CN102354606B - Preparation method of photoanode of dye-sensitized solar cell - Google Patents

Preparation method of photoanode of dye-sensitized solar cell Download PDF

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CN102354606B
CN102354606B CN 201110290900 CN201110290900A CN102354606B CN 102354606 B CN102354606 B CN 102354606B CN 201110290900 CN201110290900 CN 201110290900 CN 201110290900 A CN201110290900 A CN 201110290900A CN 102354606 B CN102354606 B CN 102354606B
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conductive glass
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dye
preparation
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CN102354606A (en
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王宁
孔德廷
何泓材
陈海军
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Institute of Electronic and Information Engineering of Dongguan UESTC
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E10/549—Organic PV cells

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Abstract

The invention discloses a preparation method of a photoanode of a dye-sensitized solar cell, and the method comprises the following steps: firstly, washing a conductive glass substrate clean, then placing the clean conductive glass substrate into deionized water and standing for standby; further placing the conductive glass substrate into a mixed reaction solution of pure ammonium fluotitanate (NH4)2TiF6, boric acid H3BO3 and polyethylene glycol PEG-400, depositing for a plurality of hours, then taking out the conductive glass substrate, washing clean with the deionized water and blow-drying at room temperature; then sintering for half an hour and further taking out; and finally soaking the conductive glass substrate containing a titanium dioxide thin film in dye N719 for a plurality of hours, then taking out and air-drying so as to form the photoanode of the dye-sensitized solar cell. The preparation method of the photoanode of the dye-sensitized solar cell has the advantages of being simple and easy to operate, having no limitations on the substrate, being higher in safety and being suitable for realization of large-scale industrial production.

