CN101692470B - Preparation method of nanocrystal solar battery photoanode - Google Patents
Preparation method of nanocrystal solar battery photoanode Download PDFInfo
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- CN101692470B CN101692470B CN2009101972993A CN200910197299A CN101692470B CN 101692470 B CN101692470 B CN 101692470B CN 2009101972993 A CN2009101972993 A CN 2009101972993A CN 200910197299 A CN200910197299 A CN 200910197299A CN 101692470 B CN101692470 B CN 101692470B
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Abstract
The invention discloses a preparation method of a nanocrystal solar battery photoanode. The preparation method comprises: by using a chemical solution method, taking a block polymer as a template and combining a quick annealing process with a spin-coating method to prepare a mesoporous TiO2 thick film with a large surface area on fluorine-doped stannic oxide conductive glass. TiO2 nanospheres are evenly dispersed in titanium precursor sol and then are dispersed in a TiO2 film after high-temperature heat treatment and tightly contact surrounding nanoparticles; and the finally obtained nanocrystal solar battery photoanode has the large specific surface area of a mesoporous material and the excellent light scattering properties of nanospheres at the same time. The preparation method has the advantages that the nanocrystal solar battery photoanode has higher porosity and larger specific surface area; the method makes use of multiple spin coating and the quick annealing process to control the thickness of the photoanode easily; and the introduction of the TiO2 nanospheres is favorable for increasing the open circuit voltage, short-circuit current density and photoelectric conversion efficiency of a nanocrystal solar battery by increasing the light collection efficiency of the photoanode.
Description
Technical field
The present invention relates to solar battery technology, specifically refer to a kind of preparation method of nanocrystal solar battery photoanode.
Background technology
The energy has constituted four big pillars of civilized society with new material, biotechnology, information technology.The energy is the main matter basis that promotes social development and economic progress, and each progress of energy technology has all promoted development of human society.Along with continuous development economic and society, the exhaustion day by day of non-renewable energy resources such as coal, oil, natural gas, the sustainable growth of energy demand, energy problem has become the serious challenge that whole mankind's survival and development face.Development new forms of energy and new energy materials are the golden key that solves energy crisis and environmental protection problem, are that the mankind enter the key subjects that 21 century must solve.It is inexhaustible, nexhaustible, safe and reliable, pollution-free that solar energy has, and is not subjected to advantages such as geographical environment restriction, more and more is subjected to paying attention to widely.The nano crystal solar cell of newly-developed is simple because of its manufacture craft, raw material are cheap, production cost is low, is adapted at non-direct light, low light condition such as cloudy down and the indoor application of light condition deficiency, and can use advantage such as flexible substrates to be subjected to the favor of scientist and industrial quarters.Yet the photoelectric conversion efficiency of nano crystal solar cell also is not enough to satisfy the demand of the large-scale commercial applications of this battery at present.
Improving the light anode of nano crystal solar cell, strengthen the collection efficiency of sunlight, is to improve the nano crystal solar cell conversion efficiency and accelerate one of important channel of nano crystal solar cell practicalization.The specific area that increases the light anode makes it adsorb more sensitization functional material, utilizes light scattering medium to increase the transmission path of sunlight in the light anode, is two kinds of effective means of improving light anode light collection efficiency.In the existing report, the ordered mesoporous material that adopts Large ratio surface made full use of the big specific area of mesoporous material and improved light collection efficiency, but the scattering effect of this electrode pair sunlight can be ignored substantially as the light anode.Also there is report to adopt the light anode of Nano microsphere,, sacrificed the specific area and the voidage of light anode, thereby can not obtain desirable light transfer characteristic though made full use of the light scattering property of microballoon as nano crystal solar cell.Given this, explore new method and prepare and a kind ofly can adsorb the sensitization functional material, can participate in electron transport again, efficiency light anode that simultaneously can also the enhanced light scattering characteristic has big meaning to the conversion efficiency that improves nano crystal solar cell.
Summary of the invention
The method that the purpose of this invention is to provide the new and effective nanocrystal solar battery photoanode of a kind of preparation of simple possible, having solved single microballoon light anode only has the problem of less specific area, has overcome the difficulty that is difficult to be possessed simultaneously than the efficiency light anode of bigger serface and good optical scattering properties.
Method of the present invention is to utilize chemical solution method, is template with the block polymer, prepares the mesoporous TiO of high surface area on FTO (mixing the tin oxide of fluorine) electro-conductive glass in conjunction with rta technique and spin-coating method
2Thick film.With TiO
2Nano microsphere is dispersed in the titanium precursor colloidal sol, TiO after the high-temperature heat treatment
2Microballoon is dispersed in TiO
2In the film, and closely contact with on every side nano particle.The nanocrystal solar battery photoanode that finally obtains has the good light scattering characteristic of big specific area of mesoporous material and microballoon simultaneously.The thickness of light anode can be by the number of times of spin coating and rta technique by hundreds of nanometer to tens a micron inner control.
