CN101625930B - Ordered nano-tube array structure electrode material, preparation method and stored energy application - Google Patents
Ordered nano-tube array structure electrode material, preparation method and stored energy application Download PDFInfo
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Abstract
The invention relates to a preparation method for electrode material of a super capacitor of an ordered nano-tube array structure. A titanium-base titanium dioxide nano-tube is used as a carrier of the electrode; metallic oxide with electrochemical activity is loaded on the tube wall surface of the nano-tube; functional electrode material of the nano-tube array structure is built, wherein the tube diameter of the nano-tube is 50-200nm, the wall thickness is 10-20nm and the length is 0.2-50 mu m. The preparation method is as follows: firstly, adopting the titanium-base titanium dioxide electrode carrier of the ordered nano-tube array structure prepared by a self-template anodic oxidation reaction synthetic method; then, taking the titanium-base titanium dioxide electrode carrier of the ordered nano-tube array structure as a working electrode and transition metal ion or noble metal ion water solution as working electrolyte, carrying out electro reduction-electro oxidation reaction by circulation, synthesizing a metallic oxide coating layer on the wall surface of the nano-meter tube in situ, and preparing electrode material with the electrochemical activity. The electrode material of the ordered nano-tube array structure is used as the stored energy application of the electrode of the super capacitor.
Description
Technical field
The present invention relates to a kind of electrode material for super capacitor and preparation method thereof and stored energy application, relate in particular to a kind of ordered nano-tube array structure electrode material and preparation method thereof and stored energy application, belong to ordered nano material and electrochemical energy storage technical field thereof.
Background technology
At present; The double electric layer capacitor that commercial ultracapacitor mainly is based on electrolyte negative ions Effect of Electric Double Layer mechanism store charge, makes up with various carbon electrode materials; Although have the advantage of low cost of manufacture and long service life; But significantly shortcoming is that energy density is very low, and energy storage efficiency is very poor.It has been generally acknowledged that based on the reversible redox reagentia of electrochemical active compound mechanism stored charge, higher specific capacitance arranged with the pseudo capacitance utensil of some noble metal/transition metal oxides or conductive polymer electrodes material.And the electro-chemical activity of these metal oxides or conducting polymer depends on factors such as its intrinsic property, surface topography, phase structure, and expansion electrochemical reaction interface can effectively be improved it and compared capacitive property.Secondly need improve the energy storage usefulness and the stability of these electrochemical active material cycle charge-discharges.The present invention proposes the Nano tube array of titanium dioxide that can regulate and control with pipe wall independence, pore distribution homogeneous, caliber is the rigid electrode skeleton; The transition metal oxide of coating decoration electro-chemical activity, metal oxide containing precious metals or conducting polymer on the nanotube wall form that arrange, coaxial heterogeneous nano-tube array structure the in order functional electrode material of bigger serface.In charge and discharge process, the interfacial electrochemistry reactive compound carries out the redox reaction of reversible embedding-move out respectively with the reactive ion of its coupling, impel its capacitive property and energy storage efficiency to be higher than the monolithic entity phase material far away.The metal oxide of these electro-chemical activities or the ordered nano-tube array structure of conducting polymer can effectively improve the electro-chemical activity and the energy storage efficiency of these electrode materials; And can effectively improve the stability of these electrode material cycle charge-discharges based on the coaxial heterogeneous nano-tube array structure of titanium dioxide rigid backbone; Thus, the functional electrode material of ordered nano-tube array structure can be realized the industrial stored energy application of high-efficiency energy-storage type ultracapacitor of new generation.
Summary of the invention
The present invention provides a kind of ordered nano-tube array structure electrode material and preparation method thereof and stored energy application, has the advantage of the high-efficiency energy-storage and the cycle charge discharge electrical stability thereof of high specific capacitance amount and power density simultaneously by the electrode material for super capacitor of the ordered nano-tube array structure of the present invention preparation.Preparation method's simple possible of the present invention, and the energy storage efficiency of electrochemical active material is very high.
