CN108417411A - A kind of ultracapacitor and preparation method thereof - Google Patents
A kind of ultracapacitor and preparation method thereof Download PDFInfo
- Publication number
- CN108417411A CN108417411A CN201810169746.3A CN201810169746A CN108417411A CN 108417411 A CN108417411 A CN 108417411A CN 201810169746 A CN201810169746 A CN 201810169746A CN 108417411 A CN108417411 A CN 108417411A
- Authority
- CN
- China
- Prior art keywords
- preparation
- electrolytic solution
- deposition
- liquid
- ultracapacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 230000008021 deposition Effects 0.000 claims abstract description 69
- 239000002071 nanotube Substances 0.000 claims abstract description 55
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 41
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003990 capacitor Substances 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 11
- 238000007743 anodising Methods 0.000 claims abstract description 5
- 238000000151 deposition Methods 0.000 claims description 75
- 239000007788 liquid Substances 0.000 claims description 70
- 239000008151 electrolyte solution Substances 0.000 claims description 69
- 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 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- 238000004544 sputter deposition Methods 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 12
- 229960001763 zinc sulfate Drugs 0.000 claims description 12
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 238000005477 sputtering target Methods 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- -1 nickel transition metal Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 11
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000005611 electricity Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000002242 deionisation method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000521257 Hydrops Species 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of ultracapacitor of present invention offer and preparation method thereof, belongs to capacitor technology field.The preparation method of ultracapacitor, includes the following steps：Nano tube array of titanium dioxide is prepared in titanium sheet using anodizing.In the surface deposition solid electrolyte of Nano tube array of titanium dioxide.In solid electrolyte transition metal oxide is deposited far from the one side in Nano tube array of titanium dioxide.Above-mentioned preparation method is simple, and obtained ultracapacitor has high quality specific capacity, the advantage of high-energy density, while can work within the scope of extremely wide temperature.
Description
Technical field
The present invention relates to capacitor technology fields, in particular to a kind of ultracapacitor and preparation method thereof.
Background technology
In order to solve a series of crises such as traditional energy exhaustion, environmental degradation that 21 century is faced, researchers are always
It is dedicated to novel, efficient, cleaning, the research and application of renewable energy source material and device.In the current various forms of energy, electricity
It can be easiest to transmission and utilize.In order to efficiently use electric energy, it is always by cleaning, the conversion of reproducible approach, storage electric energy
One important subject.
Ultracapacitor (Supercapacitor) is also referred to as electrochemical capacitor (Electrochemical
Capacitor), double layer capacitor (Electrical Double-Layer Capacitor), gold capacitance, farad electricity
Hold, is a kind of new type of energy storage device between traditional capacitor and battery.Its energy storage basic principle is：When to electrode charge
When, the electrode surface charge in ideal polarized electrode state will attract the counter ions in surrounding electrolyte solution, make these
Ion invests and forms electric double layer on electrode surface, constitutes electric double layer capacitance.Since the distance of two charge layers is very small (general
0.5mm or less), special electrode structure is used in addition, makes electrode surface area at ten thousand times of increase, to generate great capacitance
Amount.Therefore ultracapacitor is not chemically reacted in the process of its energy storage, this storage come energy storage by polarized electrolytic matter
Energy process is reversible, because of this, ultracapacitor can be hundreds thousand of times with repeated charge, and the long-life is its maximum
Feature.In addition, another mechanism, is happened at the quick Faradaic processes on surface because having capacitive kinetic characteristics quilt
Referred to as fake capacitance, this capacitance have higher specific capacity and are provided simultaneously with good multiplying power property and stability.
The specific discharge capacity and energy density of existing ultracapacitor have certain limitation, cannot reach the need of client
It asks.There are three types of the capacitors for being directed to energy type application target currently on the market, and one is double layer capacitor, electrode material is
Activated carbon, electrolyte are organic electrolyte solutions, and operating voltage 2.7V, energy density is by activated carbon working mechanism (specific capacity
It 80F/g) is limited, is 3 ￣ 8Wh/kg, the service life 1,000,000 times, operating temperature is limited by organic solvent, about -45 DEG C of ￣ 70
℃；Another is Asymmetric Supercapacitor, an extremely activated carbon, in addition an extremely nickel hydroxide, using a pole electric double layer,
The operation principle of one pole fake capacitance, since, as electrolyte solvent, voltage reaches 1.2V, and energy density is up to 10Wh/ using water
Kg, working life are about 100,000 times；Finally one is lithium-ion capacitor, a pole uses activated carbon, and another pole is using pre- embedding
The graphite of lithium, operation principle are electric double layer capacitance+lithium ion insertion/deintercalation, have high voltage (3.8V), high-energy density (15
￣ 20Wh/kg), longer life (100,000 times) and operating temperature (- 20 ￣ 60 for being limited to lithium ion insertion/deintercalation process
℃)。
Invention content
The purpose of the present invention is to provide a kind of preparation methods of ultracapacitor, and above-mentioned preparation method is simple, are easy behaviour
Make.
