CN103896330A - Modified titanium dioxide, preparation method thereof and solar cell prepared thereby - Google Patents
Modified titanium dioxide, preparation method thereof and solar cell prepared thereby Download PDFInfo
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Abstract
The invention relates to modified titanium dioxide, a preparation method thereof and a dye-sensitized solar cell. The modified titanium dioxide is modified through the following steps of (a) providing titanium dioxide powder; (b) dispersing the titanium dioxide in water so as to form a sizing agent; and (c) carrying out hydrothermal treatment on the sizing agent for 12-96 hours at 150-240DEG C. The dye-sensitized solar cell prepared by the modified titanium dioxide has high photoelectric conversion efficiency.
Description
Technical field
The present invention relates to the manufacture method of a kind of modifying titanium dioxide and this modifying titanium dioxide.The invention still further relates to the dye sensitization solar battery forming with this modifying titanium dioxide.There is high photoelectric transformation efficiency with the dye sensitization solar battery that modifying titanium dioxide of the present invention forms.
Background technology
For solving global energy crisis and reducing environmental pollution, the solar cell that solar radiant energy directly can be converted to electric energy is the new problem that actively innovation is researched and developed in recent years, wherein, dye-sensitized solar cells is the organic photovoltaic cell that belongs to the third generation, compared with traditional list (many) crystal silicons or non-crystal silicon solar cell, it is high that dye sensitization solar battery has theoretical conversion efficiency, technique is simple, transparency is good, low cost and other advantages, expand and have sizable benefiting for commercialization, there is great development potentiality, can become the main flow of following solar battery technology development of new generation.
Dye sensitization solar battery is mainly made up of light anode, dye sensitizing agent, redox electrolytes matter, photocathode etc.Core component light anode plays load sensitizing agent, the effect of collection and conduction electron.
Titanium dioxide membrane electrode provided is conventional light anode.Therefore for this smooth anode, the performance of titanium dioxide film directly affects the photoelectric transformation efficiency of whole solar cell.Generally speaking, titanium dioxide film properties is mainly determined by the many factors such as performance and film of the titanium dioxide that forms this film itself.
Conventional titanium dioxide manufacture method comprises sol-gel method and gas phase P25 titania powder method at present:
The method that sol-gel method is prepared titanium dioxide comprises long period dispergation step and heat treatment step subsequently at a certain temperature, but dispergation process is not easy to control, the slurry repeatability of preparing is poor, and this is a very large problem for suitability for industrialized production.In addition, if the titanium dioxide making with gel gel method forms film, dry rear this film more or less can ftracture, and causes photoelectric transformation efficiency to reduce.
Gas phase P25 titania powder method is a kind of method of the P25 of production type titania powder, and this P25 type titania powder obtains by titanium tetrachloride hydrogen flame, and reactive mode is as follows:
TiCl
4+2H
2+O
2→TiO
2+4HCl
P25 type titanium dioxide is a kind of very thin white powder, and the hydrogen-oxygen group on surface makes it have wetting ability, and this product is without any pigment feature.The median size of basic granules is approximately 21nm, the size of particle and 4g/cm
3density make it have 50m
2the special surface of/g.P25 type titanium dioxide belongs to mixed crystal type, and the weight ratio of anatase octahedrite and rutile is approximately 80/20, because two kinds of mixing up of structure have increased TiO
2intracell defect concentration, has increased the concentration of current carrier, and electronics, number of cavities are increased, and makes it have the stronger TiO that is captured in
2the ability of the solution component (water, oxygen, organism) on surface.
Prepare titanium dioxide with gas phase P25 powder method and have advantages of that price is low, reproducible; Its shortcoming is that powder dispersiveness is lower, and the slurry transmitance of preparing is low, and reference area is little, and P25 contains Rutile Type, and the photoelectric transformation efficiency of the dye sensitization solar battery of preparing is like this low.
Therefore, prior art need to be to carrying out modification with various existing titania powders, thereby improve its powder dispersiveness, film-forming properties, rheological etc., and improve with this titanium dioxide the photoelectric transformation efficiency as the solar cell of light anodic formation.
Prior art also needs to provide a kind of titanium dioxide through modification, this titanium dioxide has high powder dispersiveness, preferably film-forming properties and rheological preferably, and has high photoelectric transformation efficiency as the solar cell of light anodic formation with this titanium dioxide.
Prior art also needs to provide a kind of solar cell using titanium deoxid film as light anodic formation, and this solar cell has high photoelectric transformation efficiency.
Summary of the invention
Therefore, a goal of the invention of the present invention is that the titania powder to preparing with various commercial runs carries out modification, thereby improve its powder dispersiveness, film-forming properties and rheological etc., improve with this titanium dioxide the photoelectric transformation efficiency as the solar cell of light anodic formation.