Electrode material for super capacitor according to the invention is following:
A kind of electrode material of ordered nano-tube array structure is an electrode holder with the titanium-based titanium dioxide nanotube, and the metal oxide of electro-chemical activity is modified in load on its tube wall face; Make up that arrange, coaxial heterogeneous nano-tube array structure in order functional electrode material, the caliber 50-200nm of nanotube wherein, wall thickness 10-20nm; Length 0.2-50 μ m, the metal oxide of above-mentioned electro-chemical activity can be selected transition metal oxide for use, metal oxide containing precious metals and their compound; For example: NiO, MnO
2, Co
2O
3, V
2O
5, RuO
2, IrO
2Or Ta
2O
5
The preparation method of the electrode material of ordered nano-tube array structure of the present invention is following:
At first, adopt self-template anodic oxidation reactions synthetic method to prepare the titanium-based titanium dioxide electrode holder of ordered nano-tube array structure.Then; Set up the three-electrode electro Chemical reaction system; With the titanium-based titanium dioxide electrode holder of ordered nano-tube array structure is work electrode, platinized platinum for being that reference electrode, concentration are that the 0.005～0.05M transition metal ions or the precious metal ion aqueous solution are working electrolyte to electrode, calomel electrode or silver-silver chloride electrode; Through circulation electroreduction-electro-oxidation reaction; Original position synthesis of metal oxide coating layer on the nanotube wall is prepared based on the functional electrode material titanium dioxide nanocrystalline skeleton, large-area ordered arrangement, heterogeneous nano-tube array structure.
Described self-template anodic oxidation reactions synthetic method is: set up bipolar electrode electrochemical reaction system; With the metal titanium sheet be that anode, platinized platinum are that the organic solution of the aqueous solution or the fluoride ion compound of negative electrode, fluoride ion compound is that electrolyte, electrochemistry operating voltage are controlled at 20 to 80V, the reaction time is controlled at 0.5 to 60h; Prepare on titanium sheet two sides all titanium dioxide of vertical-growth nanotube through electrochemical anodization reaction; With this nanotube is that self-template carries out the anodic oxidation reactions of secondary at least, prepares the titanium-based titanium dioxide electrode holder of the ordered nano-tube array structure that pipe wall independence, pore distribution homogeneous, caliber can regulate and control.
Described fluoride ion compound is hydrogen fluoride, ammonium fluoride or sodium fluoride.
Organic solvent in the organic solution of described fluoride ion compound is ethylene glycol, glycerine or N, the N-dimethylacetylamide.
The electrode material of ordered nano-tube array structure of the present invention is as the stored energy application of electrode of super capacitor.
Electrode material for super capacitor of the present invention has the following advantages:
(1) metal oxide-coated of electro-chemical activity forms coaxial heterogeneous nano tube structure on the titanium dioxide skeleton; Can effectively enlarge the reaction specific area; And the energy storage efficiency of the metal oxide of raising electro-chemical activity, be applied to the high-efficiency energy-storage function that faraday's ultracapacitor is realized high specific capacitance amount and power density.
(2) electrode material has the nano-tube array structure of large-area ordered arrangement, in electrochemical reaction process, help in the nanochannel the ion mass transfer and along the electrical conductivity of nanotube wall.The titania nanotube rigid-skeleton can prevent the avalanche of nanochannel, guarantees the stability of electrode material at continuous cycle charge discharge electric process, improves the useful life of ultracapacitor.
Description of drawings
Fig. 1. (A) TiO that grows in the Ti substrate
2The scanning electron microscope diagram sheet of ordered nano-tube array electrode carrier; (B) TiO
2The scanning electron microscope diagram sheet of the coaxial heterogeneous ordered nano-tube array electrode of the nickel oxide of nanotube rigid backbone load modification electro-chemical activity.
TiO grows in Fig. 2 .Ti substrate
2Ordered nano-tube array electrode carrier and Ni (OH)
2-TiO
2, NiO-TiO
2The X ray diffracting spectrum of coaxial heterogeneous nanometer pipe array electrode.
Fig. 3 .NiO-TiO
2Coaxial heterogeneous nanometer pipe array electrode in 1.0M NaOH aqueous electrolyte, (A) charging and discharging curve under the different electric current density; (B) with 2mA cm
-2The cycle charge-discharge curve of constant current density.
