CN103395833B - Dye-sensitized solar cell based on silicon dioxide/titanium dioxide composite photo-anode, preparation method and applications - Google Patents
Dye-sensitized solar cell based on silicon dioxide/titanium dioxide composite photo-anode, preparation method and applications Download PDFInfo
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- CN103395833B CN103395833B CN201310342850.5A CN201310342850A CN103395833B CN 103395833 B CN103395833 B CN 103395833B CN 201310342850 A CN201310342850 A CN 201310342850A CN 103395833 B CN103395833 B CN 103395833B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention provides a dye-sensitized solar cell based on a silicon dioxide/titanium dioxide composite photo-anode, a preparation method and applications. The preparation method is concretely as follows: tetra-n-butyl titanate is hydrolyzed in acid condition, and concentrated to gel through a hydrothermal reaction; the gel is coated on an FTO or ITO conducting glass matrix and calcined to form a silicon dioxide/titanium dioxide composite photo-anode. The dye-sensitized solar cell takes full advantage of effective doping of silicon dioxide in titanium dioxide and inhibition of recombination of photoinduced electrons and electrolytes, and therefore the efficiency of transition of photoinduced electrons from dye excited states to silicon dioxide/titanium dioxide composite photo-anode conduction bands is greatly raised. The dye-sensitized solar cell is advantaged by large open-circuit voltage, high short-circuit current, high photoelectric conversion efficiency, simple and convenient preparation method, low cost and large improvement space.
Description
Technical field
The invention belongs to new energy materials technical field, be specifically related to DSSC based on earth silicon/titanic oxide complex light anode and its preparation method and application.
Background technology
DSSC is a kind of by titanium dioxide photo anode, sensitizing dyestuff, I
-/ I
3 -electrolyte and electrode is formed solar energy can be changed into the electrochemical appliance of electric energy.
Within 1991, by the Gr tzel research group of Lausanne, SUI Gao Deng engineering institute, take nano porous titanium dioxide as semiconductor anode, Ru complex compound is sensitizing dyestuff, I
-/ I
3 -for redox electrolytes matter, platinum be to electrode assembling the prototype of DSSC, its photoelectric conversion efficiency is 7.1%, has opened thus the prelude of DSSC research.The photoelectric conversion efficiency of this battery in 1997 has been increased to 11%.Through the effort of 15 years, researchers successfully developed the DSSC of different morphologies and structure, but efficiency raising is less, far below its theoretical value.Therefore, develop a kind of DSSC cheap, reproducible, that photoelectric conversion efficiency is high and become the necessary condition that it is able to extensive use.
In recent years, have research to adopt rare earth-doped titanium dioxide to do light anode material, the Gao Jun of the photoelectric conversion efficiency of the DSSC of assembling is lower than 8%.
Summary of the invention
The object of the present invention is to provide a kind of DSSC based on earth silicon/titanic oxide complex light anode and its preparation method and application, described earth silicon/titanic oxide complex light anode preparation method is simple and easy to do, cost is lower, the DSSC of assembling, open circuit voltage is large, short circuit current is high, electricity conversion is high.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
The preparation method of the DSSC based on earth silicon/titanic oxide complex light anode, comprises the following steps:
(1), by tetra-n-butyl titanate: the volume ratio of water is that 8-12:100 mixes, stirring at room, filtering and washing;
(2) in the product, acetic acid and nitric acid dropping being obtained to step (1), acetic acid volumetric usage is identical with tetra-n-butyl titanate consumption, acetic acid and nitric acid volume ratio are 5-15:0.5-1, at 60 ℃-80 ℃, stir, the volume ratio that adds water to cumulative volume and acetic acid consumption is 150-200:10, and sealing is stirred to and presents light blue transparent colloid;
(3), step (2) gained colloid is moved in hydrothermal reaction kettle, 200 ℃ of reaction 12-24h, finally remove the supernatant liquor in reactor, obtain white colloid;
