CN110415988A - AAO template is the graphene quantum dot nanotube GO/YCoO of bracket3The preparation of nano-array electrode material - Google Patents
AAO template is the graphene quantum dot nanotube GO/YCoO of bracket3The preparation of nano-array electrode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 141
- 239000002096 quantum dot Substances 0.000 title claims abstract description 116
- 239000002071 nanotube Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000007772 electrode material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 89
- 239000002243 precursor Substances 0.000 claims abstract description 60
- 238000004528 spin coating Methods 0.000 claims abstract description 46
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 31
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 22
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000000502 dialysis Methods 0.000 claims abstract description 9
- 238000007743 anodising Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 39
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 33
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 19
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- 239000002270 dispersing agent Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
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- 239000000047 product Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
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- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
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- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- 241000208340 Araliaceae Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
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- 239000003990 capacitor Substances 0.000 description 24
- 229910044991 metal oxide Inorganic materials 0.000 description 15
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- 230000005621 ferroelectricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- 230000033116 oxidation-reduction process Effects 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- 238000011105 stabilization Methods 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- VYQRBKCKQCRYEE-UHFFFAOYSA-N ctk1a7239 Chemical compound C12=CC=CC=C2N2CC=CC3=NC=CC1=C32 VYQRBKCKQCRYEE-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
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- 230000005291 magnetic effect Effects 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
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- 238000012163 sequencing technique Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- 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
- H01G11/30—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
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
AAO template is the graphene quantum dot nanotube GO/YCoO of bracket3The preparation of nano-array electrode material, includes the following steps；Step (1) the nanometer porous array AAO template controllable using two step anodizings preparation aperture；Step (2) electrochemical stripping method etching removing Staudenmaier legal system obtains graphene GO nanometer sheet；The filtered filtrate dialysis treatment of film, which is filtered, with polytetrafluoroethylene (PTFE) obtains graphene GO quantum dot solution；Step (3) deposits graphene GO quantum dot using electrochemical deposition method in the duct of AAO template, forms AAO/GO quantum dot nano pipe array；Step (4): YCoO is deposited in the AAO/GO quantum dot nano array tube that step (3) obtains with vacuum spin-coating method3Colloidal sol precursor array；The AAO/GO/YCoO that step (5) calcining step (4) obtains3Colloidal sol precursor is allowed to be converted into AAO/GO/YCoO3Nano-tube array, to form the nano-tube array AAO/GO/YCoO of coaxial heterogeneous structure3Electrode material.The characteristics of there is the present invention energy density can be improved, high comprehensive performance.
Description
Technical field
The present invention relates to nano material preparation and electrochemical energy storage technical field, in particular to AAO template be bracket stone
Black alkene quantum dot nano pipe GO/YCoO3The preparation of nano-array electrode material.
Background technique
The Optimalities such as there is alumilite process AAO film stabilization, high temperature resistant, good insulating, hole to be evenly distributed, hole density height
Can, and preparation process is simple, applied widely to the material for preparing product, can prepare many different materials, no using it
With the material of the one-dimensional nano structure of pattern.It is template using porous type AAO, growing preparation nano material by confinement effect is
A kind of very convenient and fast approach of economical and effective, and uniform, neat nano-array can be grown using the template.Based on AAO
The electrode material that template prepares nano-array is widely used in terms of the electrode material preparation of supercapacitor.Wang etc.
Using porous anodic aluminium oxide as template, nickel hydroxide nano line has been synthesized using coordination precipitation-decomposition method.Nano wire is fabricated to
Electrode, in 6molL-1KOH electrolyte solution in, utilize its super electricity of cyclic voltammetric and constant current charge-discharge technical research
Container performance, the nano line electrode have good electrochemical capacitance performance, when current density is 5mA cm–2When, single electrode specific volume
The maximum value of amount has reached 833Fg–1.Chen etc. is using chemical deposition and 500 DEG C of heat-treating methods in porous aluminas AAO mould
Electrode material for super capacitor γ-MnO has successfully been synthesized in plate2Nanotube.Electrochemical specific capacity is up to 566Fg–1, circulation
Electrochemical specific capacity is able to maintain 90% or more after 1000 times.
Take AAO template can to the pattern of electrode material carry out controllable preparation, increase electrode specific surface area make electrode with
Electrolyte comes into full contact with, and can preferably excavate potentiality of the material prepared as electrode.
Graphene GO is the New Two Dimensional atomic crystal being made of carbon atom with the monoatomic layer that sp2 hydridization connects, and is mesh
Preceding most thin two-dimensional material；For graphene as new carbon, physical structure stabilization, large specific surface area, electric conductivity are good, tool
There are excellent physical and chemical properties, all shows potential answer in the fields such as chemistry and energy and material, microelectronics, information, physics
Use prospect.GO is modified using other conductive materials or the compound GO based composites that obtain have become electrode of super capacitor
The hot spot of investigation of materials.Graphene GO has 2630m2.g-1Big specific surface area, excellent ionic conductivity and carrier transport
Ability (electron mobility 2 × 105cm2.V-1s-1), enable it with the obvious advantage in terms of energy storage, this is also that GO graphene can be used for surpassing
The reason of grade capacitor.
Quasi-zero dimension graphene GO CdS quantum dots, since the movement of its electronics in all directions is all restricted,
Quantum dot local effect is significant, thus has unique physics, chemical property.Graphene quantum dot and conventional semiconductors quantum dot
It compares, the resistance to strong acid of graphene quantum dot, highly basic and photoetch, stable structure；Adjustable band gap width；Easily realize function of surface
Change；Thickness can thin to the one monatomic, characteristics such as chemical stability is good, be with the environment-friendly type amount without high toxicity metallic element
Son point material.Graphene quantum dot preparation is broadly divided into enlargement method and top-down diminution method from bottom to top.Graphene GO
Quantum dot reduces method technology of preparing and is related to hydro-thermal method, stripping method, strong acid oxidizing process, solvent-thermal method, electrochemical process, electron beam spoke
According to, Ozone, hydrogen method, gas thermal method, magnetron sputtering technique, 11 kinds of methods such as irradiation.Stripping method and hydro-thermal method are graphene amounts
The major technique of son point diminution method technology of preparing.The technologies such as electrochemical process, strong acid oxidizing process, solvent-thermal method are also developed.
Graphene-metal oxide composite material is as electrode material for super capacitor, high intrinsic of one side graphene
Conductivity provides quick transmission channel for electronics, greatly improves the charge-discharge velocity of material；Another aspect metal oxide electricity
Pole has good ionic conductivity since its oxidation and reduction reaction are reversible on chemistry and structure；Metal oxide
It is easier to carry out electronics in hydrous oxide lattice structure and proton moves jump, so as to cause the insertion and extraction of proton, pass through oxygen
Change reduction reaction and provides higher capacitance for electrode.Therefore, metal oxide electrode can cause fake capacitance reversible process and
The electrode reaction can be made to be deep into electrode interior, energy is stored in three-dimensional space, improve specific energy.In addition, by metal oxygen
Compound and the compound reunion that can effectively avoid graphene of graphene, to improve effective contact surface of electrolyte and electrode material
Product, and then improve the capacitive property of material.The metal oxide compound with graphene mainly has RuO at present2、MnO2、Co3O4、
NiO etc..