TiO grows in Fig. 4 .Ti substrate
2Ordered nano-tube array electrode carrier, RuO
2Membrane electrode and RuO
2-TiO
2The X ray diffracting spectrum of coaxial heterogeneous nanometer pipe array electrode.
Fig. 5 .Ti base RuO
2Membrane electrode (0.9mg cm
-2RuO
2) and RuO
2-TiO
2Coaxial heterogeneous ordered nano-tube array electrode (0.3mg cm
-2RuO
2) at 1.0M H
2SO
4Aqueous electrolyte and 1.2mA cm
-2Charging and discharging curve under the constant current density condition.
Fig. 6 .RuO
2-TiO
2Coaxial heterogeneous ordered nano-tube array electrode is at 1.0M H
2SO
4Aqueous electrolyte and 0.2mAcm
-2Cycle charge-discharge curve under the constant current density condition.
Embodiment
Embodiment 1
A kind of electrode material for super capacitor of ordered nano-tube array structure.Earlier on base material titanium sheet the two sides all the Nano tube array of titanium dioxide that can regulate and control of growth tube wall independence, pore distribution homogeneous, caliber be the rigid electrode skeleton; On the nanotube wall, deposit metal oxide then with electro-chemical activity; Form the bigger serface functional electrode material of the coaxial heterogeneous nano-tube array structure of arrangement in order, and be applied to faraday's ultracapacitor.
The preparation method of electrode material for super capacitor of the present invention is following:
At first; Adopt self-template anodic oxidation reactions synthetic method; Behind the titanium sheet process anodic oxidation reactions first time; Sonicated is removed the surface titanium dioxide rete, and is that self-template carries out the electrochemical anodization reaction of secondary at least with this titanium-based titanium dioxide nanotube, generates the titanium dioxide of the ordered nano-tube array structure that pipe wall independence, pore distribution homogeneous, caliber can regulate and control.Secondly; Adopt the electrochemical deposition synthetic method; More than the Nano tube array of titanium dioxide of preparation is an electrode holder; The transition metal ions or the precious metal ion aqueous solution are the reaction electrolyte, through the metal oxide and the Heterogeneous Composite thing thereof of the synthetic electro-chemical activity of circulation electroreduction-electroxidation method original position on the nanotube wall, prepare and have metal oxide electro-chemical activity, ordered nano-tube array structure-titanium dioxide electrode material for super capacitor.
Titanium-based titanium dioxide nanotube array electrode carrier material used in the present invention is a self-template with the titanium sheet of the anodized first time, and adopting at least, the anodic oxidation reactions synthetic method of secondary prepares; The thing coat of the electro-chemical activity that electrode material for super capacitor used in the present invention relates to can be nickel oxide or ruthenium-oxide, can also be the transition metal oxide of some other electro-chemical activity, metal oxide containing precious metals or conducting polymer.
The scanning electron microscope diagram sheet of Fig. 1 (A) shows and adopts the synthetic titanium dioxide ordered nano-tube of self-template anodic oxidation reactions to have the characteristic that pipe wall independence, pore distribution homogeneous, caliber can be regulated and control.It is rigid backbone that the scanning electron microscope diagram sheet of Fig. 1 (B) shows with the titania nanotube, and the nickel oxide of electro-chemical activity applies modification tube wall face and forms electrode material for super capacitor large-area ordered arrangement, heterogeneous nano-tube array structure.
