CN105575667A - Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2 - Google Patents

Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2 Download PDF

Info

Publication number
CN105575667A
CN105575667A CN201510953588.7A CN201510953588A CN105575667A CN 105575667 A CN105575667 A CN 105575667A CN 201510953588 A CN201510953588 A CN 201510953588A CN 105575667 A CN105575667 A CN 105575667A
Authority
CN
China
Prior art keywords
siw
tio
dye
solar cell
sensitized solar
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510953588.7A
Other languages
Chinese (zh)
Inventor
杨玉林
姜艳霞
范瑞清
王平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN201510953588.7A priority Critical patent/CN105575667A/en
Publication of CN105575667A publication Critical patent/CN105575667A/en
Pending legal-status Critical Current

Links

Classifications

    • 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 of a dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2, and aims to solve the problems that the light absorption of a TiO2-based dye-sensitized solar cell N79 in visible light regions is relatively weak, a large number of defect states of TiO2 itself lead to severe recombination of interfaces photon-generated carriers, the injection efficiency of photon-generated electrons from the dye to a TiO2 conduction band is low due to a relatively wide band gap, and the improvement of cell photovoltaic conversion efficiency is limited. The method comprises the steps of: firstly, preparing SiW11Cu/TiO2 powder; secondly, preparing SiW11Cu/TiO2-P25 powder; and thirdly, preparing the dye-sensitized solar cell photocathode. The dye-sensitized solar cell photocathode is used to prepare a dye-sensitized solar cell.