Another goal of the invention of the present invention is to provide a kind of titanium dioxide through modification, this titanium dioxide has high powder dispersiveness, preferably film-forming properties and rheological preferably, and has high photoelectric transformation efficiency as the solar cell of light anodic formation with this titanium dioxide.
Another goal of the invention of the present invention is to provide a kind of solar cell using titanium deoxid film as light anodic formation, and this solar cell has high photoelectric transformation efficiency.
Therefore, one aspect of the present invention is to provide a kind of modifying titanium dioxide, and it makes with the following method:
(a) provide titania powder;
(b) this titania powder is dispersed in water, forms slurry;
(c) at the temperature of 150-240 ℃ by this slurry water thermal treatment 12-96 hour.
Another aspect of the present invention provides a kind of method of modifying of titanium dioxide, and it comprises the steps:
(a) provide titania powder;
(b) this titania powder is dispersed in water, forms slurry;
(c) at the temperature of 150-240 ℃ by this slurry water thermal treatment 12-96 hour.
One side more of the present invention is to provide a kind of dye sensitization solar battery, and it comprises light anode, dye sensitizing agent, redox electrolytes matter, photocathode, it is characterized in that described smooth anode modifying titanium dioxide of the present invention makes.
Accompanying drawing explanation
, further illustrate by reference to the accompanying drawings the present invention below, in accompanying drawing:
Fig. 1 is scanning electronic microscope (SEM) figure of the prepared titanium dioxide of comparative example 2;
Fig. 2 is the SEM figure of the prepared titanium deoxid film of embodiment 3;
Fig. 3 is the SEM figure of the prepared titanium deoxid film of comparative example 3;
Fig. 4 is the SEM figure of the prepared titanium deoxid film of embodiment 5;
Fig. 5 is monochromatic incident photon-electronic switch efficiency of comparative example 2, embodiment 2 and embodiment 4;
Fig. 6 is the surface topography 3D figure of the prepared titanium deoxid film of comparative example 4;
Fig. 7 is the surface topography 3D figure of the prepared titanium deoxid film of embodiment 6;
Fig. 8 is the prepared slurry photo of comparative example 5;
Fig. 9 is the prepared slurry photo of embodiment 6.
Embodiment
The present invention relates to a kind of modifying titanium dioxide, its method of modifying comprises the steps:
(a) provide titania powder;
Titania powder for modification is without particular limitation, can be the conventional titania powder of this area, and this titania powder can commercially availablely obtain.
In an embodiment of the invention, technical grade nano titanium dioxide powder is provided, described titania powder can be commercially available, the nano titanium dioxide powders such as such as P25 type, ST21 type or Detitanium-ore-type, maybe can make by various currently known methodss, for example, be made by vapor phase process, sulfuric acid process, hydrolysis method, sol-gel method etc.
Described sol-gel method is take organic or inorganic salt as raw material, is hydrolyzed, polycondensation in organic medium, makes solution obtain gel through sol gel process, and gel is dry through heating (or freezing), calcination obtains product.
Described vapor phase process is by TiCl
4in the oxyhydrogen flame of gas importing high temperature, carry out vapor phase hydrolysis, chemical equation is:
TiCl
4+2H
2+O
2→TiO
2+4HCl。
Be preferably, described titanium dioxide is the titanium dioxide that vapor phase process makes, or the nano titanium dioxide powder such as P25 type, ST21 type or Detitanium-ore-type.
(b) this titania powder is dispersed in water, forms slurry;
The method that titania powder is dispersed in water is without particular limitation, as long as the method can form homodisperse water paste.For example, described dispersing method can be magnetic agitation, ultrasonic, shearing etc.
In yet another embodiment of the present invention, at 10-30 ℃, better, under the condition of 15-20 ℃, described titania powder is dispersed in water, after fully mixing, forms slurry.Described water is preferably deionized water.
The mass ratio of described titania powder and water is without particular limitation, as long as titania powder can form uniform dispersion.In an example of the present invention, the mass ratio of described titania powder and water is 1:5-1:50, is preferably 1:10-1:30, is preferably 1:15-1:25.
In addition,, for promoting the dispersion of titania powder in water, can use pH adjusting agent to regulate the pH value of dispersion liquid.Applicable pH adjusting agent is without particular limitation, can be any known pH adjusting agent in this area.In an example of the present invention, described pH adjusting agent is selected from various acid or alkali, such as acetic acid, nitric acid, hydrochloric acid, ammoniacal liquor, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide etc., preferably acetic acid, nitric acid, ammoniacal liquor, trimethylammonium hydroxide.