Embodiment 3
Present embodiment is NiO-TiO
2Ordered nano-tube array structure electrode material for super capacitor and concrete stored energy application example thereof.Metal titanium sheet is at difference acetone and alcohol solvent ultrasonic cleaning 20min, at HF (3.3M)-HNO
3(5.6M) carry out chemical polishing processing 15s in the aqueous solution and form fresh pure titanium metal surface.Setting up two electrode electro Chemical reaction systems, is anode with the titanium sheet, and platinized platinum is a negative electrode, H
3PO
4(0.5M)-glycol/water (50/50 of HF (0.15M); V/V) mixed solution is a working electrolyte; React 2h under the constant voltage 30V condition; Adopt the electrode holder material of the titanium sheet two sides growth titania nanotube of self-template anodic oxidation reactions synthetic method preparation, change into the Detitanium-ore-type crystal through titania nanotube behind 450 ℃ of heat treatment 2h by amorphous state again.Setting up the three-electrode electro Chemical reaction system then, is work electrode with top synthetic titanium-based titanium dioxide nanotube, and platinized platinum is to electrode, and saturated calomel electrode is a reference electrode, 0.02M Ni (Ac)
2The aqueous solution is the reaction electrolyte, with-1.0mA cm
-2Electro-reduction reaction 8min under the galvanostatic conditions; On titanium dioxide nano-tube support, generate the metallic nickel sedimentary deposit; In 1.0M NaOH aqueous electrolyte, the work electrode electromotive force is cyclic voltammetry scan 15min in 0 to 0.9V vs.SCE scope then, and electro-oxidation reaction generates the nickel hydroxide sedimentary deposit.Generate NiO-TiO through 300 ℃ of heat treatment dehydration 2h at last
2The electrode material for super capacitor of ordered nano-tube array structure.
Fig. 2 shows Ti base TiO
2Ordered nano-tube electrode holder and Ni (OH)
2-TiO
2, NiO-TiO
2The X ray diffracting spectrum of coaxial heterogeneous nanotube electrode.Wherein (a) is the titania nanotube (TiO that grows on the titanium base
2/ Ti) XRD figure spectrum except Ti metallicity diffraction maximum occurring, also hkl crystal face { 101} and { the 200} characteristic diffraction peak shows TiO occurs with 48.2 ° of positions in 2 θ=25.4 ° on the collection of illustrative plates
2Has anatase phase crystal structure.(b) be the synthetic Ni (OH) of circulation electroreduction-electro-oxidation reaction
2-TiO
2The XRD figure of coaxial heterogeneous nanotube spectrum, collection of illustrative plates are presented at 2 θ=19.6 ° and 33.4 ° of positions and hkl crystal face { 001} and { the 100} characteristic diffraction peak shows Ni (OH) occurs
2Has hexagonal system structure.(c) be that the heat treatment dehydration generates NiO-TiO
2The XRD figure of coaxial heterogeneous nanotube spectrum, collection of illustrative plates are presented at 2 θ=43.5 ° and hkl crystal face { 200} and { the 111} characteristic diffraction peak shows that NiO has cubic crystal structure occur with 37.5 °.Therefore, the NiO-TiO that synthesizes large-area ordered arrangement, coaxial heterogeneous nano-tube array structure according to the inventive method
2Have and efficiently discharge and recharge active cubic crystal structure NiO.
Fig. 3 A shows NiO-TiO
2The ordered nano-tube array structure electrode in 1.0M NaOH aqueous electrolyte, potential windows be-0.1 to 0.5V and different electric current density condition under charging and discharging curve.When the constant current density that discharges and recharges is controlled at respectively is 0.5,1.0,1.5 with 2.0mA cm
-2The time, this electrode faraday is respectively 72.8,69.6 than electric capacity, 67.1 with 65.1mF cm
-2Fig. 3 B shows NiO-TiO
2The ordered nano-tube array structure electrode is constant current cycle charge-discharge curve in 1.0M NaOH aqueous electrolyte.When the constant current density that discharges and recharges is controlled at 2.0mA cm
-2, 1000 later NiO-TiO of cycle charge-discharge
2The specific capacitance of electrode only decays 7.6%, therefore, and the NiO-TiO of the inventive method preparation
2The ordered nano-tube array structure electrode has cycle charge discharge electrical stability preferably.