Description

A kind of based on heteropoly acid SiW 11cu 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 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode.
Background technology
The absorption of conventional dyes sensitization solar battery N719 dyestuff to visible region is more weak, 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, increase the weight of the recombination reaction of charge carrier, 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 2the absorption of radical dye sensitization solar battery N719 dyestuff to visible region is more weak, 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 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode.
A kind of based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by SiW 11cu is dissolved in distilled water and obtains light blue settled solution; Isopropyl titanate is dropwise instilled in n-butanol, obtains settled solution, be i.e. titanium isopropoxide solution; With the speed of 60/min, light blue settled solution is added drop-wise in titanium isopropoxide solution under the condition stirred, obtains turbid solution; Be heat 3h ~ 8h under the water bath condition of 30 DEG C ~ 80 DEG C in temperature by turbid solution, be then heat 2h ~ 5h under the condition of 60 DEG C ~ 100 DEG C in temperature, obtain gel; Gel is transferred to dry 10h ~ 15h in the vacuum drying chamber of 30 DEG C ~ 80 DEG C, then temperature is warming up to 85 DEG C ~ 100 DEG C from 30 DEG C ~ 80 DEG C, be be incubated 2h ~ 5h under the condition of 85 DEG C ~ 100 DEG C in temperature, finally be put in Muffle furnace, be calcine 0.5h ~ 5h under the condition of 300 DEG C ~ 500 DEG C in temperature, be cooled to room temperature, grinding, obtains SiW 11cu/TiO 2powder; The concentration of described light blue settled solution is 0.01mg/mL ~ 25mg/mL; The volume ratio of described isopropyl titanate and n-butanol is 0.2 ~ 3; The volume ratio of described light blue settled solution and titanium isopropoxide solution is 1:(1 ~ 10);
Two, by SiW 11cu/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 11cu/TiO 2-P25 powder; Described SiW 11cu/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:(1 ~ 20); Described SiW 11cu/TiO 2powder is with SiW 11cu and butyl titanate are that raw material is prepared by sol-gal process;
Three, by SiW 11cu/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 ~ 12 slurries, obtains multilayer SiW 11cu/TiO 2-P25 film, then to multilayer SiW 11cu/TiO 2-P25 film heats from room temperature to 400 DEG C ~ 600 DEG C with the heating rate of 1 DEG C/min, is be incubated 0.1h ~ 1.5h under the condition of 400 DEG C ~ 600 DEG C, obtains based on heteropoly acid SiW in temperature 11cu modifies TiO 2dye-sensitized solar cell anode; Described SiW 11cu/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:(0.1 ~ 0.5); Described SiW 11cu/TiO 2the mass ratio of-P25 powder and terpinol is 1:(2 ~ 7); Described SiW 11cu/TiO 2the mass ratio of-P25 powder and ethanol is 1:(2 ~ 5).
A kind of based on heteropoly acid SiW 11cu modifies TiO 2the application of dye-sensitized solar cell anode be by based on heteropoly acid SiW 11cu 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 11cu 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 11cu modifies TiO 2light anode material, enhances the response range of light anode in visible region, improves battery to the utilance of sunlight; SiW 11cu modifies TiO 2tiO can be made 2energy gap reduce, flat-band potential is shuffled, Fermi energy level decline, increase electronics inject TiO from dyestuff 2the actuating force of conduction band, is conducive to the increase of short circuit current; SiW 11cu 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 11cu 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 11cu modifies TiO 2the photoelectric conversion efficiency of light anode cell is 8.29%, and short circuit current is 17.84mA/cm 2, compare with blank battery, photoelectric current improves 32.3%, and battery efficiency improves 34.6%.
Accompanying drawing explanation
Fig. 1 is SiW described in embodiment one step one 11cu/TiO 2the stereoscan photograph of powder;
The SiW of Fig. 2 for obtaining in the titanic oxide nano powder described in embodiment two and embodiment one step one 11cu/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 11cu/TiO 2powder;
The SiW of Fig. 3 for obtaining in the titanic oxide nano powder described in embodiment two and embodiment one step one 11cu/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 11cu/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 11cu 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 11cu 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 11cu 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 11cu 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 11cu 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 11cu 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 11cu 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 11cu 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 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by SiW 11cu is dissolved in distilled water and obtains light blue settled solution; Isopropyl titanate is dropwise instilled in n-butanol, obtains settled solution, be i.e. titanium isopropoxide solution; With the speed of 60/min, light blue settled solution is added drop-wise in titanium isopropoxide solution under the condition stirred, obtains turbid solution; Be heat 3h ~ 8h under the water bath condition of 30 DEG C ~ 80 DEG C in temperature by turbid solution, be then heat 2h ~ 5h under the condition of 60 DEG C ~ 100 DEG C in temperature, obtain gel; Gel is transferred to dry 10h ~ 15h in the vacuum drying chamber of 30 DEG C ~ 80 DEG C, then temperature is warming up to 85 DEG C ~ 100 DEG C from 30 DEG C ~ 80 DEG C, be be incubated 2h ~ 5h under the condition of 85 DEG C ~ 100 DEG C in temperature, finally be put in Muffle furnace, be calcine 0.5h ~ 5h under the condition of 300 DEG C ~ 500 DEG C in temperature, be cooled to room temperature, grinding, obtains SiW 11cu/TiO 2powder; The concentration of described light blue settled solution is 0.01mg/mL ~ 25mg/mL; The volume ratio of described isopropyl titanate and n-butanol is 0.2 ~ 3; The volume ratio of described light blue settled solution and titanium isopropoxide solution is 1:(1 ~ 10);