Another object of the present invention is to provide a kind of ultracapacitors that above-mentioned preparation method obtains, and have high quality ratio
The advantage of capacity, high-energy density.
Realization that the present invention adopts the following technical solutions：
A kind of preparation method of ultracapacitor, includes the following steps：
(1), Nano tube array of titanium dioxide is prepared in titanium sheet using anodizing；
(2), in the surface deposition solid electrolyte of Nano tube array of titanium dioxide；
(3), in solid electrolyte transition metal oxide is deposited far from the one side in Nano tube array of titanium dioxide.
Further, it is anode with titanium sheet in above-mentioned steps (1), platinum is cathode in electricity in preferred embodiments of the present invention
Solve and carry out anodic oxidation 1-5h in liquid, after anneal at a temperature of 450-550 DEG C 2.5-3.5h.
Further, in preferred embodiments of the present invention, above-mentioned electrolyte is that ammonium fluoride is dissolved in ethylene glycol and deionization
It is made in the mixed solution of water.
Further, in preferred embodiments of the present invention, in above-mentioned steps (2), using Nano tube array of titanium dioxide as
Work pole, and platinized platinum is used as to electrode, and Ag/AgCl carries out electrochemical deposition as reference electrode in depositing liquid.
Further, in preferred embodiments of the present invention, the preparation method of above-mentioned deposition liquid is：By sodium sulphate be dissolved in from
Electrolytic solution is formed in sub- water, vulcanized sodium will be added and be dissolved in the first deposition of formation liquid in electrolytic solution, lithium sulfate is dissolved in electrolysis
The second deposition liquid is formed in solution, and zinc sulfate is dissolved in electrolytic solution and forms third deposition liquid.
Further, in preferred embodiments of the present invention, it is above-mentioned successively first deposit liquid, in electrolytic solution, it is second heavy
It is scanned in hydrops, electrolytic solution, the first deposition liquid, electrolytic solution, third deposition liquid and electrolytic solution.
Further, in preferred embodiments of the present invention, in above-mentioned steps (3), transition metal oxide is selected from five oxidations
Any one in two vanadium, manganese dioxide and nickel oxide.
Further, in preferred embodiments of the present invention, the specific method of above-mentioned deposition transition metal oxide is：It utilizes
Vanadium or manganese or nickel transition metal carry out magnetron sputtering deposition as target.
Further, in preferred embodiments of the present invention, the specific method of above-mentioned deposition vanadic anhydride is：With vanadium metal
As sputtering target material, oxygen as working gas, argon gas as carrier gas, sputtering power is 180-250W, underlayer temperature is
Sputtering sedimentation is carried out under conditions of 350-500 DEG C.
A kind of ultracapacitor that the preparation method of above-mentioned ultracapacitor is prepared.
The advantageous effect of preparation method for the ultracapacitor that presently preferred embodiments of the present invention provides is：Use anodic oxidation
Method prepares Nano tube array of titanium dioxide in titanium sheet, forms the cathode of ultracapacitor, obtains Nano tube array of titanium dioxide,
The capacitor that a large amount of independent cast super capacitors can be formed and be unified into, makes the ultracapacitor subsequently obtained have high quality
Specific capacity, the advantage of high-energy density.In the surface deposition solid electrolyte of Nano tube array of titanium dioxide, solid can be limited
For electrolyte in the growth on nano-tube array surface, it is nanometer scale to make growth thickness, makes all to be formed on each nanotube negative
The miniature nanoscale Asymmetric Supercapacitor of pole/electrolyte/anode class nucleocapsid in this way, to lead on minimum area
It crosses nano-tube array and forms high specific capacity and quick charging and discharging capabilities.In solid electrolyte far from titanium dioxide
The one side of nano-tube array deposits transition metal oxide, forms the anode of ultracapacitor, makes the positive and negative anodes of ultracapacitor
Between have high contact area, thickness of electrode is relatively thin, can metric density higher, electrode capacity bigger.
The ultracapacitor that the preparation method of ultracapacitor provided by the invention is prepared has the beneficial effect that：Have
High quality specific capacity, the advantage of high-energy density can work within the scope of extremely wide temperature.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings and also belong to protection scope of the present invention.
Fig. 1 is the process flow chart of the preparation method of ultracapacitor provided by the invention.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
The preparation method of ultracapacitor provided in an embodiment of the present invention is specifically described below.
