CN103334142A - Preparation method of autodoped modified high-conductivity TiO2 nanotube array - Google Patents

Preparation method of autodoped modified high-conductivity TiO2 nanotube array Download PDF

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CN103334142A
CN103334142A CN2013102403905A CN201310240390A CN103334142A CN 103334142 A CN103334142 A CN 103334142A CN 2013102403905 A CN2013102403905 A CN 2013102403905A CN 201310240390 A CN201310240390 A CN 201310240390A CN 103334142 A CN103334142 A CN 103334142A
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张延荣
周鹤
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Abstract

The invention provides a preparation method of an autodoped modified high-conductivity TiO2 nanotube array, which comprises the following steps: growing TiO2 nanotubes on a titanium sheet in a fluorine-containing electrolyte by using a two-electrode system, and calcining at 400-700 DEG C in an air atmosphere; and polarizing the calcined TiO2 nanotube array under constant negative potential in an inert electrolyte for some time to obtain the autodoped (Ti<3+>-doped) modified high-conductivity TiO2 nanotube array. The invention is simple in technique, can easily control the doping amount, and can greatly enhance the conductivity of the TiO2 nanotubes, so that the prepared autodoped modified TiO2 nanotube array not only can be used in the fields of environmental treatment, photoelectric conversion, catalytic hydrogen production and the like, but also can be used in the fields of super capacitors, lithium ion batteries and other energy storage devices.

Description

A kind of high conductivity TiO of auto-doping modification 2The nano-tube array preparation method
Technical field
The invention belongs to technical field of nano material, more particularly, relate to a kind of preparation method of high conductivity Nano tube array of titanium dioxide of auto-doping modification.
Background technology
In recent years, because the fast development of electronic science and technology, its demand to high-performance, jumbo energy storage components and parts is also growing, and people begin to seek green, new nano material substitutes traditional energy storage material efficiently.Utilize the titania nanotube of anonizing preparation, because its high-sequential, specific surface area are big, safety and stability, advantageous properties such as controllability on synthetic, and bringing into play crucial effects in many scientific domains such as environmental improvement, catalyzing manufacturing of hydrogen and energy storage.Yet the semiconductor property that titanium dioxide is intrinsic---poorly conductive, electrochemical activity are low, have greatly limited its application on energy storage.How titanium dioxide being carried out modification, is its gordian technique place in the energy storage field of development to improve its electroconductibility and electrochemical activity.For this reason, Chinese scholars has been carried out a large amount of research, and the result shows that it is a kind of effective modified method that titanium dioxide is mixed.At present, the most successful adulterating method is with TiO 2Nanotube is calcined in atmosphere of hydrogen and TiO is introduced in the oxygen room 2Lattice, hydroxide radical (OH) is introduced TiO 2Surface (X.Lu, G.Wang, et al.Hydrogenated TiO 2Nanotube arrays for supercapacitors, Nano Letters, 2012,12,1690-1696).Though this method has promoted TiO greatly 2The ratio electric capacity of nanotube, but consider it to the requirement of extra starting material (hydrogen) and equipment, still not a kind of method of economy.
Summary of the invention
The objective of the invention is at above present situation, a kind of electroconductibility that improves Nano tube array of titanium dioxide is provided, strengthen the auto-doping (Ti of its energy storage capability 3+Mix) modification TiO 2The preparation method of nano-tube array.
The technical scheme that adopts for the technical problem that solves the present invention's proposition is:
A kind of high conductivity TiO of auto-doping modification 2The electrochemical preparation method of nano-tube array may further comprise the steps:
(1) utilize two electrode systems to prepare TiO 2Nanotube: as anode, platinized platinum or graphite or glass carbon is as negative electrode with titanium metal or titanium alloy, adds a constant potential electrolysis for some time to make self-assembly TiO in the electrolytic solution of fluoride 2Nano-tube array.
(2) with step (1) prepared with titanium metal or the titanium alloy TiO as substrate 2Nano-tube array is put into retort furnace and is calcined, and makes its crystallization.
(3) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: the TiO of the crystallization that step (2) is prepared 2Nano-tube array is steady-state polarization under negative potential, in the inertia electrolytic solution, obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
As improvement of the present invention, in the described step (1), fluorochemical contained in the electrolytic solution can be Neutral ammonium fluoride, Sodium Fluoride and/or hydrofluoric acid, and its concentration is 0.1～1.5mol/L, is preferably 0.4～1mol/L.
As improvement of the present invention, in the described step (1), used electrolyte solvent is deionized water.
