably drop coating on manganese bioxide/carbon nano tube composite membrane, 80 DEG C vacuum drying
12 hours, obtain with double-deck combination electrode film.Fig. 3 is manganese dioxide/carbon nanometer prepared by the embodiment of the present invention 1
The scanning electron microscope (SEM) photograph of pipe/shape memory polyurethane laminated film, Fig. 4 is manganese dioxide/carbon nanometer prepared by the embodiment of the present invention 1
The cross-sectional scans electron microscope of pipe/shape memory polyurethane laminated film, as seen from Figure 4, it has obvious double-decker.
3gPVA the and 6g concentrated sulfuric acids are added in the deionized water of 30mL, are stirred 4 hours in 85 DEG C of water-baths, obtained
PVA/H2SO4Colloidal electrolyte.
By resulting PVA/H2SO4Colloidal electrolyte equably spreads into the manganese dioxide/carbon nanometer of two panels formed objects
Pipe/shape memory polyurethane combination electrode film (1 × 2.5cm2) on, and it is placed in two after ventilation removing excessive moisture
Piece film carries out compression process, pressure position 0.1MPa, and pressing time is 20min, is assembled into flexible super capacitor.
Gained flexible super capacitor stable performance under 0～0.8V window voltages, area specific capacitance is 18.7mF/
cm2。
The capacitor performance for preparing is measured using assay method of the present invention, as a result such as Fig. 5～Fig. 7 institutes
Show, wherein, Fig. 5 is cyclic voltammetry curve figure of the ultracapacitor of the preparation of the embodiment of the present invention 1 under differently curved angle；By
Fig. 5 can be seen that figure coincide substantially under differently curved angle, i.e., specific capacitance is held essentially constant, and show excellent flexible
Performance.Fig. 6 is cyclic voltammetric of the assembling ultracapacitor of the preparation of the embodiment of the present invention 1 before and after folding, sizing, shape are recovered
Curve map；As seen from Figure 6, its specific capacitance is also held essentially constant, and shows excellent foldability energy.Fig. 7 is this
Ultracapacitor cutting Posterior circle volt-ampere curve figure prepared by bright embodiment 1；As seen from Figure 7, respectively cutting 1/2,1/4 is former
After beginning size, its cyclic voltammetry curve is reduced in multiplying power, i.e. area specific capacitance is held essentially constant, i.e., cutting is for capacitor
Can be without impact.
Embodiment 2
80 DEG C are heated to after 1g CNTs, the 75mL concentrated sulfuric acids, 25mL red fuming nitric acid (RFNA)s are well mixed, are reacted 4 hours, to filter
Film suction filtration, cyclic washing to neutrality obtains functionalized carbon nano-tube after vacuum drying.
By 80mg functionalized carbon nano-tubes, 0.75mmol potassium permanganate, the 5mL concentrated sulfuric acids be configured to 100mLpH values for 4 it is mixed
Solution is closed, is reacted mixed solution 6 minutes under 700W microwave actions after 60KHz is ultrasonically treated 4 hours, wash products, to filter
Film suction filtration, cyclic washing to neutrality obtains manganese dioxide/carbon nanotube composite material after vacuum drying.By 100mg titanium dioxides
Manganese/carbon nano tube compound material is distributed in 50mL ethanol, and compound concentration is 2mg/mL dispersion liquids.Take 20mL homogeneous dispersions ground
It is coated to surface of plate glass (2.5 × 7.5cm2), uniform manganese bioxide/carbon nano tube is obtained after ethanol evaporating completely and is combined
Film.
By in 10g shape memory polyurethanes grain dissolution to 100mL dimethylacetamide solvents, fill in 80 DEG C of water-baths
Divide stirring 4 hours, equably drop coating is on manganese bioxide/carbon nano tube composite membrane after particle is completely dissolved, and 90 DEG C of vacuum are dry
Dry 12 hours, obtain with double-deck combination electrode film.
6gPVA the and 6g concentrated sulfuric acids are added in the deionized water of 60mL, are stirred 4 hours in 85 DEG C of water-baths, obtained
PVA/H2SO4Colloidal electrolyte.
By resulting PVA/H2SO4Colloidal electrolyte equably spreads into the manganese dioxide/carbon nanometer of two panels formed objects
Pipe/shape memory polyurethane combination electrode film (1 × 2.5cm2) on, and it is placed in two after ventilation removing excessive moisture
Piece film carries out compression process, pressure position 0.1MPa, and pressing time is 30min, it is assembled into flexible super capacitor.
Gained flexible super capacitor stable performance under 0～0.8V window voltages, area specific capacitance is 69.1mF/
cm2。
Embodiment 3
80 DEG C are heated to after 1g CNTs, the 75mL concentrated sulfuric acids, 25mL red fuming nitric acid (RFNA)s are well mixed, are reacted 4 hours, to filter
Film suction filtration, cyclic washing to neutrality obtains functionalized carbon nano-tube after vacuum drying.
By 80mg functionalized carbon nano-tubes, 1.5mmol potassium permanganate, the 5mL concentrated sulfuric acids be configured to 100mLpH values for 3 it is mixed
Close solution,；Mixed solution is reacted 8 minutes under 800W microwave actions after 70KHz is ultrasonically treated 3 hours, wash products, to filter
Film suction filtration, cyclic washing to neutrality obtains manganese dioxide/carbon nanotube composite material after vacuum drying.By 100mg titanium dioxides
Manganese/carbon nano tube compound material is distributed in 50mL ethanol, and compound concentration is 2mg/mL dispersion liquids.Take 20mL homogeneous dispersions ground
It is coated to surface of plate glass (2.5 × 7.5cm2), uniform manganese bioxide/carbon nano tube is obtained after ethanol evaporating completely and is combined
Film.