Fig. 1 is the process flow chart of the preparation method of ultracapacitor provided by the invention.Referring to Fig. 1, super capacitor
The preparation method of device, includes the following steps：
(1), Nano tube array of titanium dioxide is prepared in titanium sheet using anodizing, obtained titania nanotube
Cathode of the array as ultracapacitor, obtains Nano tube array of titanium dioxide, can form a large amount of independent super electricity of cast
The capacitor for holding and being unified into makes the ultracapacitor subsequently obtained have high quality specific capacity, the advantage of high-energy density.
Electrolyte is that ammonium fluoride is dissolved in ethylene glycol and the mixed solution of deionized water to be made.Wherein, in electrolyte, second
The volume of glycol accounts for the 10%-30% of electrolyte volume.
First by titanium sheet pass through acetone, absolute ethyl alcohol and deionized water supersound washing, after with titanium sheet be anode, platinum is cathode
Carry out anodic oxidation 1-5h in the electrolytic solution, after anneal at a temperature of 450-550 DEG C 2.5-3.5h, obtain titanium dioxide
Nano-tube array.The caliber of titania nanotube is 50-100nm, and pipe range is 1-100 μm, the titanium dioxide under the conditions of this
Nanotube has higher quality specific capacity, the energy density of bigger in the ultracapacitor finally obtained.
Preferably, when carrying out anodic oxidation, constant temperature stirring is carried out in electrolytic cell, temperature is 30-50 DEG C, profit
Anodic oxidation is carried out with constant pressure source, wherein voltage 20-50v carries out anodic oxidation under this temperature condition, can be easily
The caliber and pipe range for controlling titania nanotube, to make the ultracapacitor subsequently obtained that there is higher quality specific volume
Amount, the energy density of bigger.
(2), in the surface deposition solid electrolyte of Nano tube array of titanium dioxide, in the table of Nano tube array of titanium dioxide
Face deposition solid electrolyte can limit growth of the solid electrolyte on nano-tube array surface, and it is nanometer to make growth thickness
Magnitude keeps the miniature nanoscale for all forming cathode/electrolyte/anode class nucleocapsid in this way on each nanotube asymmetric super
Grade capacitor, to form high specific capacity and quick charge and discharge electric energy by nano-tube array on minimum area
Power.
Deposition liquid preparation method be：Sodium sulphate is dissolved in deionized water and forms electrolytic solution, it is molten by vulcanized sodium is added
The first deposition liquid is formed in electrolytic solution, and lithium sulfate is dissolved in electrolytic solution and forms the second deposition liquid, zinc sulfate is dissolved in
Third is formed in electrolytic solution deposits liquid.
That is, first preparing blank cleaning solution, the first deposition liquid, the second deposition liquid and third deposition liquid respectively, wherein prepare empty
The concrete mode of cleaning solution is in vain：Anhydrous sodium sulfate is dissolved in deionized water, the electricity of a concentration of 0.08-0.12mol/L is obtained
Solution is solved, preferably：The electrolytic solution of 0.1mol/L.
Electrolytic solution is divided into four parts, portion is used as blank cleaning solution；Vulcanized sodium is dissolved in a electrolytic solution, is obtained
The first deposition liquid of a concentration of 2.2-2.8mmol/L of vulcanized sodium, the first deposition liquid of preferably 2.5mmol/L.In a electricity
Lithium sulfate is dissolved in solution solution, obtains the second deposition liquid of a concentration of 2.2-2.8mmol/L of lithium sulfate, preferably
The second deposition liquid of 2.5mmol/L.Zinc sulfate is dissolved in a electrolytic solution, obtains a concentration of 2.2- of zinc sulfate
The third of 2.8mmol/L deposits liquid, and the third of preferably 2.5mmol/L deposits liquid.
Titania nanotube is passed sequentially through to the supersound washing of acetone, absolute ethyl alcohol and deionized water.With titanium dioxide
Nano-tube array is used as work pole, platinized platinum to electrode, and Ag/AgCl carries out electrochemistry as reference electrode in depositing liquid
Deposition.In the surface deposition solid electrolyte of Nano tube array of titanium dioxide, solid electrolyte can be further limited in nanometer
The growth of pipe array surface, it is nanometer scale to make growth thickness, also, its thickness is more uniform, obtained ultracapacitor
Charging and discharging capabilities it is stronger.
Successively first deposit liquid, in electrolytic solution, the second deposition liquid, electrolytic solution, the first deposition liquid, electrolytic solution,
Third, which deposits, carries out cyclic voltammetry voltage scanning in liquid and electrolytic solution.Cyclic voltammetry voltage scanning is carried out, keeps solid electric
Matter stratified sedimentation is solved on the surface of Nano tube array of titanium dioxide, can preferably control the growth of solid electrolyte, thickness
Control more uniform, the charging and discharging capabilities for the ultracapacitor that a further height obtains.