Description

A kind of preparation method of dye-sensitized solar cell anode
Technical field
The present invention relates to solar cell, specifically refer to a kind of preparation method of dye-sensitized solar cell anode.
Background technology
1991, the people such as Switzerland professor Gratzel developed the DSSC based on porous titanium dioxide thin-film and organic dyestuff formation, and its electricity conversion can reach 7.1%-7.9%.The advantages such as DSSC is with abundant raw materials, and cost is low, and preparation technology is relatively simple become the new study hotspot of solar energy industry.DSSC is mainly by the porous titanium dioxide thin-film that is coated on the conductive substrates, dye sensitizing agent, and electrolyte consists of electrode.Wherein titanium deoxid film plays a part separated charge and transportation electronics in battery, is the important component part of DSSC.
The preparation method of titanium deoxid film mainly contains the methods such as hydrothermal synthesis method, sol-gel process, powder coated method, electrochemical deposition method, magnetron sputtering and plasma spray at present.Wherein the method for normal use is sol-gel process.The process of tradition preparation of titanium dioxide thin film by sol-gel method for photocatalytic air purification is: be first that colloidal tio 2 is prepared in the precursor hydrolysis with the titanate ester compound, process through 200 ℃ autoclave, add the surfactant grinding behind the filtering solvent and make colloidal tio 2.Then through directly filming, silk screen printing, the methods such as spin coating deposition of titanium oxide on conductive substrates is prepared titanium dioxide electrodes through 500 ℃ of sintering again.Because in sol-gel process prepares the technique of titanium dioxide, need to process through the hot high pressure still, cause this process energy consumption large, dangerous high, and the follow-up membrane process that is coated with is not suitable for the complicated shape substrate, is unfavorable for mass production.
The patent No. is that ZL200910218663, notification number are the Chinese invention patent of CN101354968B, a kind of dye-sensitized solar cell anode and preparation method thereof is disclosed, comprise the steps: that (1) is 10～50nm with particle size, thickness is that the nano titania porous membrane of 10～50um puts into 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, with drying in the air ten after the absolute ethyl alcohol flushing; (2) nano-porous film after the above-mentioned dye sensitization is put into the mixed solution that volume ratio is the cruel and cyclohexane of 1: 10～1: 50 positive silicic acid second, press 1%～5% of mixed liquor volume and add surfactant, mix rear immersion 20～60 minutes, add ammoniacal liquor by 40%～70% of the cruel volume of positive silicic acid second, soaking at room temperature 1～12 hour, reactive deposition one deck nanometer titanium dioxide silicon layer; (3) above-mentioned steps is modified rear resulting nano-porous film 10 -5～10 -3Soaked in the ethanolic solution of mol/L dyestuff 1～24 hour, and with drying after the absolute ethyl alcohol flushing, namely formed dye-sensitized solar cell anode.Said method has also avoided having now the deficiency of traditional sol-gel process, and the performance of the dye-sensitized solar cell anode that must make in production application also is not very desirable.
Summary of the invention
The purpose of this invention is to provide a kind of simple and easy to do, unrestricted to substrate, fail safe is higher and be suitable for the preparation method of the dye-sensitized solar cell anode of mass industrialized production
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of preparation method of dye-sensitized solar cell anode, comprise the steps: that (1) cleans up the electro-conductive glass substrate after, put into the deionized water set aside for use; (2) at room temperature, compound concentration is the pure ammonium titanium fluoride (NH of 0.1～0.9mol/L 4) 2TiF 6The aqueous solution and concentration are the boric acid H of 0.1～0.9mol/L 3BO 3The aqueous solution is with pure ammonium titanium fluoride (NH 4) 2TiF 6With boric acid H 3BO 3Mix rear adding polyethylene glycol PEG-400, namely make reactant liquor; (3) the electro-conductive glass substrate in the step (1) is put into the reactant liquor that step (2) makes, take out behind deposition 2～36h, rinse well with deionized water, dry up under the room temperature; And then after 350～560 ℃ of lower sintering are after 15～50 minutes, take out, finish the preparation at the titanium deoxid film on the surface of electro-conductive glass substrate; (4) to be immersed in concentration be 4 * 10 with the titanium deoxid film electro-conductive glass substrate that contains of step (3) preparation -4～2 * 10 -4Among the dyestuff N719 of mol/L, take out behind 5～8h and dry, can form dye-sensitized solar cell anode.
The cleaning process of described electro-conductive glass substrate is as follows: the electro-conductive glass substrate is placed on soaks 6～20 minutes in the washing agent first, use Ultrasonic Cleaning; Electro-conductive glass substrate after then above-mentioned steps being processed is put into the cleaning fluid Ultrasonic Cleaning 6～20 minutes that deionized water, ammoniacal liquor and hydrogen peroxide be made into; Then the electro-conductive glass substrate after above-mentioned steps being processed was put into the cleaning fluid ultrasonic cleaning that is comprised of deionized water, hydrochloric acid and hydrogen peroxide 6～20 minutes; Electro-conductive glass substrate after at last above-mentioned steps being processed is rinsed well with deionized water, puts into the deionized water set aside for use.
Described pure ammonium titanium fluoride (NH 4) 2TiF 6With boric acid H 3BO 3Mixed liquor in, carry out following ligand exchange reaction: [TiF 6] 2-+ nH 2O＜=〉TiF 6-n(OH) n 2++ nHF, the boric acid of adding and F -Reaction forms the exchange reaction that complex ion moves right this balanced reaction and accelerated ligand: H 3BO 3+ 4HF＜=〉BF 4 -+ H 3O ++ 2H 2O has finally consumed the not F of coordination -, accelerated the carrying out of hydrolysis, by [TiF 6] 2-[the Ti (OH) that forms of hydrolysis 6] 2-Dehydration makes TiO 2Film forms at the electro-conductive glass substrate that immerses solution.
