CN108597889A - A kind of transition metal hydrotalcite-reduced graphene nanotube fibers electrode material and preparation method thereof and a kind of ultracapacitor - Google Patents
A kind of transition metal hydrotalcite-reduced graphene nanotube fibers electrode material and preparation method thereof and a kind of ultracapacitor Download PDFInfo
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- CN108597889A CN108597889A CN201810331852.7A CN201810331852A CN108597889A CN 108597889 A CN108597889 A CN 108597889A CN 201810331852 A CN201810331852 A CN 201810331852A CN 108597889 A CN108597889 A CN 108597889A
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- nanotube
- ultracapacitor
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 144
- 239000002071 nanotube Substances 0.000 title claims abstract description 112
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 76
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 73
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 70
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 70
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 70
- 239000000835 fiber Substances 0.000 title claims abstract description 66
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 21
- 241000446313 Lamella Species 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002322 conducting polymer Substances 0.000 claims abstract description 12
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 12
- 239000000470 constituent Substances 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 90
- 239000011259 mixed solution Substances 0.000 claims description 37
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 28
- 238000004070 electrodeposition Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 230000005611 electricity Effects 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 8
- 239000013305 flexible fiber Substances 0.000 abstract description 8
- 238000005452 bending Methods 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 41
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000001035 drying Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 239000011668 ascorbic acid Substances 0.000 description 14
- 229960005070 ascorbic acid Drugs 0.000 description 14
- 235000010323 ascorbic acid Nutrition 0.000 description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 13
- 229910002651 NO3 Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 12
- 239000006230 acetylene black Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 11
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000003618 dip coating Methods 0.000 description 9
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- -1 iron ion Chemical class 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229940075397 calomel Drugs 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000006193 liquid solution Substances 0.000 description 5
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- 239000003990 capacitor Substances 0.000 description 4
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- 238000011065 in-situ storage Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
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- 239000012462 polypropylene substrate Substances 0.000 description 4
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- 238000007654 immersion Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- 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
- H01G11/84—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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention provides a kind of transition metal hydrotalcite reduced graphene nanotube fibers electrode materials, including reduced graphene nanotube and the transition metal hydrotalcite nano lamella for being supported on reduced graphene nanotube surface；The reduced graphene nanotube is hollow tubular structure；The constituent of the reduced graphene nanotube includes reduced graphene and conducting polymer.Electrode material provided by the invention is a kind of flexible fiber electrode, electrochemical performance, there is good capacitive property using the ultracapacitor that electrode material provided by the invention is positive electrode assembling, constant current charge-discharge performance is good, further, there is good flexibility with the ultracapacitor of flexible base material assembling, under different bending degree, cyclic voltammetry curve does not change substantially, there is good wearable property.
Description
Technical field
The present invention relates to the technical field of capacitor, more particularly to a kind of transition metal hydrotalcite-reduced graphene nanometer
Pipe fiber electrode material and preparation method thereof and a kind of ultracapacitor.
Background technology
From smartwatch manufacturer IBM in 2000 issued operation Linux system watchpad 1.0 after, it is various can
Wearable device is quickly a dark horse, and people can obtain personal need by mobile phone, intelligent earphone, wrist-watch, glasses, ring
The information wanted is linked up with the external world.Wearable electronic is just towards small, light-weight, thickness is thin, more comfortably, is more bonded
The direction of curve of human body is fast-developing, and more stringent requirements are proposed for this power supply module to wearable device.Currently, research is most
Extensive flexible energy storage device is all-solid-state supercapacitor, and all-solid-state supercapacitor is generally by flexible electrode and solid-state electricity
Matter composition is solved, has many advantages, such as high power density, the operating condition of the cycle life of length, fast charge-discharge velocity and safety,
Researchers are received more and more to pay close attention to.
Electrode material has been largely fixed the performance of all-solid-state supercapacitor, at present all-solid-state supercapacitor electricity
Pole material mainly has graphene fiber, RuO2、MnO2Deng the material with fake capacitance characteristic.But these electrode materials are electric at present
Chemical property is still poor, limits the practical application of ultracapacitor.
Invention content
In view of this, present invention aims at provide a kind of transition metal hydrotalcite-reduced graphene nanotube fibers electricity
Pole material and preparation method thereof and a kind of ultracapacitor.Transition metal hydrotalcite-reduced graphene nanometer provided by the invention
Pipe fiber electrode material is a kind of flexible fiber electrode, and electrochemical performance；The super electricity being assembled into the electrode material
Container energy density is high, has good capacitive character, constant current charge-discharge performance good.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A kind of transition metal hydrotalcite-reduced graphene nanotube fibers electrode material, including reduced graphene nanotube
With the transition metal hydrotalcite nano lamella for being supported on the reduced graphene nanotube surface；
The reduced graphene nanotube is hollow tubular structure；The constituent of the reduced graphene nanotube includes
Reduced graphene and conducting polymer.
Preferably, the pipe thickness of the reduced graphene nanotube is 5~11 μm；The reduced graphene nanotube
Outer diameter is 60~100 μm.
Preferably, the thickness of the transition metal hydrotalcite nano lamella is 5~20nm；The transition metal hydrotalcite is received
The grain size of transition metal hydrotalcite nano piece is 300~500nm in rice lamella.
Preferably, the mass ratio of the reduced graphene nanotube and transition metal hydrotalcite nano lamella is 10~20:
1。
The present invention provides the preparation methods of electrode material described in said program, include the following steps：
Transition metal hydrotalcite nano lamella is grown in reduced graphene nanotube surface, obtains transition metal hydrotalcite-
Reduced graphene nanotube fibers electrode material；The constituent of the reduced graphene nanotube includes reduced graphene and leads
Electric polymer；
The method of the growth transition metal hydrotalcite nano lamella includes hydrothermal deposition method and electrochemical deposition method.