As improvement of the present invention, in the described step (1), used electrolyte solvent is the mixture of water and alcohol.Wherein, used alcohol can be ethylene glycol or glycerine, and water is 0.01～5 with the volume ratio of alcohol, is preferably 0.1～1.
As improvement of the present invention, in the described step (1), adding constant voltage is 10～70V, is preferably 20～30V.
As improvement of the present invention, in the described step (1), the feeding voltage time is 10min～24h, is preferably 1h～6h.
As improvement of the present invention, in the described step (2), calcining temperature is 400～700 ℃, and calcination time is 1～16h, is preferably 2～6h.
As improvement of the present invention, described step (3) is carried out in two electrode systems.Wherein, negative electrode is the TiO of the prepared crystallization of step (2) 2Nano-tube array, anode can be platinized platinum or graphite or glass carbon, steady-state polarization voltage is 1V～10V, is preferably 2V～5V, is preferably 4V especially.
As improvement of the present invention, described step (3) is carried out in three-electrode system.Wherein, working electrode is the TiO of the prepared crystallization of step (2) 2Nano-tube array, counter electrode can be platinized platinum or graphite or glass carbon, and reference electrode can be saturated calomel electrode or Ag/AgCl electrode, and steady-state polarization voltage is-1V～-2V, be preferably-1.2～-1.7V, be preferably especially-1.4V.
As improvement of the present invention, in the described step (3), inertia electrolytic solution can be acid, alkali and/or salts solution, and its concentration is 0.01～5mol/L, is preferably 0.1～1mol/L.
As improvement of the present invention, in the described step (3), the steady-state polarization time is 5s～1h, is preferably 5～30min, is preferably 20min especially.
Advantage of the present invention is embodied in:
(1) the present invention successfully prepares auto-doping modification TiO 2Nano-tube array is with the TiO before the modification 2Nano-tube array is compared, this auto-doping modification TiO 2The electroconductibility of nano-tube array improves greatly, shows energy storage performance enhancing, superior;
(2) compare with traditional heat treating process, the present invention is from preparation TiO 2Nanotube all adopts electrochemical process to it is carried out modification, and technology is simple, has saved starting material and equipment;
(3) the present invention adopts electrochemical process to TiO 2Nanotube carries out modification, just can control the amount in the oxygen room of introducing by factors such as control voltage, electrolytic solution compositions, thereby make the high conductivity TiO of the auto-doping modification that makes 2Nano-tube array not only can be used for fields such as environmental improvement, opto-electronic conversion, catalyzing manufacturing of hydrogen, can also be used for ultracapacitor, lithium ion battery homenergic storage art.
Description of drawings
Fig. 1 is prepared auto-doping high conductivity TiO 2The sem photograph of nano-tube array;
Fig. 2 is 450 ℃ of auto-doping modification front and back TiO of calcining down 2The XRD spectra of nano-tube array (a: after the auto-doping modification, b: before the auto-doping modification, down together);
Fig. 3 is the TiO before and after the auto-doping modification 2The XPS spectrum figure of nano-tube array;
Fig. 4 is the TiO before and after the auto-doping modification 2The alternating-current impedance spectrogram of nano-tube array;
Fig. 5 is the TiO before and after the auto-doping modification 2The cyclic voltammetry curve of nano-tube array.
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described further.Need to prove at this, understand the present invention for the explanation of these embodiments for helping, but do not constitute limitation of the invention.In addition, below in each embodiment of described the present invention involved technical characterictic just can not make up mutually as long as constitute conflict each other.
