CN103498182A - Preparation method of titanium dioxide nanotube array with orientation structure - Google Patents
Preparation method of titanium dioxide nanotube array with orientation structure Download PDFInfo
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- CN103498182A CN103498182A CN201310426257.9A CN201310426257A CN103498182A CN 103498182 A CN103498182 A CN 103498182A CN 201310426257 A CN201310426257 A CN 201310426257A CN 103498182 A CN103498182 A CN 103498182A
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Abstract
The invention provides a preparation method of a titanium dioxide nanotube array with an orientation structure. The preparation method comprises the technological process and steps: placing a polished titanium sheet into NH4F, H2O and ethylene glycol for preparing the titanium dioxide nanotube array by adopting an anodic oxidization method, performing ultrasonic and nitrogen-purging to remove a thin membrane prepared after primary oxidization, then continuously performing secondary anodic oxidization, and washing the prepared titanium dioxide nanotube array in isopropanol; respectively annealing at the temperature of 450 DEG C at the temperature rise speed of 0.5DEG C/min under vacuum situation, insulating for two hours, annealing in the air, and comparing. The prepared titanium dioxide nanotube array with the aperture of about 100nm and the tube wall thickness of about 10nm is orderly in structure, the highly-crystallized orderly titanium dioxide nanotube array can be obtained under the vacuum annealing condition, the super capacitance capacity can achieve 9.44mF cm<-2>, a lithium battery can achieve 319mAh g<-1>, the prepared high crystallization-oriented titanium dioxide nanotube array has good application prospects in the aspect of energy storage.
Description
Technical field
The present invention relates to the preparation method of a kind of preparation method's of Nano tube array of titanium dioxide, particularly a kind of orientation texture Nano tube array of titanium dioxide.
Background technology
In more than ten years recently, Nano semiconductor is widely studied in the application in various fields, this is because Nano semiconductor not only has body phase character as chemical stability, electricity are led, high catalytic performance, also has optics, electricity, catalysis, the magnetic property of the uniqueness that the existence of band gap causes.Wherein, nano-tube array, owing to having unique structure such as nano level aperture size, high-specific surface area, makes this material have unique physics, chemical property, has the status of not replacing in the materialogy field.
Nano tube array of titanium dioxide has application very widely, TiO at energy field
2the nano-tube array tubular structure orderly by oneself height determines that its surface has good adsorptivity, and the large and marshalling of its specific surface area, can adsorb more dye molecule by the ratio nano porous membrane, and almost can make whole dye molecules all with TiO
2molecule directly contacts, the interface electron transfer speed of photo-generated carrier is fast, thereby there is more excellent optical absorption characteristics, also improved the opto-electronic conversion performance simultaneously, and it has manufacture craft simply and the cheap characteristics of cost of manufacture, therefore in dye sensitization solar battery, become desirable material.In addition, the tubular structure of its high-sequential provides conductive channel for lithium cell and ultracapacitor, can provide passage for absorption and the transfer of lithium ion.Therefore, while applying as energy storage, the major issue faced is exactly to improve the electroconductibility of titania nanotube.At present the method great majority of the height-oriented texture of preparation are doping method, and its subject matter is that the cost that adulterates such as rare earth metal heavy metal is too high, seriously polluted, is difficult to obtain pure titanium dioxide.
In the titanium dioxide of the height-oriented texture of preparation, at first Hua Gui Yang adopts and adds hydrofluoric acid in the precursor titanium tetrafluoride agent obtains the high titanium dioxide nanocrystalline that exposes (001) face as morphology control, someone follows up and has done a large amount of work again subsequently, improve the ratio of (001) exposure, nanocrystalline for every field by what obtain, all obtained good effect.A. the people such as Ali regulates and controls the texture of titanium dioxide nano-film by neodymium-doped, has improved the intensity of (004) face.The people's such as Sangwook Lee research explanation reaches the purpose of regulation and control texture by the content of regulating water in the anonizing preparation process, but this is not the key factor of the regulation and control of orientation texture, because the titanium pipe of preparing is that amorphous exists, annealing conditions only has by the crystallization of annealing ability, so should be the key factor of regulation and control texture.Our group once adopted at AN the plumbous material that has obtained having certain orientation texture of doping, but its orientation texture is not strong, and adopted the Heavy Metal Pollution environment.