ABO3Perovskite material is because its unique ferroelectricity, piezoelectricity, magnetics, charge transport quality make it in fuel cell, urges
Agent, high-temperature superconductor etc., which have, to be widely applied.The perovskite nanotube studied at present is also only with titanate nanotube system
It is classified as master, also mainly investigates ferroelectricity and electromagnetic performance and photocatalysis performance in aspect of performance, and is studied about electrochemical energy storage
Report it is also less.The research of perovskite nano-tube array is still in initial stage, wherein the research of cobaltatess nano-tube array
Less and YCoO3The research of nano-tube array is then less, this makes its more difficult formation receive due to the particularity of perovskite crystal structure
Mitron.In view of the arrays such as metal oxide nanotubes, carbon nanotube, nonmetal oxide nanotube absorption, catalyst carrier,
Gas sensitive etc. all shows excellent performance, if that some perovskite YCoO with superperformance3System
Perhaps its chemical property can be improved at nano-tube array and obtains completely newly answering in terms of electrode material for super capacitor energy storage
With.Preparing nano-tube array method (hard template method, soft template method and hydrothermal synthesis method etc.) at present, there are no be applied to perovskite
YCoO3In the preparation of nano-tube array.In conclusion present invention determine that a kind of electrode material for super capacitor AAO/GO/YCoO3
The preparation method of nano-array pipe.
Summary of the invention
The purpose of the present invention is to provide the graphene quantum dot nanotube GO/YCoO that AAO template is bracket3Nano-array
The preparation of electrode material, by changing the structure of electrode material and utilizing GO/YCoO3Synergistic effect so that final products
Energy density can be improved, high comprehensive performance.To achieve the goals above, the technical solution adopted by the present invention is that:
AAO template is the graphene quantum dot nanotube GO/YCoO of bracket3The preparation of nano-array electrode material, including
Following steps；
Step (1):
Using the controllable nanometer porous array AAO template in two step anodizings preparation aperture, pore diameter range 30nm-
100nm；
Step (2):
Removing graphene GO nanometer sheet as made from Staudenmaier method is etched with electrochemical process；It is taken out with polytetrafluoroethylene (PTFE)
Filtrate after membrane filtration, dialysis treatment obtain graphene GO quantum dot solution, and filtrate is the phosphoric acid containing graphene GO quantum dot
Salt buffer；
Step (3):
Graphene GO quantum dot is deposited in the duct of AAO template using electrochemical deposition method, forms AAO/GO quantum dot
Nano-tube array；
Step (4):
YCoO is deposited in the AAO/GO quantum dot nano array tube that step (3) obtains with vacuum spin-coating method3Body before colloidal sol
Volume array；
Step (5):
The AAO/GO/YCoO that calcining step (4) obtains3Colloidal sol precursor is allowed to be converted into AAO/GO/YCoO3Nanotube battle array
Column, to form the nano-tube array AAO/GO/YCoO of coaxial heterogeneous structure3Electrode material.
Use phosphoric acid salt electrolyte by after graphene GO nanometer sheet electrochemical etching poly- four in step (2) step (3)
Vinyl fluoride filtering, filtrate dialysis treatment obtains graphene GO quantum dot solution, then GO quantum dot is electrochemically-deposited in AAO template and is received
In metre hole road.
YCoO in step (4) step (5)3Nanotube deposition key step in AAO/GO quantum dot nano pipe
Are as follows: (1) YCoO3The preparation of colloidal sol precursor；(2) vacuum spin-coating method deposits YCoO in AAO/GO quantum dot nano pipe3Before colloidal sol
Body；(3) AAO/GO/YCoO is calcined3Colloidal sol precursor is allowed to be converted into coaxial heterogeneous structure AAO/GO/YCoO3Nanotube battle array
Column.
Described (1) YCoO3The preparation of colloidal sol precursor:
By molar ratio be 1:1 Co salt and Y salt dissolution in deionized water, stirring be allowed to clarify, then and (0.4-
0.6M) citric acid mixes, Co salt: Y salt: the molar ratio of citric acid is 1:1:2,30-60min is stirred at 60-90 DEG C to uniform,
Ammonium hydroxide is slowly added dropwise to adjust the pH value of solution between 6~7, solution will be stirred continuously in the process, so that its mixing is equal
Even, when the pH value of solution is transferred to 6~7, faint electropositive is presented in sol particles, and negative electricity is presented in AAO/GO template inner wall
Property.
(2) vacuum spin-coating method in AAO/GO quantum dot nano pipe deposits YCoO3Colloidal sol precursor:
To YCoO obtained in (1)3Dispersing agent is added in colloidal sol precursor, sonic oscillation disperses YCoO3Colloidal sol precursor,
Dispersing agent and YCoO3Mass ratio be 8-12:1, AAO/GO quantum dot nano pipe array is placed in closed container, interior pressure
For 0.01-0.05MPa, guarantee the vacuum degree of closed container, YCoO is added dropwise to AAO template face3Colloidal sol precursor, ultrasonic immersing
10-30min, the then first low speed 200-400r/min spin coating 10-30s in whirler, then 2500-3500r/min high speed
Spin coating 60s, the dry 10-30min at 80 DEG C -150 DEG C of drying box, ultrasound is impregnated, vacuum spin coating can effectively improve AAO/GO amount
YCoO in son point nanotube3The compactedness of colloidal sol precursor prepares the nano-tube array of high-sequential, repeats above-mentioned ultrasound leaching
Stain, the spin coating of spin coating vacuum and vacuum drying process 2-6 times, YCoO3Colloidal sol precursor is deposited on AAO/GO quantum dot nano pipe
Wall.
The dispersing agent can be one or more of mixing of ethyl cellulose, lauryl sodium sulfate or methyl anyl alcohol.
(3) coaxial heterogeneous structure AAO/GO/YCoO3The formation of nanometer pipe array electrode material:
By the AAO/GO/YCoO after vacuum drying in (2)3Colloidal sol precursor is first risen in Muffle furnace with low heating rate
300-500 DEG C of pretreatment 4h, reaction that citric acid organic matter burns at 300 DEG C and nitrate is decomposed at 400 DEG C or so, then at
900-1000 DEG C of calcining 48-96h, goes cooled to room temperature after moisture removal and dispersing agent.
