CN108648927A - A kind of electrode of super capacitor and preparation method thereof based on titanium oxide nanotubes - Google Patents
A kind of electrode of super capacitor and preparation method thereof based on titanium oxide nanotubes Download PDFInfo
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- CN108648927A CN108648927A CN201810397281.7A CN201810397281A CN108648927A CN 108648927 A CN108648927 A CN 108648927A CN 201810397281 A CN201810397281 A CN 201810397281A CN 108648927 A CN108648927 A CN 108648927A
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000002071 nanotube Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000005611 electricity Effects 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 238000002791 soaking Methods 0.000 abstract description 16
- 238000007654 immersion Methods 0.000 abstract description 7
- 239000012670 alkaline solution Substances 0.000 abstract 2
- 238000005253 cladding Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
- 238000009434 installation Methods 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 239000010936 titanium Substances 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910003087 TiOx Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of electrode of super capacitor and preparation method thereof based on titanium oxide nanotubes.At room temperature, the TiO prepared by anodic oxidation2The TiO that nanotube or various patterns are modified2Nanotube is made annealing treatment, and electrochemical reduction doping is carried out in potassium hydroxide solution, then in H2O2It is impregnated in aqueous solution certain time, finally by the TiO of immersion treatment2Application of electrode is in the preparation of ultracapacitor.This method is not necessarily to special installation, is handled by the electrochemical doping in alkaline solution, improves TiO2The electric conductivity and capacitance of electrode.Pass through H2O2The immersion treatment of aqueous solution makes crystalline state TiO2Surface portion crystalline transformation is amorphous, and the structure of this amorphous cladding crystal is conducive to doped stabilization, to improve TiO2The stability of electrode capacitance cycle；The present invention combines H by the electrochemical doping processing in alkaline solution2O2Aqueous solution soaking makes the ultracapacitor cycle life based on titanium oxide nanotubes greatly improve, to be preferably applied for electrochemical energy storage field.
Description
Technical field
The invention belongs to electrochemical technology fields, are related to a kind of easy, cheap, the high circulation service life based on TiOx nano
Electrode of super capacitor of pipe and preparation method thereof.
Background technology
Titanium oxide is a kind of N-shaped semiconductor material with wide forbidden band, and energy gap is 3.0 ~ 3.2 eV, has unique physics
Chemical property.Recently with the development of constantly bringing forth new ideas of nano material preparation technology, the titanium oxide of nanostructure causes that people's is wide
General concern.Wherein, titanium oxide nanotubes are because of specific surface area and specific surface energy with bigger, better adsorption capacity and unique
Electron-transport path, before making it have wide application in fields such as dye-sensitized solar cells, photocatalysis, ultracapacitors
Scape.Particularly with titanium oxide nanotubes prepared by anodizing, because being the in-situ preparation on Titanium base, Titanium base can be direct
As collector, it can be used as electrode of super capacitor without binder and use, therefore, the super electricity of titanium oxide nanotubes in recent years
The application study of container electrode material is gradually taken seriously.
However, being compared with other electrode material for super capacitor, the specific volume of TiOx nano tube material is relatively low, cannot meet
The application requirement of ultracapacitor.For this purpose, people improve the specific volume of titania meterial using various methods, mainly there is two at present
Major class method：Doping and increase specific surface area.For example, Zhu Xufei etc. discloses a kind of method improving titania meterial specific volume
（Patent 201310095453.2）：Reversely powering up pressure processing is carried out to Titanium oxide electrode, realizes the electrochemical doping to titanium oxide,
Enhance its chemical property, improves electrode conductivuty and specific volume.Tension and relaxation etc. discloses a kind of side for improving Titanium oxide electrode capacitance
Method（Patent 201410413665.5）：By the immersion treatment to Titanium oxide electrode in deionized water or villiaumite solution, increase
The specific surface area of electrode, to make its capacitive property greatly improve.In addition, also by by titanium oxide nanotubes in ammonium titanium fluoride
Hydro-thermal process in aqueous solution（H. Cui, et al., ElectrochimicaActa 253 (2017) 455-462）, or
It is handled in high-temperature high-pressure steam（H. Fan, et al., Journal of Power Sources 357 (2017) 230-
240）, change nanotube microscopic appearance, increase the specific surface area and specific volume of electrode.