Embodiment 4
Present embodiment is RuO
2-TiO
2Ordered nano-tube array structure electrode material for super capacitor and concrete stored energy application example thereof.Described in the preparation of titanium dioxide nanotube electrode carrier material such as the embodiment 3.Set up the three-electrode electro Chemical reaction system then, more than synthetic titanium-based titanium dioxide nanotube is a work electrode, and platinized platinum is for being reference electrode to electrode and saturated calomel electrode, RuCl
3(0.02M)-HCl (0.005M) aqueous solution is the reaction electrolyte, with-1.0mA cm
-2Constant current electro-reduction reaction 30min generates the metal Ru sedimentary deposit on titanium dioxide nano-tube support; Then with 1.0M H
2SO
4The aqueous solution is in the working electrolyte, and the work electrode electromotive force is cyclic voltammetry scan 15min in 0 to 1.0V scope, and electro-oxidation reaction generates the ruthenium oxide hydration sedimentary deposit.Behind 150 ℃ of heat treatment reaction 2h, generate RuO at last
2-TiO
2The electrode material for super capacitor of heterogeneous nano-tube array structure.In the contrast experiment, replace titanium-based titanium dioxide nanotube to prepare RuO under the same conditions with pure titanium sheet
2Membrane electrode.
Fig. 4 shows Ti basal growth TiO
2The ordered nano-tube electrode holder, RuO
2Membrane electrode, RuO
2-TiO
2The X ray diffracting spectrum of coaxial heterogeneous nanotube electrode.Wherein (a) is Ti base TiO
2The XRD figure of nanotube electrode carrier spectrum, the hkl crystal face that occurs with 48.2 ° of positions in 2 θ=25.4 ° { 101} and { the 200} characteristic diffraction peak shows TiO
2Has anatase phase crystal structure.(b) be Ti base RuO
2The XRD figure spectrum of membrane electrode; (c) be Ti base RuO
2-TiO
2The XRD figure spectrum of coaxial heterogeneous nanotube electrode.(b) and (c) collection of illustrative plates the hkl crystal face of weak intensity all occurs { the 100} characteristic diffraction peak shows the RuO that electrochemistry is synthetic in ° position, 2 θ=42.2
2And RuO
2-TiO
2All there is the Ru metallic crystal of trace, but orthorhombic system RuO all do not occur in ° position, 2 θ=28.2
2The hkl crystal face { the 110} characteristic diffraction peak shows RuO thus
2And RuO
2-TiO
2All do not form the crystal phase structure, and still have impalpable structure.Therefore, according to the synthetic large-area ordered arrangement of the inventive method, coaxial heterogeneous nano-tube array RuO
2-TiO
2Have and efficiently discharge and recharge active impalpable structure RuO
2
Fig. 5 shows Ti base RuO
2Membrane electrode and RuO
2-TiO
2Coaxial heterogeneous ordered nano-tube array electrode is at 1.0MH
2SO
4Aqueous electrolyte and 1.2mA cm
-2Charging and discharging curve under the constant current density condition.Experimental result shows that discharge and recharge the potential windows scope is-0.5 to 0.7V, and the steady state working voltage of functional electrode is 1.2V, and this value has approached the upper limit (UL) voltage of ultracapacitor in aqueous electrolyte.RuO
2The specific capacitance of membrane electrode is 241F g
-1, and RuO
2-TiO
2The specific capacitance of coaxial heterogeneous ordered nano-tube array electrode reaches 640F g
-1Corresponding power density be respectively 0.8 with 2.4kw kg
-1Therefore, the RuO for preparing according to the inventive method
2-TiO
2Heterogeneous nano-tube array adopts TiO
2Ordered nano-tube can effectively improve RuO as electrode holder
2Than electric capacity and power density performance.
Fig. 6 shows RuO
2-TiO
2The cycle charge-discharge curve of coaxial heterogeneous ordered nano-tube array structure electrode.Experimental result is presented at 1.0M H
2SO
4In the aqueous electrolyte, 0.2mA cm
-2Constant current density and-0.2 to 0.65V discharges and recharges under the condition of potential windows scope, arranges coaxial heterogeneous nanotube RuO in order
2-TiO
2Electrode is decayed less than 2.0% the RuO that therefore prepares according to the inventive method at the specific capacitance that discharges and recharges continuously after 1000 times
2-TiO
2The ordered nano-tube array structure electrode has extraordinary cycle charge discharge electrical stability.