In the whole process, AAO/GO quantum dot nano pipe die plate is as a minitype channel, YCoO3Colloidal sol precursor is received
Mitron forming core, growth in GO quantum dot nano pipe, are converted into heterojunction structure AAO/GO/YCoO under calcining heat treatment3Nanotube
Array.
YCoO3Precursor colloidal sol forms YCoO3The key reaction that nano-tube array occurs has:
Beneficial effects of the present invention:
The present invention forms nano-array by sequencing described in step (3), (4), (5), ultimately forms AAO/GO/
YCoO3The nanometer pipe array electrode material of coaxial heterogeneous structure, plays YCoO to the maximum extent3With the association of GO quantum dot nano pipe
Same-action improves the compatibility of the volume change of electrode.
Coaxial heterogeneous structure AAO/GO/YCoO prepared by the present invention3Stone can be preferably thinned in nanometer pipe array electrode structure
The thickness of black alkene effectively prevent the reunion of graphene oxide, realizes the removing of graphene oxide；AAO/GO/YCoO3Coaxial heterogeneous
Nano-tube array structure can form the parallel connection of capacitor back-to-back, further improve the capacitive property of electrode material；This structure
Big specific surface area, AAO/GO/YCoO3The energy that the good contact and synergistic effect of storeroom help to improve capacitor is close
Degree.
The ABO of nanostructure in the present invention3Perovskite type metal oxide array deposition is in graphene GO quantum dot nano
Pipe surface, the structure and mechanical property of graphene GO quantum dot nano pipe limit nanostructure ABO in oxidation-reduction process3Calcium
The mechanically deform of titanium ore type metal oxide, avoids the destruction of electrode material, obtains better stability.In addition, deposition
Graphene GO quantum nanoparticles pipe array has stress relaxation, and it is broken to reduce capacitor material structure during charging and discharging
It is bad.
The present invention has played the compatibility of the excellent electric conductivity and volume of graphene GO quantum dot, be utilized vacuum spin coating with
And the multiple action of capillary force and solution static pressure effectively improves YCoO in dipping process3In the heavy of AAO/GO quantum dot nano pipe
Product rate and compactedness, the energy density of electrode material is improved in the case where not reducing power density and cycle life.Its
Performance indicator are as follows: specific capacity >=370F/g, energy density >=60Wh/kg, 1000 times circulation after capacity retention >=90%.
Detailed description of the invention
Fig. 1 is coaxial heterogeneous structure AAO/GO/YCoO3The XRD diagram of nano-tube nano array.
Fig. 2 is the YCoO deposited in AAO/GO nanotube3EDS spectrogram.
Fig. 3 is coaxial heterogeneous structure AAO/GO/YCoO3Nano-tube array CV curve.
Fig. 4 is coaxial heterogeneous structure AAO/GO/YCoO3Nano-tube array GCD curve.
Specific embodiment
Graphene and metal oxide are compounded to form capacitor electrode material and have become a hot topic of research at present, but the number of plies compared with
Few graphene and the research that metal oxide nano array is compounded to form electrode material for super capacitor are few.And electrode material
Structure be the key that influence capacitor performance.Therefore the present invention is considering the big specific surface area of nano material, dimensional effect, stone
The excellent electric conductivity of black alkene, big volume compatibility and perovskite ABO3The objects such as the big specific capacitance of nanostructured metal oxides
On the basis of Physicochemical performance, with AAO stencil design and graphene GO quantum dot nano pipe is prepared, then assisted with ultrasonic disperse
Vacuum spin-coating method deposits perovskite YCoO in graphene GO quantum dot nano pipe3Obtain coaxial heterogeneous structure AAO/GO/YCoO3
Nano-tube array combination electrode, the biggish YCoO of the compound specific capacitance of graphene quantum dot nanotube to conduct electricity very well3Metal oxygen
The excellent electrode material for super capacitor of compound nano-array forming properties solves the low key of super capacitor material energy densities
Technical problem develops the novel potential energy storage super capacitor that the existing high energy density of one kind has high power density again
The preparation method of electrode material used in device, to realize that energy density of new generation is bigger, graphene composite Nano of longer life expectancy
Metal oxide electrode material industrialization lays the foundation, and provides strong technical support for the promotion of relevant industries product, should
The electrode material of method preparation applies the economic benefit and social benefit for being expected to bring in supercapacitor.
The present invention is described in further detail below in conjunction with the accompanying drawings.
Symmetric form electric chemical super capacitor of the present invention coaxial heterogeneous nanometer pipe array electrode materials A AO/GO/YCoO3
Preparation method, the process that main technological steps include has:
(1) the nanometer porous array AAO template controllable using two step anodizings preparation aperture, pore diameter range 30nm-
100nm；(2) electrochemical stripping method etching removing Staudenmaier legal system obtains graphene GO nanometer sheet；It is taken out with polytetrafluoroethylene (PTFE)
Filtrate dialysis treatment after membrane filtration obtains graphene GO quantum dot solution；(3) electrochemical deposition method is in the duct of AAO template
Graphene GO quantum dot is deposited, AAO/GO quantum dot nano pipe array is formed；(4) it is received with vacuum spin-coating method in AAO/GO quantum dot
YCoO is deposited in rice array tube3Colloidal sol precursor array；(5) AAO/GO/YCoO is calcined3Colloidal sol precursor is allowed to be converted into AAO/
GO/YCoO3Nano-tube array, to form the nano-tube array AAO/GO/YCoO of coaxial heterogeneous structure3Electrode material.Coaxial variable
Matter structure AAO/GO/YCoO3The XRD diagram of nano-tube array is as shown in Figure 1.Fig. 1 is shown really can by above-mentioned processing step
Form AAO/GO/YCoO3Coaxial heterogeneous nano-tube array structure.In the preparation method, AAO pore size of template size influences
YCoO3The preparation of nanotube should guarantee to control YCoO while the large scale aperture of template as far as possible3The quality of sol particles.It is formed
Nano-tube array AAO/GO/YCoO3Sequence determine the coaxial heterogeneous structure for the nanometer pipe array electrode to be formed, and then influence it
Chemical property.
GO quantum dot is effectively inlaid into the formation GO quantum nanoparticles pipe array in AAO template with electrochemical process by the present invention.
Reduce between graphene sheet layer can there is a phenomenon where congestions to be superimposed, discrete graphene and the number of plies that graphene is thinned, In
The surface AAO forms electric double layer, and nano-array GO/AAO structure preferably prevents the reunion of graphene oxide, realizes graphene oxide
Removing, the thickness of graphene is thinned, the specific surface area of electrode increases and the transport capability of electronic and ionic improves, and specific capacitance increases
Greatly.