(4), extracting waste colloid, add and account for the nanocrystalline gas phase titanium dioxide P25 and the nano silicon that accounts for tetra-n-butyl titanate quality 0.5 ~ 9% that tetra-n-butyl titanate quality is 1-10%, add again deionized water to cumulative volume to equate with the cumulative volume of step (2), stir, ultrasonic;
(5) and then put into reactor, 200 ℃ of hydro-thermal 8-12 h reactions obtain colloids;
(6), OP emulsifying agent is added drop-wise in isopropyl alcohol to preparation OP emulsifier solution;
(7), the colloid that in step (5), reaction obtains is removed to supernatant liquor, extracting waste colloid adds and accounts for the OP emulsifier solution making in the polyethylene glycol of tetra-n-butyl titanate mass ratio 0.5～1% and step (6), continuation is concentrated makes colloid, and the volume ratio of described OP emulsifier solution and tetra-n-butyl titanate is 1-3:10;
(8), colloid prepared by step (7) is applied on electro-conductive glass, controlling thickness is 5～15 μ m, through 450 ℃ of high-temperature calcinations, forms nano silicon/titania coextruded film;
(9), will in the N719 of described earth silicon/titanic oxide laminated film immersion 0.2～0.5 mM or N3 dye solution, form dye sensitization earth silicon/titanic oxide complex light anode;
(10), dye sensitization earth silicon/titanic oxide complex light anode prepared by step (9) and standard platinum be to electrode combination, and drip and contain I
-/ I
3 -electrolyte be assembled into DSSC.
Further, the particle diameter of the nano silicon in described step (4) is 10-50 nm.
Further, in described step (6), the volume ratio of OP and isopropyl alcohol is 1:10-50.
Further, in described step (7), concentrated temperature is 80-120 ℃.
Further, in described step (10), contain I
-/ I
3 -electrolyte by the acetonitrile solution of 0.01 ~ 0.06 M iodine, 0.08 ~ 0.12 M lithium iodide, 0.4 ~ 0.8 M tetrabutylammonium iodide and 0.4 ~ 0.6 M 4-tert .-butylpyridine, formed.
The present invention also provides the earth silicon/titanic oxide complex light anode radical dye sensitization solar battery that utilizes described preparation method to prepare.
The open circuit voltage of described solar cell is that 700 ~ 800 mV, short circuit current are 20 ~ 25 mAcm
-2, fill factor, curve factor is 0.55 ~ 0.7, photoelectric conversion efficiency is 8 ~ 10.5%.
Earth silicon/titanic oxide complex light anode radical dye sensitization solar battery described in the present invention also provides is in the application as in Blast Furnace Top Gas Recovery Turbine Unit (TRT).
Compared with prior art, advantage of the present invention and good effect are: the invention provides a kind of DSSC based on earth silicon/titanic oxide complex light anode and preparation method thereof, specifically with tetra-n-butyl titanate, under acid condition, be hydrolyzed, and mix nano silicon, by hydro-thermal reaction and be condensed into colloid and be coated on FTO or ITO electro-conductive glass matrix, through calcining, form earth silicon/titanic oxide complex light anode.The photoelectric conversion efficiency of the DSSC of assembling is 8 ~ 10.5%.
The present invention makes full use of silicon dioxide to the Effective Doping of titanium dioxide and suppresses light induced electron and electrolytical compound, thereby greatly improve light induced electron, is transitted to the efficiency of earth silicon/titanic oxide complex light anode conduction band by dyestuff excitation state.Earth silicon/titanic oxide complex light anode preparation method of the present invention is simple and easy to do, with low cost, room for improvement is large, and the DSSC open circuit voltage assembled is large, short circuit current is high, optoelectronic transformation efficiency is high.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
The preparation method of the DSSC based on earth silicon/titanic oxide complex light anode of the present invention comprises the following steps:
1. 10 mL tetra-n-butyl titanates are added drop-wise in 100 mL distilled water to stirring at room 30 min, filtering and washing.
By 10 mL acetic acid and 0.8 mL nitric acid dropping in the product of step 1,80 ℃ are stirred 15 min, adding water to cumulative volume is 170 mL, 80 ℃ airtight is stirred to light blue transparent colloid.