Embodiment 1
1) substrate pre-treatment: pure titanium sheet polishing to surperficial no marking, is cleaned drying in acetone, ethanol, deionized water for ultrasonic respectively then;
2) preparation electrolytic solution: take by weighing a certain amount of NH 4F is dissolved in the electrolytic solution that is mixed with 1mol/L in the mixture that volume ratio is 1: 9 deionized water and glycerine;
3) anodic oxidation prepares TiO 2Nanotube: be anode with the titanium sheet after handling, platinized platinum is negative electrode, depresses at the 20V direct current of voltage regulation and carries out anodic oxidation reactions 3h, and reaction is used washed with de-ionized water after finishing, and at air drying, obtains amorphous TiO 2Nano-tube array;
3) with amorphous TiO 2Nanotube places retort furnace, and at 450 ℃ of following calcining 2h, naturally cooling obtains the TiO of anatase crystal 2Nano-tube array, its XRD spectra is as shown in Figure 1;
4) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: in two electrode systems, be anode with the platinized platinum, the TiO of crystallization 2Nanotube is negative electrode, 0.5mol/L Na 2SO 4Solution is electrolytic solution, adds 4V volts DS electrolysis 20min, obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
Embodiment 2
1) substrate pre-treatment: pure titanium sheet polishing to surperficial no marking, is cleaned drying in acetone, ethanol, deionized water for ultrasonic respectively then;
2) preparation electrolytic solution: take by weighing a certain amount of NaF and be dissolved in the electrolytic solution that is mixed with 0.1mol/L in the mixture that volume ratio is 1: 100 deionized water and ethylene glycol;
3) anodic oxidation prepares TiO 2Nanotube: be anode with the titanium sheet after handling, graphite is negative electrode, depresses at the 10V direct current of voltage regulation and carries out anodic oxidation reactions 24h, and reaction is used washed with de-ionized water after finishing, and at air drying, obtains amorphous TiO 2Nano-tube array;
3) with amorphous TiO 2Nanotube places retort furnace, and at 700 ℃ of following calcining 1h, naturally cooling obtains the TiO of anatase crystal 2Nano-tube array;
4) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: in two electrode systems, be anode with graphite, the TiO of crystallization 2Nanotube is negative electrode, and 5mol/L HCl is electrolytic solution, adds 1V volts DS electrolysis 1h, obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
Embodiment 3
1) substrate pre-treatment: pure titanium sheet polishing to surperficial no marking, is cleaned drying in acetone, ethanol, deionized water for ultrasonic respectively then;
2) preparation electrolytic solution: take by weighing a certain amount of NH 4It is the electrolytic solution that is mixed with 1.5mol/L in 5: 1 deionized water and the glycerol mixture that F is dissolved in volume ratio;
3) anodic oxidation prepares TiO 2Nanotube: be anode with the titanium sheet after handling, glass carbon is negative electrode, depresses at the 70V direct current of voltage regulation and carries out anodic oxidation reactions 10min, and reaction is used washed with de-ionized water after finishing, and at air drying, obtains amorphous TiO 2Nano-tube array;
3) with amorphous TiO 2Nanotube places retort furnace, and at 400 ℃ of following calcining 16h, naturally cooling obtains the TiO of anatase crystal 2Nano-tube array;
4) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: in two electrode systems, be anode with glass carbon, the TiO of crystallization 2Nanotube is negative electrode, and 0.01mol/L NaOH is electrolytic solution, adds 10V volts DS electrolysis 5s, obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
Embodiment 4
1) substrate pre-treatment: after the ultrasonic cleaning of pure titanium sheet usefulness deionized water, the immersion volume ratio is 1: 3: 6 HF, HNO 3, H 2Etching 1min in the O mixed solution uses washed with de-ionized water immediately, and is dry in nitrogen gas stream;
2) anodic oxidation prepares TiO 2Nanotube: be anode with the titanium sheet after handling, platinized platinum is negative electrode, and the 0.4mol/L HF aqueous solution is electrolytic solution, depresses at the 30V direct current of voltage regulation and carries out anodic oxidation reactions 2h, and reaction is used washed with de-ionized water after finishing, and at air drying, obtains amorphous TiO 2Nano-tube array;
3) with amorphous TiO 2Nanotube places retort furnace, and at 600 ℃ of following calcining 6h, naturally cooling obtains the TiO of crystallization 2Nano-tube array;
4) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: in three-electrode system, with the TiO of crystallization 2Nano-tube array is working electrode, and glass-carbon electrode is counter electrode, and saturated calomel electrode is reference electrode, the H of 0.1mol/L 2SO 4Be electrolytic solution, steady-state polarization 5min under-1.4V current potential obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
Embodiment 5
1) substrate pre-treatment: after the ultrasonic cleaning of pure titanium sheet usefulness deionized water, the immersion volume ratio is 1: 3: 6 HF, HNO 3, H 2Etching 1min in the O mixed solution uses washed with de-ionized water immediately, and is dry in nitrogen gas stream;
