CN103130268A - High-efficiency nanocrystal titanium dioxide preparation method - Google Patents
High-efficiency nanocrystal titanium dioxide preparation method Download PDFInfo
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- CN103130268A CN103130268A CN2013100912648A CN201310091264A CN103130268A CN 103130268 A CN103130268 A CN 103130268A CN 2013100912648 A CN2013100912648 A CN 2013100912648A CN 201310091264 A CN201310091264 A CN 201310091264A CN 103130268 A CN103130268 A CN 103130268A
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Abstract
The invention provides a high-efficiency nanocrystal titanium dioxide preparation method. According to the experiment method, a water system, chelator, acid, a titanium source and other common experiment chemicals react under hydrothermal conditions for a certain time to prepare a high-efficiency nanocrystal titanium dioxide material; the crystal form of the prepared titanium dioxide is in an anatase structure, and the size is 40 nm; and the prepared nanocrystal titanium dioxide can achieve excellent photoelectric conversion efficiency when being used for a solar cell. According to the invention, the preparation process is simple, and the reaction substances are common, so that the cost is low; the preparation method is high in titanium dioxide yield and one-step preparation amount, and is environment-friendly; and meanwhile, enlarged experiments indicate that the product nanocrystal titanium dioxide can still have high photovoltaic property when being used for a solar cell. Thus, the high-efficiency titanium dioxide is suitable for large-scale production and application, and has favorable development prospects.
Description
Technical field
The present invention relates to a kind of preparation method of efficient nano crystal titanium dioxide and in the application in photovoltaic field, specifically that the product that obtains after certain temperature hydrothermal treatment consists for some time is successively through after water and alcohol washing, obtain a kind of anatase nanometer crystal titanium dioxide small-particle, this nanocrystalline small-particle is applied to obtain on solar cell good electricity conversion.
Background technology
Since twentieth century the 80s and 90s, nano titanium oxide was as a kind of type material exploitation, nano titanium oxide has a wide range of applications at coating, catalyzer, solar cell, cosmetics of everyday use, sensor numerous areas, and this is wherein in the application in photovoltaic field and prepare efficient nano-crystalline titanium dioxide as the focus of current titanium dioxide applied research, is attracting people to pay close attention to greatly always.
Nano-crystalline titanium dioxide is mainly to prepare dye sensitization solar battery in the application in photovoltaic field at present.The principle of work of battery is as follows: during the agent of titanium dioxide surface absorption one deck dye photoactivation, under the irradiation of sunlight, become excited state after ground state dyestuff absorb light, then excited state arrives TiO with electronic injection
2Conduction band and complete the separation of current carrier, then be transferred to electrode through the outer loop.I in electrolyte solution
3-Obtain electronics on to electrode and be reduced into I
-And the oxidation state dyestuff after electronic injection is reduced into ground state, I
-Self is oxidized to I
3, and complete whole circulation.
Nano-crystalline titanium dioxide causes people's research interest owing to having outstanding physico-chemical property, these unique character cause these materials to have ultra-fine little structure (granular size＜50nm), small particle size causes producing quantum limitation effect, have simultaneously high surface-area, these character make nano-crystalline titanium dioxide can be good at being applied to dye sensitization solar battery with respect to other structure nano materials.At present be unfavorable for large-scale application production about the most complex process of the preparation method of nano-crystalline titanium dioxide is loaded down with trivial details, though perhaps the amount of the simple preparation of method is less, performance is lower.Therefore use simple process to prepare the main direction that a large amount of efficient nano crystal titanium dioxides have become the dye sensitization solar battery study on the industrialization.