3. 140 mL colloids are moved in hydrothermal reaction kettle, 200 ℃ of reaction 12 h, finally remove the supernatant liquor in reactor, obtain white colloid.
4. extracting waste colloid, add and account for the nanocrystalline gas phase titanium dioxide P25 and the nano silicon (particle diameter is 10-50 nm) that accounts for tetra-n-butyl titanate quality 0.5 ~ 9% that tetra-n-butyl titanate quality is 1-10%, add again 30 mL deionized water to 170 mL, stir, ultrasonic 30 min.
5. again put into reactor, 200 ℃ of hydro-thermal 12 h reactions obtain white colloid.
6. 1 mL OP is added drop-wise in 10 mL isopropyl alcohols, preparation OP emulsifier solution, the volume ratio of described OP and isopropyl alcohol is 1:10-50.
7. colloid reaction in step 5 being obtained removes supernatant liquor, and extracting waste colloid adds and accounts for the OP emulsifier solution making in the polyethylene glycol of tetra-n-butyl titanate mass ratio 0.5～1% and 1 mL step 6, in 80 ℃ of concentrated colloids that make.
8. the colloid of preparation is applied on electro-conductive glass, controlling thickness is 5 ~ 15 μ m, through 450 ℃ of high-temperature calcinations, prepares earth silicon/titanic oxide laminated film.
9. will in the N719 of described earth silicon/titanic oxide laminated film immersion 0.2 ~ 0.5 mM or N3 dyestuff, form dye sensitization earth silicon/titanic oxide complex light anode.
10. the dye sensitization earth silicon/titanic oxide complex light anode of being prepared by step 9 and standard platinum are to electrode combination, and dropping contains I
-/ I
3 -electrolyte be assembled into DSSC, described in contain I
-/ I
3 -electrolyte by the acetonitrile solution of 0.01 ~ 0.06 M iodine, 0.08 ~ 0.12 M lithium iodide, 0.4 ~ 0.8 M tetrabutylammonium iodide and 0.4 ~ 0.6 M 4-tert .-butylpyridine, formed.
By said method, can obtain open circuit voltage is 700 ~ 800 mV, and short circuit current is 20 ~ 25 mAcm
-2, fill factor, curve factor is 0.55 ~ 0.7, the earth silicon/titanic oxide complex light anode radical dye sensitization solar battery that photoelectric conversion efficiency is 8 ~ 10.5%.DSSC of the present invention can be used as Blast Furnace Top Gas Recovery Turbine Unit (TRT) application.
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although the present invention is had been described in detail with reference to previous embodiment, for the person of ordinary skill of the art, the technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (8)
1. the preparation method of the DSSC based on earth silicon/titanic oxide complex light anode, is characterized in that comprising the following steps:
(1), by tetra-n-butyl titanate: the volume ratio of water is that 8-12:100 mixes, stirring at room, filtering and washing;
(2) in the product, acetic acid and nitric acid dropping being obtained to step (1), acetic acid volumetric usage is identical with tetra-n-butyl titanate consumption, acetic acid and nitric acid volume ratio are 5-15:0.5-1, at 60 ℃-80 ℃, stir, the volume ratio that adds water to cumulative volume and acetic acid consumption is 150-200:10, and sealing is stirred to and presents light blue transparent colloid;
(3), step (2) gained colloid is moved in hydrothermal reaction kettle, 200 ℃ of reaction 12-24h, finally remove the supernatant liquor in reactor, obtain white colloid;
(4), extracting waste colloid, add and account for the nanocrystalline gas phase titanium dioxide P25 and the nano silicon that accounts for tetra-n-butyl titanate quality 0.5 ~ 9% that tetra-n-butyl titanate quality is 1-10%, add again deionized water to cumulative volume to equate with the cumulative volume of step (2), stir, ultrasonic;
(5) and then put into reactor, 200 ℃ of hydro-thermal 8-12 h reactions obtain colloids;
(6), OP emulsifying agent is added drop-wise in isopropyl alcohol to preparation OP emulsifier solution;
(7), the colloid that in step (5), reaction obtains is removed to supernatant liquor, extracting waste colloid adds and accounts for the OP emulsifier solution making in the polyethylene glycol of tetra-n-butyl titanate mass ratio 0.5～1% and step (6), continuation is concentrated makes colloid, and the volume ratio of described OP emulsifier solution and tetra-n-butyl titanate is 1-3:10;
(8), colloid prepared by step (7) is applied on electro-conductive glass, controlling thickness is 5～15 μ m, through 450 ℃ of high-temperature calcinations, forms nano silicon/titania coextruded film;
(9), will in the N719 of described earth silicon/titanic oxide laminated film immersion 0.2～0.5 mM or N3 dye solution, form dye sensitization earth silicon/titanic oxide complex light anode;
(10), dye sensitization earth silicon/titanic oxide complex light anode prepared by step (9) and standard platinum be to electrode combination, and drip and contain I
-/ I
3 -electrolyte be assembled into DSSC.