Preferably, it by electrochemical workstation, is deposited in three-electrode system：Nano tube array of titanium dioxide is as work
Make pole, platinized platinum is used as to electrode, and Ag/AgCl is as reference electrode, and (- 0.4 ￣ 1V of potential window, sweep in the first deposition liquid successively
Retouch rate 10mV/s), electrolytic solution (potential window -0.4 ￣ 1V, sweep speed 10mV/s), the second deposition liquid (electrochemical window
- 0.2 ￣ 0.2V, sweep speed 10mV/s of mouth), electrolytic solution (potential window -0.2 ￣ 0.2V, sweep speed 10mV/s), the
One deposition liquid (potential window -0.4 ￣ 1V, sweep speed 10mV/s), electrolytic solution (- 0.4 ￣ 1V of potential window, scanning speed
Rate 10mV/s), third deposits liquid (potential window -0.4 ￣ 0.1V, sweep speed 10mV/s), electrolytic solution (potential window -
0.4 ￣ 0.1V, sweep speed 10mV/s) in deposited, generally select cycle 2 times.
It is sequentially depositing in above-mentioned different solution, the charging and discharging capabilities of obtained ultracapacitor are most strong, super
Effective contact area bigger between the positive electrode and negative electrode of capacitor.
(3), transition metal oxide, shape are deposited far from the one side in Nano tube array of titanium dioxide in solid electrolyte
At the anode of ultracapacitor, make that there is high contact area between the positive and negative anodes of ultracapacitor, thickness of electrode is relatively thin, makes
Its energy density higher, electrode capacity bigger.
Preferably, any one of transition metal oxide in vanadic anhydride, manganese dioxide and nickel oxide.Deposition
The specific method of transition metal oxide is：Using vanadium or manganese or nickel transition metal as target, magnetron sputtering deposition is carried out.
Deposition vanadic anhydride specific method be：Using vanadium metal as sputtering target material, oxygen as working gas, argon gas
As carrier gas, sputtering sedimentation is carried out under conditions of sputtering power is 180-250W, underlayer temperature is 350-500 DEG C.
Specifically, V is prepared using magnetron sputtering coater on substrate2O5Film.Excitaton source using copper target (Cu, K α=
0.15406nm), sputtering target material is the vanadium metal of purity 99.99%, and the vacuum for controlling vacuum chamber is 2.0 × 10- 4Pa, work gas
Pressure is 2.2Pa, target-substrate distance 5cm.When sputtering, it is passed through high-purity oxygen (99.99%) and is used as working gas, argon gas
(99.99%) it is used as carrier gas.By changing substrate temperature, sputtering power and oxygen (O2) and argon gas (Ar) flow-rate ratio,
V is prepared under different conditions2O5, film sample.Preferably, village bottom temperature is 350-500 DEG C, O2/ Ar intrinsic standoff ratios are 1%-
10%, sputtering power 180-250W.
Manganese dioxide is similar with the mode of the magnetron sputtering of nickel oxide.It is finally obtained by way of above-mentioned magnetron sputtering
Each nanotube of ultracapacitor is respectively formed on the class nucleocapsid of cathode, solid electrolyte and anode, has higher
Specific capacity, the ability of fast charging and discharging are better able to meet the needs of client.
It is close that the ultracapacitor that the preparation method of above-mentioned ultracapacitor is prepared has high quality specific capacity, high-energy
The advantage of degree can work within the scope of extremely wide temperature, the ability with fast charging and discharging.
Embodiment 1
A kind of preparation method of ultracapacitor, includes the following steps：(1), it is prepared in titanium sheet using anodizing
Nano tube array of titanium dioxide.(2), in the surface deposition solid electrolyte of Nano tube array of titanium dioxide.(3), in solid electricity
Solve matter deposits transition metal oxide far from the one side in Nano tube array of titanium dioxide.
Embodiment 2
A kind of preparation method of ultracapacitor, includes the following steps：(1), ammonium fluoride is dissolved in ethylene glycol and deionization
Electrolyte is made in the mixed solution of water, with titanium sheet be anode, platinum be cathode carry out anodic oxidation 3h in the electrolytic solution, after
Anneal 3h at a temperature of 500 DEG C, obtains Nano tube array of titanium dioxide.
(2), sodium sulphate is dissolved in deionized water and forms electrolytic solution, addition vulcanized sodium is dissolved in electrolytic solution and is formed
Lithium sulfate is dissolved in electrolytic solution and forms the second deposition liquid, zinc sulfate is dissolved in electrolytic solution and forms the by the first deposition liquid
Three deposition liquid, using Nano tube array of titanium dioxide as work pole, platinized platinum as to electrode, Ag/AgCl as reference electrode, according to
It is secondary first deposit liquid, in electrolytic solution, the second deposition liquid, electrolytic solution, the first deposition liquid, electrolytic solution, third deposit liquid
Make the surface deposition solid electricity of Nano tube array of titanium dioxide with electrochemical deposition is carried out by cyclic voltammetry in electrolytic solution
Xie Zhi.