Regulating the pH value of the solution reaching without particular limitation, can be any pH value that is applicable to dispersion, for example, dispersion liquid can be adjusted to pH1-13, is preferably pH4-9.
(c) at the temperature of 150-240 ℃ by this slurry water thermal treatment 12-96 hour.
The inventive method comprises that the titanium dioxide water pulp to obtaining carries out the step of hydrothermal treatment consists above, it is included at the temperature of 150-240 ℃, more fortunately at the temperature of 170-220 ℃, better at the temperature of 190-210 ℃ by the water paste hydrothermal treatment consists 12-96 hour making above, better 16-90 hour, better 18-80 hour, preferably 20-60 hour.For example hydrothermal treatment consists 15 hours, 30 hours, 35 hours etc.
The pressure of hydrothermal treatment consists is without particular limitation, can be normal pressure.In a better example of the present invention, under pressurized conditions, carry out hydrothermal treatment consists, applicable pressure is 2-4MPa, is preferably 2.2-3.8MPa, preferably 2.4-3Mpa, more preferably 2.5-2.8Mpa.
The concrete grammar of hydrothermal treatment consists is without particular limitation, can be hydro-thermal treatment method known in the art.
The method of modifying of titanium dioxide of the present invention also optionally comprises the steps:
D) washing and redispersion
Can wash the titania slurry through hydrothermal treatment consists.Applicable washing composition is without particular limitation, can be any washing composition known in the art, and such as alcohol, ether and ester etc., better use alcohols washing composition, for example, use ethanol as washing composition.
In an embodiment of the invention, after hydrothermal treatment consists, be 5000-9000rpm by the water-based titania slurry obtaining at rotating speed, better, under the condition of 6000-8000rpm, use whizzer to carry out centrifugal 10-30 minute, better 15-25 minute, then adding ethanol, is 5000-9000 at rotating speed after stirring, better centrifugal drying under the condition of 6000-8000rpm rpm, centrifugation time is 10-30 minute, better 15-25 minute.Repeat above-mentioned ethanol stirring-centrifugation step 2-4 time, until slurry turns white.
Can be by the titania slurry redispersion through washing in organic solvent.Applicable organic solvent is without particular limitation, can be any organic solvent known in the art, such as methyl alcohol, ethanol, acetone, benzene, acetonitrile, hexanaphthene etc., preferred alcohol.
Applicable redispersion method is without particular limitation, can be any dispersing method known in the art.For example it can be the dispersing method arbitrarily such as magnetic agitation, ball milling, mechanical stirring.For improving the stability of dispersion liquid, can in described dispersion liquid, add additive (for example dispersion agent).Applicable additive has, for example C
1 -6alkylcellulose, as methylcellulose gum, ethyl cellulose or mixture; Applicable additive also comprises Terpineol 350.Comprise such as acetic acid, ethylene glycol or its mixture etc. for improving dispersed suitable dispersant.
In yet another embodiment of the present invention, the above-mentioned titania slurry through hydrothermal treatment consists is dispersed in alcoholic solvent, then adds wherein C
1-6alkylcellulose and alcohol.Described C
1-6alkylcellulose comprises the ethyl cellulose of different viscosity, is preferably the ethanolic soln of ethyl cellulose, and the mass content of ethyl cellulose in ethanol be 5-30%, preferably 8-25%, and more preferably 9-15%, is preferably 10%.In a better example of the present invention, to above-mentioned ethyl cellulose, Terpineol 350 and the described dispersion agent of adding in the titanium dioxide of centrifugal drying, making content of titanium dioxide is 15-25%, and ethyl cellulose cellulose content is 5-15%, Terpineol 350 content is 60-80%, and described dispersant is 0-5%.
In yet another embodiment of the present invention, by above-mentioned titanium dioxide, C
1-6the mixture magnetic agitation of alkylcellulose and Terpineol 350 is more than 12 hours, then carry out high-shear and disperse 10-15 minute, ultrasonic dispersion 10-15 minute, subsequently finely dispersed slurry is removed to desolventizing with Rotary Evaporators evaporation, carry out the about 20-40 minute of roll-in with three-roller again, obtain the titania slurry of modification, seal up for safekeeping for subsequent use.
There is following characteristics with the titanium dioxide of the inventive method modification:
Specific surface area is about 40.0-80.0m
2/ g, preferred about 57.2-62.0m
2/ g;
Aperture is about 10.0-30.0nm, is preferably about 17.2-21.2nm;
Particle diameter is about 7.0-50.0nm, is preferably 20-30nm;
Porosity is 50-60%, is preferably 53.6-58.8%;
Roughness is 90-110 μ m
-1, be preferably about 91.7-107.4 μ m
-1.
