CN105390293A - Preparation method for dye-sensitized solar cell photo anode based on heteropolyacid SiW11Ni modified TiO2 - Google Patents

Preparation method for dye-sensitized solar cell photo anode based on heteropolyacid SiW11Ni modified TiO2 Download PDF

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CN105390293A
CN105390293A CN201510953579.8A CN201510953579A CN105390293A CN 105390293 A CN105390293 A CN 105390293A CN 201510953579 A CN201510953579 A CN 201510953579A CN 105390293 A CN105390293 A CN 105390293A
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siw
tio
dye
sensitized solar
solar cell
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杨玉林
姜艳霞
范瑞清
王平
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • 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

Abstract

The invention relates to a preparation method for a dye-sensitized solar cell photo anode based on heteropolyacid SiW11Ni modified TiO2, which aims to solve problems that the absorption strength of a TiO2-based dye-sensitized solar cell in a visible region is low, severe recombination of interface photo-generated carriers occurs because TiO2 self has a large number of defect modes, and due to wide band gaps, the efficiency of injecting photo-generated electrons into the TiO2 conduction band through dye is low and the improvement on cell photoelectric conversion efficiency is limited. The preparation method comprises the steps: 1, preparation of SiW11Ni/TiO2-P25 powders; 2, preparation of a dye-sensitized solar cell photo anode. According to the preparation method for the dye-sensitized solar cell photo anode based on the heteropolyacid SiW11Ni modified TiO2, the dye-sensitized solar cell photo anode based on the heteropolyacid SiW11Ni modified TiO2 is used for preparing dye-sensitized solar cells.

Description

A kind of based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode
Technical field
The present invention relates to a kind of based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode.
Background technology
The Energy harvesting of conventional dyes sensitization solar battery to visible region is few, the absorption spectrum of battery is not mated with solar spectrum, limits the lifting of battery efficiency.
Heteropoly acid can absorb visible ray, therefore heteropolyacid material is used for the photoresponse scope that can strengthen battery in DSSC, improves battery to the utilance of sunlight, thus improves the photoelectric conversion efficiency of battery.But, because the conductivity of heteropoly acid powder is poor, use it for the complex centre serving as photo-generated carrier in the middle of DSSC, serious Interface composites reaction can hinder the transmission of electronics, reduce photoelectric current, the photoelectric conversion efficiency of battery is declined.
Summary of the invention
The present invention is to solve TiO 2radical dye sensitization solar battery is weak in visible region absorption intensity, TiO 2itself there is the compound that a large amount of defect states causes serious interface photo-generated carrier, and the light induced electron that greater band gap causes injects TiO by dyestuff 2conduction band efficiency is low, limits the problem that cell photoelectric conversion efficiency improves, and provides a kind of based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode.
A kind of based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by SiW 11ni/TiO 2powder mixes with P25 titanium dioxide, and putting into Muffle furnace is calcine 0.5h ~ 5h under the condition of 100 DEG C ~ 500 DEG C in temperature, naturally cools to room temperature, obtains SiW 11ni/TiO 2-P25 powder; Described SiW 11ni/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:(1 ~ 20); Described SiW 11ni/TiO 2powder is with SiW 11ni and butyl titanate are that raw material is prepared by sol-gal process;
Two, by SiW 11ni/TiO 2-P25 powder, ethyl cellulose, terpinol and ethanol mix, and stir and obtain slurry, using 250 order silk screens as basis material, basis material prints 4 ~ 10 slurries, obtains multilayer SiW 11ni/TiO 2-P25 film, then to multilayer SiW 11ni/TiO 2-P25 film heats from room temperature to 450 DEG C ~ 600 DEG C with the heating rate of 1 DEG C/min, is be incubated 0.1h ~ 1h under the condition of 450 DEG C ~ 600 DEG C, obtains based on heteropoly acid SiW in temperature 11ni modifies TiO 2dye-sensitized solar cell anode; Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:(0.1 ~ 0.5); Described SiW 11ni/TiO 2the mass ratio of-P25 powder and terpinol is 1:(2 ~ 7); Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethanol is 1:(2 ~ 5).