The preparation method of dye-sensitized solar cell anode of the present invention adopts liquid phase deposition to prepare titanium deoxid film, liquid phase deposition neither needs the process of hot high pressure still also not need the follow-up membrane process that is coated with, directly conductive substrates is immersed in the mixed liquor of ammonium titanium fluoride, boric acid and surfactant in room temperature, take out sintering after deposition a period of time, just prepare titanium dioxide electrodes.Based on the hydrolysis of ammonium titanium fluoride in weakly acidic condition, to wherein adding macromolecular compound (serving as surfactant), deposition of titanium oxide film on conducting glass substrate, avoid for a long time high warm still reaction and numerous and diverse membrane process that is coated with, can make the DSSC suitable with the sol-gel process electricity conversion simultaneously.
The titanium deoxid film for preparing DSSC with respect to traditional sol-gel process, advantage of the present invention is, do not need the hot still reaction of HTHP and be coated with membrane process, only need deposit the preparation that just can finish whole titanium dioxide film, method is simple, reaction condition is gentle, process safety.
Description of drawings
Accompanying drawing 1 is the preparation method's of dye-sensitized solar cell anode of the present invention production procedure schematic diagram;
Accompanying drawing 2 is the i-v curve figure of the battery of the preparation method's of dye-sensitized solar cell anode of the present invention light anode assembling.
Embodiment
The invention will be further described below in conjunction with Figure of description:
Embodiment one
As shown in Figure 1, the invention discloses a kind of preparation method of dye-sensitized solar cell anode, comprise the steps: that (1) cleans up the electro-conductive glass substrate after, put into the deionized water set aside for use; (2) at room temperature (25 ℃), compound concentration are that compound concentration is the (NH of 0.3mol/L 4) 2TiF 6The aqueous solution, boric acid concentration is 0.2mol/L, gets the PEG-400 that every kind of medicine 4ml mixes rear adding 0.48g; (3) configure reactant liquor after, conducting glass substrate is placed wherein, take out behind the deposition 24h, rinse well with deionized water, dry up under the room temperature; (4) and then at 450 ℃ of lower sintering take out after half an hour, finish the preparation of titanium deoxid film; (5) the above-mentioned light anode that obtains soaked 8 hours in the organic solvent of the dyestuff of 3 * 10-4mol/L, taking-up is dried, can form dye-sensitized solar cell anode, dye-sensitized solar cell anode is adopted iodine/lithium iodide electrolyte, the electro-conductive glass conduct of platinum plating is to electrode, be assembled into battery, and carry out the photoelectric properties test.
The cleaning process of described electro-conductive glass substrate is as follows: first the electro-conductive glass substrate is placed in the washing agent and soaked 10 minutes, use Ultrasonic Cleaning; Electro-conductive glass substrate after then above-mentioned steps being processed is put into the cleaning fluid Ultrasonic Cleaning 10 minutes that deionized water, ammoniacal liquor and hydrogen peroxide be made into; Then the electro-conductive glass substrate after above-mentioned steps being processed was put into the cleaning fluid ultrasonic cleaning that is comprised of deionized water, hydrochloric acid and hydrogen peroxide 10 minutes; Electro-conductive glass substrate after at last above-mentioned steps being processed is rinsed well with deionized water, puts into the deionized water set aside for use.
Described pure ammonium titanium fluoride (NH 4) 2TiF 6With boric acid H 3BO 3Mixed liquor in, carry out following ligand exchange reaction: [TiF 6] 2-Ten nH 2O＜=〉TiF 6-n(OH) n 2-+ nHF, the boric acid of adding and F -Reaction forms the exchange reaction that complex ion moves right this balanced reaction and accelerated ligand: H 3BO 3+ 4HF＜=〉BF 4 -+ H 3O ++ 2H 2O has finally consumed the not F of coordination -, accelerated the carrying out of hydrolysis, by [TiF 6] 2-[the Ti (OH) that forms of hydrolysis 6] 2-Dehydration makes TiO 2Film forms at the electro-conductive glass substrate that immerses solution.
Embodiment two
Different from embodiment one is: at room temperature (25 ℃), compound concentration are that compound concentration is the (NH of 0.3mol/L 4) 2TiF 6The aqueous solution, boric acid concentration is 0.2mol/L, gets the PEG-400 that every kind of medicine 4ml mixes rear adding 0.96g.After configuring reactant liquor, conducting glass substrate is placed wherein, taken out behind the deposition 24h, rinse well with deionized water, dry up under the room temperature.And then take out after half an hour at 450 ℃ of lower sintering, finish the preparation of titanium deoxid film.The above-mentioned light anode that obtains was soaked 8 hours in the organic solvent of the dyestuff of 3 * 10-4mol/L, and taking-up is dried, and adopts iodine/lithium iodide electrolyte, and the electro-conductive glass of platinum plating is assembled into battery as to electrode, and carries out the photoelectric properties test.
Fig. 2 is the photoelectric current voltage curve of the dye-sensitized cell of the light anode assembling of employing liquid phase deposition preparation.The battery current density that can be calculated the light anode assembling that adopts the liquid phase deposition preparation by figure is 13.05mA/cm -2, open circuit voltage is 0.742V, and fill factor, curve factor is 0.63, and electricity conversion is 6.1%.
The above is preferred embodiment of the present invention only, is not that the present invention is done any pro forma restriction; But the those of ordinary skill of all industry is all implemented the present invention with the above shown in the by specification accompanying drawing swimmingly; But all those skilled in the art can utilize the disclosed above technology contents and a little change, the modification of making and the equivalent variations that develops within not breaking away from the technical solution of the present invention scope, be equivalent embodiment of the present invention; Simultaneously, the change of any equivalent variations that all foundations essence technology of the present invention is done above embodiment, modify with differentiation etc., all still belong within the protection range of technical scheme of the present invention.