Preferably, the method for the growth transition metal hydrotalcite nano lamella is electrochemical deposition method, including following step
Suddenly：
Transition metal mixed salt solution is immersed using reduced graphene nanotube as working electrode, with to electrode and reference electrode
Middle carry out electrochemical deposition obtains transition metal hydrotalcite-reduced graphene nanotube fibers electrode material；
The transition metal mixed salt solution includes two kinds of transition metal ions；
The transition metal mixed salt solution is the mixed solution or transition metal nitrate and mistake of transition metal nitrate
Cross the mixed solution of metal hydrochloride.
Preferably, in the transition metal mixed salt solution concentration of two kinds of transition metal ions be independently 0.1~
0.2mol/L。
Preferably, the electrochemical deposition deposits for constant voltage；The voltage of the electrochemical deposition is -0.9~-1.1V；
The time of the electrochemical deposition is 5~100s.
The present invention provides a kind of ultracapacitors, including substrate, anode, cathode and electrolyte, which is characterized in that described
The positive electrode of ultracapacitor is transition metal hydrotalcite-reduced graphene nanotube fibers electrode material described in said program
Transition metal hydrotalcite-reduced graphene nanotube fibers electrode material that described in material or said program prepared by preparation method.
Preferably, the negative material of the ultracapacitor is reduced graphene nanotube-active carbon combined electrode；It is described
The substrate of ultracapacitor is flexible substrates；The electrolyte of the ultracapacitor is that polyvinyl alcohol/potassium hydroxide gel is entirely solid
State electrolyte.
The present invention provides a kind of transition metal hydrotalcite-reduced graphene nanotube fibers electrode materials, including reduction
Graphene nano pipe and the transition metal hydrotalcite nano lamella for being supported on the reduced graphene nanotube surface；The reduction
Graphene nano pipe is hollow tubular structure；The constituent of the reduced graphene nanotube includes reduced graphene and conduction
Polymer.Electrode material provided by the invention is a kind of flexible fiber electrode, and the hollow structure of reduced graphene nanotube increases
The accessible area of electrode and electrolyte, improves the utilization rate of active component, and transition metal hydrotalcite nano chip arrays hang down
Straight ordering growth forms nanoscale twins, increases the specific surface area of electrode material, be in reduced graphene nanotube surfaces externally and internally
The quick expanding of ion and redox reaction provide effective channel.Electrode material chemical property provided by the invention is excellent
Different, energy density is high, is a kind of excellent electrode material for super capacitor.
The present invention also provides a kind of ultracapacitor, ultracapacitor provided by the invention is with the electricity described in said program
Pole material is anode, has good capacitive property, constant current charge-discharge performance is good, further, is assembled with flexible base material
Ultracapacitor have good flexibility, under different bending degree, cyclic voltammetry curve does not change substantially.Embodiment
The result shows that ultracapacitor provided by the invention is in 0.25mA cm-2Under specific capacitance can reach 177.9mF cm-2, energy
Metric density can reach 8.89 μ Wh cm-2。
Description of the drawings
Fig. 1 is reduced graphene nanotube prepared by the embodiment of the present invention 1 and RGO-CoNi-LDH fiber electrodes surface
The X ray diffracting spectrum of cobalt nickel hydrotalcite sheet；
Fig. 2 is the scanning electron microscope (SEM) photograph of reduced graphene nanotube prepared by the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture of RGO-CoNi-LDH fiber electrodes prepared by the embodiment of the present invention 1；
Fig. 4 is the scanning electron microscope (SEM) photograph in RGO-CoNi-LDH fiber electrodes section prepared by the embodiment of the present invention 1；
Fig. 5 is the cyclic voltammetry curve figure of ultracapacitor prepared by the embodiment of the present invention 5~8；
Fig. 6 is cyclic voltammetry curve figure of the ultracapacitor of the preparation of the embodiment of the present invention 5 under different scanning rates；
Fig. 7 is the constant current charge-discharge curve graph of ultracapacitor prepared by the embodiment of the present invention 5；
Fig. 8 is cyclic voltammetry curve figure of the ultracapacitor of the preparation of the embodiment of the present invention 5 under differently curved degree.
Specific implementation mode
The present invention provides a kind of transition metal hydrotalcite-reduced graphene nanotube fibers electrode materials, including reduction
Graphene nano pipe and the transition metal hydrotalcite nano lamella for being supported on the reduced graphene nanotube surface；The reduction
Graphene nano pipe is hollow tubular structure；The constituent of the reduced graphene nanotube includes reduced graphene and conduction
Polymer.
Transition metal hydrotalcite provided by the invention-reduced graphene nanotube fibers electrode material includes reduced graphene
Nanotube；The constituent of the reduced graphene nanotube includes reduced graphene and conducting polymer.In the present invention, institute
It is preferably 1.5~2 to state the mass ratio of reduced graphene and conducting polymer in reduced graphene nanotube:1, more preferably 2:1；
The pipe thickness of the reduced graphene nanotube is preferably 5~11 μm, more preferably 6~8 μm；The reduced graphene nanometer
The outer diameter of pipe is preferably 60~100 μm, more preferably 70~90 μm, most preferably 80 μm.
Transition metal hydrotalcite provided by the invention-reduced graphene nanotube fibers electrode material includes being supported on reduction
The transition metal hydrotalcite nano lamella of graphene nano pipe surface.In the present invention, the transition metal hydrotalcite nano piece
The vertical ordering growth of array forms nanoscale twins in reduced graphene nanotube surfaces externally and internally；The transition metal hydrotalcite is received
The thickness of rice lamella is preferably 5~20nm, more preferably 10~15nm；Transition gold in the transition metal hydrotalcite nano lamella
The grain size for belonging to hydrotalcite nano piece is preferably 300~500nm, more preferably 350~450nm.