A kind of based on heteropoly acid SiW 11ni modifies TiO 2the application of dye-sensitized solar cell anode be by based on heteropoly acid SiW 11ni modifies TiO 2dye-sensitized solar cell anode as anode for the preparation of DSSC.
Beneficial effect of the present invention:
Adopt of the present invention based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode, compared with the DSSC formed with traditional dye sensitization light anode, the DSSC of this smooth anode composition has following advantage:
SiW 11ni modifies TiO 2light anode material, enhances TiO 2in the response range of visible region, improve the utilance to sunlight; SiW 11ni modifies TiO 2tiO can be made 2energy gap reduce, flat-band potential is shuffled, and Fermi energy level declines, and increases the actuating force of electron injection, is conducive to the increase of short circuit current; SiW 11ni modifies TiO 2in photo-anode film, electron transport ability is enhanced, and the compound of photo-generated carrier is effectively suppressed, and is conducive to improving charge collection efficiency in battery.This SiW 11ni modifies TiO 2the light anode cell of powder can suppress the recombination reaction of photo-generated carrier, extends carrier lifetime in battery, reduces dark current, is conducive to improving battery efficiency.Based on above characteristic, SiW 11ni modifies TiO 2the photoelectric conversion efficiency of light anode cell is 8.15%, and short circuit current is 17.51mA/cm 2, compare with blank battery, photoelectric current improves 31.9%, and battery efficiency improves 26.9%.
Accompanying drawing explanation
Fig. 1 is SiW described in embodiment one step one 11ni/TiO 2the stereoscan photograph of powder;
Fig. 2 is SiW described in the titanic oxide nano powder described in embodiment two and embodiment one step one 11ni/TiO 2the ultraviolet-visible absorption spectra figure of powder, wherein 1 is the titanic oxide nano powder described in embodiment two, and 2 is SiW described in embodiment one step one 11ni/TiO 2powder;
Fig. 3 is SiW described in the titanic oxide nano powder described in embodiment two and embodiment one step one 11ni/TiO 2powder flat band voltage curve, wherein 1 is the titanic oxide nano powder described in embodiment two, and 2 is SiW described in embodiment one step one 11ni/TiO 2powder;
Fig. 4 is the TiO obtained with embodiment two under dark-state condition 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the AC impedance spectrogram of DSSC under illumination condition prepared of dye-sensitized solar cell anode, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode;
Fig. 5 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the short circuit current of the DSSC prepared of dye-sensitized solar cell anode under simulation 1.5G sunlight and open circuit voltage curve, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode;
Fig. 6 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the open circuit voltage attenuation curve of DSSC prepared of dye-sensitized solar cell anode, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode;
Fig. 7 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the electricity conversion of the DSSC prepared of dye-sensitized solar cell anode under simulation 1.5G sunlight, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode.
Embodiment
Embodiment one: the one of present embodiment is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by SiW 11ni/TiO 2powder mixes with P25 titanium dioxide, and putting into Muffle furnace is calcine 0.5h ~ 5h under the condition of 100 DEG C ~ 500 DEG C in temperature, naturally cools to room temperature, obtains SiW 11ni/TiO 2-P25 powder; Described SiW 11ni/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:(1 ~ 20); Described SiW 11ni/TiO 2powder is with SiW 11ni and butyl titanate are that raw material is prepared by sol-gal process;
Two, by SiW 11ni/TiO 2-P25 powder, ethyl cellulose, terpinol and ethanol mix, and stir and obtain slurry, using 250 order silk screens as basis material, basis material prints 4 ~ 10 slurries, obtains multilayer SiW 11ni/TiO 2-P25 film, then to multilayer SiW 11ni/TiO 2-P25 film heats from room temperature to 450 DEG C ~ 600 DEG C with the heating rate of 1 DEG C/min, is be incubated 0.1h ~ 1h under the condition of 450 DEG C ~ 600 DEG C, obtains based on heteropoly acid SiW in temperature 11ni modifies TiO 2dye-sensitized solar cell anode; Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:(0.1 ~ 0.5); Described SiW 11ni/TiO 2the mass ratio of-P25 powder and terpinol is 1:(2 ~ 7); Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethanol is 1:(2 ~ 5).
