CN101982417A - Preparation method of titanium dioxide nanocrystalline sol - Google Patents
Preparation method of titanium dioxide nanocrystalline sol Download PDFInfo
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- CN101982417A CN101982417A CN 201010293035 CN201010293035A CN101982417A CN 101982417 A CN101982417 A CN 101982417A CN 201010293035 CN201010293035 CN 201010293035 CN 201010293035 A CN201010293035 A CN 201010293035A CN 101982417 A CN101982417 A CN 101982417A
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- titanium dioxide
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- colloidal sol
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Abstract
The invention discloses a preparation method of titanium dioxide nanocrystalline sol used in dye sensitized solar cells. The preparation process comprises the following steps: precursor hydrolyzation, hydro-thermal treatment and product separation. The preparation method is characterized by comprising the following steps: converting organic titanium salt into amorphous titanium dioxide at the normal temperature through hydrolyzation; carrying out hydro-thermal treatment on the amorphous titanium dioxide at alkalic condition; and finally separating the product to obtain the titanium dioxide nanocrystalline. The titanium dioxide nanocrystalline particles have good monodispersity, do not agglomerate, have good contact with a conducting glass substrate after a thin film is formed, and high mechanical strength, and is suitable for preparing light anode of the dye sensitized solar cell.
Description
Technical field
The present invention is applicable to the nano material preparation technical field, particularly a kind of preparation method who is suitable for dye sensitization solar battery light with titanium dioxide nanocrystalline colloidal sol.
Background technology
Along with the high speed development of human society, human demand to the energy constantly increases, and energy problem day by day becomes the focus that people pay close attention to.Human use's main energy sources is fossil energies such as oil, coal, Sweet natural gas at present.But as Nonrenewable energy resources, fossil energy can't satisfy human secular demand.Sun power has the incomparable advantage of other resource forms as a kind of renewable resources.Though the utilization of sun power has caused scientist's interest very early, its application is not extensive.Up to the outburst of 1970's oil crisis, countries in the world just are used for research and development in the fund of the renewable energy source domain amount of having high input.Except the problem of simple reserves and economic aspect, the mankind also must consider another aspect---ecology and environmental problem.Combustion of fossil fuels (particularly coal) serious environment pollution, and, also can produce " Greenhouse effect " along with the increasing of carbonic acid gas in the atmosphere.
With conversion of solar energy is that electric energy is a kind of important form of utilizing sun power.In more than ten years in the past, the potential economic worth of utilizing the semiconductor light electrochemical cell to replace conventional solid-state photovoltaic semiconductor solar cell to finish conversion of solar energy manifests day by day.Conventional solar cell utilizes highly purified perfect cystal material to make usually, and the quite complicated technology of the preparation of p-n junction needs, thereby causes the price of this class battery very expensive.And utilizing the semiconductor light electrochemical cell under the identical condition of output rating, cost has only about 1/10th of conventional solar cell.1991, Michael
Deng people's reported first dye sensitization solar battery, can reach 7.1% under the solar simulated irradiation.1993,
Reported that once more photoelectric transformation efficiency reaches 10% dye sensitization solar battery.1998,
Further develop all-solid-state dye-sensitized solar cell Deng the people, the monochromatic light ray electrical efficiency reaches 33%.
Dye sensitization solar battery will become the representative of solar cell of new generation with its lower cost of manufacture and simple production technique.Semi-conducting electrode in the dye sensitization solar battery is to be prepared from by having anatase structured titanium deoxid film.Because the energy gap of anatase structured titanium dioxide is 3.2eV, so have the short ultraviolet ray of wavelength that anatase structured titanium dioxide can only absorb the ratio seldom of accounting in the sunlight.The long light of the wavelength of the overwhelming majority then is not utilized in the sunlight.In order to make full use of the long part of sunlight medium wavelength, make it can adsorb sensitizing dye that last layer can expand to absorb light visible region thereby need make porous membrane to titanium dioxide to strengthen the absorption of light, improve electricity conversion.So dye sensitization solar battery mainly is made of the semi-conducting electrode that is adsorbed with sensitizing dye, the counter electrode of having catalyzer and the redox electrolytes matter between two electrodes.The process that whole photoelectricity transforms comprises: (1) is adsorbed on dye molecule on the working electrode surface and receives and excite and transit to excited state under the visible light effect; (2) owing to the excited state instability, electronics is injected into the TiO than low-lying level very soon
2Conduction band, this moment, dye molecule became oxidation state; (3) enter TiO
2Electronics in the conduction band transports in Na crystal porous membrane and is collected by conductive glass, flows to counter electrode by external circuit then, produces photoelectric current; (4) dye molecule of oxidation state is by the I in the electrolytic solution
-Be reduced to ground state, make dye molecule obtain regeneration, I
-Be oxidized to I
-3(5) I in the while ionogen
-3Be diffused into negative electrode (counter electrode) and obtain electron reduction and become I from negative electrode
-, finish the circulation of a photoelectrochemistry reaction.