In the present invention, the transition metal hydrotalcite is preferably transition metal neatly well known to those skilled in the art
Stone, specific such as cobalt nickel hydrotalcite, ferro-cobalt hydrotalcite, nickel-ferric spinel and nickel aluminum hydrotalcite.
In the present invention, the mass ratio of the reduced graphene nanotube and transition metal hydrotalcite nano lamella is preferably
10~20:1, more preferably 15:1.
The present invention provides the preparation methods of electrode material described in said program, include the following steps：
Transition metal hydrotalcite nano lamella is grown in reduced graphene nanotube surface, obtains transition metal hydrotalcite-
Reduced graphene nanotube fibers electrode material；The constituent of the reduced graphene nanotube includes reduced graphene and leads
Electric polymer.
In the present invention, the method for the growth transition metal hydrotalcite nano lamella is preferably hydrothermal deposition method or electrification
Learn sedimentation.
In the present invention, when the method is electrochemical deposition method, the preparation method preferably includes following steps：
Using reduced graphene nanotube as working electrode, transition metal mixed salt solution is immersed with to electrode and reference electrode
Middle carry out electrochemical deposition obtains transition metal hydrotalcite-reduced graphene nanotube fibers electrode material；
The transition metal mixed salt solution includes two kinds of transition metal ions；
The transition metal mixed salt solution is the mixed solution or transition metal nitrate and mistake of transition metal nitrate
Cross the mixed solution of metal hydrochloride.
For the present invention using reduced graphene nanotube as working electrode, the preparation method of the reduced graphene nanotube is preferred
Include the following steps：
Reducing agent, conducting polymer are dissolved in graphene oxide water solution, mixed solution is obtained；
The mixed solution is injected in capillary, is heated after capillary both ends are sealed, obtains reduced graphene
Nanotube.
Reducing agent, conducting polymer are dissolved in graphene oxide water solution by the present invention, obtain mixed solution.In this hair
In bright, the reducing agent is preferably the mixture of one or more of ascorbic acid, sodium citrate and hydroxylamine hydrochloride, more preferably
For ascorbic acid；Preferably poly- (3,4- the ethene dioxythiophenes)-polystyrolsulfon acid of the conducting polymer, polyaniline and poly- pyrrole
Cough up the mixture of middle one or more, more preferably poly- (3,4-rthylene dioxythiophene)-polystyrolsulfon acid；In the present invention,
Conducting polymer can increase the electric conductivity of reduced graphene nanotube, promote the formation of hollow structure.
In the present invention, the concentration of graphene oxide is preferably 6mg/mL~12mg/ in the graphene oxide water solution
ML, the present invention do not have particular/special requirement to the source of the graphene oxide water solution, use side well known to those skilled in the art
Method, which is prepared or bought, to be used.In the present invention, the mass ratio of the reducing agent and graphene oxide is preferably 1：0.5
~1.5, more preferably 1:1；Mass fraction of the conducting polymer in mixed solution is preferably 5%~40%, more preferably
It is 10%~35%, most preferably 15%~25%；The present invention does not have the dissolving method of the reducing agent and conducting polymer
Particular/special requirement, will reducing agent, conducting polymer and graphene oxide water solution mix after stir to being completely dissolved.
After obtaining mixed solution, the present invention injects mixed solution in capillary, is added after capillary both ends are sealed
Heat obtains reduced graphene nanotube fibers electrode.In the present invention, packing volume ratio of the mixed solution in capillary
Preferably 8~9:10, more preferably 8:10；In the present invention, it is 0.9mm that the capillary, which is most preferably internal diameter, and outer diameter is
The fusing point capillary of 1.1mm；The present invention does not have particular/special requirement to the method for sealing capillary both ends, uses people in the art
Method is sealed known to member, in a specific embodiment of the present invention, it is preferable to use alcohol blast burner is by capillary both ends
It is sealed after fusing.
After capillary both ends are sealed, the present invention heats the capillary after sealing, obtains reduced graphene nanometer
Pipe.In the present invention, the heating preferably includes the carry out successively first heating and the second heating, the temperature of first heating
Preferably 80~90 DEG C, more preferably 85 DEG C；The time of first heating is preferably 2~4h, more preferably 2.5~3.5h；
In the first heating process, redox reaction occurs for reducing agent and graphene oxide, generates the gases such as carbon dioxide, to shape
At hollow graphene nano pipe structure；After the completion of first heating, the present invention preferably opens the capillary both ends of sealing, carries out
Second heating；The temperature of second heating is preferably 80~90 DEG C, more preferably 85 DEG C；The time of second heating is preferred
For 9~15h, more preferably 10~14h, most preferably 11~13h；The present invention carries out graphene nano pipe by the second heating
It is dry, wet fiber is dried to dry fibers, improves the mechanical performance of reduced graphene nanotube；The present invention preferably sets capillary
It is heated in drying box.
After the completion of heating, the present invention preferably stands capillary to room temperature, is then crushed capillary, by reduced graphene
Nanotube takes out.
After obtaining reduced graphene nanotube, the present invention is immersed by reduced graphene nanotube, to electrode and reference electrode
Electrochemical deposition is carried out in transition metal mixed salt solution, obtains transition metal hydrotalcite-reduced graphene nanotube fibers electricity
Pole material.In the present invention, the transition metal mixed salt solution includes two kinds of transition metal ions, the transition metal from
Son is preferably cobalt ions, nickel ion, iron ion, titanium ion, vanadium ion, chromium ion and manganese ion；The transition metal salt mixing
Solution is preferably the mixed solution of transition metal nitrate or the mixed solution of transition metal nitrate and transition metal hydrochloride,
More preferably CoCl2·6H2O and Ni (NO3)2Mixed solution, the NiCl of 6HO2·6H2O and Co (NO3)2The mixing of 6HO is molten
Liquid or FeCl3·6H2O and Ni (NO3)2The mixed solution of 6HO, most preferably CoCl2·6H2O and Ni (NO3)26HO's is mixed
Close solution；The independent preferably 0.1~0.2mol/ of the concentration of two kinds of transition metal ions in the transition metal mixed salt solution
L, more preferably 0.15mol/L.