The present invention also provides a kind of dye sensitization solar battery, and it comprises light anode, dye sensitizing agent, redox electrolytes matter, photocathode.
The dye sensitizing agent, redox electrolytes matter and the photocathode that are applicable to dye sensitization solar battery of the present invention are without particular limitation, can be any dye sensitizing agent known in the art, redox electrolytes matter and photocathode.
For example, can adopt the known N3 dyestuff of prior art or " black dyes " as dye sensitizing agent:
Can adopt I
-/ I
- 3redox couple is as ionogen.In an example of the present invention, use 0.5MLiI, 0.05M I
2with the solution of 0.5M4-tertiary butyl piperidines in 3-methoxypropionitrile as ionogen; Also can use the conventional Z960(1M1 in this area, the LiI of 3-methylimidazole salt compounded of iodine (DMII), 50mM, the I of 30mM
2, 0.5M tert .-butylpyridine and 0.1MGuNCS be at the mixing solutions of acetonitrile and valeronitrile) solid electrolyte.
Can adopt different methods to plate Pt, carbon or conductive polymers etc. on the metal sheets such as conductive glass or titanium plate, aluminium sheet and prepare photocathode.Dye sensitization solar battery of the present invention adopts modifying titanium dioxide of the present invention as light anode.
The preparation method of dye sensitization solar battery of the present invention is without particular limitation, can be ordinary method known in the art, only uses modifying titanium dioxide of the present invention as light anode material.
In an example of the present invention, the preparation method of described dye sensitization solar battery comprises the steps:
Modifying titanium dioxide slurry of the present invention is printed on to the SnO of doped with fluorine
2conductive glass (FTO) is upper, makes the titanium deoxid film as solar battery light anode; Applicable printing process is without particular limitation, can be conventional printing process known in the art.The indefiniteness example of described printing process comprises, such as silk screen printing, roller coat, brushing etc.
On this titanium deoxid film, flood dyestuff, described dyestuff comprises such as N3 dyestuff, N719 dyestuff, Z907 dyestuff, Z991 dyestuff, " black dyes " or D131 organic dye etc., preferably uses Z907 dyestuff and Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
In addition, before printing titanium dioxide, can be to the SnO of doped with fluorine
2conductive glass cleans, and to remove impurity and the dirt of glass surface, then carries out uv irradiating 15-35 minute, better 20-30 minute.SnO to the doped with fluorine after cleaning subsequently
2conductive glass carries out titanium tetrachloride pre-treatment.
The SnO of described doped with fluorine
2conductive glass cleans and comprises the following steps: by ultrasonic glass shelf 10-20 minute, better 15 minutes, re-use the ultrasonic 10-20 minute of deionized water, better 15 minutes with ethanol; By the SnO of doped with fluorine
2conductive glass is placed on shelf, uses ultrasonic detergent 10-20 minute, better 15 minutes, re-uses water wash 3-8 minute, better 5 minutes; Use the ultrasonic 10-20 minute of dilute nitric acid solution, better 15 minutes, re-use deionized water drip washing 3-8 minute, better 5 minutes; Use the ultrasonic 10-20 minute of sodium hydroxide alkaline solution, better 15 minutes, re-use deionized water drip washing 3-8 minute, better 5 minutes; Use the ultrasonic 10-20 minute of deionized water, better 15 minutes, re-use acetone drip washing 3-8 minute 5 minutes; Use the ultrasonic 10-20 minute of acetone, better 15 minutes, then it is for subsequent use to Tumble Dry.
The SnO of described doped with fluorine
2the titanium tetrachloride processing of conductive glass comprises the following steps: the SnO that makes doped with fluorine
2conductive glass stands uv irradiating 20-35 minute, better 30 minutes, then at 60-80 ℃, uses 35-45mM, better the TiCl of 40mM under better 70 ℃ of conditions
4the aqueous solution is processed 20-35 minute, better 30 minutes; After taking out, water and ethanol rinse, dry for standby.
Then use automatic screen printing machine silk screen ST325 the titania slurry of described modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, dry 8-15 minute at 100 ℃, better 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, is warming up to approximately 500 ℃ and be incubated 20-35 minute, better 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.