(3), using vanadium metal as sputtering target material, oxygen as working gas, argon gas as carrier gas, it is in sputtering power
Depositing far from the one side in Nano tube array of titanium dioxide in solid electrolyte under conditions of 200W, underlayer temperature are 400 DEG C
Vanadic anhydride.
Embodiment 3
A kind of preparation method of ultracapacitor, includes the following steps：(1), ammonium fluoride is dissolved in ethylene glycol and deionization
Electrolyte is made in the mixed solution of water, titanium sheet is passed through to the supersound washing of acetone, absolute ethyl alcohol and deionized water, is with titanium sheet
Anode, platinum be cathode in the electrolytic solution in electrolytic cell with voltage be 20v under conditions of carry out constant temperature and be stirred to react 1h, after 450
Anneal 2.5h at a temperature of DEG C, obtains Nano tube array of titanium dioxide.
(2), anhydrous sodium sulfate is dissolved in deionized water, obtains the electrolytic solution of a concentration of 0.08mol/L, will be electrolysed molten
Liquid is divided into four parts, and portion is used as blank cleaning solution；Vulcanized sodium is dissolved in a electrolytic solution, obtains a concentration of of vulcanized sodium
The first deposition liquid of 2.2mmol/L, dissolves lithium sulfate in a electrolytic solution, obtains a concentration of 2.2mmol/L of lithium sulfate
Second deposition liquid, dissolve zinc sulfate in a electrolytic solution, obtain a concentration of 2.2mmol/L of zinc sulfate third deposition
Liquid.The supersound washing that titania nanotube is passed sequentially through to acetone, absolute ethyl alcohol and deionized water, passes through electrochemical operation
It stands, using Nano tube array of titanium dioxide as work pole, platinized platinum is used as to electrode, and Ag/AgCl is as reference electrode, in three electrodes
System is deposited, successively in the first deposition liquid (potential window -0.4 ￣ 1V, sweep speed 10mV/s), electrolytic solution (current potential
Window -0.4 ￣ 1V, sweep speed 10mV/s), the second deposition liquid (potential window -0.2 ￣ 0.2V, sweep speed 10mV/s),
Electrolytic solution (potential window -0.2 ￣ 0.2V, sweep speed 10mV/s), (- 0.4 ￣ 1V of potential window, sweep the first deposition liquid
Retouch rate 10mV/s), electrolytic solution (potential window -0.4 ￣ 1V, sweep speed 10mV/s), third deposits liquid (electrochemical window
Mouthful -0.4 ￣ 0.1V, sweep speed 10mV/s), in electrolytic solution (potential window -0.4 ￣ 0.1V, sweep speed 10mV/s)
It is deposited, generally selects cycle 2 times.
(3), V is prepared using magnetron sputtering coater on substrate2O5Film.Excitaton source using copper target (Cu, K α=
0.15406nm), sputtering target material is the vanadium metal of purity 99.99%, and the vacuum for controlling vacuum chamber is 2.0 × 10- 4Pa, work gas
Pressure is 2.2Pa, target-substrate distance 5cm.When sputtering, it is passed through high-purity oxygen (99.99%) and is used as working gas, argon gas
(99.99%) it is used as carrier gas.Village bottom temperature is 350 DEG C, O2Solid under conditions of/Ar intrinsic standoff ratios are 1%, sputtering power is 180W
Body electrolyte prepares V far from the one side in Nano tube array of titanium dioxide2O5Film sample.
Embodiment 4
A kind of preparation method of ultracapacitor, includes the following steps：(1), ammonium fluoride is dissolved in ethylene glycol and deionization
Electrolyte is made in the mixed solution of water, titanium sheet is passed through to the supersound washing of acetone, absolute ethyl alcohol and deionized water, is with titanium sheet
Anode, platinum be cathode in the electrolytic solution in electrolytic cell with voltage be 50v under conditions of carry out constant temperature and be stirred to react 5h, after 550
Anneal 3.5h at a temperature of DEG C, obtains Nano tube array of titanium dioxide.