The method of the nanocrystal solar battery photoanode of the present invention's preparation comprises the steps:
1. the preparation of titanium precursor colloidal sol
The block polymer of 1～3 gram is dissolved in the absolute ethyl alcohol of 15-30ml, and the dissolving back drips the concentrated hydrochloric acid of 1.0～3.0ml and the acetylacetone,2,4-pentanedione of 0.2～1.0ml fully, stirs 30 minutes; Dropwise 5～15ml titanium precursor liquid solution while stirring adds 0～1ml deionized water again after 30 minutes then; At room temperature stir and to obtain titanium precursor colloidal sol in 0.5～6 hour.
The titanium precursor liquid solution is tetra-n-butyl titanate or isopropyl titanate or tetraethyl titanate.
Block polymer is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene or di-block copolymer polystyrene-poly oxygen ethene.
Absolute ethyl alcohol can substitute with n-butanol or isopropyl alcohol.
2.TiO
2The preparation of microballoon and titanium precursor complex sol
With TiO
2Nano microsphere joins in the titanium precursor colloidal sol, adopts ultrasonic wave to disperse colloidal sol 20-60 minute, makes TiO
2Microballoon fully is uniformly dispersed.TiO wherein
2Nano microsphere is of a size of 200-800nm, and mass fraction is 0.5-20%.
3. the preparation of nanocrystal solar battery photoanode
Utilize the spin-coating method film forming, with combination flooding colloidal sol film forming on the FTO electro-conductive glass of 2 gained, rotating speed is 1000～3000 rev/mins, and the spin coating time is 20～60 seconds;
After the film forming,, naturally cool to room temperature with the short annealing 5～30 minutes under 400～500 ℃ of temperature in air atmosphere of the film on the electro-conductive glass;
Repeatedly repeat above spin coating and rta technique step and can obtain the TiO of thickness at hundreds of nanometer to tens micron
2Film; Last TiO
2Thick film naturally cooled to room temperature at 400～500 ℃ of heat treatment 2-4 hours, promptly got and can arrive the nanocrystal solar battery photoanode with bigger serface and good light scattering properties.
Wherein the FTO electro-conductive glass is for mixing the fin oxide condutire layer of fluorine in deposition on glass.
The present invention utilizes multiple spin coating and the rta technique can be at the thickness of hundreds of nanometer regulation and control nanocrystal solar battery photoanode in tens micrometer ranges.
Advantage of the present invention is: nanocrystal solar battery photoanode has higher porosity and bigger specific area; Utilize multiple spin coating and rta technique, be easy to control the thickness of light anode; TiO
2The introducing of Nano microsphere by improving the light collection efficiency of light anode, thereby helps improving open circuit voltage, short-circuit current density and the photoelectric conversion efficiency of nano crystal solar cell.
Description of drawings
Fig. 1: TiO
2The SEM figure of Nano microsphere and nanocrystal solar battery photoanode.
Fig. 2: introduce and do not introduce TiO
2The nanocrystal solar battery photoanode of Nano microsphere see through spectrum.
Fig. 3: introduce and do not introduce TiO
2The absorption spectrum of the nanocrystal solar battery photoanode of Nano microsphere after sensitization.
Fig. 4: introduce and do not introduce TiO
2IV curve under the illumination of the nanocrystal solar battery photoanode correspondence of Nano microsphere.
Embodiment:
Embodiment 1:
Preparation titanium precursor colloidal sol: the block polymer of 1.5 grams is dissolved in the absolute ethyl alcohol of 15ml, and the dissolving back drips the concentrated hydrochloric acid of 1.2ml and the acetylacetone,2,4-pentanedione of 0.2ml fully, stirs 30 minutes; Drip the 7ml tetra-n-butyl titanate while stirring, add the 0.2ml deionized water after 30 minutes again; At room temperature stir and obtained titanium precursor colloidal sol in 3 hours.
Preparation TiO
2Microballoon and titanium precursor complex sol: with TiO
2Nano microsphere joins in the titanium precursor colloidal sol, and ultrasonic dispersion 30 minutes makes TiO
2Microballoon fully is uniformly dispersed, TiO
2The mass fraction of Nano microsphere is 1.5%.
Clean the FTO electro-conductive glass: with the ultrasonic cleaning 20 minutes in chloroform of FTO electro-conductive glass, used the acetone ultrasonic cleaning then 20 minutes, continued in absolute ethyl alcohol ultrasonic cleaning 20 minutes, N
2Dry up, standby.
Spin coating thin films: utilize spin-coating method, with the TiO of preparation
2Microballoon and titanium precursor complex sol be in FTO film forming on glass, 2000 rev/mins of rotating speeds, and the spin coating time is 20 seconds.
Short annealing removes template: after the film forming, 500 ℃ of following short annealings 10 minutes, atmosphere was air, naturally cools to room temperature then with sample, removed template and made the film crystallization simultaneously.