The present invention deposits YCoO in AAO/GO nano-tube array with vacuum spin-coating method3AAO/GO/YCoO is received in array, formation3
Coaxial heterogeneous nanometer pipe array electrode material.The YCoO deposited in AAO/GO nanotube3EDS spectrogram is as shown in Figure 2.Fig. 2 table
Bright YCoO3It is deposited in AAO/GO nano-tube array.YCoO3It is supported on graphene GO quantum dot nano pipe, further prevents
The reunion of graphene layer, YCoO3Nanotube is inserted between graphene layer, the conductive network of large area is constituted, in composite material
Inside forms electron propagation ducts, while AAO/GO/YCoO3Coaxial heterogeneous nanotube sandwich structure, can form back-to-back
The parallel connection of capacitor forms the heterojunction structure of the metal oxide of graphene GO quantum dot and nanostructure, plays the association of the two
Same effect realizes organic system of the Faraday effect effect of electrochemistry double-layer capacitor non-faraday effect and pseudocapacitors
One.The capacitive for improving electrode material improves the chemical property of coaxial heterogeneous nanometer pipe array electrode material.Coaxial heterogeneous
Structure AAO/GO/YCoO3Nano-tube array CV curve is as shown in Figure 3.AAO/GO/YCoO as can be seen from Figure 33CV curve surround
Area ratio AAO/GO and AAO the area that surrounds of CV curve it is all big, illustrate AAO/GO/YCoO3The specific capacitance of nano-tube array
It is all larger than the specific capacitance of AAO and AAO/GO.
Coaxial heterogeneous nano-tube array AAO/GO/YCoO of the invention3Electrode material excellent in stability.Nanostructure
YCoO3Array deposition limits in oxidation-reduction process in surface of graphene oxide, the structure and mechanical property of graphene oxide
Nanostructure YCoO3Mechanically deform, avoid the destruction of electrode material, obtain better stability.In addition, deposition graphite
The nano-array of alkene quantum dot has stress relaxation, reduces the structure destruction during capacitor material charging and discharging.Together
Axis heterojunction structure AAO/GO/YCoO3Nano-tube array GCD curve is as shown in Figure 4.Fig. 4 shows coaxial heterogeneous nano-tube array
AAO/GO/YCoO3Electrode material has excellent stability.
The present invention effectively avoids in traditional design graphene film relative to collector disordered orientation and lamination is made side by side
At ion and electron-transport difficulty weakness, make full use of good electric conductivity in graphene quantum dot pipe face, prepare same
Axis heterogeneous structural nano array AAO/GO/YCoO3Hollow edged electrode sandwich structure further plays graphene quantum dot same
High conduction performance in plane improves metal oxide capacitive.
The coaxial heterogeneous structure AAO/GO/YCoO that the present invention constructs3Nano-tube array electrode material for super capacitor energy
Density is high.The electrode material that the present invention constructs has played the compatibility of the excellent electric conductivity and volume of graphene GO quantum dot,
The multiple action that capillary force and solution static pressure in vacuum spin coating and dipping process is utilized effectively improves YCoO3In AAO/GO
The deposition rate and compactedness of quantum dot nano pipe, electrode material is improved in the case where not reducing power density and cycle life
The energy density of material.Its performance indicator are as follows: specific capacity >=370F/g, energy density >=60Wh/kg, 1000 times circulation after capacitor protect
Holdup >=90%
Coaxial heterogeneous nano-tube array AAO/GO/YCoO of the present invention3The main step of 4 for including in electrode material preparation process
Suddenly there is good universality.Equally applicable other anodic oxidation templates；Suitable for removing YCoO3Except other perovskite metals
Oxide；Suitable for other carbon materials (graphite, graphite alkene, carbon nanotube, carbon nanometer paper etc.) in addition to GO；Suitable for calcium titanium
The heterojunction structure of mine metal oxide and carbon material it is compound etc., there is good universality.
Embodiment 1:
Step (1):
Prepare the nano-array AAO template of the two-sided through-hole of aperture 30nm: alumilite process routinely prepares two-sided logical
The nano-array AAO template in hole comprising the pretreatment of aluminium sheet；Polishing treatment；Two step anodic oxidation processes；Reaming.
Step (2):
It forms the Staudenmaier method preparation of graphene used in GO quantum dot nano pipe array: 5g graphite is added
In 500mL round-bottomed flask, 45mL concentrated nitric acid and the 87.5mL concentrated sulfuric acid are added under the conditions of ice-water bath, 55g potassium chlorate is added in batches,
120h is reacted at room temperature after ice-water bath 2h.After reaction, excessive distilled water is added, filters, is washed filter cake with hydrochloric acid and water
Wash neutrality.It is dried in vacuo at 60 DEG C.The graphene heat-treated at 950 DEG C in Muffle furnace is Staudenmaier method
GO.The GO of Staudenmaier method preparation is ready for use on electrochemical stripping and forms GO quantum dot.
The preparation of graphene GO quantum dot:
(1) pretreatment Staudenmaier method first prepares graphene GO: using the GO of preparation as anode and cathode, in concentration
It is electrolysed for D.C. regulated power supply constant potential 5V in the aqueous sulfuric acid of 0.05 mol/L, electrolysis time 0.5h, sulfate ion ruler
Very little spacing between being greater than graphene layer, effectively can carry out intercalation and separation to graphene GO, make the graphene on anode and cathode surface
Expansion.Secondly, oxygen evolution potential 1.25V potentiostatic deposition hydrone generates hydroxyl and oxygen radical, chemistry cuts cutting graphite alkene,
Generate oxygen-containing functional group.
(2) pretreating graphite alkene GO film directly as working electrode, platinum filament is used as to electrode, and Ag/AgCl electrode is made
For reference electrode, phosphate buffer solution (PH=6.8) is used as electrolyte.Cyclic voltammetry scan, electricity are carried out to graphene film
Press-3-3V of range, sweep speed 0.2Vs-1.With the increase of scanning circle number, graphene film is constantly etched, graphene GO amount
Son point constantly generates in the electrolytic solution.
(3) residue in film removal solution is filtered using the polytetrafluoroethylene (PTFE) of aperture 30nm.It is residual in solution by removing
The filtrate of object room temperature dialysis 48h in the bag filter that molecular cut off is 2000Da is stayed, graphene quantum dot dispersion is obtained.
Step (3):
It is prepared by the electrochemical process of graphene GO quantum dot nano pipe array:
AAO template one side is gold-plated, and as working electrode, platinum filament is used as to electrode, and graphene GO quantum dot solution is made
For electro-deposition electrolyte.The positive voltage of application 3V in gold-plated AAO template, continuous deposition 3 hours.As work electricity
Pole, platinum filament are used as to electrode, and graphene GO quantum dot solution is as electro-deposition electrolyte.Apply 3V in gold-plated AAO template
Positive voltage, continuous deposition 3 hours.At -70 DEG C, it is freeze-dried under vacuum degree 4Pa for 24 hours, ice crystal in freezing dry process
Form driving graphene oxide layer curling, in freeze-drying process graphene oxide layer a part in ice another part outside ice
Cause non-uniform stress that lamella is caused to crimp.Surface is rinsed with deionized water, then 150 DEG C of annealing 3h, in this way in AAO template
In obtained AAO/GO graphene quantum dot nano-tube array.AAO/GO graphene quantum dot nano-tube array after freezing shows
Preferable structural stability, higher specific surface area, are conducive to improve its specific capacitance.