In the present invention, described is preferably platinum electrode, graphite electrode or gold electrode to electrode；The platinum electrode is preferably platinum
Line electrode or platinum plate electrode；The reference electrode is preferably standard calomel electrode or silver/fluorination silver electrode.In the present invention, institute
It is preferably constant voltage deposition to state electrochemical deposition；The voltage of the electrochemical deposition is preferably 0.9~1.1V, more preferably
1.0V；The time of the electrochemical deposition is preferably 5~100s, more preferably 10~80s, most preferably 30~60s.
In the present invention, under electrochemical action, the nitrate anion in mixed solution occurs reduction and generates hydroxyl, transition gold
Belong to ion and hydroxide ion is co-precipitated, it is raw to carry out vertical orderly original position in reduced graphene nanotube surfaces externally and internally
It is long, transition metal hydrotalcite nano array is formed, finally forms transition metal neatly in reduced graphene nanotube surfaces externally and internally
Stone nanoscale twins.
The present invention provides a kind of ultracapacitors, including substrate, anode, cathode and electrolyte；The ultracapacitor
Positive electrode be said program described in transition metal hydrotalcite-reduced graphene nanotube fibers electrode material or above-mentioned side
Transition metal hydrotalcite-reduced graphene nanotube fibers electrode material prepared by preparation method described in case.
In the present invention, the negative material of the ultracapacitor is preferably that reduced graphene nanotube-activated carbon is compound
Electrode；The substrate of the ultracapacitor is preferably flexible substrates, more preferably non-transparent flexible substrate, and the present invention is to described transparent
The type of flexible substrates does not have particular/special requirement, using non-transparent flexible substrate well known to those skilled in the art, specifically such as
Polyethylene terephthalate (PET), polypropylene, polypropylene (PP), polyvinyl chloride (PVC) or polystyrene (PS)；It is described
Electrolyte is preferably PVA/KOH gel all solid state electrolytes.
In the present invention, the preparation method of the reduced graphene nanotube-active carbon combined electrode preferably includes following
Step：
Dip-coating 3~6 times in colloidal solution by reduced graphene nanotube, obtain reduced graphene nanotube-activated carbon
Combination electrode；The colloidal solution be activated carbon, acetylene black and polyvinylidene fluoride mixed solution.
In the present invention, the colloidal solution be activated carbon, acetylene black and polyvinylidene fluoride mixed solution；It is described mixed
The solvent for closing solution is preferably ethyl alcohol；The quality of the activated carbon and the volume ratio of solvent are preferably 1.5~2.5g:5mL, it is more excellent
It is selected as 2g:5mL；The mass ratio of the activated carbon, acetylene black and polyvinylidene fluoride is preferably 80:10:10；The present invention is to colloid
The preparation method of solution does not have particular/special requirement, and activated carbon, acetylene black, polyvinylidene fluoride and solvent are directly mixed.
In the present invention, the time independent preferably 5~10min, more preferably 6~8min of the single dip-coating；The present invention preferably will
Reduced graphene nanotube after dip-coating is dried at room temperature for, and then carries out dip-coating next time；Specific side of the present invention to dip-coating
Method does not have particular/special requirement, and reduced graphene nanotube fibers electrode is totally immersed in colloidal solution.
By taking electrolyte is PVA/KOH gels all solid state electrolyte, substrate is flexible substrates as an example, the ultracapacitor
Preparation method includes the following steps：
It is heated after KOH, polyethylene alcohol and water are mixed, obtains colloidal solution；
It is done after transition metal hydrotalcite-reduced graphene nanotube fibers electrode material is impregnated in the colloidal solution
It is dry, obtain positive electrode；
Reduced graphene nanotube-active carbon combined electrode is dry after being impregnated in colloidal solution, obtains negative electrode；
On a flexible substrate by positive electrode fixation parallel with the negative electrode, the flexibility for being fixed with positive and negative electrode is obtained
Substrate；
It is dry after the flexible substrates surface covering rubber liquid solution for being fixed with positive and negative electrode, obtain ultracapacitor.
The present invention heats after mixing KOH, polyethylene alcohol and water, obtains colloidal solution.In the present invention, the colloid is molten
The concentration of polyvinyl alcohol is preferably 0.05~0.1g/mL in liquid, more preferably 0.06~0.08g/mL；Point of the polyvinyl alcohol
Son amount preferably 12~160,000, more preferably 13~150,000；The concentration of KOH is preferably 0.5~1mol/L in the colloidal solution,
More preferably 0.6~0.8mol/L.In the present invention, the temperature of the heating is preferably 80~90 DEG C, more preferably 85 DEG C, this
Invention does not have particular/special requirement to the time of the heating, is heated to KOH and polyvinyl alcohol is completely dissolved；The present invention is to described
Water does not have particular/special requirement, and matter water, preferably deionization are electrolysed using ultracapacitor well known to those skilled in the art
Water.