For ultracapacitor, other than the requirement of Fabrication of High Specific Capacitance, while high charge and discharge circulation life is required, that is, existed
During charge and discharge cycles, the capacitance of capacitor should keep stable.Although the above method can improve the specific volume of titania meterial,
But its capacitance cyclical stability is poor.For example, anodizing obtain titanium oxide nanotubes by electrochemical doping, in 2 M
Li2SO4It in solution, is tested using cyclic voltammetry, the capacity retention after 2500 circle of cycle is only 65%（H.Wu, et al. ,
ElectrochimicaActa 116 (2014) 129-136）.For another example, after titanium oxide nanotubes room temperature bubble being handled,
The Na of 0.5 M concentration2SO4Electrochemical doping is carried out in solution, in 2 M Li2SO4In solution, 2000 are tested with cyclic voltammetry
Capacity retention after circle is 78%（C. Zhang, et al., Journal of Materials Science, 52
(2016) 1-7）.Such cyclical stability cannot be satisfied its application in ultracapacitor field.Therefore, it improves and is based on oxygen
The ultracapacitor capacitance cyclical stability for changing titanium nanotube has important actual application value.
Invention content
The purpose of the present invention is to provide a kind of easy, efficient super capacitor electrode of the raising based on titanium oxide nanotubes
The method of pole cycle life stability can preferably meet the application requirement in energy storage device field.
Realize that the technical solution of the object of the invention is：A kind of electrode of super capacitor based on titanium oxide nanotubes and
Preparation method includes the following steps：
The first step, to TiO2Nanotube or the TiO of microscopic appearance modification2Nanotube is made annealing treatment, and crystalline state TiO is obtained2
Nanotube；
Second step, with crystalline state TiO2Nanotube is working electrode, and graphite flake is to electrode, and saturated calomel electrode is reference electrode
In three-electrode system, using potassium hydroxide solution as electrolyte, electrochemical doping processing is carried out by cyclic voltammetry, is based on
The electrode of super capacitor of titanium oxide nanotubes, wherein working electrode and be 2.5 cm, cycle volt to two electrode spacings of electrode
The potential range of peace be the V of -1.6 V ~ 0, sweep speed be 100mV/s, a concentration of 2M ~ 6M of potassium hydroxide solution, scanning the number of turns be 5 ~
20 circles；
Third walks, the H2O2 for being 10% ~ 30% in mass fraction based on the electrode of super capacitor of titanium oxide nanotubes that will be obtained
30s ~ 5min is impregnated in aqueous solution, it is dry after washing.
Further, in the first step, to TiO2Nanotube is using hydro-thermal in room temperature water immersion treatment, ammonium titanium fluoride aqueous solution
Processing or high-temperature high-pressure steam processing method carry out microscopic appearance modification.
Further, in the first step, with 5oThe heating rate of C/min, is warming up to 150o2 h are kept the temperature after C, continue thereafter with liter
Temperature is to 450o3 h are kept the temperature after C, last Temperature fall obtains crystalline state TiO2Nanotube.
Ultracapacitor based on titanium oxide nanotubes, the electrode of above method preparation is described as the preparation of two electrodes
Ultracapacitor.
Compared with prior art, the present invention its remarkable advantage is：（1）By TiO2Electrode material is in alkaline potassium hydroxide solution
Middle progress electrochemical doping processing, can significantly improve TiO2The capacitance and stability of electrode.（2）By TiO2Electrode is in H2O2Water
Immersion treatment is carried out in solution, can more significantly improve TiO2The stability of electrode is based on titanium oxide nanotubes to improve
Ultracapacitor cycle life, when capacitor charging/discharging loop test 10000 encloses above, capacitance sustainment rate up to 99% with
On.（3）The method is easy, economically and efficiently improves the cycle life of such ultracapacitor, it is made to have in energy storage field
Better application prospect.
Specific implementation mode
It is further illustrated the present invention below by comparative example and embodiment.