Two, by SiW 11cu/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 11cu/TiO 2-P25 powder; Described SiW 11cu/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:(1 ~ 20); Described SiW 11cu/TiO 2powder is with SiW 11cu and butyl titanate are that raw material is prepared by sol-gal process;
Three, by SiW 11cu/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 ~ 12 slurries, obtains multilayer SiW 11cu/TiO 2-P25 film, then to multilayer SiW 11cu/TiO 2-P25 film heats from room temperature to 400 DEG C ~ 600 DEG C with the heating rate of 1 DEG C/min, is be incubated 0.1h ~ 1.5h under the condition of 400 DEG C ~ 600 DEG C, obtains based on heteropoly acid SiW in temperature 11cu modifies TiO 2dye-sensitized solar cell anode; Described SiW 11cu/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:(0.1 ~ 0.5); Described SiW 11cu/TiO 2the mass ratio of-P25 powder and terpinol is 1:(2 ~ 7); Described SiW 11cu/TiO 2the mass ratio of-P25 powder and ethanol is 1:(2 ~ 5).
Embodiment two: present embodiment and embodiment one unlike: the concentration of light blue settled solution described in step one is 20mg/mL.Other steps and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the volume ratio of isopropyl titanate described in step one and n-butanol is 1.Other steps and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: described in step one, the volume ratio of light blue settled solution and titanium isopropoxide solution is 1:5.Other steps and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: putting into Muffle furnace in step 2 is calcine 3h under the condition of 200 DEG C in temperature.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 11cu/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:9.Other steps and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six 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 six.
Embodiment eight: one of present embodiment and embodiment one to seven are unlike SiW described in step 3 11cu/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 seven.
Embodiment nine: one of present embodiment and embodiment one to eight are unlike SiW described in step 3 11cu/TiO 2the mass ratio of-P25 powder and terpinol is 1:5.Other steps and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine are unlike SiW described in step 3 11cu/TiO 2the mass ratio of-P25 powder and ethanol is 1:4.Other steps and parameter identical with one of embodiment one to nine.
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 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by the SiW of 0.01g ~ 1g 11cu is dissolved in 40mL ~ 100mL distilled water and obtains light blue settled solution; 5mL ~ 15mL isopropyl titanate is dropwise instilled in 5mL ~ 10mL n-butanol, obtains settled solution, be i.e. titanium isopropoxide solution; With the speed of 60/min, light blue settled solution is added drop-wise in titanium isopropoxide solution under the condition stirred, obtains turbid solution; Be heat 3h ~ 8h under the water bath condition of 30 DEG C ~ 80 DEG C in temperature by turbid solution, be then heat 2h ~ 5h under the condition of 60 DEG C ~ 100 DEG C in temperature, obtain gel; Gel is transferred to dry 10h ~ 15h in the vacuum drying chamber of 30 DEG C ~ 80 DEG C, then temperature is warming up to 85 DEG C ~ 100 DEG C from 30 DEG C ~ 80 DEG C, be be incubated 2h ~ 5h under the condition of 85 DEG C ~ 100 DEG C in temperature, finally be put in Muffle furnace, be calcine 0.5h ~ 5h under the condition of 300 DEG C ~ 500 DEG C in temperature, be cooled to room temperature, grinding, obtains SiW 11cu/TiO 2powder;
One, by SiW 11cu/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 11cu/TiO 2-P25 powder; Described SiW 11cu/TiO 2the mass ratio of powder and P25 titanium dioxide is 2:8; Described SiW 11cu/TiO 2powder is with SiW 11cu and butyl titanate are that raw material is prepared by sol-gal process;
Two, by SiW 11cu/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 11cu/TiO 2-P25 film, then to multilayer SiW 11cu/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 11cu modifies TiO 2dye-sensitized solar cell anode; Described SiW 11cu/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:0.27; Described SiW 11cu/TiO 2the mass ratio of-P25 powder and terpinol is 1:4.68; Described SiW 11cu/TiO 2the mass ratio of-P25 powder and ethanol is 1:2.98.
SiW described in the present embodiment step one 11cu/TiO 2powder to prepare concrete operation step as follows:
By 0.3mL ~ 0.6mLHNO 3with 0.1g ~ 2gSiW 11cu 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 11cu/TiO 2powder, described HNO 3mass fraction be 50% ~ 70%.
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 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 3join in 50mL ~ 100mL deionized water with 0.1g ~ 3gF127 and mix and stir, obtain mixed solution, with the speed of 60/min, 0.02mol/L ~ 0.05mol/L butyl titanate is added drop-wise in mixed solution under the condition stirred, 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 11cu/TiO 2the stereoscan photograph of powder, the as can be seen from the figure pattern of synthetic product.
The SiW of Fig. 2 for obtaining in the titanic oxide nano powder described in embodiment two and embodiment one step one 11cu/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 11cu/TiO 2powder; As can be seen from the figure SiW 11cu modifies TiO 2after expand TiO 2at the absorption region in light district.
The SiW of Fig. 3 for obtaining in the titanic oxide nano powder described in embodiment two and embodiment one step one 11cu/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 11cu/TiO 2powder; As can be seen from the figure SiW 11cu 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 11cu 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 11cu modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode; As can be seen from the figure SiW 11the TiO that Cu 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 11cu 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 11cu 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 11cu 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 11cu modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode; As can be seen from the figure SiW 11cu 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 11cu 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 11cu modifies TiO 2the DSSC prepared of dye-sensitized solar cell anode; As can be seen from the figure SiW 11cu modifies TiO 2light anode cell has higher electricity conversion.