After obtaining colloidal solution, the present invention exists transition metal hydrotalcite-reduced graphene nanotube fibers electrode material
It is dry after being impregnated in the colloidal solution, obtain positive electrode.In the present invention, the time of the immersion is preferably 5~10min,
More it is selected as 6~8min；The present invention does not have particular/special requirement to the temperature of immersion, without carrying out additional heating or cooling；This hair
The bright volume to immersion colloidal solution does not have particular/special requirement, can will cross metal hydrotalcite-reduced graphene nanotube fibers
Electrode material is totally submerged.In the present invention, the temperature of the drying is preferably 40~70 DEG C, more preferably 60 DEG C；Institute
It is preferably 5~10min to state the dry time, more preferably 6~8min；The drying is preferably dried in vacuo；The present invention is to institute
Stating vacuum drying vacuum degree does not have particular/special requirement, can be dried under vacuum.
The present invention is dry after impregnating reduced graphene nanotube-active carbon combined electrode in colloidal solution, is born
Electrode.In the present invention, the soaking conditions are consistent with said program, and details are not described herein；The condition of the drying and above-mentioned
Scheme is consistent, and details are not described herein.
After obtaining positive electrode and negative electrode, the present invention is fixed on flexible substrates by the positive electrode is parallel with the negative electrode
On, obtain the flexible substrates for being fixed with positive and negative electrode.In the present invention, the spacing of the positive electrode and negative electrode is preferably 0.01
~0.05mm, more preferably 0.03mm；The independent preferably 2~4cm of the effective length of the positive electrode and negative electrode, more preferably
For 2.5~3.5cm；The present invention does not have particular/special requirement to the method for the fixed positive and negative electrode, ripe using those skilled in the art
The fixing means known.
It obtains after being fixed with the flexible substrates of positive and negative electrode, the present invention is in the flexible substrates table for being fixed with positive and negative electrode
Face covers drying after colloidal solution, obtains ultracapacitor.In the present invention, the temperature of the drying is preferably 40~70 DEG C,
More preferably 60 DEG C；The time of the drying is preferably 12~for 24 hours, more preferably 15~20h；The drying is preferably that vacuum is dry
It is dry；The present invention does not have particular/special requirement to the vacuum drying vacuum degree, can be dried under vacuum.This hair
The bright overlay capacity to the colloidal solution does not have particular/special requirement, and positive and negative electrode can be completely covered.
In the present invention, electrolyte is PVA/KOH gels all solid state electrolyte in said program, substrate is that flexible substrates obtain
The ultracapacitor arrived is a kind of flexible fiber shape all-solid-state supercapacitor, has flexible light weight, small, light-weight spy
Point has wearable property.
With reference to embodiment to transition metal hydrotalcite provided by the invention-reduced graphene nanotube fibers electrode material
Material and preparation method thereof and a kind of ultracapacitor are described in detail, but they cannot be interpreted as protecting the present invention
The restriction of range.
Embodiment 1
Ascorbic acid (AA) and poly- (3,4- ethene dioxythiophenes)-polystyrolsulfon acid (PEDOT/PSS) are dissolved in oxidation
In graphene (GO) solution (a concentration of 6mg/mL of graphene oxide), mixed solution is obtained；The mass ratio of AA and GO is 1:1,
Mass fractions of the PEDOT/PSS in mixed solution is 25%.
It is 0.9mm, in the fusing point capillary that outer diameter is 1.1mm by mixed solution injection internal diameter, two is sealed with alcohol blast burner
End, then puts it into 90 DEG C of drying boxes, after heating 2 hours, opens capillary both ends, continues to keep the temperature of original heating
Degree is 12 hours dry in drying box, obtains reduced graphene (RGO) nanotube that outer diameter is 60 μm, pipe thickness is 5 μm.
Using electrochemical deposition method in RGO nanotube surfaces externally and internally growth in situ CoNi-LDH：By reduced graphene (RGO)
Nanotube fibers electrode, platinum line electrode and standard calomel electrode are inserted into CoCl2·6H2O and Ni (NO3)2·6H2The mixed solution of O
Electrochemical deposition, sedimentation time 50s are carried out in 50mL, operating voltage is -1V, CoCl2·6H2O and Ni (NO3)2·6H2O's
Concentration in mixed solution is 0.15mol/L；After the completion of deposition, 60 after post-depositional electrode is cleaned with deionized water
Dry 60min in DEG C baking oven obtains cobalt nickel hydrotalcite-reduced graphene nanotube fibers electrode (RGO-CoNi-LDH fiber electricity
Pole).
Using X-ray diffraction method to the reduced graphene nanotube being prepared and RGO-CoNi-LDH fiber electrodes surface
Cobalt nickel hydrotalcite sheet be detected, gained X ray diffracting spectrum is as shown in Figure 1；According to Fig. 1 as can be seen that reduction graphite
(002) of alkene nanotube, the diffraction maximum of (004) have respectively appeared in 26.41 ° and 54.51 °；(012) of cobalt nickel hydrotalcite,
(015), the diffraction maximum of (110) has respectively appeared in 35 °, 44.2 °, 60.4 °, and (003) peak has appeared in 11.7 °, illustrates cobalt nickel
The growth in reduced graphene nanotube surface of hydrotalcite nano piece has certain orientation.
The reduced graphene nanotube being prepared is observed using scanning electron microscope, gained scanning electron microscope (SEM) photograph such as Fig. 2
Scanning electron microscope (SEM) photograph shown, that wherein Fig. 2 (a), which is scale, to be obtained when being 20 μm, Fig. 2 (b) is scale when being 200nm to the sides Fig. 2 (a)
The scanning electron microscope (SEM) photograph that frame portion point is observed；According to fig. 2 as can be seen that reduced graphene nanotube surface has fold knot
Structure, this structure can increase the specific surface area of electrode, be conducive to the growth of hydrotalcite nano piece.