From above-mentioned process as can be seen the preparation of titanium dioxide photo anode be a very critical step the production of dye sensitization solar battery, the pattern of titanium dioxide and character will be directly connected to the photoelectric transformation efficiency of battery.Method commonly used at present is a Prepared by Sol Gel Method titanium dioxide, and this method needs the dispergation of long period at a certain temperature, carries out hydro-thermal reaction afterwards, has taken a large amount of time.And condition is not easy control, and final product property is not good, influences the application of dye sensitization solar battery.
Summary of the invention
The purpose of this invention is to provide a kind of under alkaline system, use hydrothermal technique preparation preparation titanium dioxide nanocrystalline particulate method, this method is simple to operate, with low cost, repeatability is strong, and the titanium dioxide nanocrystalline particle monodispersity of preparing is not well, reunite, film of preparing and conductive glass substrate have good connectivity, the physical strength height.
The objective of the invention is to realize that by following technical proposals a kind of preparation method of titanium dioxide nanocrystalline colloidal sol, preparation process comprise hydrolysis, suction filtration, hydrothermal treatment consists, centrifugation, it is characterized in that: this method comprises the steps:
1) under vigorous stirring, in water, dropwise adds organic titanium salt, produce white precipitate;
2) with the white depositions suction filtration that obtains, use deionized water wash repeatedly;
3) product after will washing is put into water heating kettle, adds alkali lye, mixes, carry out hydro-thermal reaction then after, be cooled to room temperature, obtain TiO 2 sol;
4) TiO 2 sol is carried out centrifugation, promptly get titanium dioxide nanocrystalline.
Organic titanium salt is titanium isopropylate or tetrabutyl titanate in the described step 1), and the concentration of the organic titanium salt aqueous solution is 0.1mol/L-2mol/L.
The described churned mechanically time is 20min-2h.
Described step 2) the suction filtration number of times is 3-5 time in.
Described step 3) neutral and alkali solution is a kind of or two or more mixture in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor or the tetramethyl-oxyammonia; The concentration of basic solution is 0.1mol/L-2mol/L.
The temperature range of described hydro-thermal reaction is 80 ℃-200 ℃; The time of hydro-thermal reaction is 2h-24h.Described hydro-thermal reaction is the thermostat(t)ed water thermal response, or segmentation thermostat(t)ed water thermal response.
Centrifugation in the described step 4) adds the deionized water ultra-sonic dispersion, and recentrifuge separates, and repeats above step 3-5 time, is neutral to product washings pH value.
Hydrolysis reaction of the present invention can be represented with following equation:
Ti
4++2H
2O＝TiO
2+4H
+ (1)
Ti
4++2OH
-＝TiO
2++H
2O (2)
TiO
2++H
2O＝TiO
2+4H
+ (3)
The white precipitate that produces after hydrolysis sintered glass funnel suction filtration, and clean repeatedly 3-5 time with deionized water, white filter cake obtained.Above-mentioned white filter cake is scattered in the basic solution, pours in the reactor after mixing, carry out hydro-thermal reaction at a certain temperature.With supercentrifuge product is separated after hydro-thermal is finished, used the deionized water repetitive scrubbing then, be neutral until washings.
The preparation method of titanium dioxide nanocrystalline colloidal sol of the present invention can not access titanium dioxide nanocrystalline particle monodispersity well, do not reunite, and film of preparing and conductive glass substrate have good connectivity, the physical strength height; And this method is simple to operate, with low cost, and repeatability is strong, is suitable for popularization production in enormous quantities and uses.
Description of drawings
Fig. 1 is the titanium dioxide nanocrystalline particulate transmission electron microscope photo of preparing.