Claims (10)

1. one kind based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode specifically carry out according to the following steps:
One, by SiW 11cu is dissolved in distilled water and obtains light blue settled solution; Isopropyl titanate is dropwise instilled in n-butanol, obtains settled solution, be i.e. titanium isopropoxide solution; With the speed of 60/min, light blue settled solution is added drop-wise in titanium isopropoxide solution under the condition stirred, obtains turbid solution; Be heat 3h ~ 8h under the water bath condition of 30 DEG C ~ 80 DEG C in temperature by turbid solution, be then heat 2h ~ 5h under the condition of 60 DEG C ~ 100 DEG C in temperature, obtain gel; Gel is transferred to dry 10h ~ 15h in the vacuum drying chamber of 30 DEG C ~ 80 DEG C, then temperature is warming up to 85 DEG C ~ 100 DEG C from 30 DEG C ~ 80 DEG C, be be incubated 2h ~ 5h under the condition of 85 DEG C ~ 100 DEG C in temperature, finally be put in Muffle furnace, be calcine 0.5h ~ 5h under the condition of 300 DEG C ~ 500 DEG C in temperature, be cooled to room temperature, grinding, obtains SiW 11cu/TiO 2powder; The concentration of described light blue settled solution is 0.01mg/mL ~ 25mg/mL; The volume ratio of described isopropyl titanate and n-butanol is 0.2 ~ 3; The volume ratio of described light blue settled solution and titanium isopropoxide solution is 1:(1 ~ 10);
Two, by SiW 11cu/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 11cu/TiO 2-P25 powder; Described SiW 11cu/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:(1 ~ 20); Described SiW 11cu/TiO 2powder is with SiW 11cu and butyl titanate are that raw material is prepared by sol-gal process;
Three, by SiW 11cu/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 ~ 12 slurries, obtains multilayer SiW 11cu/TiO 2-P25 film, then to multilayer SiW 11cu/TiO 2-P25 film heats from room temperature to 400 DEG C ~ 600 DEG C with the heating rate of 1 DEG C/min, is be incubated 0.1h ~ 1.5h under the condition of 400 DEG C ~ 600 DEG C, obtains based on heteropoly acid SiW in temperature 11cu modifies TiO 2dye-sensitized solar cell anode; Described SiW 11cu/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:(0.1 ~ 0.5); Described SiW 11cu/TiO 2the mass ratio of-P25 powder and terpinol is 1:(2 ~ 7); Described SiW 11cu/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 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that the concentration of light blue settled solution described in step one is 20mg/mL.
3. one according to claim 1 is based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that the volume ratio of isopropyl titanate described in step one and n-butanol is 1.
4. one according to claim 1 is based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that the volume ratio of light blue settled solution and titanium isopropoxide solution described in step one is 1:5.
5. one according to claim 1 is based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that putting into Muffle furnace in step 2 is calcine 3h under the condition of 200 DEG C in temperature.
6. one according to claim 1 is based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step 2 11cu/TiO 2the mass ratio of powder and P25 titanium dioxide is 1:9.
7. one according to claim 1 is based on heteropoly acid SiW 11cu 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.
8. one according to claim 1 is based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step 3 11cu/TiO 2the mass ratio of-P25 powder and ethyl cellulose is 1:0.3.
9. one according to claim 1 is based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step 3 11cu/TiO 2the mass ratio of-P25 powder and terpinol is 1:5.
10. one according to claim 1 is based on heteropoly acid SiW 11cu modifies TiO 2the preparation method of dye-sensitized solar cell anode, it is characterized in that SiW described in step 3 11cu/TiO 2the mass ratio of-P25 powder and ethanol is 1:4.
CN201510953588.7A 2015-12-15 2015-12-15 Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2 Pending CN105575667A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510953588.7A CN105575667A (en) 2015-12-15 2015-12-15 Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510953588.7A CN105575667A (en) 2015-12-15 2015-12-15 Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2