Using transmission electron microscope to the cobalt nickel hydrotalcite nano piece on the RGO-CoNi-LDH fiber electrodes surface being prepared into
Row observation, gained transmission electron microscope picture is as shown in figure 3, the transmission electron microscope picture that wherein Fig. 3 (e), which is scale, to be obtained when being 20 μm, Fig. 3
(f) transmission electron microscope picture Fig. 3 (e) Blocked portions being observed when be scale being 200nm；According to fig. 3 as can be seen that water
Talcum nanoscale twins are porous array structure, and the specific surface area that this porous array structure increases electrode is the quick expansion of ion
It dissipates and redox reaction provides effective channel.
The section for the RGO-CoNi-LDH fiber electrodes being prepared is observed using scanning electron microscope, gained scanning electricity
Mirror figure is as shown in figure 4, the scanning electron microscope (SEM) photograph that wherein Fig. 4 (g), which is scale, to be obtained when being 20 μm, and Fig. 4 (h) is scale when being 200nm
The scanning electron microscope (SEM) photograph that Fig. 4 (g) Blocked portions are observed；According to Fig. 4 as can be seen that cobalt nickel hydrotalcite nano lamella is former
Position is grown on reduced graphene nanotube surfaces externally and internally, and more active components are provided for electrode.
Embodiment 2
Ascorbic acid (AA) and poly- (3,4- ethene dioxythiophenes)-polystyrolsulfon acid (PEDOT/PSS) are dissolved in oxidation
In graphene (GO) solution (a concentration of 8mg/mL of graphene oxide), mixed solution is obtained；The mass ratio of AA and GO is 1:1,
Mass fractions of the PEDOT/PSS in mixed solution is 5%.
It is 0.9mm, in the fusing point capillary that outer diameter is 1.1mm by mixed solution injection internal diameter, two is sealed with alcohol blast burner
End, then puts it into 85 DEG C of drying boxes, after heating 3 hours, opens capillary both ends, continues to keep the temperature of original heating
Degree is 9 hours dry in drying box, obtains reduced graphene (RGO) nanotube that outer diameter is 70 μm, pipe thickness is 8 μm.
Using electrochemical deposition method in RGO nanotube surfaces externally and internally growth in situ CoNi-LDH：By reduced graphene (RGO)
Nanotube, platinum line electrode and standard calomel electrode are inserted into CoCl2·6H2O and Ni (NO3)2·6H2In the mixed solution 50mL of O into
Row electrochemical deposition, sedimentation time 25s, operating voltage are -1V, CoCl2·6H2O and Ni (NO3)2·6H2O's is molten in mixing
Concentration in liquid is 0.15mol/L；After the completion of deposition, after post-depositional electrode is cleaned with deionized water in 60 DEG C of baking ovens
Dry 60min, obtains cobalt nickel hydrotalcite-reduced graphene nanotube fibers electrode (RGO-CoNi-LDH fiber electrodes).
Gained RGO nanotubes and RGO-CoNi-LDH fiber electrodes are detected according to the method in embodiment 1, gained
As a result similar with embodiment 1.
Embodiment 3
Ascorbic acid (AA) and poly- (3,4- ethene dioxythiophenes)-polystyrolsulfon acid (PEDOT/PSS) are dissolved in oxidation
In graphene (GO) solution (a concentration of 9mg/mL of graphene oxide), mixed solution is obtained；The mass ratio of AA and GO is 1:1,
Mass fractions of the PEDOT/PSS in mixed solution is 30%.
It is 0.9mm, in the fusing point capillary that outer diameter is 1.1mm by mixed solution injection internal diameter, two is sealed with alcohol blast burner
End, then puts it into 85 DEG C of drying boxes, after heating 4 hours, opens capillary both ends, continues to keep the temperature of original heating
Degree is 12 hours dry in drying box, obtains reduced graphene (RGO) nanotube that outer diameter is 80 μm, pipe thickness is 9 μm.
Using electrochemical deposition method in RGO nanotube surfaces externally and internally growth in situ CoNi-LDH：By reduced graphene (RGO)
Nanotube, platinum line electrode and standard calomel electrode are inserted into CoCl2·6H2O and Ni (NO3)2·6H2In the mixed solution 50mL of O into
Row electrochemical deposition, sedimentation time 75s, operating voltage are -1V, CoCl2·6H2O and Ni (NO3)2·6H2O's is molten in mixing
Concentration in liquid is 0.15mol/L；After the completion of deposition, after post-depositional electrode is cleaned with deionized water in 60 DEG C of baking ovens
Dry 45min, obtains cobalt nickel hydrotalcite-reduced graphene nanotube fibers electrode (RGO-CoNi-LDH fiber electrodes).
Gained RGO nanotubes and RGO-CoNi-LDH fiber electrodes are detected according to the method in embodiment 1, gained
As a result similar with embodiment 1.
Embodiment 4
Ascorbic acid (AA) and poly- (3,4- ethene dioxythiophenes)-polystyrolsulfon acid (PEDOT/PSS) are dissolved in oxidation
In graphene (GO) solution (a concentration of 12mg/mL of graphene oxide), mixed solution is obtained；The mass ratio of AA and GO is 1:1,
Mass fractions of the PEDOT/PSS in mixed solution is 40%.
It is 0.9mm, in the fusing point capillary that outer diameter is 1.1mm by mixed solution injection internal diameter, two is sealed with alcohol blast burner
End, then puts it into 90 DEG C of drying boxes, after heating 4 hours, opens capillary both ends, continues to keep the temperature of original heating
Degree is 15 hours dry in drying box, obtains reduced graphene (RGO) nanotube that outer diameter is 100 μm, pipe thickness is 11 μm.