(2), anhydrous sodium sulfate is dissolved in deionized water, obtains the electrolytic solution of a concentration of 0.12mol/L, will be electrolysed molten
Liquid is divided into four parts, and portion is used as blank cleaning solution；Vulcanized sodium is dissolved in a electrolytic solution, obtains a concentration of of vulcanized sodium
The first deposition liquid of 2.8mmol/L, dissolves lithium sulfate in a electrolytic solution, obtains a concentration of 2.8mmol/L of lithium sulfate
Second deposition liquid, dissolve zinc sulfate in a electrolytic solution, obtain a concentration of 2.8mmol/L of zinc sulfate third deposition
Liquid.The supersound washing that titania nanotube is passed sequentially through to acetone, absolute ethyl alcohol and deionized water, passes through electrochemical operation
It stands, using Nano tube array of titanium dioxide as work pole, platinized platinum is used as to electrode, and Ag/AgCl is as reference electrode, in three electrodes
System is deposited, successively in the first deposition liquid (potential window -0.4 ￣ 1V, sweep speed 10mV/s), electrolytic solution (current potential
Window -0.4 ￣ 1V, sweep speed 10mV/s), the second deposition liquid (potential window -0.2 ￣ 0.2V, sweep speed 10mV/s),
Electrolytic solution (potential window -0.2 ￣ 0.2V, sweep speed 10mV/s), (- 0.4 ￣ 1V of potential window, sweep the first deposition liquid
Retouch rate 10mV/s), electrolytic solution (potential window -0.4 ￣ 1V, sweep speed 10mV/s), third deposits liquid (electrochemical window
Mouthful -0.4 ￣ 0.1V, sweep speed 10mV/s), in electrolytic solution (potential window -0.4 ￣ 0.1V, sweep speed 10mV/s)
It is deposited, generally selects cycle 2 times.
(3), manganese dioxide membrane is prepared using magnetron sputtering coater on substrate.Excitaton source using copper target (Cu, K α=
0.15406nm), sputtering target material is the manganese metal of purity 99.99%, and the vacuum for controlling vacuum chamber is 2.0 × 10- 4Pa, work gas
Pressure is 2.2Pa, target-substrate distance 5cm.When sputtering, it is passed through high-purity oxygen (99.99%) and is used as working gas, argon gas
(99.99%) it is used as carrier gas.Village bottom temperature is 500 DEG C, O2Under conditions of/Ar intrinsic standoff ratios are 10%, sputtering power is 250W
Solid electrolyte prepares manganese dioxide membrane sample far from the one side in Nano tube array of titanium dioxide.
Embodiment 5
A kind of preparation method of ultracapacitor, includes the following steps：(1), ammonium fluoride is dissolved in ethylene glycol and deionization
Electrolyte is made in the mixed solution of water, titanium sheet is passed through to the supersound washing of acetone, absolute ethyl alcohol and deionized water, is with titanium sheet
Anode, platinum be cathode in the electrolytic solution in electrolytic cell with voltage be 40v under conditions of carry out constant temperature and be stirred to react 3h, after 520
Anneal 3h at a temperature of DEG C, obtains Nano tube array of titanium dioxide.
(2), anhydrous sodium sulfate is dissolved in deionized water, obtains the electrolytic solution of a concentration of 0.1mol/L, will be electrolysed molten
Liquid is divided into four parts, and portion is used as blank cleaning solution；Vulcanized sodium is dissolved in a electrolytic solution, obtains a concentration of of vulcanized sodium
The first deposition liquid of 2.5mmol/L, dissolves lithium sulfate in a electrolytic solution, obtains a concentration of 2.5mmol/L of lithium sulfate
Second deposition liquid, dissolve zinc sulfate in a electrolytic solution, obtain a concentration of 2.5mmol/L of zinc sulfate third deposition
Liquid.The supersound washing that titania nanotube is passed sequentially through to acetone, absolute ethyl alcohol and deionized water, passes through electrochemical operation
It stands, using Nano tube array of titanium dioxide as work pole, platinized platinum is used as to electrode, and Ag/AgCl is as reference electrode, in three electrodes
System is deposited, successively in the first deposition liquid (potential window -0.4 ￣ 1V, sweep speed 10mV/s), electrolytic solution (current potential
Window -0.4 ￣ 1V, sweep speed 10mV/s), the second deposition liquid (potential window -0.2 ￣ 0.2V, sweep speed 10mV/s),
Electrolytic solution (potential window -0.2 ￣ 0.2V, sweep speed 10mV/s), (- 0.4 ￣ 1V of potential window, sweep the first deposition liquid
Retouch rate 10mV/s), electrolytic solution (potential window -0.4 ￣ 1V, sweep speed 10mV/s), third deposits liquid (electrochemical window
Mouthful -0.4 ￣ 0.1V, sweep speed 10mV/s), in electrolytic solution (potential window -0.4 ￣ 0.1V, sweep speed 10mV/s)
It is deposited, generally selects cycle 2 times.