Fig. 2 is the titanium dioxide nanocrystalline particulate XRD figure of preparing.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
The titanium isopropylate of 0.1mol/L is dropwise splashed in the deionized water of 200ml, and vigorous stirring 20min obtains white precipitation; To have sedimentary suspension liquid and slowly pour into and carry out suction filtration in the sintered glass funnel, during with deionized water repetitive scrubbing 3 times; Then white filter cake is added in the tetramethylammonium hydroxide aqueous solution of 0.1mol/L, stir; At 80 ℃ of following hydro-thermal reaction 8h, be warming up to 200 ℃ of hydro-thermal reaction 16h then, obtain nattier blue TiO 2 sol after naturally cooling to room temperature; Nattier blue colloidal sol equivalent centrifuge tube of packing into is carried out centrifugation, after the solid-liquid separation, the clear liquid on centrifuge tube upper strata is outwelled, add the deionized water ultra-sonic dispersion, recentrifuge separates, and repeats above step 3 time; Measure till the pH value to 7 of TiO 2 sol, promptly get titanium dioxide nanocrystalline.
Embodiment 2
The titanium isopropylate of 2mol/L is dropwise splashed in the deionized water of 1000ml, and vigorous stirring 2h obtains white precipitation; To have sedimentary suspension liquid and slowly pour into and carry out suction filtration in the sintered glass funnel, during with deionized water repetitive scrubbing 3 times; White filter cake is added in the ammonium hydroxide aqueous solution of 2mol/L, stir; At 200 ℃ of hydro-thermal reaction 24h, obtain nattier blue TiO 2 sol after the cooling naturally; Nattier blue colloidal sol equivalent centrifuge tube of packing into is carried out centrifugation, after the solid-liquid separation clear liquid on centrifuge tube upper strata is outwelled, add the deionized water ultra-sonic dispersion, recentrifuge separates, and repeats above step 3 time; Measure till the pH value to 7 of TiO 2 sol, promptly get titanium dioxide nanocrystalline.
Embodiment 3
The titanium isopropylate of 1mol/L is dropwise splashed in the deionized water of 400ml, and vigorous stirring 30min obtains white precipitation; To have sedimentary suspension liquid and slowly pour into and carry out suction filtration in the sintered glass funnel, during with deionized water repetitive scrubbing 3 times; White filter cake is added in the potassium hydroxide aqueous solution of 0.6mol/L, stir; At 120 ℃ of following hydro-thermal reaction 6h, be warming up to 200 ℃ of hydrothermal treatment consists 16h then, obtain nattier blue TiO 2 sol after the cooling naturally; Nattier blue colloidal sol equivalent centrifuge tube of packing into is carried out centrifugation, after the solid-liquid separation clear liquid on centrifuge tube upper strata is outwelled, add the deionized water ultra-sonic dispersion, recentrifuge separates, and repeats above step 4 time; Measure till the pH value to 7 of TiO 2 sol, promptly get titanium dioxide nanocrystalline.
Embodiment 4
The tetrabutyl titanate of 0.1mol/L is dissolved in the deionized water of 600ml, and vigorous stirring 50min obtains white precipitation.To have sedimentary suspension liquid and slowly pour into and carry out suction filtration in the sintered glass funnel, during with deionized water repetitive scrubbing 4 times.White filter cake is added in 0.5mol/L sodium hydroxide and the 0.5mol/L ammoniacal liquor, stir with glass stick, 160 ℃ of hydro-thermal reaction 15h obtain nattier blue TiO 2 sol after the cooling naturally; Nattier blue colloidal sol equivalent centrifuge tube of packing into is carried out centrifugation, after the solid-liquid separation clear liquid on centrifuge tube upper strata is outwelled, add the deionized water ultra-sonic dispersion, recentrifuge separates, and repeats above step 5 time; PH value with test paper measurement TiO 2 sol till 7, promptly gets titanium dioxide nanocrystalline.
Embodiment 5
The tetrabutyl titanate of 0.8mol/L is dissolved in the deionized water of 200ml, and vigorous stirring 1h obtains white precipitation.To have sedimentary suspension liquid and slowly pour into and carry out suction filtration in the sintered glass funnel, during with deionized water repetitive scrubbing 5 times; White filter cake is added in 0.5mol/L sodium hydroxide, 0.5mol/L lithium hydroxide and the 0.5mol/L ammoniacal liquor, stir with glass stick, 80 ℃ of hydro-thermal reaction 2h are warming up to 160 ℃ of hydro-thermal reaction 10h then; Naturally obtain nattier blue TiO 2 sol after the cooling; Nattier blue colloidal sol equivalent centrifuge tube of packing into is carried out centrifugation, after the solid-liquid separation clear liquid on centrifuge tube upper strata is outwelled, add the deionized water ultra-sonic dispersion, recentrifuge separates, and repeats above step 3 time; PH value with test paper measurement TiO 2 sol till 7, promptly gets titanium dioxide nanocrystalline.