In yet another embodiment of the present invention, the method of modifying of titanium dioxide of the present invention comprises the steps: 5-10g nanometer anatase titania to be dissolved in 100-200g water, use pH adjusting agent that pH is adjusted to 4-9, it was fully mixed in magnetic agitation 4-12 hour.This mixture is transferred in hydrothermal reaction kettle, under 100-300 ℃ of condition, carries out hydro-thermal reaction 12-48 hour.The titanium dioxide blends obtaining obtains white solid through after centrifugal and washing with alcohol three times, this white solid is transferred in beaker with solvent, and disperses.The content that records titanium dioxide after being uniformly dispersed is 1-10%.Take this titania solution of 50-200g, and add wherein cellulosic ethanolic soln (10-30g) and Terpineol 350 (10-30g), magnetic agitation 6-24 hour.Then carry out high-shear 5-30 minute, ultrasonic 5-30 minute, uses Rotary Evaporators evaporation to remove ethanol, obtains titanium dioxide dope.Through three-roller roll-in, obtain the titania slurry of modification.When use, the slurry silk screen printing of this modification can be obtained to titanium dioxide film, be assembled into battery.
Below explanation and non-limiting example are used for further describing the embodiment that literary composition discloses, but not limit the scope of the invention.The version that those skilled in the art can understand embodiment can fall within the scope of the invention, and the scope of the invention is only defined by the claims.
embodiment
1.
the material using in embodiment:
Nanometer anatase titania: purchased from Shanghai Jiang Hu company limited
Titanic oxide nano ST21: former purchased from Japanese stone
Titanic oxide nano P25: purchased from Degussa
2. test method
1. the test of photoelectric properties
At room temperature, use YSS-150A type solar simulator and ADCMT-6246 type tester, the current-voltage curve of test dye sensitization solar battery, then draw the open circuit voltage of battery, short-circuit current, packing factor, and calculate thus the photoelectric transformation efficiency of battery.Light source is xenon source AM1.5, and the intensity of light source is 100mW/cm
2, the useful area of battery is 0.1884cm
2.
2. monochromatic incident photon-electronic switch efficiency (IPCE test):
At room temperature, use monochromatic incident photon-electronic switch efficiency of CEP-1500 type quantum efficiency of solar battery test system and test dye sensitization solar battery.
3. scanning electron microscope (SEM) test:
Use the S-4800 of Hitachi type field emission scanning electron microscope observe the titanium deoxid film surface topography of composition light anode and carry out microstructure analysis.
4. surface topography 3D figure observation:
Use Nikon RSI MM3000 observation titanium dioxide film surface topography and thickness.
5. particle diameter, surface-area, aperture, porosity, roughness
Surface-area, aperture, pore volume directly record by the U.S. ASAP2020 of micromeritics company type specific surface area analysis instrument, and particle diameter, porosity and roughness are calculated according to following formula:
Particle diameter=6000/ (surface-area × 3.84)
Porosity=pore volume/(pore volume+1/3.84)
Roughness=(1-porosity) × 3.84 × surface-area
1. prepare modifying titanium dioxide
8g nanometer anatase titania is dissolved in 150g water, and magnetic agitation fully mixes it in 6 hours.This mixture is transferred in hydrothermal reaction kettle, under 200 ℃ of conditions, carries out hydro-thermal reaction 24 hours.The titanium dioxide blends obtaining obtains white solid through after centrifugal and washing with alcohol three times, this white solid is transferred in beaker with ethanol, and carries out magnetic agitation.The content that records titanium dioxide after stirring is 5%.
Take this titania solution of 100g, and add wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain the titania slurry of modification.
By the performance of this modifying titanium dioxide of test method measuring above, the results are shown in table 1.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.
On this titanium deoxid film, flood Z907 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 2.
1. prepare modifying titanium dioxide
8g nanometer anatase titania is dissolved in 150g water, uses ammoniacal liquor that pH is adjusted to 9, magnetic agitation fully mixes it in 6 hours.This mixture is transferred in hydrothermal reaction kettle, under 200 ℃ of conditions, carries out hydro-thermal reaction 24 hours.The titanium dioxide blends obtaining obtains white solid through after centrifugal and washing with alcohol three times, this white solid is transferred in beaker with ethanol, and carries out magnetic agitation.The content that records titanium dioxide after stirring is 5%.
Take this titania solution of 100g, and add wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain the titania slurry of modification.
By the performance of this modifying titanium dioxide of test method measuring above, the results are shown in table 1.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.
On this titanium deoxid film, flood Z907 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 2.Its photoelectric properties are as shown in Fig. 5 curve 1.
comparative example 1
1. prepare modifying titanium dioxide
5g nanometer anatase titania is dissolved in ethanol, after magnetic agitation is even, adds wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain titanium deoxide slurry.
By the performance of this modifying titanium dioxide of test method measuring above, the results are shown in table 1.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.
On this titanium deoxid film, flood Z907 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 2.
Table 1 is the BET result of the prepared titanium dioxide of embodiment 1,2 and comparative example 1.Associative list 1 can find out, nanometer anatase titania is after hydrothermal treatment consists modification, and 17nm is brought up to from 12nm in the aperture of titanium dioxide, and this is conducive to the conduction of electronics, and roughness obviously reduces.