Comparative example 1
Acetone and NaOH solution is used to remove Ti piece surface greases first.Then Ti pieces are put into chemical polishing solution（HF : H3NO3 :
H2O volume ratios are 1: 1 : 2）In about 15 s, remove surface film oxide.It is cleaned later with deionized water, last room temperature wind
It is dry for use.Using the Ti pieces handled well as working electrode, graphite rod is to electrode, is 0.5 wt% NH in electrolyte4F and 2
vol% H2In the ethylene glycol solution of O, water bath with thermostatic control 20oUnder C, with constant current 20mA/cm2Anodic oxidation 22.5min, oxidation terminate
Afterwards, it is rinsed, is air-dried with deionized water.
To TiO2Nanotube films are made annealing treatment, with 5oThe heating rate of C/min, is warming up to 150o2 h are kept the temperature after C, with
After be continuously heating to 450o3 h are kept the temperature after C, last Temperature fall obtains crystalline state TiO2Electrode.
To the TiO of crystalline state2Electrode carries out electrochemical doping processing.With TiO2Electrode is working electrode, and graphite rod is to electricity
Pole, two electrode spacings are 2.5 cm, and 0.5M metabisulfite solutions are electrolyte, and the potential range of cyclic voltammetric is -2.2V ~ 0V, with
Doping is completed after sweeping fast 10 circle of 100mV/s scannings.
Take above-mentioned two panels TiO2Electrode（1cm×1cm）As two electrodes of ultracapacitor, centre diaphragm paper（1cm×
1cm）It separates, and 0.5M sulfuric acid solutions is added dropwise as capacitor electrolyte.Be encapsulated in button cell shell, with tablet press machine with
The pressure of 60kN compresses battery case, makes the contact of each close structure to get to ultracapacitor.
The ultracapacitor prepared is subjected to constant current charge-discharge test, with 0.5mA/cm in the voltage range of 0.9V2
Current density constant current charge-discharge 1000 enclose.The capacitance of 1st circle is 7.67mF, and the capacitance of coulombic efficiency 98%, the 1000th circle is
5.37 mF, coulombic efficiency 97%, capacity retention 70.0%.
Embodiment 1
Size, pretreatment, anodic oxidation and the annealing process of Ti pieces are the same as comparative example 1.
Electrochemical doping processing is carried out to the TiO2 electrodes of crystalline state.Using TiO2 electrodes as working electrode, graphite rod is to electricity
Pole, two electrode spacings are 2.5 cm, and 2M potassium hydroxide solutions are electrolyte, and the potential range of cyclic voltammetric is the V of -1.6 V ~ 0,
It is to complete doping after 100mV/s scannings 5 are enclosed to sweep speed.
The electrolyte and preparation method of ultracapacitor are the same as comparative example 1.
The ultracapacitor prepared is subjected to constant current charge-discharge test, with 0.5mA/cm2 in the voltage range of 0.9V
Current density constant current charge-discharge 10000 enclose.The capacitance of 1st circle is 7.37mF, coulombic efficiency 99%, the capacitance of the 10000th circle
For 6.78 mF, coulombic efficiency 98%, capacity retention 92%.
Embodiment 2
Size, pretreatment, anodic oxidation and the annealing process of Ti pieces are the same as comparative example 1.
To the TiO of crystalline state2Electrode carries out electrochemical doping processing.With TiO2Electrode is working electrode, and graphite rod is to electricity
Pole, two electrode spacings are 2.5 cm, and 2M potassium hydroxide solutions are electrolyte, and the potential range of cyclic voltammetric is the V of -1.6 V ~ 0,
It is to complete doping after 100mV/s scannings 5 are enclosed to sweep speed.Then the H for being 30% in mass fraction2O20.5min is impregnated in solution, is used
Deionized water is rinsed well and is dried.
The electrolyte and preparation method of ultracapacitor are the same as comparative example 1.
The ultracapacitor prepared is subjected to constant current charge-discharge test, with 0.5mA/cm in the voltage range of 0.9V2
Current density constant current charge-discharge 10000 enclose.The capacitance of 1st circle is 7.32mF, coulombic efficiency 99%, the capacitance of the 10000th circle
For 7.26 mF, coulombic efficiency 98%, capacity retention 99.2%.