Further specify preparation method of the present invention below by the accompanying drawing product.The accompanying drawing 1 titanium dioxide nanocrystalline particulate transmission electron microscope photo for preparing shows among the figure not obtain titanium dioxide nanocrystalline particle monodispersity well, do not reunite.
Fig. 2 is the titanium dioxide nanocrystalline particulate XRD figure of preparing, with XRD analysis titanium dioxide granule be anatase structured, particle diameter is about complete, the uniform particle diameter of 20nm. crystalline form.
Claims (8)
1. the preparation method of a titanium dioxide nanocrystalline colloidal sol, it is characterized in that: this method comprises the steps:
1) under vigorous stirring, in water, dropwise adds organic titanium salt, produce white precipitate;
2) with the white depositions suction filtration that obtains, use deionized water wash repeatedly;
3) product after will washing is put into water heating kettle, adds alkali lye, mixes, and carries out hydro-thermal reaction then, is cooled to room temperature, obtains TiO 2 sol;
4) TiO 2 sol is carried out centrifugation, promptly get titanium dioxide nanocrystalline.
2. the preparation method of a kind of titanium dioxide nanocrystalline colloidal sol as claimed in claim 1 is characterized in that: organic titanium salt is titanium isopropylate or tetrabutyl titanate in the described step 1), and the concentration of the organic titanium salt aqueous solution is 0.1mol/L-2mol/L.
3. the preparation method of a kind of titanium dioxide nanocrystalline colloidal sol as claimed in claim 1 is characterized in that: the described mechanical stirring time is 20min-2h.
4. the preparation method of a kind of titanium dioxide nanocrystalline colloidal sol as claimed in claim 1 is characterized in that: the suction filtration number of times is 3-5 time described step 2).
5. the preparation method of a kind of titanium dioxide nanocrystalline colloidal sol as claimed in claim 1 is characterized in that: described step 3) neutral and alkali solution is one or more the mixture in sodium hydroxide, potassium hydroxide, lithium hydroxide, ammoniacal liquor or the tetramethyl-oxyammonia; The concentration of basic solution is 0.1mol/L-2mol/L.
6. the preparation method of a kind of titanium dioxide nanocrystalline colloidal sol as claimed in claim 1 is characterized in that: the temperature range of described hydro-thermal reaction is 80 ℃-200 ℃; The time of hydro-thermal reaction is 2h-24h.
7. the preparation method of a kind of titanium dioxide nanocrystalline colloidal sol as claimed in claim 6 is characterized in that: described hydro-thermal reaction is the thermostat(t)ed water thermal response, or segmentation thermostat(t)ed water thermal response.
8. the preparation method of a kind of titanium dioxide nanocrystalline colloidal sol as claimed in claim 1 is characterized in that: centrifugation adds the deionized water ultra-sonic dispersion in the described step 4), and recentrifuge separates, and repeats above step 3-5 time, is neutral to product washings pH value.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544382A (en) * | 2012-03-21 | 2012-07-04 | 浙江大学 | Preparation method for organic solar battery with reverse structure |
| CN102887561A (en) * | 2012-10-24 | 2013-01-23 | 浙江工商大学 | Treatment method of chrome-containing dyeing wastewater |
| CN103769608A (en) * | 2014-02-20 | 2014-05-07 | 北京碧水源膜科技有限公司 | Nano-silver sol separating method |
| CN103803644A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for controlling product crystal form and morphology of titanium-based nanometer material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792817A (en) * | 2005-11-17 | 2006-06-28 | 上海交通大学 | Process for preparing anatase type nano crystal TiO2 solar energy cell material |
-
2010
- 2010-09-27 CN CN 201010293035 patent/CN101982417A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792817A (en) * | 2005-11-17 | 2006-06-28 | 上海交通大学 | Process for preparing anatase type nano crystal TiO2 solar energy cell material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544382A (en) * | 2012-03-21 | 2012-07-04 | 浙江大学 | Preparation method for organic solar battery with reverse structure |
| CN102887561A (en) * | 2012-10-24 | 2013-01-23 | 浙江工商大学 | Treatment method of chrome-containing dyeing wastewater |
| CN103803644A (en) * | 2012-11-14 | 2014-05-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for controlling product crystal form and morphology of titanium-based nanometer material |
| CN103803644B (en) * | 2012-11-14 | 2016-08-17 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method controlling titanium-based nano material product form and pattern |
| CN103769608A (en) * | 2014-02-20 | 2014-05-07 | 北京碧水源膜科技有限公司 | Nano-silver sol separating method |
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Open date: 20110302 |