Summary of the invention
The object of the invention is to overcome the preparation method that the prior art deficiency provides the efficient nano crystal titanium dioxide that a kind of productive rate is high, technique is simple, with low cost.The present invention is achieved by the following technical solutions: sequestrant is joined in aqueous systems, continue to add acid after stirring and dissolving, after mixing, solution adds the titanium source, after stirring for some time, the solution that is made into is packed into in the teflon-lined stainless steel cauldron, sealing, react for some time under the condition of certain temperature, obtain the nano-crystalline titanium dioxide small-particle after the product process washing of preparation, alcohol wash, oven dry.This nano-crystalline titanium dioxide is applied to can obtain higher electricity conversion on solar cell.
The preparation method of a kind of efficient nano crystal titanium dioxide that the present invention proposes, its concrete steps are as follows:
(1) preparation reaction soln: 20ml～60ml water is joined in the beaker of 100ml, continuing to add 0.05g～0.5gEDTA under stirring, add 0.5g～5g citric acid after substance dissolves to be added, slowly add 1～10g titanium sulfate after stirring 5～20min, continue to stir until the solution clarification.
(2) thermal treatment: the solution for preparing is poured in reactor and with still put into baking oven, at 100～250 ℃ of lower thermal treatment 6～24h.
(3) collect product: the supernatant liquor of solution after thermal treatment is outwelled, and precipitation obtains product through 70 ℃ of oven dry after twice, alcohol wash successively successively.
The present invention with water as reactive group at the bottom of liquid, with sequestrant, acid, titanium source as reaction solvent, adopt an easy step heat treating method to prepare nano-crystalline titanium dioxide, can obtain the titanium dioxide of different physico-chemical properties by controlling solution component proportioning, temperature of reaction and reaction times, use it for dye sensitization solar battery and can obtain totally different photoelectric conversion performance.Prepared nano-crystalline titanium dioxide is Detitanium-ore-type, and size is applied to dye sensitization solar battery and can obtains higher electricity conversion about the 40nm left and right.
Preparation technology of the present invention is simple, reaction reagent is cheap and easy to get, reaction conditions is easy to control, products collection efficiency is larger, and the nano-crystalline titanium dioxide stable in properties that makes has higher commercial application prospect in the photovoltaic field.
Description of drawings:
Fig. 1 (a) is the low magnification FESEM Electronic Speculum figure of the nano-crystalline titanium dioxide of embodiment 1 preparation, is (b) the high-amplification-factor FESEM Electronic Speculum figure of the nano-crystalline titanium dioxide of embodiment 1 preparation
Fig. 2 is the X-ray diffractogram of the nano-crystalline titanium dioxide of embodiment 1 preparation
Fig. 3 is the I-V performance diagram of the dye sensitization solar battery of embodiment 2 preparations
Fig. 4 is the I-V performance diagram of the dye sensitization solar battery of embodiment 3 preparations
Fig. 5 is the I-V performance diagram of the dye sensitization solar battery of embodiment 4 preparations
Fig. 6 is the I-V performance diagram of the dye sensitization solar battery of embodiment 5 preparations
Embodiment:
The present invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention, but protection scope of the present invention is not limited by the cases cited.
Embodiment 1
0.2gEDTA is joined in 40ml water, add the 2g citric acid under continuing to stir, slowly add titanium sulfate after stirring 5min, be stirred to the solution clarification, the solution of preparing is joined in the stainless steel cauldron that contains polytetrafluoroethylliner liner, sealing,
Put in 150 ℃ of baking ovens, be cooled to room temperature after reaction 12h and take out reactor, outwell supernatant liquor, the precipitate with deionized water that obtains is washed successively with ethanol separate, drying obtains product under 70 ℃.
Embodiment 2
Titanium dioxide and commercial P25 that example 1 is prepared make respectively dye sensitization solar battery.
Preparation process is as follows:
(1) clean conductive glass: glass is first used flushing with clean water, then use respectively washings, distilled water, dehydrated alcohol ultrasonic cleaning 20min, naturally dry, the glass after cleaning is put into watch-glass.