Embodiment 3
Size, pretreatment, anodic oxidation, annealing and the electrochemical doping treatment process of Ti pieces change H with embodiment 12O2Solution
Mass fraction is 10%, soaking time 2min.Ultracapacitor and constant current charge-discharge test condition are prepared with embodiment 1.1st
The capacitance of circle is 7.72 mF, and the capacitance of coulombic efficiency 99%, the 10000th circle is 7.65mF, coulombic efficiency 99%, capacitance guarantor
Holdup is 99.1%.
Embodiment 4
The sizes of Ti pieces, pretreatment, anodic oxidation, annealing process are with embodiment 1, potassium hydroxide solution when changing electrochemical doping
A concentration of 6M, scanning the number of turns 15 enclose, H2O2H in solution2O2Mass fraction is 15%, soaking time 1.5min.Other electricity
Chemical doping, H2O2Solution soaking conditions prepare ultracapacitor and constant current charge-discharge test condition with embodiment 1.1st circle
Capacitance is 7.83 mF, and the capacitance of coulombic efficiency 99%, the 10000th circle is 7.77mF, coulombic efficiency 97%, capacity retention
It is 99.3%.
Embodiment 5
Size, pretreatment, anodic oxidation and the annealing process of Ti pieces are with embodiment 1, and potassium hydroxide is molten when changing electrochemical doping
A concentration of 3M of liquid, the scanning number of turns 10 are enclosed, H2O2H in solution2O2Mass fraction is 20%, soaking time 4min.Other electricity
Chemical doping, H2O2Solution soaking conditions prepare ultracapacitor and constant current charge-discharge test condition with embodiment 1.1st circle
Capacitance is 7.62 mF, and the capacitance of coulombic efficiency 98%, the 10000th circle is 7.56mF, coulombic efficiency 98%, capacity retention
It is 99.2%.
Embodiment 6
Size, pretreatment, anodic oxidation and the annealing process of Ti pieces are with embodiment 1, and potassium hydroxide is molten when changing electrochemical doping
A concentration of 4M of liquid, the scanning number of turns 20 are enclosed, H2O2H in solution2O2Mass fraction is 25%, soaking time 5min.Other electricity
Chemical doping, H2O2Solution soaking conditions prepare ultracapacitor and constant current charge-discharge test condition with embodiment 1.1st circle
Capacitance is 7.18mF, and coulombic efficiency is that the capacitance of 99% the 10000th circle is 7.13mF, coulombic efficiency 99%, the capacitance of capacitor
Conservation rate is 99.3%.
Embodiment 7
Size, pretreatment, anodic oxidation and the annealing process of Ti pieces are with embodiment 1, and potassium hydroxide is molten when changing electrochemical doping
A concentration of 5M of liquid, the scanning number of turns 10 are enclosed, H2O2H in solution2O2Mass fraction is 20%, soaking time 3.5min.Other
Electrochemical doping, H2O2Solution soaking conditions prepare ultracapacitor and constant current charge-discharge test condition with embodiment 1.1st circle
Capacitance be 7.75 mF, coulombic efficiency 100%, the 10000th circle capacitance be 7.68mF, coulombic efficiency 99%, capacitance keep
Rate is 99.1%.
Embodiment 8
Size, pretreatment, anodic oxidation and the annealing process of Ti pieces are with embodiment 1, and potassium hydroxide is molten when changing electrochemical doping
A concentration of 3.5M of liquid, the scanning number of turns 10 are enclosed, H2O2H in solution2O2Mass fraction is 15%, soaking time 2.5min.Its
His electrochemical doping, H2O2Solution soaking conditions prepare ultracapacitor and constant current charge-discharge test condition with embodiment 1.1st
The capacitance of circle is 7.37 mF, and the capacitance of coulombic efficiency 100%, the 10000th circle is 7.32mF, coulombic efficiency 97%, capacitance guarantor
Holdup is 99.3%.