Embodiment two: present embodiment and embodiment one unlike: putting into Muffle furnace in step one is calcine 3h under the condition of 200 DEG C in temperature.Other steps and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are unlike SiW described in step one 11ni/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:10.Other steps and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are unlike SiW described in step one 11ni/TiO 2powder to prepare concrete operation step as follows:
By 0.3mL ~ 0.6mLHNO 3with 0.1g ~ 2gSiW 11ni joins in 50mL ~ 100mL deionized water and mixes and stir, and obtains mixed solution, is added drop-wise in mixed solution under the condition stirred with the speed of 60/min by 0.02mol/L ~ 0.06mol/L butyl titanate, after dropping terminates, be heat 3h ~ 8h under the water bath condition of 80 DEG C ~ 100 DEG C in temperature by mixed solution, obtain the mixture of colloidal sol shape, the mixture of colloidal sol shape is transferred in the water heating kettle of sealing, then be react 12h ~ 24h in the baking oven of 160 DEG C ~ 200 DEG C in temperature, deionized water is first adopted to wash 4 times product after reaction terminates, absolute ethanol is adopted to wash 4 times again, naturally cool to room temperature, then with the centrifugal speed of 3000rpm ~ 15000rpm, centrifugation is carried out to product, obtain solid, solid first adopts deionized water to wash 2 ~ 6 times, adopt absolute ethanol washing again 2 ~ 6 times, then the dry 2h ~ 5h of vacuum drying chamber of 100 DEG C is placed in, finally be put in Muffle furnace, be calcine 0.5h ~ 5h under the condition of 300 DEG C ~ 600 DEG C in temperature, be cooled to room temperature, obtain SiW 11ni/TiO 2powder.Other steps and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: be incubated 0.5h under the condition of 500 DEG C in temperature in step 2.Other steps and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are unlike SiW described in step 2 11ni/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:0.3.Other steps and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are unlike SiW described in step 2 11ni/TiO 2the mass ratio of-P25 powder and terpinol is 1:5.Other steps and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven are unlike SiW described in step 2 11ni/TiO 2the mass ratio of-P25 powder and ethanol is 1:4.Other steps and parameter identical with one of embodiment one to seven.
Beneficial effect of the present invention is verified by following examples:
Embodiment one: the one of the present embodiment is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by SiW 11ni/TiO 2powder mixes with P25 titanium dioxide, and putting into Muffle furnace is calcine 2h under the condition of 500 DEG C in temperature, naturally cools to room temperature, obtains SiW 11ni/TiO 2-P25 powder; Described SiW 11ni/TiO 2the mass ratio of powder and P25 titanium dioxide is 2:8; Described SiW 11ni/TiO 2powder is with SiW 11ni and butyl titanate are that raw material is prepared by sol-gal process;
Two, by SiW 11ni/TiO 2-P25 powder, ethyl cellulose, terpinol and ethanol mix, and stir and obtain slurry, using 250 order silk screens as basis material, basis material prints 4 ~ 10 slurries, obtains multilayer SiW 11ni/TiO 2-P25 film, then to multilayer SiW 11ni/TiO 2-P25 film heats from room temperature to 450 DEG C ~ 600 DEG C with the heating rate of 1 DEG C/min, is be incubated 0.5h under the condition of 500 DEG C, obtains based on heteropoly acid SiW in temperature 11ni modifies TiO 2dye-sensitized solar cell anode; Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:0.27; Described SiW 11ni/TiO 2the mass ratio of-P25 powder and terpinol is 1:4.68; Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethanol is 1:2.98.