Step (4):
YCoO is deposited in vacuum spin-coating method AAO/GO/ template3Nano-array
(1)YCoO3The preparation of colloidal sol precursor
0.2M Y(NO3)3With 0.2MCo (NO3)2Dissolution in deionized water, stirring be allowed to clarify.Then by they and
The mixing of 0.4M citric acid, is stirred until homogeneous at 90 DEG C.Ammonium hydroxide is slowly added dropwise to adjust the pH value of solution between 6~7, herein
In the process, solution will be stirred continuously, so that it is uniformly mixed.When the pH value of solution is transferred between 6~7, sol particles are in
Existing faint electropositive, and elecrtonegativity is presented in the inner wall of AAO template.Therefore, generated between sol particles and the inner wall of AAO template
Electrostatic interaction, as a result colloidal sol ion enters and is attracted to the inner wall of template, is conducive to sol particles by concentration and reacts first quilt
It is converted into gelular ion, then forms nanotube.
(2) vacuum spin-coating method deposits YCoO in AAO/GO quantum dot nano pipe3Colloidal sol precursor:
To improve YCoO3The mobility of colloidal sol precursor, to YCoO3Dispersing agent, sonic oscillation point are added in colloidal sol precursor
Dissipate YCoO3Colloidal sol precursor, dispersing agent and YCoO3Mass ratio be 8:1.The dispersing agent of addition can be ethyl cellulose, dodecane
One or more of mixing of base sodium sulphate or methyl anyl alcohol.AAO/GO quantum dot nano pipe array is placed in closed container,
Interior pressure is 0.01MPa, guarantees the vacuum degree of closed container.YCoO is added dropwise to AAO template face3Colloidal sol precursor, ultrasonic immersing
30min, the then first low speed 400r/min spin coating 10s in whirler, then 2500r/min high speed spin coating 60s, in drying box
Dry 30min at 80 DEG C.Ultrasound is impregnated, vacuum spin coating can effectively improve YCoO in AAO/GO quantum dot nano pipe3Body before colloidal sol
The compactedness of body prepares the nano-tube array of high-sequential.Repeat above-mentioned ultrasonic immersing, the spin coating of spin coating vacuum and vacuum drying
Process 2 times.YCoO3Colloidal sol precursor is deposited on AAO/GO quantum dot nano tube wall.
Step (5):
(3) coaxial heterogeneous structure AAO/GO/YCoO3The formation of nanometer pipe array electrode material.
By the AAO/GO/YCoO after vacuum drying3Colloidal sol precursor first rises to 300 DEG C in Muffle furnace with low heating rate
4h is pre-processed, because of citric acid organic matter in 300 DEG C of burnings and nitrate is decomposed reaction in 400 DEG C or so, is forged then at 900 DEG C
Burn 96h, remove moisture removal and ethyl alcohol cooled to room temperature, in the whole process, AAO/GO template as a minitype channel,
YCoO3Colloidal sol precursor nanotube is formed in this channel, is grown, and nested type AAO/GO/YCoO is converted under calcining3Nanometer
Pipe array.Pass through vacuum spin coating YCoO3Precursor colloidal sol forms YCoO3The key reaction that nano-tube array occurs has:
Building is with coaxial heterogeneous structure AAO/GO/YCoO3Nano-tube array is the supercapacitor of electrode material.
With AAO/GO/YCoO3Nano-array is capacitor symmetry electrode, 1M NaSO4For electrolyte, polytetrafluoroethylene (PTFE) be every
Film is assembled into symmetric form supercapacitor.With AAO/GO/YCoO3Nano-array is working electrode, platinum electrode is to electrode, calomel
Electrode SCE makees reference electrode and constitutes three-electrode system.Nested type AAO/GO/ is tested using occasion China CHI660E electrochemical workstation
YCoO3 nano-array is the chemical property of electrode material.
Embodiment 2
Step (1): the nano-array AAO template of the preparation two-sided through-hole of aperture 100nm, implementation steps are the same as embodiment 1.
Step (2): the preparation method Staudenmaier of graphene used in GO quantum dot nano pipe array is formed with implementation
Example 1
The preparation of graphene GO quantum dot:
(1) pretreatment Staudenmaier method first prepares graphene GO: using the GO of preparation as anode and cathode, in concentration
It is electrolysed for D.C. regulated power supply constant potential 18V in the aqueous sulfuric acid of 0.8 mol/L, electrolysis time 4h, sulfate ion size
Greater than spacing between graphene layer, intercalation and separation effectively can be carried out to graphene GO, keep the graphene on anode and cathode surface swollen
It is swollen.Secondly, oxygen evolution potential 1.5V potentiostatic deposition hydrone generates hydroxyl and oxygen radical, chemistry cuts cutting graphite alkene, produces
Raw oxygen-containing functional group.
(2) pretreating graphite alkene GO film directly as working electrode, platinum filament is used as to electrode, and Ag/AgCl electrode is made
For reference electrode, phosphate buffer solution (PH=6.8) is used as electrolyte.Cyclic voltammetry scan, electricity are carried out to graphene film
Press-3-3V of range, sweep speed 0.5Vs-1.With the increase of scanning circle number, graphene film is constantly etched, graphene GO amount
Son point constantly generates in the electrolytic solution.
(3) residue in film removal solution is filtered using the polytetrafluoroethylene (PTFE) of aperture 100nm.It is residual in solution by removing
The filtrate of object room temperature dialysis 72h in the bag filter that molecular cut off is 12000Da is stayed, graphene quantum dot dispersion is obtained.
Step (3):
It is prepared by the electrochemical process of graphene GO quantum dot nano pipe array:
AAO template one side is gold-plated, and as working electrode, platinum filament is used as to electrode, and graphene GO quantum dot solution is made
For electro-deposition electrolyte.The positive voltage of application 6V in gold-plated AAO template, continuous deposition 5 hours.As work electricity
Pole, platinum filament are used as to electrode, and graphene GO quantum dot solution is as electro-deposition electrolyte.Apply 6V in gold-plated AAO template
Positive voltage, continuous deposition 5 hours.At -70 DEG C, 48h is freeze-dried under vacuum degree 4Pa, ice crystal in freezing dry process
Form driving graphene oxide layer curling, in freeze-drying process graphene oxide layer a part in ice another part outside ice
Cause non-uniform stress that lamella is caused to crimp.Surface is rinsed with deionized water, then 150 DEG C of annealing 3h, in this way in AAO template
In obtained AAO/GO graphene quantum dot nano-tube array.AAO/GO graphene quantum dot nano-tube array after freezing shows
Preferable structural stability, higher specific surface area, are conducive to improve its specific capacitance.