Embodiment 5
A kind of electrode material of ordered nano-tube array structure is an electrode holder with the titanium-based titanium dioxide nanotube, and the metal oxide of electro-chemical activity is modified in load on its tube wall face; Make up that arrange, coaxial heterogeneous nano-tube array structure in order functional electrode material, the caliber 50-200nm of nanotube wherein, wall thickness 10-20nm; Length 0.2-50 μ m, the caliber of the nanotube of present embodiment are 50,70,100,125 or 200nm, wall thickness 10,12,15 or 20nm; Length 0.2,0.9,10,35 or 50 μ m, the metal oxide of above-mentioned electro-chemical activity can be selected transition metal oxide for use, metal oxide containing precious metals or conducting polymer; For example: NiO, MnO
2, Co
2O
3, V
2O
5, RuO
2, IrO
2Or Ta
2O
5
The preparation method of the electrode material of ordered nano-tube array structure of the present invention is following:
At first adopt self-template anodic oxidation reactions synthetic method to prepare the titanium-based titanium dioxide electrode holder of ordered nano-tube array structure; Then; Set up the three-electrode electro Chemical reaction system; With the titanium-based titanium dioxide electrode holder of ordered nano-tube array structure is work electrode, platinized platinum for being that reference electrode, concentration are that the 0.005～0.05M transition metal ions or the precious metal ion aqueous solution are working electrolyte to electrode, calomel electrode or silver-silver chloride electrode; Through circulation electroreduction-electro-oxidation reaction; The metal oxide coating layer of the synthetic electro-chemical activity of original position is prepared based on the functional electrode material titanium dioxide nanocrystalline skeleton, large-area ordered arrangement, heterogeneous nano-tube array structure on the nanotube wall.
Described self-template anodic oxidation reactions synthetic method is: set up bipolar electrode electrochemical reaction system; With the metal titanium sheet be that anode, platinized platinum are that the organic solution of the aqueous solution or the fluoride ion compound of negative electrode, fluoride ion compound is that electrolyte, electrochemistry operating voltage are controlled at 20 to 80V, the reaction time is controlled at 0.5 to 60h; Prepare on titanium sheet two sides all titanium dioxide of vertical-growth nanotube through electrochemical anodization reaction; With this nanotube is that self-template carries out the anodic oxidation reactions of secondary at least, prepares the titanium-based titanium dioxide electrode holder of the ordered nano-tube array structure that pipe wall independence, pore distribution homogeneous, caliber can regulate and control.
Described fluoride ion compound is hydrogen fluoride, ammonium fluoride or sodium fluoride.
Organic solvent in the organic solution of described fluoride ion compound is ethylene glycol, glycerine or N, the N-dimethylacetylamide.
Claims (7)
1. the electrode material of an ordered nano-tube array structure; It is characterized in that with the titanium-based titanium dioxide nanotube being electrode holder; The metal oxide of electro-chemical activity is modified in load on its tube wall face, makes up that arrange, coaxial heterogeneous nano-tube array structure in order functional electrode material, wherein the caliber 50-200nm of nanotube; Wall thickness 10-20nm, length 0.2-50 μ m.
2. the electrode material of ordered nano-tube array structure according to claim 1 is characterized in that the electro-chemical activity metal oxide comprises transition metal oxide, metal oxide containing precious metals and their compound.