(2) titanium tetrachloride pre-treatment: will wash good conductive glass and be immersed in the 50mM titanium tetrachloride solution for preparing, after 70 ℃ of processing 30min, it is stand-by that the taking-up conductive glass washes oven dry with water.
(3) preparation of titania slurry: take respectively titanium dioxide and each 0.05g of P25 of example 1 preparation, put into agate mortar, add a certain amount of ethyl cellulose and Terpineol 350, ethanol, obtain titania slurry after grinding 30min.
(4) preparation titanium dioxide electrodes: adopt silk screen print method that titania slurry is coated on conductive glass, take out titanium tetrachloride processing 30min after the light anode for preparing is put into 450 ℃ of calcining 30min of retort furnace, continue to put into retort furnace after oven dry and calcine 30min.
(5) soak dyestuff: the titanium dioxide electrodes that sintering is completed immerses in N719 solution, and the normal temperature lucifuge is soaked 24 rear taking-ups, the alcohol wash oven dry, and so far titanium dioxide electrodes preparation is fully.
(6) photoelectric properties test: with the titanium dioxide electrodes of preparation and Pt good to electrode package after, pour into electrolytic solution at 100mW/cm
2Carry out the photoelectric properties test under sunlight intensity.
Embodiment 3
0.2gEDTA is joined in 40ml water, add respectively citric acid, sulfuric acid, hydrofluoric acid, nitric acid, hydrochloric acid under continuing to stir, slowly add titanium sulfate after stirring 5min, be stirred to the solution clarification, the solution of preparing is joined in the stainless steel cauldron that contains polytetrafluoroethylliner liner, sealing, put in 150 ℃ of baking ovens, be cooled to room temperature after reaction 12h and take out reactor, outwell supernatant liquor, the precipitate with deionized water that obtains is washed successively with ethanol separate, drying obtains product under 70 ℃.The method of the product use-case 2 that obtains is prepared titanium dioxide electrodes and carries out the photoelectric properties test.
Embodiment 4
0.2gEDTA is joined in 40ml water, add the 2g citric acid under continuing to stir, slowly add titanium sulfate after stirring 5min, be stirred to the solution clarification, the solution of preparing is joined in the stainless steel cauldron that contains polytetrafluoroethylliner liner, sealing, be respectively put in 150 ℃, 180 ℃, 200 ℃ baking ovens, be cooled to room temperature after reaction 12h and take out reactor, outwell supernatant liquor, the precipitate with deionized water that obtains is washed successively with ethanol separate, drying obtains product under 70 ℃.The method of the product use-case 2 that obtains is prepared titanium dioxide electrodes and carries out the photoelectric properties test.
0.2gEDTA is joined in 40ml water, add the 2g citric acid under continuing to stir, slowly add respectively titanium sulfate, titanium tetrachloride after stirring 5min, be stirred to the solution clarification, the solution of preparing is joined in the stainless steel cauldron that contains polytetrafluoroethylliner liner, sealing, put in 150 ℃ of baking ovens, be cooled to room temperature after reaction 12h and take out reactor, outwell supernatant liquor, the precipitate with deionized water that obtains is washed successively with ethanol separate, drying obtains product under 70 ℃.The method of the product use-case 2 that obtains is prepared titanium dioxide electrodes and carries out the photoelectric properties test.
Claims (7)
1. the preparation method of an efficient nano crystal titanium dioxide, it is characterized in that, sequestrant is joined in aqueous systems, continue to add acid after stirring and dissolving, add the titanium source after solution mixes, the solution that is made into is packed into in the teflon-lined stainless steel cauldron after stirring for some time, sealing, react for some time under the condition of certain temperature, obtain the TiO that diameter is 40nm after the product process washing of preparation, alcohol wash, oven dry
2Small-particulate materials, the crystal formation that measures are Detitanium-ore-type.