High-temperature heat treatment: repeat above spin coating and rta technique each 10 times, preparation has certain thickness titanium dioxide film.Be warming up to 500 ℃ with 10 ℃/min then, be incubated 4 hours, naturally cool to room temperature, obtain the light anode of the nano crystal solar cell of big reference area and good light scattering properties.
The present embodiment thickness of the nanocrystal solar battery photoanode of preparation down is 3.2 μ m.
The assembling of battery: nanocrystal solar battery photoanode is the assembled battery device after the N719 dye sensitization.Light anode and to filling liquid electrolyte between the electrode, main component is 0.6M DMII, 0.05M I
2, the anhydrous acetonitrile of 0.1M LiI and 0.5M TBP.With sputter thickness be 100nm Pt electro-conductive glass as battery to electrode.
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 have provided the TiO of present embodiment preparation respectively
2(Fig. 1 a is TiO to the SEM figure of Nano microsphere and nanocrystal solar battery photoanode
2The SEM figure of Nano microsphere, Fig. 1 b are the surperficial SEM figure of light anode, and Fig. 1 c is the side SEM figure of light anode), introduce and do not introduce TiO
2The nanocrystal solar battery photoanode of Nano microsphere see through spectrum, introduce and do not introduce TiO
2The absorption spectrum of the nanocrystal solar battery photoanode of Nano microsphere after the N719 sensitization, and introduce and do not introduce TiO
2IV curve under the illumination of the nanocrystal solar battery photoanode correspondence of Nano microsphere, wherein TiO is not introduced in a representative
2The light anode of Nano microsphere, TiO is introduced in the b representative
2Light anode behind the Nano microsphere.
The main body part of the SEM chart prescribed electrode of Fig. 1 is mesoporous TiO
2Film, lower floor's correspondence of the white portion among the surperficial SEM figure TiO
2Nano microsphere, TiO
2Microballoon " is inlayed " at mesoporous TiO
2The inside of film, and tightly " piling up " on every side of microballoon TiO
2Nano particle.The spectrum that sees through of Fig. 2 shows TiO
2The introducing of Nano microsphere has reduced the optical transmittance characteristic of light anode, mainly is because the scattering of microballoon causes.The absorption spectrum of Fig. 3 shows, owing to the scattering of microballoon, has improved the light collection efficiency of light anode.IV curve under the AM1.5 etalon optical power of Fig. 4 shows TiO
2The introducing of microballoon makes the nano crystal solar cell short-circuit current density by 10.2mA.cm
-2Bring up to 10.9mA.cm
-2, open circuit voltage is brought up to 670mV by 650mV, and photoelectric conversion efficiency has improved 11%.
Claims (4)
1. the preparation method of a nanocrystal solar battery photoanode is characterized in that it comprises the steps:
A. the preparation of titanium precursor colloidal sol
The block polymer of 1.5 grams is dissolved in the absolute ethyl alcohol of 15ml, and the dissolving back drips the concentrated hydrochloric acid of 1.2ml and the acetylacetone,2,4-pentanedione of 0.2ml fully, stirs 30 minutes; Under stirring condition, in solution, drip 7ml titanium precursor liquid solution then, add the 0.2ml deionized water after 30 minutes again; At room temperature stir and to obtain titanium precursor colloidal sol in 3 hours;
B.TiO
2The preparation of microballoon and titanium precursor complex sol
The TiO of 200-800nm will be of a size of
2Nano microsphere joins in the titanium precursor colloidal sol, utilizes ultrasonic wave to disperse colloidal sol 30 minutes, makes TiO
2What microballoon was full and uniform is dispersed in the colloidal sol, wherein TiO
2The mass fraction of Nano microsphere in colloidal sol is 1.5%;
C. the preparation of nanocrystal solar battery photoanode
Utilize the spin-coating method film forming, in the fin oxide condutire of mixing fluorine film forming on glass, rotating speed is 2000 rev/mins with the complex sol of B step gained, and the spin coating time is 20 seconds;
After the film forming, will mix fin oxide condutire film rapid thermal treatment in quick anneal oven on glass of fluorine, annealing temperature is 500 ℃, and the time is 10 minutes, and atmosphere is air, naturally cools to room temperature then;
Repeatedly repeat above spin coating and annealing process step and can obtain the TiO of thickness at hundreds of nanometer to tens micron
2Thick film; TiO then
2Thick film naturally cools to room temperature 500 ℃ of heat treatments 4 hours, promptly obtains having the nanocrystal solar battery photoanode of bigger serface and good light scattering properties.
2. the preparation method of a kind of nanocrystal solar battery photoanode according to claim 1, it is characterized in that: said block polymer is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene or di-block copolymer polystyrene-poly oxygen ethene.
3. the preparation method of a kind of nanocrystal solar battery photoanode according to claim 1, it is characterized in that: said titanium precursor liquid solution is tetra-n-butyl titanate or isopropyl titanate or tetraethyl titanate.
4. the preparation method of a kind of nanocrystal solar battery photoanode according to claim 1 is characterized in that: said absolute ethyl alcohol can be substituted by n-butanol or isopropyl alcohol.
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