2. the preparation method of the DSSC based on earth silicon/titanic oxide complex light anode according to claim 1, is characterized in that: the particle diameter of the nano silicon in described step (4) is 10-50 nm.
3. the preparation method of the DSSC based on earth silicon/titanic oxide complex light anode according to claim 1, is characterized in that: in described step (6), the volume ratio of OP and isopropyl alcohol is 1:10-50.
4. the preparation method of the DSSC based on earth silicon/titanic oxide complex light anode according to claim 1, is characterized in that: in described step (7), concentrated temperature is 80-120 ℃.
5. the preparation method of the DSSC based on earth silicon/titanic oxide complex light anode according to claim 1, is characterized in that: in described step (10), contain I
-/ I
3 -electrolyte by the acetonitrile solution of 0.01 ~ 0.06 M iodine, 0.08 ~ 0.12 M lithium iodide, 0.4 ~ 0.8 M tetrabutylammonium iodide and 0.4 ~ 0.6 M 4-tert .-butylpyridine, formed.
6. the DSSC based on earth silicon/titanic oxide complex light anode making according to the preparation method described in claim 1-5 any one.
7. the DSSC based on earth silicon/titanic oxide complex light anode according to claim 6, is characterized in that: the open circuit voltage of described solar cell is that 700 ~ 800 mV, short circuit current are 20 ~ 25 mAcm
-2, fill factor, curve factor is 0.55 ~ 0.7, photoelectric conversion efficiency is 8 ~ 10.5%.
8. the DSSC based on earth silicon/titanic oxide complex light anode according to claim 6 is in the application as in Blast Furnace Top Gas Recovery Turbine Unit (TRT).
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| CN106086921B (en) * | 2016-06-14 | 2018-05-08 | 大连理工大学 | Si/TiO is constructed in a kind of crystal face induction2The preparation method of complex light anode |
| CN106587282B (en) * | 2016-12-08 | 2020-02-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Double-functional multi-template molecularly imprinted photoelectric anode material and preparation and application thereof |
| CN106847516B (en) * | 2017-03-17 | 2018-10-26 | 宁波高新区远创科技有限公司 | A kind of preparation method of dye-sensitized solar cell anode material |
| CN106876145A (en) * | 2017-03-24 | 2017-06-20 | 湖北大学 | A kind of solar cell TiO2/SiO2Core shell structure light anode and preparation method thereof |
| CN109003822A (en) * | 2018-07-21 | 2018-12-14 | 欧陈珍 | Dye-sensitized solar cells based on titanium dioxide core shell particles light anode |
| CN113782815B (en) * | 2021-08-17 | 2023-03-14 | 浙江工业大学 | Lithium ion battery and method for activating dead lithium by light assistance |
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| TWI460865B (en) * | 2010-04-15 | 2014-11-11 | Nat Univ Tsing Hua | Material of dye sensitized solar cell and producing method thereof |
| CN103050289B (en) * | 2013-01-18 | 2015-12-23 | 中国海洋大学 | Two-sided DSSC of polyaniline transparent counter electrode base and its preparation method and application |
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