Embodiment 9
The sizes of Ti pieces, pretreatment, anode oxidation process are the same as embodiment 1.Titanium oxide nanotubes are carried out at ammonium titanium fluoride immersion
Reason, by titanium oxide nanotubes made from anodic oxidation in the ammonium titanium fluoride aqueous solution of 0.01 M, hydro-thermal process at 120 DEG C
Then 45min carries out Annealing Crystallization processing.Annealing process, electrochemical doping processing, H2O2Solution soaking conditions prepare super electricity
Container and constant current charge-discharge test condition are the same as embodiment 4.1st circle capacitance be 12.65 mF, coulombic efficiency 99%, the 10000th
The capacitance of circle is 12.56mF, and the capacity retention of coulombic efficiency 99%, capacitor is 99.3%.
Embodiment 10
The sizes of Ti pieces, pretreatment, anode oxidation process are the same as embodiment 1.Room temperature bubble processing is carried out to titanium oxide nanotubes, it will
Titanium oxide nanotubes made from anodic oxidation in deionized water, impregnate 72h at 25 DEG C, then carry out Annealing Crystallization processing.It moves back
Ignition technique, electrochemical doping processing, H2O2Solution soaking conditions prepare ultracapacitor and constant current charge-discharge test condition with real
Apply example 3.The capacitance of 1st circle is 25.08 mF, and the capacitance of coulombic efficiency 99%, the 10000th circle is 24.85mF, and coulombic efficiency is
96%, capacity retention 99.1%.
Embodiment 11
The sizes of Ti pieces, pretreatment, anode oxidation process are the same as embodiment 1.Steam treatment is carried out to titanium oxide nanotubes, will be had
The Ti pieces of titanium oxide nanotubes are fitted into the 50mL polytetrafluoroethylene (PTFE) water heating kettle liners for filling water, TiOx nano tube portion not with
Water contacts, and water heating kettle is kept to 1 hour and cooled to room temperature at 180 DEG C.Then Annealing Crystallization processing is carried out to titanium oxide.
Annealing conditions, electrochemical doping processing, H2O2Solution soaking conditions prepare ultracapacitor and constant current charge-discharge test condition is same
The capacitance that embodiment the 2, the 1st is enclosed is 29.9 mF, and the capacitance of coulombic efficiency 100%, the 10000th circle is 29.66mF, coulombic efficiency
It is 98%, the capacity retention of capacitor is 99.2%.
Each embodiment detail parameters comparison sees attached list 1.
Table 1
| Number | Specially treated | KOH concentration/M | Scan the number of turns/circle | H2O2Concentration/wt% | Soaking time/min | First lap capacitance/mF | Condenser capacitance conservation rate |
| Comparative example 1 | Nothing | Nothing | Nothing | Nothing | Nothing | 7.67 | 70% |
| Embodiment 1 | Nothing | 2 | 5 | Nothing | Nothing | 7.37 | 92% |
| Embodiment 2 | Nothing | 2 | 5 | 30 wt% | 0.5 | 7.32 | 99.2% |
| Embodiment 3 | Nothing | 2 | 5 | 10 wt% | 2 | 7.72 | 99.1% |
| Embodiment 4 | Nothing | 6 | 15 | 15 wt% | 1.5 | 7.83 | 99.3% |
| Embodiment 5 | Nothing | 3 | 10 | 20 wt% | 4 | 7.62 | 99.2% |
| Embodiment 6 | Nothing | 4 | 20 | 25 wt% | 5 | 7.18 | 99.3% |
| Embodiment 7 | Nothing | 5 | 10 | 20 wt% | 3.5 | 7.75 | 99.1% |
| Embodiment 8 | Nothing | 3.5 | 10 | 15 wt% | 2.5 | 7.37 | 99.3% |
| Embodiment 9 | Ammonium titanium fluoride immersion treatment | 6 | 15 | 15 wt% | 1.5 | 12.65 | 99.3% |
| Embodiment 10 | The processing of room temperature bubble | 2 | 5 | 10 wt% | 2 | 25.08 | 99.1% |
| Embodiment 11 | Steam treatment | 2 | 5 | 30 wt% | 0.5 | 29.9 | 99.2% |
Claims (5)
1. the preparation method of the electrode of super capacitor based on titanium oxide nanotubes, which is characterized in that include the following steps：
The first step, to TiO2Nanotube or the TiO of microscopic appearance modification2Nanotube is made annealing treatment, and crystalline state TiO is obtained2
Nanotube；
Second step, with crystalline state TiO2Nanotube is working electrode, and graphite flake is to electrode, and saturated calomel electrode is reference electrode
In three-electrode system, using potassium hydroxide solution as electrolyte, electrochemical doping processing is carried out by cyclic voltammetry, is based on
The electrode of super capacitor of titanium oxide nanotubes, wherein working electrode and be 2.5 cm, cycle volt to two electrode spacings of electrode
The potential range of peace be the V of -1.6 V ~ 0, sweep speed be 100mV/s, a concentration of 2M ~ 6M of potassium hydroxide solution, scanning the number of turns be 5 ~
20 circles；
Third walks, the H2O2 for being 10% ~ 30% in mass fraction based on the electrode of super capacitor of titanium oxide nanotubes that will be obtained
30s ~ 5min is impregnated in aqueous solution, it is dry after washing.