2) anodic oxidation prepares TiO 2Nanotube: be anode with the titanium sheet after handling, glass carbon is negative electrode, 0.75mol/L NH 4The F aqueous solution is electrolytic solution, depresses at the 40V direct current of voltage regulation and carries out anodic oxidation reactions 1h, and reaction is used washed with de-ionized water after finishing, and at air drying, obtains amorphous TiO 2Nano-tube array;
3) with amorphous TiO 2Nanotube places retort furnace, and at 550 ℃ of following calcining 3h, naturally cooling obtains the TiO of crystallization 2Nano-tube array;
4) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: in three-electrode system, with the TiO of crystallization 2Nano-tube array is working electrode, and glass-carbon electrode is counter electrode, and the Ag/AgCl electrode is reference electrode, and 1mol/L KCl solution is electrolytic solution, and steady-state polarization 10min under-1V current potential obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
Embodiment 6
1) substrate pre-treatment: after the ultrasonic cleaning of pure titanium sheet usefulness deionized water, the immersion volume ratio is 1: 3: 6 HF, HNO 3, H 2Etching 1min in the O mixed solution uses washed with de-ionized water immediately, and is dry in nitrogen gas stream;
2) anodic oxidation prepares TiO 2Nanotube: be anode with the titanium sheet after handling, graphite is negative electrode, takes by weighing a certain amount of NH 4It is the electrolytic solution that is mixed with 0.5mol/L in 1: 1 deionized water and the ethylene glycol mixture that F is dissolved in volume ratio; , to depress at the 25V direct current of voltage regulation and to carry out anodic oxidation reactions 3h, reaction is used washed with de-ionized water after finishing, and at air drying, obtains amorphous TiO 2Nano-tube array;
3) with amorphous TiO 2Nanotube places retort furnace, and at 500 ℃ of following calcining 4h, naturally cooling obtains the TiO of crystallization 2Nano-tube array;
4) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: in three-electrode system, with the TiO of crystallization 2Nano-tube array is working electrode, and platinized platinum is counter electrode, and the Ag/AgCl electrode is reference electrode, and 0.25mol/L KOH is electrolytic solution, and steady-state polarization 15min under-2V current potential obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
TiO according to the auto-doping modification that described embodiment is prepared 2Nano-tube array carries out interpretation of result:
1.XRD spectrogram: the TiO before and after the auto-doping modification 2It is that places such as 25.2,38.4,40.1,48.2 have absorption peak that the XRD spectra of nano-tube array all shows as at 2 θ angles, corresponds to titanium substrate and Detitanium-ore-type TiO respectively 2Nano-tube array (as shown in FIG.) shows TiO before and after cathodic reduction is handled 2Nano-tube array structure does not change.
2.XPS spectrogram: the TiO before and after the auto-doping modification 2The XPS spectrum figure of nano-tube array all show as 458.5 and 464.3eV near absorption peak is arranged, be respectively Ti2p 1/2And Ti2p 3/2The characteristic peak of track.With the TiO before the auto-doping modification 2Nano-tube array is compared, the TiO after the auto-doping modification 2The absorption peak of nano-tube array all has a negative bias by a small margin to move, and shows the TiO after the auto-doping modification 2There is more oxygen room in the nano-tube array.
3. ac impedance spectroscopy: the TiO before and after the auto-doping modification relatively 2The ac impedance spectroscopy of nano-tube array can be found the TiO after the modification 2The real part of nano-tube array impedance spectrum has reduced greatly, and has also reduced in the one-tenth ring trend of low frequency range impedance spectrum, and more close to straight line, shows the capacitive properties of better electroconductibility and enhancing.
4. cyclic voltammetry curve: in the cyclic voltammetry scan process, the TiO after the auto-doping modification 2The current density of nano-tube array increases significantly, and the shape of its cyclic voltammetry curve shows superior capacitive properties near rectangle.
By above-mentioned analysis as can be known, the TiO of the auto-doping modification of the method for present embodiment preparation 2Nano-tube array contains more oxygen room before than modification, thereby shows better electroconductibility, has obtained energy storage performance enhancing, superior.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment and accompanying drawing.So everyly do not break away from the equivalence of finishing under the spirit disclosed in this invention or revise, all belong to the scope of protection of the invention.

Claims (10)

1. TiO 2The electrochemical preparation method of nano-tube array may further comprise the steps:
(1) utilize two electrode systems to prepare TiO 2Nanotube: as anode, platinized platinum or graphite or glass carbon add 10～70V constant potential electrolysis 10min～24h and make self-assembly TiO as negative electrode in the electrolytic solution of fluoride with titanium metal or titanium alloy 2Nano-tube array;
(2) with the prepared TiO of step (1) 2Nano-tube array is put into retort furnace and is calcined 1h～16h down at 400～700 ℃, makes its crystallization;
(3) cathodic reduction Processing of Preparation auto-doping TiO 2Nano-tube array: the TiO of the crystallization that step (2) is prepared 2Nano-tube array is steady-state polarization under negative potential, in the inertia electrolytic solution, obtains the high conductivity TiO of auto-doping modification 2Nano-tube array.