3. the electrode material of ordered nano-tube array structure according to claim 2 is characterized in that the electro-chemical activity metal oxide is NiO, MnO
2, Co
2O
3, V
2O
5, RuO
2, IrO
2Or Ta
2O
5
4. the preparation method of the electrode material of the described ordered nano-tube array structure of claim 1 is characterized in that:
At first; Adopt self-template anodic oxidation reactions synthetic method to prepare the titanium-based titanium dioxide electrode holder of ordered nano-tube array structure; Then; Set up the three-electrode electro Chemical reaction system; With the titanium-based titanium dioxide electrode holder of ordered nano-tube array structure is work electrode, platinized platinum for being that reference electrode, concentration are that the 0.005～0.05M transition metal ions or the precious metal ion aqueous solution are working electrolyte to electrode, calomel electrode or silver-silver chloride electrode; Through circulation electroreduction-electro-oxidation reaction, the metal oxide coating layer of the synthetic electro-chemical activity of original position is prepared based on the functional electrode material titanium dioxide nanocrystalline skeleton, large-area ordered arrangement, heterogeneous nano-tube array structure on the nanotube wall; The method of the metal oxide coating layer of the synthetic electro-chemical activity of original position is one of following two kinds of methods on the nanotube wall:
Method one: with 0.02M Ni (Ac)
2The aqueous solution is the reaction electrolyte, with-1.0mAcm
-2Electro-reduction reaction 8min under the galvanostatic conditions; On titanium dioxide nano-tube support, generate the metallic nickel sedimentary deposit; Then in 1.0M NaOH aqueous electrolyte; The work electrode electromotive force is cyclic voltammetry scan 15min in 0 to 0.9V vs.SCE scope, and electro-oxidation reaction generates the nickel hydroxide sedimentary deposit, generates NiO-TiO through 300 ℃ of heat treatment dehydration 2h at last
2The electrode material for super capacitor of ordered nano-tube array structure;
Method two: with RuCl
3(0.02M)-HCl (0.005M) aqueous solution is the reaction electrolyte, with-1.0mA cm
-2Constant current electro-reduction reaction 30min generates the metal Ru sedimentary deposit on titanium dioxide nano-tube support; Then with 1.0M H
2SO
4The aqueous solution is in the working electrolyte, and the work electrode electromotive force is cyclic voltammetry scan 15min in 0 to 1.0V scope, and electro-oxidation reaction generates the ruthenium oxide hydration sedimentary deposit.
5. preparation method according to claim 4 is characterized in that:
Self-template anodic oxidation reactions synthetic method is: set up bipolar electrode electrochemical reaction system; With the metal titanium sheet be that anode, platinized platinum are that the organic solution of the aqueous solution or the fluoride ion compound of negative electrode, fluoride ion compound is that electrolyte, electrochemistry operating voltage are controlled at 20 to 80V, the reaction time is controlled at 0.5 to 60h; Prepare on titanium sheet two sides all titanium dioxide of vertical-growth nanotube through electrochemical anodization reaction; With this nanotube is that self-template carries out the anodic oxidation reactions of secondary at least, prepares the titanium-based titanium dioxide electrode holder of the ordered nano-tube array structure that pipe wall independence, pore distribution homogeneous, caliber can regulate and control.
6. preparation method according to claim 5 is characterized in that the fluoride ion compound is hydrogen fluoride, ammonium fluoride or sodium fluoride.
7. preparation method according to claim 5 is characterized in that the organic solvent in the organic solution of fluoride ion compound is ethylene glycol, glycerine or N, the N-dimethylacetylamide.
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| CN105448536B (en) * | 2015-11-26 | 2018-05-25 | 合肥工业大学 | Nickel oxide/TiOx nano composite material and preparation method thereof and stored energy application |
| CN108330524B (en) * | 2018-01-08 | 2019-11-08 | 武汉科技大学 | Nano nickel titanium dioxide nanotube array perforated membrane and preparation method thereof |
| CN109192552B (en) * | 2018-09-26 | 2020-05-12 | 河北工业大学 | Method for preparing polyaniline-titanium dioxide nanotube array composite electrode in one step |
| CN110102301B (en) * | 2019-05-20 | 2021-04-20 | 上海海事大学 | Method for preparing nano metal oxide load based on anodic oxidation method |
| CN110571067A (en) * | 2019-09-27 | 2019-12-13 | 四川大学 | Super capacitor electrode material and preparation method thereof |
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| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| CN101191248A (en) * | 2006-12-01 | 2008-06-04 | 西南交通大学 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
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| CN1598075A (en) * | 2004-07-29 | 2005-03-23 | 大连理工大学 | Titanium dioxide nano tube electrode and its preparation process and application |
| CN101191248A (en) * | 2006-12-01 | 2008-06-04 | 西南交通大学 | Method for preparing titanium dioxide nano tube array on titanium-substrate material surface |
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