The Nano tube array of titanium dioxide prepared for anonizing is continued to use the air this traditional technology of annealing always, and the titanium pipe obtained does not have orientation texture, thereby electroconductibility is poor, has greatly limited the performance performance of practical application.So, prepare the Nano tube array of titanium dioxide structure with height-oriented texture by a kind of quick, easy, efficient method and extremely be necessary.
Summary of the invention
One of purpose of the present invention is to provide a kind of easy, method of preparing quickly the Nano tube array of titanium dioxide of height-oriented texture.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of Nano tube array of titanium dioxide of orientation texture is characterized in that the concrete steps of the method are:
A. adopt anonizing, pretreated titanium sheet is carried out to two-step anodization, ionogen and the impurity of Virahol ultrasonic cleaning to wash the nano-tube array remained on surface off, obtain TiO
2nano-tube array;
B. by step a gained TiO
2nano-tube array is warming up to 400-500 ℃ with the heat-up rate of 0.5-1.5 ℃/min, at vacuum annealing insulation 1-3h, then is down to room temperature with the rate of temperature fall with 0.5-1.5 ℃/min, obtains the Nano tube array of titanium dioxide of orientation texture.
The pretreatment process of above-mentioned titanium sheet is: preparation HF, HNO
3, H
2the polishing fluid that the O volume ratio is 1:4:5, immerse 60s in polishing fluid by the titanium sheet and carry out polishing, with deionized water, cleans subsequently, then uses N
2dry up.
In above-mentioned anonizing, ionogen used is by NH
4f, H
2o and ethylene glycol press that the mass ratio of 0.3:2:97.7 is formulated, and anodised voltage is 50v, and the time is 2 hours.
Nano tube array of titanium dioxide prepared by the present invention is structurally ordered, aperture 100nm left and right, and thickness of pipe 10nm left and right can obtain the orderly Nano tube array of titanium dioxide of highly crystalline under the condition of vacuum annealing, and its super capacitor capacity reaches 9.44 mF cm
-2, lithium cell reaches 319 mAh g
-1, known by above data, the Nano tube array of titanium dioxide of highly crystalline trend prepared by the present invention has very large prospect aspect energy storage.
The advantage of the inventive method is: the preparation method is easy, can industry amplify.Preparation process does not produce environmental pollutant, belongs to environmentally friendly preparation technology.Its capacity of super capacitor is the hundred times of common annealing condition.Its lithium battery capacity is 1.5 times of common annealing condition.
The annealing device that the present invention adopts is the tube furnace of being furnished with mechanical pump.
The accompanying drawing explanation
The XRD diffractogram that Fig. 1 is Nano tube array of titanium dioxide structure of the present invention;
Fig. 2 Nano tube array of titanium dioxide is at 0.5 M Na
2sO
4cyclic voltammogram in solution, sweeping speed is 100 mVs
-1;
Fig. 3 Nano tube array of titanium dioxide rate charge-discharge figure, a figure is vacuum annealing, the comparative sample that b figure is air annealing.
Embodiment
(1) at first, preparation HF, HNO
3, H
2the polishing fluid that the O volume ratio is 1:4:5, immerse 60s by the titanium sheet and carry out polishing, with deionized water, cleans subsequently, then uses N
2dry up.
(2) pretreated titanium sheet is dipped into and contains 0.3wt%NH
4f, 2wt%H
2in the electrolytic solution of O and ethylene glycol (500ml), carry out anodic oxidation 2h under the voltage of 50V, blow the once oxidation film is come off in deionized water for ultrasonic and with nitrogen subsequently, anodic oxidation 2h, ionogen and the impurity to wash the nano-tube array remained on surface off at Virahol ultrasonic cleaning 15min afterwards again in electrolytic solution before in addition.
(3) two-step anodization is prepared to TiO
2nano-tube array in tube furnace with the intensification of 0.5 ℃/min and rate of temperature fall under 450 degree in vacuum (mechanical pump, 10
-1pa) annealing insulation 2h.
(4) using Nano tube array of titanium dioxide as working electrode, silver silver chloride electrode is as reference electrode, and platinum wire electrode is as to electrode.Electrode is inserted to three slot electrodes, the in-built Na of groove
2sO
4(0.5M), use electrochemistry work group station, at sweep velocity 100 mVs
-1, test under sweep limit 0V～0.8V condition, obtain cyclic voltammogram.Calculate capacity of super capacitor by cyclic voltammogram.
(5) using Nano tube array of titanium dioxide as negative pole, the lithium sheet, as positive pole, carries out charge-discharge test with battery test system at 1V ~ 3V, obtains capacity, circulation, the performance of multiplying power.