SiW described in the present embodiment step one 11ni/TiO 2powder to prepare concrete operation step as follows:
By 0.3mL ~ 0.6mLHNO 3with 0.1g ~ 2gSiW 11ni joins in 50mL ~ 100mL deionized water and mixes and stir, and obtains mixed solution, is added drop-wise in mixed solution under the condition stirred with the speed of 60/min by 0.02mol/L ~ 0.06mol/L butyl titanate, after dropping terminates, be heat 3h ~ 8h under the water bath condition of 80 DEG C ~ 100 DEG C in temperature by mixed solution, obtain the mixture of colloidal sol shape, the mixture of colloidal sol shape is transferred in the water heating kettle of sealing, then be react 12h ~ 24h in the baking oven of 160 DEG C ~ 200 DEG C in temperature, deionized water is first adopted to wash 4 times product after reaction terminates, absolute ethanol is adopted to wash 4 times again, naturally cool to room temperature, then with the centrifugal speed of 3000rpm ~ 15000rpm, centrifugation is carried out to product, obtain solid, solid first adopts deionized water to wash 2 ~ 6 times, adopt absolute ethanol washing again 2 ~ 6 times, then the dry 2h ~ 5h of vacuum drying chamber of 100 DEG C is placed in, finally be put in Muffle furnace, be calcine 0.5h ~ 5h under the condition of 300 DEG C ~ 600 DEG C in temperature, be cooled to room temperature, obtain SiW 11ni/TiO 2powder, described SiW 11ni to prepare concrete operation step as follows: take SiW 11be dissolved in distilled water, after stirring 10min ~ 20min, put into water-bath continuation stirring 10min ~ 20min that temperature is 40 DEG C, obtain solution, then stir condition under with the speed of 60/min by concentration for 0.5molL -1niSO 4solution is added drop-wise in solution, reaction 10min ~ 20min, filter, in filtrate, add KCl, after continuing to stir 10min ~ 20min, under temperature is the condition of 5 DEG C, place crystallization, to its recrystallization after crystallization, obtain crystal, crystal is transferred in vacuum drying oven, be dry under the condition of 50 DEG C in temperature, obtain green block SiW 11ni crystal, described SiW 11quality and the volume ratio of distilled water be 1g:(3 ~ 5) mL, described SiW 11quality and concentration be 0.5molL -1niSO 4the volume ratio of solution is 1g:(0.5 ~ 1) mL, described SiW 11be 1:(0.2 ~ 0.5 with the mass ratio of KCl).
Embodiment two: a kind of TiO of the present embodiment 2the preparation method of dye-sensitized solar cell anode specifically carries out according to the following steps:
Titanic oxide nano powder, ethyl cellulose, terpinol and ethanol are mixed, stir and obtain slurry, use 250 order silk screens to carry out silk screen printing to slurry, the effective area of silk screen is 0.16cm 2, in the vertical direction printing 4 ~ 10 times, obtains multilayer TiO 2film, then to multilayer TiO 2film heats from room temperature to 500 DEG C with the heating rate of 1 DEG C/min, is to be incubated 0.5h under the condition of 500 DEG C in temperature, obtains TiO 2dye-sensitized solar cell anode; The mass ratio of described titanic oxide nano powder and ethyl cellulose is 1:0.27; The mass ratio of described titanic oxide nano powder and terpinol is 1:4.68; The mass ratio of described titanic oxide nano powder and ethanol is 1:2.98.