2. preparation method according to claim 1 is characterized in that, in the described step (1), contained fluorochemical is Neutral ammonium fluoride, Sodium Fluoride and/or hydrofluoric acid in the electrolytic solution, and its concentration is 0.1mol/L～1.5mol/L, is preferably 0.4mol/L～1mol/L.
3. preparation method according to claim 1 is characterized in that, in the described step (1), used electrolyte solvent is deionized water, perhaps the mixture of water and alcohol; Wherein, used alcohol is ethylene glycol or glycerine, and water is 0.01: 1～5: 1 with the volume ratio of alcohol, is preferably 0.1: 1～1: 1.
4. preparation method according to claim 1 is characterized in that, described step (3) is carried out in two electrode systems; Wherein, negative electrode is the TiO of the prepared crystallization of step (2) 2Nano-tube array, anode are platinized platinum or graphite or glass carbon, and steady-state polarization voltage is 1V～10V.
5. preparation method according to claim 1 is characterized in that, described step (3) is carried out in three-electrode system; Wherein, working electrode is the TiO of the prepared crystallization of step (2) 2Nano-tube array, counter electrode are platinized platinum or graphite or glass carbon, and reference electrode is saturated calomel electrode or Ag/AgCl electrode, steady-state polarization voltage is-and 1V～-2V.
6. according to the described preparation method of one of claim 1-5, it is characterized in that in the described step (3), inertia electrolytic solution is acid, alkali and/or salts solution, its concentration is 0.01～5mol/L.
7. according to the described preparation method of one of claim 1-5, it is characterized in that in the described step (3), the steady-state polarization time is 5s～1h.
8. according to the preparation method described in the claim 4, it is characterized in that in the described step (3), steady-state polarization voltage is 2V～5V, is preferably 4V especially.
9. according to the preparation method described in the claim 5, it is characterized in that, in the described step (3), steady-state polarization voltage is-1.2～-1.7V, be preferably especially-1.4V.
10. according to the described preparation method of one of claim 1-5, it is characterized in that in the described step (3), inertia electrolytic solution is acid, alkali and/or salts solution, its concentration is 0.1～1mol/L; In the described step (3), the steady-state polarization time is 5min～30min, is preferably 20min especially.
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CN103726092A (en) * 2013-12-31 2014-04-16 天津新实能源科技有限公司 Method for preparing auto-doping black titanium dioxide
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CN104016306A (en) * 2014-06-30 2014-09-03 哈尔滨工业大学 Preparation method of semiconductor oxide nanotube/ZSM-5 molecular sieve composite material
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CN110158108A (en) * 2019-06-11 2019-08-23 铜仁学院 Material containing trivalent titanium ion auto-dope titanium dioxide and preparation method thereof and energy storage device
CN111185148A (en) * 2020-02-21 2020-05-22 大连理工大学 Ce-Zn modified TiO2Preparation method and application of nanotube array composite catalytic material
CN111185148B (en) * 2020-02-21 2022-09-02 大连理工大学 Ce-Zn modified TiO 2 Preparation method and application of nanotube array composite catalytic material
CN112430827A (en) * 2020-11-30 2021-03-02 上海应用技术大学 Reduced Si-doped titanium dioxide nanotube photoanode and preparation method thereof
CN113061923A (en) * 2021-03-12 2021-07-02 华中科技大学 High-activity electrochemical reactorDoped TiO 22Nanotube-based material, preparation and application thereof
CN113061923B (en) * 2021-03-12 2022-08-02 华中科技大学 High-activity electrochemical self-doping TiO 2 Nanotube-based material, preparation and application thereof
CN113097473A (en) * 2021-03-31 2021-07-09 福州大学 Nano-structured anatase titanium dioxide and preparation method and application thereof
CN114843119A (en) * 2022-04-30 2022-08-02 上海应用技术大学 Preparation method of black Ti-P-O nanotube array electrode material for super capacitor
CN114843119B (en) * 2022-04-30 2023-11-07 上海应用技术大学 Preparation method of black Ti-P-O nanotube array electrode material for super capacitor
CN114873714A (en) * 2022-06-16 2022-08-09 杭州晓水环保技术有限公司 Solar energy floating basin is administered to coastal area high salt river course normal position

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Application publication date: 20131002