Step (4):
YCoO is deposited in vacuum spin-coating method AAO/GO/ template3Nano-array
(1)YCoO3The preparation of colloidal sol precursor
0.3M Y(NO3)3With 0.3MCo (NO3)2Dissolution in deionized water, stirring be allowed to clarify.Then by they and
The mixing of 0.6M citric acid, is stirred until homogeneous at 90 DEG C.Ammonium hydroxide is slowly added dropwise to adjust the pH value of solution between 6~7, herein
In the process, solution will be stirred continuously, so that it is uniformly mixed.When the pH value of solution is transferred between 6~7, sol particles are in
Existing faint electropositive, and elecrtonegativity is presented in the inner wall of AAO template.Therefore, generated between sol particles and the inner wall of AAO template
Electrostatic interaction, as a result colloidal sol ion enters and is attracted to the inner wall of template, is conducive to sol particles by concentration and reacts first quilt
It is converted into gelular ion, then forms nanotube.
(2) vacuum spin-coating method deposits YCoO in AAO/GO quantum dot nano pipe3Colloidal sol precursor:
To improve YCoO3The mobility of colloidal sol precursor, to YCoO3Dispersing agent, sonic oscillation point are added in colloidal sol precursor
Dissipate YCoO3Colloidal sol precursor, dispersing agent and YCoO3Mass ratio be 12:1.The dispersing agent of addition can be ethyl cellulose, 12
One or more of mixing of sodium alkyl sulfate or methyl anyl alcohol.AAO/GO quantum dot nano pipe array is placed in closed container,
Its interior pressure is 0.05MPa, guarantees the vacuum degree of closed container.YCoO is added dropwise to AAO template face3Colloidal sol precursor, ultrasound leaching
Stain 30min, the then first low speed 200r/min spin coating 30s in whirler, then 3500r/min high speed spin coating 60s, in drying
Dry 10min at 150 DEG C of case.Ultrasound is impregnated, vacuum spin coating can effectively improve YCoO in AAO/GO quantum dot nano pipe3Before colloidal sol
The compactedness of body prepares the nano-tube array of high-sequential.It is dry to repeat above-mentioned ultrasonic immersing, the spin coating of spin coating vacuum and vacuum
Dry process 6 times.YCoO3Colloidal sol precursor is deposited on AAO/GO quantum dot nano tube wall.
Step (5):
(3) coaxial heterogeneous structure AAO/GO/YCoO3The formation of nanometer pipe array electrode material.
By the AAO/GO/YCoO after vacuum drying3Colloidal sol precursor first rises to 500 DEG C in Muffle furnace with low heating rate
4h is pre-processed, because of citric acid organic matter in 300 DEG C of burnings and nitrate is decomposed reaction in 400 DEG C or so, then at 1000 DEG C
Calcine 48h, remove moisture removal and ethyl alcohol cooled to room temperature, in the whole process, AAO/GO template as a minitype channel,
YCoO3Colloidal sol precursor nanotube is formed in this channel, is grown, and nested type AAO/GO/YCoO is converted under calcining3Nanometer
Pipe array.Pass through vacuum spin coating YCoO3Precursor colloidal sol forms YCoO3The key reaction that nano-tube array occurs has:
Building is with coaxial heterogeneous structure AAO/GO/YCoO3Nano-tube array is the supercapacitor of electrode material.
With AAO/GO/YCoO3Nano-array is capacitor symmetry electrode, 1M NaSO4For electrolyte, polytetrafluoroethylene (PTFE) be every
Film is assembled into symmetric form supercapacitor.It is to electrode, calomel by working electrode, platinum electrode of AAO/GO/YCoO3 nano-array
Electrode SCE makees reference electrode and constitutes three-electrode system.Nested type AAO/GO/ is tested using occasion China CHI660E electrochemical workstation
YCoO3 nano-array is the chemical property of electrode material.
Embodiment 3.
Step (1): the nano-array AAO template of the preparation two-sided through-hole of aperture 70nm, implementation steps are the same as embodiment 1.
Step (2): the preparation method Staudenmaier of graphene used in GO quantum dot nano pipe array is formed with implementation
Example 1
The preparation of graphene GO quantum dot:
(1) pretreatment Staudenmaier method first prepares graphene GO: using the GO of preparation as anode and cathode, in concentration
It is electrolysed for D.C. regulated power supply constant potential 10V in the aqueous sulfuric acid of 0.4 mol/L, electrolysis time 2h, sulfate ion size
Greater than spacing between graphene layer, intercalation and separation effectively can be carried out to graphene GO, keep the graphene on anode and cathode surface swollen
It is swollen.Secondly, oxygen evolution potential 1.35V potentiostatic deposition hydrone generates hydroxyl and oxygen radical, chemistry cuts cutting graphite alkene, produces
Raw oxygen-containing functional group.
(2) pretreating graphite alkene GO film directly as working electrode, platinum filament is used as to electrode, and Ag/AgCl electrode is made
For reference electrode, phosphate buffer solution (PH=6.8) is used as electrolyte.Cyclic voltammetry scan, electricity are carried out to graphene film
Press-3-3V of range, sweep speed 0.3Vs-1.With the increase of scanning circle number, graphene film is constantly etched, graphene GO amount
Son point constantly generates in the electrolytic solution.
(3) residue in film removal solution is filtered using the polytetrafluoroethylene (PTFE) of aperture 70nm.It is residual in solution by removing
The filtrate of object room temperature dialysis 60h in the bag filter that molecular cut off is 7000Da is stayed, graphene quantum dot dispersion is obtained.
Step (3):
It is prepared by the electrochemical process of graphene GO quantum dot nano pipe array:
AAO template one side is gold-plated, and as working electrode, platinum filament is used as to electrode, and graphene GO quantum dot solution is made
For electro-deposition electrolyte.The positive voltage of application 4V in gold-plated AAO template, continuous deposition 4 hours.As work electricity
Pole, platinum filament are used as to electrode, and graphene GO quantum dot solution is as electro-deposition electrolyte.Apply 4V in gold-plated AAO template
Positive voltage, continuous deposition 3 hours.At -70 DEG C, 36h is freeze-dried under vacuum degree 4Pa, ice crystal in freezing dry process
Form driving graphene oxide layer curling, in freeze-drying process graphene oxide layer a part in ice another part outside ice
Cause non-uniform stress that lamella is caused to crimp.Surface is rinsed with deionized water, then 150 DEG C of annealing 3h, in this way in AAO template
In obtained AAO/GO graphene quantum dot nano-tube array.AAO/GO graphene quantum dot nano-tube array after freezing shows
Preferable structural stability, higher specific surface area, are conducive to improve its specific capacitance.