Described in present embodiment, titanic oxide nano powder is prepared by sol gel synthesis, and concrete operation step is as follows:
By 0.3mL ~ 0.6mLHNO 3with 0.1g ~ 3gSiW 11ni joins in 50mL ~ 100mL deionized water and mixes and stir, and obtains mixed solution, is added drop-wise in mixed solution under the condition stirred with the speed of 60/min by 0.02mol/L ~ 0.05mol/L butyl titanate, after dropping terminates, be heat 4h ~ 8h under the water bath condition of 80 DEG C ~ 100 DEG C in temperature by mixed solution, obtain the mixture of colloidal sol shape, the mixture of colloidal sol shape is transferred in the water heating kettle of sealing, then be react 12h ~ 30h in the baking oven of 160 DEG C ~ 200 DEG C in temperature, deionized water is first adopted by product to wash after reaction terminates 3 ~ 5 times, absolute ethanol is adopted to wash again 3 ~ 5 times, naturally cool to room temperature, then with the centrifugal speed of 3000rpm ~ 15000rpm, centrifugation is carried out to product, obtain solid, solid first adopts deionized water to wash 2 ~ 5 times, adopt absolute ethanol washing again 2 ~ 5 times, then the dry 1h ~ 5h of vacuum drying chamber of 100 DEG C is placed in, finally be put in Muffle furnace, be calcine 0.5h ~ 6h under the condition of 300 DEG C ~ 600 DEG C in temperature, be cooled to room temperature, obtain titanic oxide nano powder.
Fig. 1 is SiW described in embodiment one step one 11ni/TiO 2the stereoscan photograph of powder, the as can be seen from the figure pattern of synthetic product.
Fig. 2 is SiW described in the titanic oxide nano powder described in embodiment two and embodiment one step one 11ni/TiO 2the ultraviolet-visible absorption spectra figure of powder, wherein 1 is the titanic oxide nano powder described in embodiment two, and 2 is SiW described in embodiment one step one 11ni/TiO 2powder; As can be seen from the figure SiW 11ni modifies TiO 2after expand TiO 2at the absorption region in light district.
Fig. 3 is SiW described in the titanic oxide nano powder described in embodiment two and embodiment one step one 11ni/TiO 2powder flat band voltage curve, wherein 1 is the titanic oxide nano powder described in embodiment two, and 2 is SiW described in embodiment one step one 11ni/TiO 2powder; As can be seen from the figure SiW 11ni modifies TiO 2after flat-band potential is shuffled, Fermi energy level declines, and the actuating force of electron injection increases, and is conducive to the increase of short circuit current.
Fig. 4 is the TiO obtained with embodiment two under dark-state condition 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the AC impedance spectrogram of DSSC under illumination condition prepared of dye-sensitized solar cell anode, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode; As can be seen from the figure SiW 11the TiO that Ni modifies 2the combined resistance of light anode cell is comparatively large, is conducive to the recombination reaction suppressing charge carrier, reduces dark current, improve the electricity conversion of battery.
Fig. 5 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the short circuit current of the DSSC prepared of dye-sensitized solar cell anode under simulation 1.5G sunlight and open circuit voltage curve, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode; As can be seen from the figure TiO 2in the expansion of visible region photoelectric respone scope, the increase of driving force of electrons, makes the short circuit current of battery significantly increase, thus improves the photoelectric conversion efficiency of battery.
Fig. 6 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the open circuit voltage attenuation curve of DSSC prepared of dye-sensitized solar cell anode, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode; As can be seen from the figure SiW 11ni modifies TiO 2in light anode cell, the life-span of charge carrier adds.
Fig. 7 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode and with embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the electricity conversion of the DSSC prepared of dye-sensitized solar cell anode under simulation 1.5G sunlight, wherein 1 is the TiO obtained with embodiment two 2light anode cell prepared by dye-sensitized solar cell anode, 2 for embodiment one obtain based on heteropoly acid SiW 11ni modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode; As can be seen from the figure SiW 11ni modifies TiO 2light anode cell has higher electricity conversion.