Table 2 is photoelectric properties results that embodiment 1,2 and the prepared titanium dioxide membrane electrode provided of comparative example 1 are assembled into dye-sensitized cell, can find out, nanometer anatase titania is after hydrothermal treatment consists modification, and the photoelectric transformation efficiency of the solar cell of being prepared by the titania slurry of this modification improves 13%.
Table 1
Table 2
1. prepare modifying titanium dioxide
8g Preparation of Nanocrystal TiO ST21 is dissolved in 150g water, and magnetic agitation fully mixes it in 12 hours.This mixture is transferred in hydrothermal reaction kettle, under 200 ℃ of conditions, carries out hydro-thermal reaction 24 hours.The titanium dioxide blends obtaining obtains white solid through after centrifugal and washing with alcohol three times, this white solid is transferred in beaker with ethanol, and carries out magnetic agitation.The content that records titanium dioxide after stirring is 5%.
Take this titania solution of 100g, and add wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain the titania slurry of modification.
By the performance of this modifying titanium dioxide of test method measuring above, the results are shown in table 3.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.The Photomicrograph of this titanium dioxide film as shown in Figure 2.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 4.
embodiment 4
1. prepare modifying titanium dioxide
8g nano titanium dioxide powder ST21 is dissolved in 150g water, uses ammoniacal liquor that pH is adjusted to 9, magnetic agitation fully mixes it in 10 hours.This mixture is transferred in hydrothermal reaction kettle, under 200 ℃ of conditions, carries out hydro-thermal reaction 24 hours.The titanium dioxide blends obtaining obtains white solid through after centrifugal and washing with alcohol three times.This white solid is transferred in beaker and carries out magnetic agitation with ethanol, what after stirring, record content of titanium dioxide is 5%.
Take this titania solution of 100g, and add wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain the titania slurry of modification.
By the performance of this modifying titanium dioxide of test method measuring above, the results are shown in table 3.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 4.Its photoelectric properties are as shown in Fig. 5 curve 2.
comparative example 2
1. prepare modifying titanium dioxide
5g nano titanium dioxide powder ST21 is dissolved in ethanol, after magnetic agitation is even, adds wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain titania slurry.
By the performance of this modifying titanium dioxide of test method measuring above, the results are shown in table 3.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.The Photomicrograph of this titanium dioxide film as shown in Figure 1.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 4.Its monochromatic incident photon-electronic switch efficiency is as shown in Fig. 5 curve 3, and table 3 is BET results of the prepared titanium dioxide of embodiment 3,4 and comparative example 2.Associative list 3 can find out, titania powder ST21 is after hydrothermal treatment consists modification, and the aperture of titanium dioxide also increases, and roughness reduces.
Table 4 is photoelectric properties results that embodiment 3,4 and the prepared titanium dioxide membrane electrode provided of comparative example 2 are assembled into dye sensitization solar battery, can find out, titania powder ST21 is after hydrothermal treatment consists modification, and the photoelectric transformation efficiency of the solar cell of being prepared by the titania slurry of this modification improves 9%.This result is consistent with the monochromatic incident photon-electronic switch efficiencies shown in Fig. 5.
Table 3
Table 4
embodiment 5:
1. prepare modifying titanium dioxide
8g Preparation of Nanocrystal TiO P25 is dissolved in 150g water, uses ammoniacal liquor that pH is adjusted to 9, magnetic agitation fully mixes it in 10 hours.This mixture is transferred in hydrothermal reaction kettle, under 200 ℃ of conditions, carries out hydro-thermal reaction 24 hours.The titanium dioxide blends obtaining obtains white solid through after centrifugal and washing with alcohol three times.This white solid is transferred in beaker with ethanol, and carried out magnetic agitation.The content that records titanium dioxide after stirring is 5%.
Take this titania solution of 100g, add wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain the titania slurry of modification.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.The Photomicrograph of this titanium dioxide film as shown in Figure 4.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 5.
Comparative example 3
1. prepare modifying titanium dioxide
5g Preparation of Nanocrystal TiO P25 is dissolved in ethanol, after magnetic agitation is even, adds wherein ethanolic soln (20g) and the Terpineol 350 (18g) of ethyl cellulose, magnetic agitation 12 hours.Then carry out high-shear 10 minutes, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain titania slurry.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.The Photomicrograph of this titanium dioxide film as shown in Figure 3.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 5.
Table 5 is photoelectric properties results that embodiment 5 and the prepared titanium dioxide membrane electrode provided of comparative example 3 are assembled into dye sensitization solar battery, can find out, titanic oxide nano P25 is after hydrothermal treatment consists modification, and the photoelectric transformation efficiency of the solar cell of being prepared by the titania slurry of this modification increases.