By in 10g shape memory polyurethanes grain dissolution to 100mL dimethylacetamide solvents, fill in 70 DEG C of water-baths
Divide stirring 5 hours, equably drop coating is on manganese bioxide/carbon nano tube composite membrane after particle is completely dissolved, and 80 DEG C of vacuum are dry
Dry 13 hours, obtain with double-deck combination electrode film.
9gPVA the and 6g concentrated sulfuric acids are added in the deionized water of 90mL, are stirred 4 hours in 85 DEG C of water-baths, obtained
PVA/H2SO4Colloidal electrolyte.
By resulting PVA/H2SO4Colloidal electrolyte equably spreads into the manganese dioxide/carbon nanometer of two panels formed objects
Pipe/shape memory polyurethane combination electrode film (1 × 2.5cm2) on, and it is placed in two after ventilation removing excessive moisture
Piece film carries out compression process, and pressure is 0.5MPa, and pressing time is 20min, is assembled into flexible super capacitor.
Gained flexible super capacitor stable performance under 0～0.8V window voltages, area specific capacitance is 34.6mF/
cm2。
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of flexible super capacitor, it is characterised in that include：
First electrode layer, the second electrode lay and the colloidal electrolyte being arranged between the first electrode layer and the second electrode lay
Layer；
The first electrode layer by CNT and manganese dioxide composite film and the poly- ammonia that is compound on the composite film
Ester film layer is formed；
The second electrode lay is by CNT and manganese dioxide composite film and the polyurethane being compound on the composite film
Film layer is formed；
The colloidal electrolyte layer is formed by polyvinyl alcohol and inorganic acid；
The CNT and manganese dioxide composite film contact with colloidal electrolyte layer.
2. flexible super capacitor according to claim 1, it is characterised in that the CNT and manganese dioxide rub
You are than being (1～3)：(1～2).
3. flexible super capacitor according to claim 1, it is characterised in that the quality of the polyvinyl alcohol and inorganic acid
Than for (1～10)：(1～10).
4. flexible super capacitor according to claim 1, it is characterised in that the CNT and manganese dioxide it is total
Quality is (30～50) with the mass ratio of polyurethane：(100～150).
5. flexible super capacitor according to claim 1, it is characterised in that the inorganic acid selected from sulfuric acid, phosphoric acid and
One or more in hydrochloric acid.
6. a kind of preparation method of ultracapacitor as claimed in any one of claims 1 to 5, wherein, it is characterised in that include：
By the compacting of first electrode layer, colloidal electrolyte layer and the second electrode lay, ultracapacitor is obtained；
The first electrode layer or the second electrode lay are prepared by the following method：
The composite film of CNT and manganese dioxide is prepared by the composite of CNT and manganese dioxide；
By polyurethane-coated on the composite film of the CNT and manganese dioxide.
7. preparation method according to claim 6, it is characterised in that the CNT and manganese dioxide composite material by
It is prepared by following method：
Mix in acid condition with potassium permanganate after CNT pretreatment, it is ultrasonically treated, react under microwave condition, obtain carbon
Nanotube and manganese dioxide composite material.
8. preparation method according to claim 7, it is characterised in that the power of the microwave is 600～800w；The acid
Property condition pH value be 0.1～5；The power of the ultrasound is 1～100KHz；Time is 0.1～10h.
9. preparation method according to claim 6, it is characterised in that the pressing pressure is 0.1～10Mpa；It is described to add
The pressure time is 1～60min.
10. preparation method according to claim 6, it is characterised in that the polyurethane-coated in the CNT and
It is specially on manganese dioxide composite film：
Polyurethane is dissolved in a solvent, heating stirring is coated on CNT and manganese dioxide composite film；The heating
Temperature is 10～150 DEG C；The mixing time is 0.1～10h；It is described to be applied to drop coating or be coated with.
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| CN107275121A (en) * | 2017-07-12 | 2017-10-20 | 广东工业大学 | A kind of ultracapacitor with self-healing and preparation method thereof |
| CN108178625A (en) * | 2018-01-19 | 2018-06-19 | 华南理工大学 | A kind of preparation method of layered solid ceramic electrolyte, total solids ultracapacitor |
| WO2021123823A1 (en) * | 2019-12-19 | 2021-06-24 | Superdielectrics Ltd | Integrated polymer materials for use in electrochemical cells |
| CN113646855A (en) * | 2019-04-10 | 2021-11-12 | 超电介质有限公司 | Method for integrating conductive nanoparticle materials into conductive cross-linked polymer films |
| CN115360024A (en) * | 2022-08-10 | 2022-11-18 | 五邑大学 | Super capacitor and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107275121A (en) * | 2017-07-12 | 2017-10-20 | 广东工业大学 | A kind of ultracapacitor with self-healing and preparation method thereof |
| CN107275121B (en) * | 2017-07-12 | 2019-12-10 | 广东工业大学 | Self-healing super capacitor and preparation method thereof |
| CN108178625A (en) * | 2018-01-19 | 2018-06-19 | 华南理工大学 | A kind of preparation method of layered solid ceramic electrolyte, total solids ultracapacitor |
| CN108178625B (en) * | 2018-01-19 | 2021-07-20 | 华南理工大学 | Preparation method of layered solid ceramic electrolyte and all-solid supercapacitor |
| CN113646855A (en) * | 2019-04-10 | 2021-11-12 | 超电介质有限公司 | Method for integrating conductive nanoparticle materials into conductive cross-linked polymer films |
| WO2021123823A1 (en) * | 2019-12-19 | 2021-06-24 | Superdielectrics Ltd | Integrated polymer materials for use in electrochemical cells |
| CN115360024A (en) * | 2022-08-10 | 2022-11-18 | 五邑大学 | Super capacitor and preparation method and application thereof |
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