Claims (8)

1. one kind based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by SiW 11ni/TiO 2powder mixes with P25 titanium dioxide, and putting into Muffle furnace is calcine 0.5h ~ 5h under the condition of 100 DEG C ~ 500 DEG C in temperature, naturally cools to room temperature, obtains SiW 11ni/TiO 2-P25 powder; Described SiW 11ni/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:(1 ~ 20); Described SiW 11ni/TiO 2powder is with SiW 11ni and butyl titanate are that raw material is prepared by sol-gal process;
Two, by SiW 11ni/TiO 2-P25 powder, ethyl cellulose, terpinol and ethanol mix, and stir and obtain slurry, using 250 order silk screens as basis material, basis material prints 4 ~ 10 slurries, obtains multilayer SiW 11ni/TiO 2-P25 film, then to multilayer SiW 11ni/TiO 2-P25 film heats from room temperature to 450 DEG C ~ 600 DEG C with the heating rate of 1 DEG C/min, is be incubated 0.1h ~ 1h under the condition of 450 DEG C ~ 600 DEG C, obtains based on heteropoly acid SiW in temperature 11ni modifies TiO 2dye-sensitized solar cell anode; Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:(0.1 ~ 0.5); Described SiW 11ni/TiO 2the mass ratio of-P25 powder and terpinol is 1:(2 ~ 7); Described SiW 11ni/TiO 2the mass ratio of-P25 powder and ethanol is 1:(2 ~ 5).
2. one according to claim 1 is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that putting into Muffle furnace in step one is calcine 3h under the condition of 200 DEG C in temperature.
3. one according to claim 1 is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step one 11ni/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:10.
4. one according to claim 1 is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step one 11ni/TiO 2powder to prepare concrete operation step as follows:
By 0.3mL ~ 0.6mLHNO 3with 0.1g ~ 2gSiW 11ni joins in 50mL ~ 100mL deionized water and mixes and stir, and obtains mixed solution, is added drop-wise in mixed solution under the condition stirred with the speed of 60/min by 0.02mol/L ~ 0.06mol/L butyl titanate, after dropping terminates, be heat 3h ~ 8h under the water bath condition of 80 DEG C ~ 100 DEG C in temperature by mixed solution, obtain the mixture of colloidal sol shape, the mixture of colloidal sol shape is transferred in the water heating kettle of sealing, then be react 12h ~ 24h in the baking oven of 160 DEG C ~ 200 DEG C in temperature, deionized water is first adopted to wash 4 times product after reaction terminates, absolute ethanol is adopted to wash 4 times again, naturally cool to room temperature, then with the centrifugal speed of 3000rpm ~ 15000rpm, centrifugation is carried out to product, obtain solid, solid first adopts deionized water to wash 2 ~ 6 times, adopt absolute ethanol washing again 2 ~ 6 times, then the dry 2h ~ 5h of vacuum drying chamber of 100 DEG C is placed in, finally be put in Muffle furnace, be calcine 0.5h ~ 5h under the condition of 300 DEG C ~ 600 DEG C in temperature, be cooled to room temperature, obtain SiW 11ni/TiO 2powder.
5. one according to claim 1 is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that under temperature is the condition of 500 DEG C, being incubated 0.5h in step 2.
6. one according to claim 1 is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step 2 11ni/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:0.3.
7. one according to claim 1 is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step 2 11ni/TiO 2the mass ratio of-P25 powder and terpinol is 1:5.
8. one according to claim 1 is based on heteropoly acid SiW 11ni modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step 2 11ni/TiO 2the mass ratio of-P25 powder and ethanol is 1:4.
CN201510953579.8A 2015-12-15 2015-12-15 Preparation method for dye-sensitized solar cell photo anode based on heteropolyacid SiW11Ni modified TiO2 Pending CN105390293A (en)

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CN107591488A (en) * 2016-07-08 2018-01-16 中国科学院苏州纳米技术与纳米仿生研究所 Multi-metal oxygen cluster compound metal complex oxide, its preparation method and application
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CN108922783A (en) * 2018-07-24 2018-11-30 长江大学 A kind of dye-sensitized solar cell anode scattering layer and preparation method thereof
CN113181899A (en) * 2021-05-10 2021-07-30 上海交通大学 Polyoxometallate-based oxide photocatalyst and preparation method and application thereof

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