For the performance of the Nano tube array of titanium dioxide that contrasts orientation texture, the spy takes traditional annealing process-air annealing to be contrasted.Above-mentioned prepared sample, carry out structure, pattern and performance test with instrument, and its test case and result thereof are as follows:
1, X-ray diffraction (XRD) is analyzed
As can be seen from Figure 1, the Nano tube array of titanium dioxide structure of preparing is anatase structured, and near the diffraction peak 2 θ are 25 ° and 39 ° is titanium dioxide anatase crystal constitutional features diffraction peak, corresponds respectively to TiO
2and TiO (101)
2(004) crystal face diffraction peak, traditional annealing process (air annealing), TiO
2(101) compare TiO
2(004) the crystal face diffraction peak is strong a lot of doubly, is therefore that what to obtain is the titanium dioxide of out of order crystallization, and the TiO of vacuum annealing
2(004) the crystal face diffraction peak is far away higher than TiO
2(101) crystal face diffraction peak.
2, ultracapacitor performance test
Referring to Fig. 2, the capacitive property of Nano tube array of titanium dioxide can pass through to measure the integral area substitution formula of cyclic voltammetry: C=Q/Δ V S (mF cm
-2) calculating: the super capacitor capacity of the Nano tube array of titanium dioxide of air annealing is 0.04mF cm
-2, vacuum annealing be 9.44 mF cm
-2.The Nano tube array of titanium dioxide of the highly crystalline trend of this high conductivity is traditional 236 times as the capacity of ultracapacitor, greatly improves its potential value.
3, lithium cell performance test
As can be seen from Figure 3, the sample of vacuum annealing is compared traditional annealing way lithium battery capacity and has been increased one times, and electric discharge has first reached 319 mAh g
-1, can also keep afterwards 200 mAh g
-1, and the theoretical capacity of anatase titanium dioxide is 168 mAh g
-1, the orderly tubular structure of this uniqueness and the existence in oxygen room have improved lithium battery capacity, and make it surpass theoretical capacity.
Claims (3)
1. the preparation method of the Nano tube array of titanium dioxide of an orientation texture is characterized in that the concrete steps of the method are:
A. adopt anonizing, pretreated titanium sheet is carried out to two-step anodization, ionogen and the impurity of Virahol ultrasonic cleaning to wash the nano-tube array remained on surface off, obtain TiO
2nano-tube array;
B. by step a gained TiO
2nano-tube array is warming up to 400-500 ℃ with the heat-up rate of 0.5-1.5 ℃/min, at vacuum annealing insulation 1-3h, then is down to room temperature with the rate of temperature fall with 0.5-1.5 ℃/min, obtains the Nano tube array of titanium dioxide of orientation texture.
2. the preparation method of the Nano tube array of titanium dioxide of orientation texture according to claim 1, is characterized in that the pretreatment process of described titanium sheet is: preparation HF, HNO
3, H
2the polishing fluid that the O volume ratio is 1:4:5, immerse the titanium sheet in polishing fluid and carry out polishing, with deionized water, cleans subsequently, then uses N
2dry up.