2. a kind of preparation method of efficient nano crystal titanium dioxide as claimed in claim 1, it is characterized in that, described titanium source can be titanium tetrachloride, titanium tetrafluoride, titanous chloride, titanium sulfate, titanyl sulfate, titanium isopropylate, tetrabutyl titanate, titanium tetrafluoride, titanium valve, titanium sheet.
3. preparation method as claimed in claim 1, it is characterized in that, described sequestrant can be quadrol, 2,2 '-dipyridyl, 1,10-phenanthrolene, oxalate, disodium ethylene diamine tetraacetate, Sodium hexametaphosphate 99, trisodium hydroxyethylene diamine triacetate, nitrilotriacetic acid(NTA) trisodium.
4. preparation method as claimed in claim 1, is characterized in that, described acid can be hydrochloric acid, acetic acid, sulfuric acid, hydrofluoric acid, Hydrogen bromide, boric acid, phosphoric acid, nitric acid, oxalic acid, citric acid, Whitfield's ointment, tartrate, phenylformic acid.
5. preparation method as claimed in claim 1 is characterized in that the mass ratio in aqueous systems and titanium source is 1: 1～40: 1, and the mol ratio in sequestrant and titanium source is 1: 10～10: 1, and acid is 1: 10～10: 1 with the mol ratio in titanium source.
6. preparation method as claimed in claim 1, is characterized in that, described aqueous systems can be that water and other liquid such as ethanol, ethylene glycol, polyoxyethylene glycol etc. are miscible.
7. preparation method as claimed in claim 1, is characterized in that, comprises that except the dissolving method that adds material stirs ultrasonic agitation, heated and stirred, Ultrasonic Heating stir in aqueous systems.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128172A (en) * | 2014-07-29 | 2014-11-05 | 南昌航空大学 | Method for regulating and controlling morphology of nano TiO2-CeO2 into ball shape, dumbbell shape or sheet shape |
| CN104437343A (en) * | 2014-09-19 | 2015-03-25 | 安徽工程大学 | Modified titanium dioxide and preparation method and application of modified titanium dioxide |
| CN104925861A (en) * | 2015-06-08 | 2015-09-23 | 浙江大学 | Shape-controllable size-controllable TiO2 mesoporous single crystal and preparation method thereof |
| CN104959133A (en) * | 2015-03-26 | 2015-10-07 | 株式会社东芝 | Titanium dioxide film for photocatalyst and preparation method thereof |
| CN105006370A (en) * | 2015-06-23 | 2015-10-28 | 南京航空航天大学 | Method for in-situ preparing CZTS counter electrode by means of solvent thermal and application of CZTS counter electrode |
| CN106140123A (en) * | 2015-03-16 | 2016-11-23 | 中智环保新材料江苏有限公司 | A kind of preparation method and applications of mesopore titania photocatalyst |
| CN106315670A (en) * | 2015-11-10 | 2017-01-11 | 河南大学 | Dispersible wedge nano titanium dioxide, and preparation method and application thereof |
| CN107381632A (en) * | 2017-08-15 | 2017-11-24 | 齐鲁工业大学 | A kind of preparation method of three-dimensional flower-shaped titanium dioxide nano material |
| CN107394257A (en) * | 2017-06-15 | 2017-11-24 | 中国科学院上海硅酸盐研究所 | A kind of method for efficiently preparing porous high-specific surface area amorphous TiPO |
| CN108704641A (en) * | 2018-06-13 | 2018-10-26 | 肖然 | A kind of preparation method of high-efficiency composite photocatalyst |
| CN112830513A (en) * | 2021-02-02 | 2021-05-25 | 安徽景成新材料有限公司 | Method for synthesizing nano titanium oxide by rheological phase method |
| CN112939482A (en) * | 2021-01-15 | 2021-06-11 | 邵阳学院 | TiO 22Nano needle film and preparation method thereof |