Table 5
Can be found out by Fig. 1-4, titanium dioxide is after hydrothermal treatment consists modification, and titanium dioxide film is more smooth, and particle disperses more even, and this is conducive to electronic conduction on the one hand, is conducive on the other hand adsorb more polychromatophilia material, thereby improves dyestuff efficiency.
embodiment 6
1. prepare modifying titanium dioxide powder
8g titanic oxide nano ST21 is dissolved in 150g water, and magnetic agitation fully mixes it in 10 hours.This mixture is transferred in hydrothermal reaction kettle, 200 ℃ of Water Under thermal responses 16 hours.The titanium dioxide blends obtaining obtains white solid through after centrifugal and washing with alcohol three times.This white solid is transferred in beaker with ethanol, and carries out magnetic agitation.(wherein ethyl cellulose mass content is 8% after stirring, to add ethyl cellulose, acetic acid and Terpineol 350, quality of acetic acid content is 1%, Terpineol 350 mass content is 71%), magnetic agitation high-shear 10 minutes after 12 hours, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain titania slurry.The viscosity of this titania slurry as shown in Figure 9.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, the titania slurry of above-mentioned modification to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.Use surface topography 3D figure observational technique to record its titanium dioxide film surface topography 3D figure, result as shown in Figure 7.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 6.
comparative example 4
1. gel gel method is prepared titanium dioxide
The ethanolic soln (tetrabutyl titanate: ethanol volume ratio is 1:2) of the tetrabutyl titanate containing 0.2mol is joined to (mass content is 0.2%) in the tetramethyl-aqua ammonia aqueous solution, wherein the mol ratio of Tetramethylammonium hydroxide and tetrabutyl titanate is 1:30, this mixture is refluxed 24 hours under 80 degree, then within 20 hours, obtain TiO 2 sol in 180 degree hydro-thermal.This colloidal sol obtains white solid through after centrifugal and washing with alcohol three times, this white solid is transferred in beaker with ethanol, and carries out magnetic agitation.(wherein ethyl cellulose mass content is 8% after stirring, to add ethyl cellulose and Terpineol 350, Terpineol 350 mass content is 72%), magnetic agitation high-shear 10 minutes after 12 hours, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain titania slurry 1.Titanium dioxide film light transmission rate prepared by this slurry is high, for improving the scattering power of titanium dioxide photo anode, in above-mentioned colloidal sol, add 200nm scattering particles (titanium dioxide mass content 20%), prepare titania slurry 2 according to above-mentioned same method.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, above-mentioned two kinds of titania slurries to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, this titanium dioxide film is made up of one deck slurry 1 and three layers of slurry 2, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.Use surface topography 3D figure observational technique to record its titanium dioxide film surface topography 3D figure, result as shown in Figure 6.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 6.
comparative example 5
1. gel gel method is prepared titanium dioxide
Under room temperature, tetrabutyl titanate and trolamine are mixed to get to presoma according to mol ratio 1:2, then add isopyknic water, obtain containing Ti
4+concentration is 0.5mol/m
3solution.Get the above-mentioned solution of 10ml and mix with isopyknic diethylenetriamine,, between 10-11 this solution is refluxed 24 hours at 94 degree with the pH of Tetramethylammonium hydroxide regulator solution, then within 3 days, obtain TiO 2 sol in 140 degree hydro-thermal.This colloidal sol obtains white solid through after centrifugal and washing with alcohol three times, this white solid is transferred in beaker with ethanol, and carries out magnetic agitation.(wherein ethyl cellulose mass content is 8% after stirring, to add ethyl cellulose and Terpineol 350, Terpineol 350 mass content is 72%), magnetic agitation high-shear 10 minutes after 12 hours, ultrasonic 10 minutes, use Rotary Evaporators evaporation to remove ethanol, obtain titanium dioxide dope.Through three-roller roll-in, obtain titania slurry 1.This titanium dioxide viscosity as shown in Figure 7.Titanium dioxide film light transmission rate prepared by this slurry is high, for improving the scattering power of titanium dioxide photo anode, in above-mentioned colloidal sol, add 200nm scattering particles (titanium dioxide mass content 20%), prepare titania slurry 2 according to above-mentioned same method.
2. prepare solar cell
Use automatic screen printing machine with silk screen ST325, above-mentioned two kinds of titania slurries to be printed onto to the SnO of pretreated doped with fluorine
2on conductive glass, this titanium dioxide film is made up of one deck slurry 1 and three layers of slurry 2, at 100 ℃, be dried 10 minutes, transfer in retort furnace and calcine, in calcining, temperature rise rate is approximately 5 ℃/min, be warming up to approximately 500 ℃ and be incubated 30 minutes, be cooled to subsequently room temperature, obtain the titanium deoxid film as solar battery light anode.