Using electrochemical deposition method in RGO nanotube surfaces externally and internally growth in situ CoNi-LDH：By reduced graphene (RGO)
Nanotube, platinum line electrode and standard calomel electrode are inserted into CoCl2·6H2O and Ni (NO3)2·6H2In the mixed solution 50mL of O into
Row electrochemical deposition, sedimentation time 100s, operating voltage are -1V, CoCl2·6H2O and Ni (NO3)2·6H2O's is molten in mixing
Concentration in liquid is 0.15mol/L；After the completion of deposition, after post-depositional electrode is cleaned with deionized water in 60 DEG C of baking ovens
Dry 45min, obtains cobalt nickel hydrotalcite-reduced graphene nanotube fibers electrode (RGO-CoNi-LDH fiber electrodes).
Gained RGO nanotubes and RGO-CoNi-LDH fiber electrodes are detected according to the method in embodiment 1, gained
As a result similar with embodiment 1.
Embodiment 5
RGO nanotubes that embodiment 1 obtains is molten in the colloid for being mixed with activated carbon (AC), acetylene black and polyvinylidene fluoride
(mass ratio of activated carbon (AC), acetylene black and polyvinylidene fluoride is 80 in liquid:10:10) dip-coating 5min continues to soak after dry
It applies, is repeated 4 times, obtains reduced graphene-Activated Carbon Fiber Electrodes (RGO-AC fiber electrodes)；Obtained electrode is sealed and is protected
It deposits.
KOH, polyvinyl alcohol are dissolved in deionized water, are heated to 90 DEG C, obtains PVA/KOH colloidal solution, controls glue
The mass concentration of polyvinyl alcohol is 0.1g/mL, a concentration of 1mol/L of KOH in liquid solution；
RGO-CoNi-LDH fiber electrodes prepared by embodiment 1 and RGO-AC fiber electrodes manufactured in the present embodiment immerse
5min in PVA/KOH colloidal solution then takes out the vacuum drying 5min at 60 DEG C, obtains positive electrode and negative electrode；It then will just
Electrode is parallel with negative electrode to be fixed in transparent flexible polypropylene substrate, and electrode effective length is 2cm, is covered on positive and negative electrode surface
PVA/KOH colloidal solution is covered, then vacuum drying for 24 hours, obtains ultracapacitor (all solid state super electricity of flexible fiber shape at 60 DEG C
Container).
Embodiment 6
RGO nanotubes that embodiment 2 obtains is molten in the colloid for being mixed with activated carbon (AC), acetylene black and polyvinylidene fluoride
(mass ratio of activated carbon (AC), acetylene black and polyvinylidene fluoride is 80 in liquid:10:10) dip-coating 5min continues to soak after dry
It applies, is repeated 3 times, obtains reduced graphene-Activated Carbon Fiber Electrodes (RGO-AC fiber electrodes)；Obtained electrode is sealed and is protected
It deposits.
KOH, polyvinyl alcohol are dissolved in deionized water, are heated to 80 DEG C, obtains PVA/KOH colloidal solution, controls glue
The mass concentration of polyvinyl alcohol is 0.05g/mL, a concentration of 0.5mol/L of KOH in liquid solution；
RGO-CoNi-LDH fiber electrodes prepared by embodiment 2 and RGO-AC fiber electrodes manufactured in the present embodiment immerse
10min in PVA/KOH colloidal solution then takes out the vacuum drying 10min at 60 DEG C, obtains positive electrode and negative electrode；Then will
Positive electrode is parallel with negative electrode to be fixed in transparent flexible polypropylene substrate, and electrode effective length is 3cm, on positive and negative electrode surface
PVA/KOH colloidal solution is covered, 18h is then dried in vacuo at 60 DEG C, obtaining ultracapacitor, (flexible fiber shape is all solid state super
Capacitor).
Embodiment 7
RGO nanotubes that embodiment 3 obtains is molten in the colloid for being mixed with activated carbon (AC), acetylene black and polyvinylidene fluoride
(mass ratio of activated carbon (AC), acetylene black and polyvinylidene fluoride is 80 in liquid:10:10) dip-coating 5min continues to soak after dry
It applies, is repeated 4 times, obtains reduced graphene-Activated Carbon Fiber Electrodes (RGO-AC fiber electrodes)；Obtained electrode is sealed and is protected
It deposits.
KOH, polyvinyl alcohol are dissolved in deionized water, are heated to 80 DEG C, obtains PVA/KOH colloidal solution, controls glue
The mass concentration of polyvinyl alcohol is 0.08g/mL, a concentration of 0.8mol/L of KOH in liquid solution；
RGO-CoNi-LDH fiber electrodes prepared by embodiment 3 and RGO-AC fiber electrodes manufactured in the present embodiment immerse
8min in PVA/KOH colloidal solution then takes out the vacuum drying 8min at 60 DEG C, obtains positive electrode and negative electrode；It then will just
Electrode is parallel with negative electrode to be fixed in transparent flexible polypropylene substrate, and electrode effective length is 3cm, is covered on positive and negative electrode surface
PVA/KOH colloidal solution is covered, 18h is then dried in vacuo at 60 DEG C, obtains ultracapacitor (all solid state super electricity of flexible fiber shape
Container).
Embodiment 8
RGO nanotubes that embodiment 4 obtains is molten in the colloid for being mixed with activated carbon (AC), acetylene black and polyvinylidene fluoride
(mass ratio of activated carbon (AC), acetylene black and polyvinylidene fluoride is 80 in liquid:10:10) dip-coating 5min continues to soak after dry
It applies, is repeated 4 times, obtains reduced graphene-Activated Carbon Fiber Electrodes (RGO-AC fiber electrodes)；Obtained electrode is sealed and is protected
It deposits.