Claims (3)

1. the preparation method of a dye-sensitized solar cell anode is characterized in that, comprises the steps:
(1) the electro-conductive glass substrate is cleaned up after, put into the deionized water set aside for use;
(2) at room temperature, compound concentration is the pure ammonium titanium fluoride (NH of 0.1～0.9mol/L 4) 2TiF 6The aqueous solution and concentration are the boric acid H of 0.1～0.9mol/L 3BO 3The aqueous solution is with pure ammonium titanium fluoride (NH 4) 2TiF 6With boric acid H 3BO 3Mix rear adding polyethylene glycol PEG-400, namely make reactant liquor;
(3) the electro-conductive glass substrate in the step (1) is put into the reactant liquor that step (2) makes, take out behind deposition 2～36h, rinse well with deionized water, dry up under the room temperature; And then take out after 15～50 minutes at 350～560 ℃ of lower sintering, finish the preparation at the titanium deoxid film on the surface of electro-conductive glass substrate;
(4) to be immersed in concentration be 4 * 10 with the titanium deoxid film electro-conductive glass substrate that contains of step (3) preparation -4～2 * 10 -4Among the dyestuff N719 of mol/L, take out behind 5～8h and dry, can form dye-sensitized solar cell anode.
2. the preparation method of dye-sensitized solar cell anode according to claim 1 is characterized in that, the cleaning process of described electro-conductive glass substrate is as follows: the electro-conductive glass substrate is placed on soaks 6～20 minutes in the washing agent first, use Ultrasonic Cleaning; Electro-conductive glass substrate after then above-mentioned steps being processed is put into the cleaning fluid Ultrasonic Cleaning 6～20 minutes that deionized water, ammoniacal liquor and hydrogen peroxide be made into; Then the electro-conductive glass substrate after above-mentioned steps being processed was put into the cleaning fluid ultrasonic cleaning that is comprised of deionized water, hydrochloric acid and hydrogen peroxide 6～20 minutes; Electro-conductive glass substrate after at last above-mentioned steps being processed is rinsed well with deionized water, puts into the deionized water set aside for use.
3. the preparation method of dye-sensitized solar cell anode according to claim 1 and 2 is characterized in that, described pure ammonium titanium fluoride (NH 4) 2TiF 6With boric acid H 3BO 3Mixed liquor in, carry out following ligand exchange reaction: [TiF 6] 2-+ nH 2O＜=〉TiF 6-n(OH) n 2++ nHF, the boric acid of adding and F-reaction form the exchange reaction that complex ion moves right this balanced reaction and accelerated ligand: H 3BO 3+ 4HF＜=〉BF 4 -+ H 3O ++ 2H 2O has finally consumed the not F of coordination -, accelerated the carrying out of hydrolysis, by [TiF 6] 2-[the Ti (OH) that forms of hydrolysis 6] 2-Dehydration makes TiO 2Film forms at the electro-conductive glass substrate that immerses solution.
CN 201110290900 2011-09-24 2011-09-24 Preparation method of photoanode of dye-sensitized solar cell Expired - Fee Related CN102354606B (en)

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CN103198927B (en) * 2013-04-07 2016-05-04 东华大学 A kind of preparation method of DSSC titanium dioxide photo anode
CN104091888B (en) * 2014-07-17 2016-08-17 湖北大学 A kind of Ca-Ti ore type solaode and preparation method thereof
CN104383902B (en) * 2014-10-20 2017-01-25 浙江理工大学 Titanate nanosheet photocatalytic membrane material, as well as preparation method and application thereof
CN104383903A (en) * 2014-11-19 2015-03-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of titanium dioxide microsphere photocatalyst
CN106925254B (en) * 2017-03-30 2019-09-03 陕西科技大学 A kind of spherical titanium oxide/stannic oxide optoelectronic pole and its preparation method and application

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CN1786264A (en) * 2005-11-01 2006-06-14 武汉理工大学 Method of low temperature preparing C axle preferrel orientation titanium dioxide film
CN101697320B (en) * 2009-10-29 2011-06-15 彩虹集团公司 Dye-sensitized solar cell photoanode and preparation method thereof
CN101948135B (en) * 2010-08-13 2012-05-16 华东理工大学 Layered-structure anatase titanium-oxide hollow hexagonal nanosheet and preparation method thereof

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