(3), nickel oxide film is prepared using magnetron sputtering coater on substrate.Excitaton source using copper target (Cu, K α=
0.15406nm), sputtering target material is the metallic nickel of purity 99.99%, and the vacuum for controlling vacuum chamber is 2.0 × 10- 4Pa, work gas
Pressure is 2.2Pa, target-substrate distance 5cm.When sputtering, it is passed through high-purity oxygen (99.99%) and is used as working gas, argon gas
(99.99%) it is used as carrier gas.Village bottom temperature is 400 DEG C, O2Solid under conditions of/Ar intrinsic standoff ratios are 8%, sputtering power is 220W
The separate of body electrolyte prepares nickel oxide film sample on one side in Nano tube array of titanium dioxide.
Experimental example
Ultracapacitor that the preparation method that detection embodiment 1-5 is provided respectively is prepared and super electricity on the market
The various performance parameters of container as a comparison case obtain table 1：
The performance of 1 ultracapacitor of table
As it can be seen from table 1 the specific discharge capacity of ultracapacitor prepared by the present invention, energy density are all than in the market
Ultracapacitor is high, and its stability is more preferable, and operating temperature range is wider, is better able to meet the needs of client.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ultracapacitor, which is characterized in that include the following steps：
(1), Nano tube array of titanium dioxide is prepared in titanium sheet using anodizing；
(2), in the surface deposition solid electrolyte of the Nano tube array of titanium dioxide；
(3), in the solid electrolyte transiting metal oxidation is deposited far from the one side in the Nano tube array of titanium dioxide
Object.
2. preparation method according to claim 1, which is characterized in that be anode with titanium sheet in the step (1), platinum is
Cathode carries out anodic oxidation 1-5h in the electrolytic solution, after anneal at a temperature of 450-550 DEG C 2.5-3.5h.
3. preparation method according to claim 2, which is characterized in that the electrolyte be by ammonium fluoride be dissolved in ethylene glycol with
It is made in the mixed solution of deionized water.
4. preparation method according to claim 1, which is characterized in that in the step (2), with the nano titania
Pipe array is used as work pole, platinized platinum to electrode, and Ag/AgCl carries out electrochemical deposition as reference electrode in depositing liquid.
5. preparation method according to claim 4, which is characterized in that it is described deposition liquid preparation method be：By sodium sulphate
It is dissolved in deionized water and forms electrolytic solution, vulcanized sodium will be added and be dissolved in the first deposition of formation liquid in the electrolytic solution, by sulphur
Sour lithium, which is dissolved in the electrolytic solution, forms the second deposition liquid, and zinc sulfate is dissolved in the electrolytic solution and forms third deposition
Liquid.
6. preparation method according to claim 5, which is characterized in that molten in the first deposition liquid, the electrolysis successively
In liquid, it is described second deposition liquid, the electrolytic solution, it is described first deposition liquid, the electrolytic solution, the third deposition liquid and
It is scanned in the electrolytic solution.
7. preparation method according to claim 1, which is characterized in that in the step (3), the transition metal oxide
Any one in vanadic anhydride, manganese dioxide and nickel oxide.
8. preparation method according to claim 7, which is characterized in that the specific method for depositing transition metal oxide is：
Using vanadium or manganese or nickel transition metal as target, magnetron sputtering deposition is carried out.
9. preparation method according to claim 8, which is characterized in that the specific method for depositing the vanadic anhydride is：
It is 180-250W, substrate in sputtering power using vanadium metal as sputtering target material, oxygen as working gas, argon gas as carrier gas
Temperature carries out sputtering sedimentation under conditions of being 350-500 DEG C.