KOH, polyvinyl alcohol are dissolved in deionized water, are heated to 80 DEG C, obtains PVA/KOH colloidal solution, controls glue
The mass concentration of polyvinyl alcohol is 0.1g/mL, a concentration of 0.1mol/L of KOH in liquid solution；
RGO-CoNi-LDH fiber electrodes prepared by embodiment 4 and RGO-AC fiber electrodes manufactured in the present embodiment immerse
10min in PVA/KOH colloidal solution then takes out the vacuum drying 8min at 60 DEG C, obtains positive electrode and negative electrode；It then will just
Electrode is parallel with negative electrode to be fixed in transparent flexible polypropylene substrate, and electrode effective length is 4cm, is covered on positive and negative electrode surface
PVA/KOH colloidal solution is covered, then vacuum drying for 24 hours, obtains ultracapacitor (all solid state super electricity of flexible fiber shape at 60 DEG C
Container).
The ultracapacitor obtained to embodiment 5~8 test loop volt-ampere curve, test condition under three electrodes are：It sweeps
Retouch rate：20 mv s, electrolyte are the KOH solution of 1mol/L, and pt electrodes are to electrode, and calomel electrode is reference electrode；Institute
The results are shown in Figure 5；According to Fig. 5 as can be seen that the ultracapacitor that embodiment 5~8 obtains has good capacitive property,
The capacitive property for the ultracapacitor (electrodeposition time 50s) that wherein embodiment 5 obtains is best.
To embodiment 5 prepare ultracapacitor under different scanning rates test loop volt-ampere curve, test condition be：
RGO-CoNi-LDH fiber electrodes connect anode, and RGO-AC fiber electrodes connect cathode, with two electrode systems in CHI 660E electrochemistry
It is tested on work station；Acquired results as shown in fig. 6, be followed successively by from top to bottom in Fig. 6 sweep speed be 20mV/s, 40mV/s,
60mV/s、80mV/s、100mV/s；According to Fig. 6 as can be seen that redox peaks occurs in curve, illustrate the super capacitor utensil
There is good capacitive property.
Constant current charge-discharge test is carried out to ultracapacitor prepared by embodiment 5, test current density is 0.25mA cm-2；
Gained constant current charge-discharge curve is as shown in Figure 7；The specific capacitance that ultracapacitor can be obtained according to the curve in Fig. 7 is 177.9mF
cm-2, energy density is 8.89 μ Wh cm-2。
The cyclic voltammetry curve for the ultracapacitor that under differently curved degree prepared by testing example 5, test condition are：
Current density 4mA cm-2；Acquired results are bent as shown in figure 8, the cyclic voltammetry curve that wherein curve 1 is bending degree when being 0 °
The cyclic voltammetry curve that line 2 is bending degree when being 180 °.According to Fig. 8 as can be seen that under differently curved degree, cyclic voltammetric
Curve does not change substantially, illustrates that ultracapacitor provided by the invention has good flexibility.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of transition metal hydrotalcite-reduced graphene nanotube fibers electrode material, including reduced graphene nanotube and
It is supported on the transition metal hydrotalcite nano lamella of the reduced graphene nanotube surface；
The reduced graphene nanotube is hollow tubular structure；The constituent of the reduced graphene nanotube includes reduction
Graphene and conducting polymer.
2. electrode material according to claim 1, which is characterized in that the pipe thickness of the reduced graphene nanotube is
5~11 μm；The outer diameter of the reduced graphene nanotube is 60~100 μm.
3. electrode material according to claim 1, which is characterized in that the thickness of the transition metal hydrotalcite nano lamella
For 5~20nm；The grain size of transition metal hydrotalcite nano piece is 300~500nm in the transition metal hydrotalcite nano lamella.
4. according to the electrode material described in claims 1 to 3 any one, which is characterized in that the reduced graphene nanotube
Mass ratio with transition metal hydrotalcite nano lamella is 10~20:1.
5. the preparation method of electrode material, includes the following steps described in Claims 1 to 4 any one：
Transition metal hydrotalcite nano lamella is grown in reduced graphene nanotube surface, obtains transition metal hydrotalcite-reduction
Graphene nano pipe fiber electrode material；The constituent of the reduced graphene nanotube includes that reduced graphene and conduction are poly-
Close object；
The method of the growth transition metal hydrotalcite nano lamella includes hydrothermal deposition method and electrochemical deposition method.
6. the preparation method of electrode material according to claim 5, which is characterized in that the growth transition metal hydrotalcite
The method of nanoscale twins is electrochemical deposition method, is included the following steps：
Using reduced graphene nanotube as working electrode, with to electrode and reference electrode immerse in transition metal mixed salt solution into
Row electrochemical deposition obtains transition metal hydrotalcite-reduced graphene nanotube fibers electrode material；
The transition metal mixed salt solution includes two kinds of transition metal ions；
The transition metal mixed salt solution is the mixed solution or transition metal nitrate of transition metal nitrate and transition gold
Belong to the mixed solution of hydrochloride.
7. the preparation method of electrode material according to claim 6, which is characterized in that the transition metal mixed salt solution
In the concentration of two kinds of transition metal ions be independently 0.1~0.2mol/L.
8. the preparation method described according to claim 6 or 7, which is characterized in that the electrochemical deposition deposits for constant voltage；Institute
The voltage for stating electrochemical deposition is -0.9~-1.1V；The time of the electrochemical deposition is 5~100s.
9. a kind of ultracapacitor, including substrate, anode, cathode and electrolyte, which is characterized in that the ultracapacitor is just
Pole material is transition metal hydrotalcite-reduced graphene nanotube fibers electrode material described in Claims 1 to 4 any one
Or transition metal hydrotalcite-reduced graphene nanotube fibers electricity prepared by preparation method described in claim 5~8 any one
Pole material.
10. ultracapacitor according to claim 9, which is characterized in that the negative material of the ultracapacitor is also
Former graphene nano pipe-active carbon combined electrode；The substrate of the ultracapacitor is flexible substrates；The ultracapacitor
Electrolyte is polyvinyl alcohol/potassium hydroxide gel all solid state electrolyte.
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