3. the preparation method of the Nano tube array of titanium dioxide of orientation texture according to claim 1, is characterized in that ionogen used in described anonizing is by NH
4f, H
2o and ethylene glycol are formulated by the mass ratio of 0.3: 2: 97.7, and anodised voltage is 45-55v, and the time is 1-3 hour.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013459A (en) * | 2015-06-29 | 2015-11-04 | 合肥工业大学 | Highly preferred orientation anatase type TiO2 nanotube array membrane and preparation method thereof |
| CN105908241A (en) * | 2016-07-04 | 2016-08-31 | 太原理工大学 | Preparing method of TiO2 nanotube array in controllable three-dimensional shape |
| CN106906507A (en) * | 2017-01-20 | 2017-06-30 | 浙江大学 | One-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization |
| CN107008239A (en) * | 2017-03-31 | 2017-08-04 | 北京师范大学 | The foam titanium composite material of superficial growth nano titania array |
| CN107268061A (en) * | 2017-05-08 | 2017-10-20 | 武汉理工大学 | A kind of additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof |
| CN107541724A (en) * | 2016-06-27 | 2018-01-05 | 中国科学院金属研究所 | A kind of preparation method of the controllable metal-oxide film of pattern and composition |
| CN108179454A (en) * | 2017-12-29 | 2018-06-19 | 重庆大学 | A kind of preparation method of the super infiltration titanium foam of water-oil separating |
| CN108330525A (en) * | 2018-01-31 | 2018-07-27 | 南京工业大学 | Preparation method of titanium oxide porous membrane SERS substrate |
| CN108411346A (en) * | 2018-02-07 | 2018-08-17 | 中国科学院深圳先进技术研究院 | Have（001）Anatase titania nano-tube array of Solute Content in Grain and its preparation method and application |
| CN108588788A (en) * | 2018-03-26 | 2018-09-28 | 新乡学院 | A kind of anatase TiO that transparent high preferred orientation is controllable2The preparation method of nano-pipe array thin film |
| WO2019218754A1 (en) * | 2018-05-14 | 2019-11-21 | 深圳市中科摩方科技有限公司 | Material having surface modified by super capacitance, preparation method therefor and application thereof |
| CN113308727A (en) * | 2020-02-26 | 2021-08-27 | 新疆知信科技有限公司 | Titanium dioxide nanotube, composite electrode based on titanium dioxide nanotube, and preparation method and application of composite electrode |
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|---|---|---|---|---|
| CN105013459B (en) * | 2015-06-29 | 2017-04-05 | 合肥工业大学 | A kind of Detitanium-ore-type TiO of height preferred orientation2Film of Nano tube array and preparation method thereof |
| CN105013459A (en) * | 2015-06-29 | 2015-11-04 | 合肥工业大学 | Highly preferred orientation anatase type TiO2 nanotube array membrane and preparation method thereof |
| CN107541724A (en) * | 2016-06-27 | 2018-01-05 | 中国科学院金属研究所 | A kind of preparation method of the controllable metal-oxide film of pattern and composition |
| CN105908241A (en) * | 2016-07-04 | 2016-08-31 | 太原理工大学 | Preparing method of TiO2 nanotube array in controllable three-dimensional shape |
| CN106906507A (en) * | 2017-01-20 | 2017-06-30 | 浙江大学 | One-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization |
| CN106906507B (en) * | 2017-01-20 | 2019-04-12 | 浙江大学 | One-dimensional anatase TiO2The method of nano-pipe array thin film preferred orientation crystallization |
| CN107008239A (en) * | 2017-03-31 | 2017-08-04 | 北京师范大学 | The foam titanium composite material of superficial growth nano titania array |
| CN107268061B (en) * | 2017-05-08 | 2019-01-25 | 武汉理工大学 | A kind of additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof |
| CN107268061A (en) * | 2017-05-08 | 2017-10-20 | 武汉理工大学 | A kind of additive Mn film of Nano tube array of titanium dioxide and gas sensor with and preparation method thereof |
| CN108179454A (en) * | 2017-12-29 | 2018-06-19 | 重庆大学 | A kind of preparation method of the super infiltration titanium foam of water-oil separating |
| CN108330525A (en) * | 2018-01-31 | 2018-07-27 | 南京工业大学 | Preparation method of titanium oxide porous membrane SERS substrate |
| CN108330525B (en) * | 2018-01-31 | 2019-08-20 | 南京工业大学 | Preparation method of titanium oxide porous membrane SERS substrate |
| CN108411346A (en) * | 2018-02-07 | 2018-08-17 | 中国科学院深圳先进技术研究院 | Have（001）Anatase titania nano-tube array of Solute Content in Grain and its preparation method and application |
| CN108411346B (en) * | 2018-02-07 | 2019-08-09 | 中国科学院深圳先进技术研究院 | Anatase titania nano-tube array and its preparation method and application with (001) Solute Content in Grain |
| CN108588788A (en) * | 2018-03-26 | 2018-09-28 | 新乡学院 | A kind of anatase TiO that transparent high preferred orientation is controllable2The preparation method of nano-pipe array thin film |
| WO2019218754A1 (en) * | 2018-05-14 | 2019-11-21 | 深圳市中科摩方科技有限公司 | Material having surface modified by super capacitance, preparation method therefor and application thereof |
| CN110896607A (en) * | 2018-05-14 | 2020-03-20 | 深圳市中科摩方科技有限公司 | Surface super-capacitance modified material and preparation method and application thereof |
| CN113308727A (en) * | 2020-02-26 | 2021-08-27 | 新疆知信科技有限公司 | Titanium dioxide nanotube, composite electrode based on titanium dioxide nanotube, and preparation method and application of composite electrode |
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Application publication date: 20140108 |