2. preparation method as described in claim 1, which is characterized in that in the first step, to TiO2Nanotube is impregnated using room temperature water
Hydro-thermal process or high-temperature high-pressure steam processing method carry out microscopic appearance modification in processing, ammonium titanium fluoride aqueous solution.
3. preparation method as described in claim 1, which is characterized in that in the first step, with 5oThe heating rate of C/min, is warming up to
150o2 h are kept the temperature after C, are continued thereafter with and are warming up to 450o3 h are kept the temperature after C, last Temperature fall obtains crystalline state TiO2Nanotube.
4. the electrode of super capacitor based on titanium oxide nanotubes prepared by preparation method as described in any one of claims 1-3.
5. the ultracapacitor based on titanium oxide nanotubes, electricity prepared by preparation method as described in any one of claims 1-3
Pole prepares the ultracapacitor as two electrodes.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101536219A (en) * | 2006-11-10 | 2009-09-16 | 富士重工业株式会社 | Electrode material, electrode material manufacturing method and nonaqueous lithium secondary battery |
| CN101684566A (en) * | 2008-09-27 | 2010-03-31 | 比亚迪股份有限公司 | Titanium dioxide nanometer membrane and preparation method thereof |
| CN101857966A (en) * | 2009-03-19 | 2010-10-13 | 北京大学 | Self-standing TiO2 nanotube array membrane and preparation method thereof |
| CN102698745A (en) * | 2012-06-06 | 2012-10-03 | 厦门大学 | Titanium dioxide nanotube carried palladium nano catalyst and preparation method of same |
| CN103165283A (en) * | 2013-03-22 | 2013-06-19 | 南京理工大学 | Method for enhancing electrochemical performance of TiO2 electrode |
| CN105448539A (en) * | 2014-08-20 | 2016-03-30 | 南京理工大学 | Method for increase capacitance of TiO2 electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101536219A (en) * | 2006-11-10 | 2009-09-16 | 富士重工业株式会社 | Electrode material, electrode material manufacturing method and nonaqueous lithium secondary battery |
| CN101684566A (en) * | 2008-09-27 | 2010-03-31 | 比亚迪股份有限公司 | Titanium dioxide nanometer membrane and preparation method thereof |
| CN101857966A (en) * | 2009-03-19 | 2010-10-13 | 北京大学 | Self-standing TiO2 nanotube array membrane and preparation method thereof |
| CN102698745A (en) * | 2012-06-06 | 2012-10-03 | 厦门大学 | Titanium dioxide nanotube carried palladium nano catalyst and preparation method of same |
| CN103165283A (en) * | 2013-03-22 | 2013-06-19 | 南京理工大学 | Method for enhancing electrochemical performance of TiO2 electrode |
| CN105448539A (en) * | 2014-08-20 | 2016-03-30 | 南京理工大学 | Method for increase capacitance of TiO2 electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111472032A (en) * | 2020-04-29 | 2020-07-31 | 南方科技大学 | Nano porous structure metal material and preparation method thereof |
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