Step (4):
YCoO is deposited in vacuum spin-coating method AAO/GO/ template3Nano-array
(1)YCoO3The preparation of colloidal sol precursor
0.25M Y(NO3)3With 0.25MCo (NO3)2Dissolution in deionized water, stirring be allowed to clarify.Then by they and
The mixing of 0.5M citric acid, is stirred until homogeneous at 90 DEG C.Ammonium hydroxide is slowly added dropwise to adjust the pH value of solution between 6~7, herein
In the process, solution will be stirred continuously, so that it is uniformly mixed.When the pH value of solution is transferred between 6~7, sol particles are in
Existing faint electropositive, and elecrtonegativity is presented in the inner wall of AAO template.Therefore, generated between sol particles and the inner wall of AAO template
Electrostatic interaction, as a result colloidal sol ion enters and is attracted to the inner wall of template, is conducive to sol particles by concentration and reacts first quilt
It is converted into gelular ion, then forms nanotube.
(2) vacuum spin-coating method deposits YCoO in AAO/GO quantum dot nano pipe3Colloidal sol precursor:
To improve YCoO3The mobility of colloidal sol precursor, to YCoO3Dispersing agent, sonic oscillation point are added in colloidal sol precursor
Dissipate YCoO3Colloidal sol precursor, dispersing agent and YCoO3Mass ratio be 10:1.The dispersing agent of addition can be ethyl cellulose, 12
One or more of mixing of sodium alkyl sulfate or methyl anyl alcohol.AAO/GO quantum dot nano pipe array is placed in closed container,
Its interior pressure is 0.03MPa, guarantees the vacuum degree of closed container.YCoO is added dropwise to AAO template face3Colloidal sol precursor, ultrasound leaching
Stain 30min, the then first low speed 300r/min spin coating 20s in whirler, then 3000r/min high speed spin coating 60s, in drying
Dry 20min at 110 DEG C of case.Ultrasound is impregnated, vacuum spin coating can effectively improve YCoO in AAO/GO quantum dot nano pipe3Before colloidal sol
The compactedness of body prepares the nano-tube array of high-sequential.It is dry to repeat above-mentioned ultrasonic immersing, the spin coating of spin coating vacuum and vacuum
Dry process 4 times.YCoO3Colloidal sol precursor is deposited on AAO/GO quantum dot nano tube wall.
Step (5):
(3) coaxial heterogeneous structure AAO/GO/YCoO3The formation of nanometer pipe array electrode material.
By the AAO/GO/YCoO after vacuum drying3Colloidal sol precursor first rises to 400 DEG C in Muffle furnace with low heating rate
4h is pre-processed, because of citric acid organic matter in 300 DEG C of burnings and nitrate is decomposed reaction in 400 DEG C or so, is forged then at 950 DEG C
Burn 72h, remove moisture removal and ethyl alcohol cooled to room temperature, in the whole process, AAO/GO template as a minitype channel,
YCoO3Colloidal sol precursor nanotube is formed in this channel, is grown, and nested type AAO/GO/YCoO is converted under calcining3Nanometer
Pipe array.Pass through vacuum spin coating YCoO3Precursor colloidal sol forms YCoO3The key reaction that nano-tube array occurs has:
Building is with coaxial heterogeneous structure AAO/GO/YCoO3Nano-tube array is the supercapacitor of electrode material.
With AAO/GO/YCoO3Nano-array is capacitor symmetry electrode, 1M NaSO4For electrolyte, polytetrafluoroethylene (PTFE) be every
Film is assembled into symmetric form supercapacitor.With AAO/GO/YCoO3Nano-array is working electrode, platinum electrode is to electrode, calomel
Electrode SCE makees reference electrode and constitutes three-electrode system.Nested type AAO/GO/ is tested using occasion China CHI660E electrochemical workstation
YCoO3Nano-array is the chemical property of electrode material.
Claims (8)
1.AAO template is the graphene quantum dot nanotube GO/YCoO of bracket3The preparation of nano-array electrode material, feature exist
In including the following steps；
Step (1):
Using the controllable nanometer porous array AAO template in two step anodizings preparation aperture；
Step (2):
Removing graphene GO nanometer sheet as made from Staudenmaier method is etched with electrochemical process；Film is filtered with polytetrafluoroethylene (PTFE)
Filtered filtrate dialysis treatment obtains graphene GO quantum dot solution；
Step (3):
Graphene GO quantum dot is deposited in the duct of AAO template using electrochemical deposition method, forms AAO/GO quantum dot nano
Pipe array；
Step (4):
YCoO is deposited in the AAO/GO quantum dot nano array tube that step (3) obtains with vacuum spin-coating method3Colloidal sol precursor battle array
Column；
Step (5):
The AAO/GO/YCoO that calcining step (4) obtains3Colloidal sol precursor is allowed to be converted into AAO/GO/YCoO3Nano-tube array, from
And form the nano-tube array AAO/GO/YCoO of coaxial heterogeneous structure3Electrode material.
2. the graphene quantum dot nanotube GO/YCoO that AAO template according to claim 1 is bracket3Nano-array electrode
The preparation of material, which is characterized in that with phosphoric acid salt electrolyte that graphene GO nanometer sheet is electric in step (2) step (3)
Teflon filtration after chemical etching, filtrate dialysis treatment obtain graphene GO quantum dot solution, then by GO quantum dot electrochemistry
It is deposited in AAO templating nanoparticles duct.
3. the graphene quantum dot nanotube GO/YCoO that AAO template according to claim 1 is bracket3Nano-array electrode
The preparation of material, which is characterized in that in the step (2):
It forms the Staudenmaier method preparation of graphene used in GO quantum dot nano pipe array: 500mL circle is added in 5g graphite
In the flask of bottom, 45mL concentrated nitric acid and the 87.5mL concentrated sulfuric acid are added under the conditions of ice-water bath, 55g potassium chlorate, ice-water bath are added in batches
120h is reacted after 2h at room temperature.After reaction, excessive distilled water is added, filter, with hydrochloric acid and water by Washing of Filter Cake in
Property, it being dried in vacuo at 60 DEG C, the graphene heat-treated at 950 DEG C in Muffle furnace is Staudenmaier method GO,
The GO of Staudenmaier method preparation is ready for use on electrochemical stripping and forms GO quantum dot；
The preparation of graphene GO quantum dot:
(1) pretreatment Staudenmaier method first prepares graphene GO: using the GO of preparation as anode and cathode, being in concentration
D.C. regulated power supply constant potential 5-18V is electrolysed in the aqueous sulfuric acid of 0.05-0.8 mol/L, electrolysis time 0.5-4h, sulfuric acid
Radical ion size is greater than spacing between graphene layer, effectively can carry out intercalation and separation to graphene GO, make anode and cathode surface
Expansion of graphene, secondly, oxygen evolution potential 1.25-1.5V potentiostatic deposition hydrone generates hydroxyl and oxygen radical, chemistry is cut out
Cutting graphite alkene is cut, oxygen-containing functional group is generated；
(2) pretreating graphite alkene GO film directly as working electrode, platinum filament is used as to electrode, and Ag/AgCl electrode is as ginseng
Than electrode, phosphate buffer solution (PH=6.8) is used as electrolyte, carries out cyclic voltammetry scan, voltage model to graphene film
Enclose-3-3V, sweep speed 0.5Vs-1.With the increase of scanning circle number, graphene film is constantly etched, graphene GO quantum
Point constantly generates in the electrolytic solution；
(3) residue in film removal solution is filtered using the polytetrafluoroethylene (PTFE) of aperture 100nm, the residue in solution will be removed
Filtrate molecular cut off be 2000-12000Da bag filter in room temperature dialyse 48-72h, obtain graphene quantum dot dispersion
Liquid.