On this titanium deoxid film, flood Z991 dyestuff.
Using the dye adsorption titanium deoxid film obtaining after saturated as light anode, assemble the solar cell that forms sandwich structure together with dye sensitizing agent, redox electrolytes matter, photocathode.
The performance of using this solar cell of face test method measuring, the results are shown in table 6.
Table 6
Table 6 is photoelectric properties results that embodiment 6 and comparative example 4,5 prepared titanium dioxide membrane electrode provided are assembled into dye sensitization solar battery, can find out, by titania powder ST21, after hydrothermal treatment consists modification, the size performance that the photoelectric transformation efficiency of the solar cell of being prepared by the titania slurry of this modification is prepared than common sol-gel method is good.Due to titanium dioxide film serious cracking (as shown in Figure 6) prepared by comparative example 4, so its photoelectric transformation efficiency is very low, low by 25% compared with embodiment six.And that the photoelectric transformation efficiency of titanium deoxid film prepared by comparative example 5 is compared than embodiment 6 is also low by 5.1%.
In addition, can be found out by Fig. 8 and Fig. 9, the prepared slurry of comparative example 5 is very hard, and rheological is very poor, is difficult to use in the printing of automatic silk screen machine, therefore cannot carry out industrialized mass production.And need print two kinds of slurries by the titanium dioxide film of comparative example four and five preparations, and the titanium dioxide film of being prepared by embodiment six only need print a kind of slurry, has greatly simplified typography.The slurry efficiency prepared by embodiment six is high, film forming properties good, rheological good, is well suited for suitability for industrialized production.
Fig. 6 and Fig. 7 are the titanium dioxide film surface topography 3D figure of the embodiment of the present invention 6 and comparative example 4.Contrasting this two width 3D figure can find out, the titania slurry film cracking phenomenon of being prepared by tetrabutyl titanate sol-gel method is serious, and by the prepared film surface of modifying titanium dioxide of the present invention evenly without cracking phenomena, therefore modifying titanium dioxide of the present invention has improved film-forming properties.
The titania slurry film forming properties of modification prepared according to the methods of the invention is good, high and Stability of Slurry good with FTO sticking power, there is not the phenomenons such as layering, compared with prior art, there is high photoelectric transformation efficiency with the dye sensitization solar battery that modifying titanium dioxide powder of the present invention forms.The inventive method technique is simple, easy handling, preparation cycle are short, cheap, reproducible, is extremely suitable for technical scale manufacture.
Claims (7)
1. a titanium dioxide for modification, it makes with the following method:
(a) provide titania powder;
(b) this titania powder is dispersed in water, forms slurry;
(c) at the temperature of 150-240 ℃ by this slurry water thermal treatment 12-96 hour.
2. modifying titanium dioxide as claimed in claim 1, is characterized in that, described titania powder is P25 type, ST21 type or anatase-type nanometer titanium dioxide powder.
3. modifying titanium dioxide as claimed in claim 1, is characterized in that, the specific surface area of described modifying titanium dioxide is about 40.0-80.0m
2/ g, preferred about 57.2-62.0m
2/ g; Aperture is about 10.0-30.0nm, is preferably about 17.2-21.2nm; Particle diameter is about 7.0-50.0nm, is preferably 20-30nm; Porosity is 50-60%, is preferably 53.6-58.8%; Roughness is 90-110 μ m
-1, be preferably about 91.7-107.4 μ m
-1.
4. a method of modifying for titanium dioxide, it comprises the steps:
(a) provide titania powder;
(b) this titania powder is dispersed in water, forms slurry;
(c) at the temperature of 150-240 ℃ by this slurry water thermal treatment 12-96 hour.
5. modifying titanium dioxide as claimed in claim 4, is characterized in that, described titania powder is P25 type, ST21 type or anatase-type nanometer titanium dioxide powder.
6. the method as described in claim 4 or 5, is characterized in that it also comprises:
(d) use alcohols washing composition to wash; With
(e) will in the titanium dioxide of washing, add alkylcellulose, Terpineol 350 and dispersion agent, then disperse.
7. a dye sensitization solar battery, it comprises light anode, dye sensitizing agent, redox electrolytes matter, photocathode, it is characterized in that described smooth anode is to make with the modifying titanium dioxide described in any one in claim 1-3.
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| CN115029020B (en) * | 2022-07-12 | 2023-11-14 | 武汉万度光能研究院有限责任公司 | Modification method of nano titanium dioxide, dispersion liquid, preparation method and application thereof |
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