10. the super capacitor that a kind of preparation method such as claim 1-9 any one of them ultracapacitors is prepared
Device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810169746.3A CN108417411B (en) | 2018-02-28 | 2018-02-28 | A kind of supercapacitor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810169746.3A CN108417411B (en) | 2018-02-28 | 2018-02-28 | A kind of supercapacitor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108417411A true CN108417411A (en) | 2018-08-17 |
| CN108417411B CN108417411B (en) | 2019-10-18 |
Family
ID=63129539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810169746.3A Expired - Fee Related CN108417411B (en) | 2018-02-28 | 2018-02-28 | A kind of supercapacitor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108417411B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114975960A (en) * | 2022-06-24 | 2022-08-30 | 合肥融捷能源材料有限公司 | Doped TiO 2 2 Nanotube-coated lithium cobalt oxide, preparation method thereof and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102017241A (en) * | 2008-02-22 | 2011-04-13 | 科罗拉多州立大学研究基金会 | Lithium-ion battery |
| JP2013073721A (en) * | 2011-09-27 | 2013-04-22 | Dainippon Screen Mfg Co Ltd | Manufacturing method of cell |
| CN103714978A (en) * | 2013-12-12 | 2014-04-09 | 中国科学院深圳先进技术研究院 | Electrode plate, preparation method thereof and super capacitor |
| CN104835648A (en) * | 2015-04-08 | 2015-08-12 | 苏州大学 | Preparation method for bismuth oxide nano-particle/titania nano-tube array |
| CN107256809A (en) * | 2017-06-29 | 2017-10-17 | 河北工业大学 | A kind of preparation method of transparent flexible ultracapacitor |
-
2018
- 2018-02-28 CN CN201810169746.3A patent/CN108417411B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102017241A (en) * | 2008-02-22 | 2011-04-13 | 科罗拉多州立大学研究基金会 | Lithium-ion battery |
| JP2013073721A (en) * | 2011-09-27 | 2013-04-22 | Dainippon Screen Mfg Co Ltd | Manufacturing method of cell |
| CN103714978A (en) * | 2013-12-12 | 2014-04-09 | 中国科学院深圳先进技术研究院 | Electrode plate, preparation method thereof and super capacitor |
| CN104835648A (en) * | 2015-04-08 | 2015-08-12 | 苏州大学 | Preparation method for bismuth oxide nano-particle/titania nano-tube array |
| CN107256809A (en) * | 2017-06-29 | 2017-10-17 | 河北工业大学 | A kind of preparation method of transparent flexible ultracapacitor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114975960A (en) * | 2022-06-24 | 2022-08-30 | 合肥融捷能源材料有限公司 | Doped TiO 2 2 Nanotube-coated lithium cobalt oxide, preparation method thereof and lithium ion battery |
| CN114975960B (en) * | 2022-06-24 | 2024-03-22 | 合肥融捷能源材料有限公司 | Doped TiO 2 Nanotube coated lithium cobaltate, preparation method thereof and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108417411B (en) | 2019-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Investigation on IrO2 supported on hydrogenated TiO2 nanotube array as OER electro-catalyst for water electrolysis | |
| US9705165B2 (en) | Lithium-air battery air electrode and its preparation method | |
| Zhang et al. | Electrosynthesis of Co 3 O 4 and Co (OH) 2 ultrathin nanosheet arrays for efficient electrocatalytic water splitting in alkaline and neutral media | |
| Jiang et al. | Electrochemical fabrication of Ni (OH) 2/Ni 3D porous composite films as integrated capacitive electrodes | |
| Cao et al. | Novel Sb-doped ruthenium oxide electrode with ordered nanotube structure and its electrocatalytic activity toward chlorine evolution | |
| CN103489661B (en) | A kind of electrode material for super capacitor and preparation method thereof | |
| Liao et al. | Amorphous FeOOH nanorods and Co 3 O 4 nanoflakes as binder-free electrodes for high-performance all-solid-state asymmetric supercapacitors | |
| Yang et al. | Rationally designed hierarchical MnO2-shell/ZnO-nanowire/carbon-fabric for high-performance supercapacitor electrodes | |
| CN109904004B (en) | Preparation method of SiC nanowire array film and application of SiC nanowire array film in supercapacitor electrode | |
| CN105448536B (en) | Nickel oxide/TiOx nano composite material and preparation method thereof and stored energy application | |
| CN111217361B (en) | Method for preparing graphene nanosheet through electrochemical cathode stripping | |
| Guo et al. | Solvothermal fabrication of three-dimensionally sphere-stacking Sb–SnO2 electrode based on TiO2 nanotube arrays | |
| CN108376617B (en) | Electrochemical preparation method and application of nano porous nickel hydroxide film | |
| Li et al. | TiO2 nanotube arrays on silicon substrate for on-chip supercapacitors | |
| CN106887338B (en) | A kind of MnO applied to supercapacitor2/H-TiO2Nano combined array electrode material and preparation method thereof | |
| Xing et al. | Electrodeposition of polyaniline in long TiO 2 nanotube arrays for high-areal capacitance supercapacitor electrodes | |
| CN111816868A (en) | Tin disulfide cladding two-dimensional lamellar Ti3C2Lithium ion battery | |
| CN108461301B (en) | MnO (MnO)2-PPy/H-TiO2Ternary core-shell hybrid array electrode material and preparation method thereof | |
| CN108987123B (en) | Ternary composite super-capacitor electrode material and preparation method thereof | |
| CN112382513B (en) | Preparation method of double-ion water system energy storage device | |
| CN104928713B (en) | The preparation method and its usage of the Ni-based production hydrogen electrode of conducting polymer cladding | |
| CN104992847B (en) | A kind of Asymmetric Supercapacitor with high power density and preparation method thereof | |
| CN108417411B (en) | A kind of supercapacitor and preparation method thereof | |
| CN106158410B (en) | A kind of preparation method of zinc oxide/graphene composite electrode material for super capacitor | |
| Wang et al. | Synthesis of ordered Ni/NiO nanocables for electrochemical capacitor application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191018 |