4. the graphene quantum dot nanotube GO/YCoO that AAO template according to claim 1 is bracket3Nano-array electrode
The preparation of material, which is characterized in that prepared by the electrochemical process of step (3) graphene GO quantum dot nano pipe array:
AAO template one side is gold-plated, and as working electrode, platinum filament is used as to electrode, and graphene GO quantum dot solution is as electricity
Deposited electrolyte applies the positive voltage of 3-6V in gold-plated AAO template, continuous deposition 3-5 hours, electric as work
Pole, platinum filament are used as to electrode, and graphene GO quantum dot solution applies 3- in gold-plated AAO template as electro-deposition electrolyte
The positive voltage of 6V continuous deposition 3-5 hours, at -70 DEG C, is freeze-dried 48h, ice in freezing dry process under vacuum degree 4Pa
Brilliant formation driving graphene oxide layer crimps, and graphene oxide layer a part another part in ice exists in freeze-drying process
Cause non-uniform stress that lamella is caused to crimp outside ice, surface is rinsed with deionized water, then 150 DEG C of annealing 3h, in this way in AAO
AAO/GO graphene quantum dot nano-tube array has been obtained in template.
5. the graphene quantum dot nanotube GO/YCoO that AAO template according to claim 1 is bracket3Nano-array electrode
The preparation of material, which is characterized in that YCoO in step (4) step (5)3Nanotube deposition is in AAO/GO quantum dot nano
Key step in pipe are as follows: (1) YCoO3The preparation of colloidal sol precursor；(2) vacuum spin-coating method is heavy in AAO/GO quantum dot nano pipe
Product YCoO3Colloidal sol precursor；(3) AAO/GO/YCoO is calcined3Colloidal sol precursor is allowed to be converted into coaxial heterogeneous structure AAO/GO/
YCoO3Nano-tube array.
6. the graphene quantum dot nanotube GO/YCoO that AAO template according to claim 5 is bracket3Nano-array electrode
The preparation of material, which is characterized in that described (1) YCoO3The preparation of colloidal sol precursor:
By molar ratio be 1:1 Co salt and Y salt dissolution in deionized water, stirring be allowed to clarify, then and (0.4-0.6M) lemon
Lemon acid-mixed is closed, Co salt: Y salt: the molar ratio of citric acid is 1:1:2, and 30-60min is stirred at 60-90 DEG C to uniform, slow drop
Add ammonium hydroxide to adjust the pH value of solution between 6~7, solution will be stirred continuously in the process, so that it is uniformly mixed, work as handle
When the pH value of solution is transferred to 6~7, faint electropositive is presented in sol particles, and elecrtonegativity is presented in AAO/GO template inner wall；
(2) vacuum spin-coating method in AAO/GO quantum dot nano pipe deposits YCoO3Colloidal sol precursor:
To YCoO obtained in (1)3Dispersing agent is added in colloidal sol precursor, sonic oscillation disperses YCoO3Colloidal sol precursor, dispersion
Agent and YCoO3Mass ratio be 8-12:1, AAO/GO quantum dot nano pipe array is placed in closed container, interior pressure is
0.01-0.05MPa guarantees the vacuum degree of closed container, and YCoO is added dropwise to AAO template face3Colloidal sol precursor, ultrasonic immersing 10-
30min, the then first low speed 200-400r/min spin coating 10-30s in whirler, then 2500-3500r/min high speed spin coating
60s, the dry 10-30min at 80 DEG C -150 DEG C of drying box, ultrasound is impregnated, vacuum spin coating can effectively improve AAO/GO quantum dot
YCoO in nanotube3The compactedness of colloidal sol precursor, prepares the nano-tube array of high-sequential, repeat above-mentioned ultrasonic immersing,
The spin coating of spin coating vacuum and vacuum drying process 2-6 times, YCoO3Colloidal sol precursor is deposited on AAO/GO quantum dot nano tube wall；
(3) coaxial heterogeneous structure AAO/GO/YCoO3The formation of nanometer pipe array electrode material:
By the AAO/GO/YCoO after vacuum drying in (2)3Colloidal sol precursor first rises to 300- in Muffle furnace with low heating rate
500 DEG C of pretreatment 4h, reaction that citric acid organic matter burns at 300 DEG C and nitrate is decomposed at 400 DEG C or so, then at 900-
1000 DEG C of calcining 48-96h, go cooled to room temperature after moisture removal and dispersing agent.
7. the graphene quantum dot nanotube GO/YCoO that AAO template according to claim 6 is bracket3Nano-array electrode
The preparation of material, which is characterized in that the dispersing agent can be the one of ethyl cellulose, lauryl sodium sulfate or methyl anyl alcohol
Kind or several mixing.
8. the graphene quantum dot nanotube GO/YCoO that AAO template according to claim 1 is bracket3Nano-array electrode
The preparation of material, which is characterized in that the controllable nanometer porous array AAO pore size of template range of the step (1) is 30nm-
100nm。
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| CN102517601A (en) * | 2011-12-31 | 2012-06-27 | 上海交通大学 | Method for preparing Cu2O/TiO2 nano-tube array electrode with grapheme assembled on surface |
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| CN107188281A (en) * | 2017-06-09 | 2017-09-22 | 北京理工大学 | A kind of research of porous graphene material in capacitive deionization |
| CN109036851A (en) * | 2018-07-10 | 2018-12-18 | 浙江大学 | A kind of graphene-based thin-film solar cells |
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| CN102517601A (en) * | 2011-12-31 | 2012-06-27 | 上海交通大学 | Method for preparing Cu2O/TiO2 nano-tube array electrode with grapheme assembled on surface |
| CN103241728A (en) * | 2012-02-14 | 2013-08-14 | 中国科学院上海微***与信息技术研究所 | Method for preparing graphene nanopore array through chemical vapor deposition by using porous anodic alumina (PAA) as template |
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