| CN113023774A (en) * | 2021-03-19 | 2021-06-25 | 晋中学院 | High-activity crystal face co-exposed anatase type TiO2Preparation method and application of nanocrystalline |
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| US20060254461A1 (en) * | 2005-05-11 | 2006-11-16 | Agency For Science, Technology, And Research | Method and solution for forming anatase titanium dioxide, and titanium dioxide particles, colloidal dispersion and film |
| CN101830496A (en) * | 2009-03-10 | 2010-09-15 | 忠南大学校产学协力财团 | Method of preparing transition metal oxide nano-particles |
| CN101934225A (en) * | 2009-06-26 | 2011-01-05 | 堺化学工业株式会社 | TiO 2 particles and preparation method thereof |
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| US20060254461A1 (en) * | 2005-05-11 | 2006-11-16 | Agency For Science, Technology, And Research | Method and solution for forming anatase titanium dioxide, and titanium dioxide particles, colloidal dispersion and film |
| CN101830496A (en) * | 2009-03-10 | 2010-09-15 | 忠南大学校产学协力财团 | Method of preparing transition metal oxide nano-particles |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128172A (en) * | 2014-07-29 | 2014-11-05 | 南昌航空大学 | Method for regulating and controlling morphology of nano TiO2-CeO2 into ball shape, dumbbell shape or sheet shape |
| CN104437343A (en) * | 2014-09-19 | 2015-03-25 | 安徽工程大学 | Modified titanium dioxide and preparation method and application of modified titanium dioxide |
| CN106140123A (en) * | 2015-03-16 | 2016-11-23 | 中智环保新材料江苏有限公司 | A kind of preparation method and applications of mesopore titania photocatalyst |
| CN104959133A (en) * | 2015-03-26 | 2015-10-07 | 株式会社东芝 | Titanium dioxide film for photocatalyst and preparation method thereof |
| CN104925861A (en) * | 2015-06-08 | 2015-09-23 | 浙江大学 | Shape-controllable size-controllable TiO2 mesoporous single crystal and preparation method thereof |
| CN105006370A (en) * | 2015-06-23 | 2015-10-28 | 南京航空航天大学 | Method for in-situ preparing CZTS counter electrode by means of solvent thermal and application of CZTS counter electrode |
| CN106315670A (en) * | 2015-11-10 | 2017-01-11 | 河南大学 | Dispersible wedge nano titanium dioxide, and preparation method and application thereof |
| CN107394257A (en) * | 2017-06-15 | 2017-11-24 | 中国科学院上海硅酸盐研究所 | A kind of method for efficiently preparing porous high-specific surface area amorphous TiPO |
| CN107394257B (en) * | 2017-06-15 | 2019-08-16 | 中国科学院上海硅酸盐研究所 | A method of efficiently preparing porous, high-specific surface area amorphous TiPO |
| CN107381632A (en) * | 2017-08-15 | 2017-11-24 | 齐鲁工业大学 | A kind of preparation method of three-dimensional flower-shaped titanium dioxide nano material |
| CN107381632B (en) * | 2017-08-15 | 2019-07-05 | 齐鲁工业大学 | A kind of preparation method of three-dimensional flower-shaped titanium dioxide nano material |
| CN108704641A (en) * | 2018-06-13 | 2018-10-26 | 肖然 | A kind of preparation method of high-efficiency composite photocatalyst |
| CN112939482A (en) * | 2021-01-15 | 2021-06-11 | 邵阳学院 | TiO 22Nano needle film and preparation method thereof |
| CN112939482B (en) * | 2021-01-15 | 2022-12-02 | 邵阳学院 | TiO (titanium dioxide) 2 Nano needle film and preparation method thereof |
| CN112830513A (en) * | 2021-02-02 | 2021-05-25 | 安徽景成新材料有限公司 | Method for synthesizing nano titanium oxide by rheological phase method |
| CN113023774A (en) * | 2021-03-19 | 2021-06-25 | 晋中学院 | High-activity crystal face co-exposed anatase type TiO2Preparation method and application of nanocrystalline |
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Application publication date: 20130605 |