Publications (1)

Publication Number Publication Date
CN105575667A true CN105575667A (en) 2016-05-11

Family

ID=55885692

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510953588.7A Pending CN105575667A (en) 2015-12-15 2015-12-15 Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2

Country Status (1)

Country Link
CN (1) CN105575667A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102509625A (en) * 2011-11-14 2012-06-20 复旦大学 In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film
CN103545111A (en) * 2013-11-05 2014-01-29 哈尔滨工业大学 Preparing method and application of P25/TiO2@SiW11Co film
CN103943365A (en) * 2014-04-25 2014-07-23 中南大学 Manufacturing method of dye-sensitized solar cell modified photo anode
US20140220731A1 (en) * 2013-02-06 2014-08-07 National Cheng Kung University Binder-free process for preparing photoanode of flexible dye-sensitized solar cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102509625A (en) * 2011-11-14 2012-06-20 复旦大学 In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film
US20140220731A1 (en) * 2013-02-06 2014-08-07 National Cheng Kung University Binder-free process for preparing photoanode of flexible dye-sensitized solar cell
CN103545111A (en) * 2013-11-05 2014-01-29 哈尔滨工业大学 Preparing method and application of P25/TiO2@SiW11Co film
CN103943365A (en) * 2014-04-25 2014-07-23 中南大学 Manufacturing method of dye-sensitized solar cell modified photo anode

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANXIA JIANG等: "Based on Cu(II) silicotungstate modified photoanode with long electron lifetime and enhanced performance in dye sensitized solar cells", 《JOURNAL OF POWER SOURCES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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

Similar Documents

Publication Publication Date Title
CN105810442B (en) A kind of manufacture method of the enhanced solar cells of g C3N4
CN103474245B (en) A kind of used by dye sensitization solar battery SnO 2 thin film electrode materials and its preparation method
CN102074374B (en) Doping dye sensitized solar cell photo anode, preparation method and application thereof
CN101567268B (en) Method for preparing ternary two-layer titanium dioxide film
CN105390293A (en) Preparation method for dye-sensitized solar cell photo anode based on heteropolyacid SiW11Ni modified TiO2
CN103943365A (en) Manufacturing method of dye-sensitized solar cell modified photo anode
CN105131021B (en) A kind of DSSC polyacid sensitizer and preparation method altogether
CN107611225B (en) A kind of double surface treatment methods improving barium stannate radical dye sensitization solar battery incident photon-to-electron conversion efficiency
CN103985547B (en) A kind of mirror-like nanometer nickel sulfide piece is to electrode and its application
CN106299141A (en) A kind of manufacture method of the perovskite solaode of composite electron transport layer structure
CN110349753B (en) Rare earth doped up-conversion titanium dioxide nanostructure composite photo-anode and preparation method and application thereof
CN108899421A (en) Full-inorganic perovskite solar battery and its preparation method and application based on polyaniline and zinc oxide photoactive layers
CN105244172B (en) A kind of preparation method and applications of dye-sensitized solar cell anode
CN105575667A (en) Preparation method of dye-sensitized solar cell photocathode based on heteropoly acid SiW11Cu modified TiO2
CN102446632A (en) Optical anode slurry for dye-sensitized solar cell and preparation method thereof as well as optical anode for dye-sensitized solar cell and dye-sensitized solar cell
CN102543456B (en) Zinc oxide membrane electrode material for dye sensitized solar cell and preparation method thereof
CN103219160A (en) Preparation method of semiconductor film with scattering layer formed by progressive TiO2 particles
CN105225839B (en) The preparation method of a kind of high efficiency zno-based dye-sensitized solar cell anode and prepared light anode thereof
CN105206428A (en) Preparation method for core shell structure-based up-conversion micro-nanosphere dye-sensitized solar battery photo anode
CN105390292A (en) Preparation method of H-TiO2 dye sensitization solar cell light anode
CN103489650A (en) Mixed-europium zinc base film material and preparing method thereof
CN105428070A (en) Preparation method of dye-sensitized solar cell photo-anode based on flower-like TiO<2> powder and blue-green fluorescent C quantum dots
CN106566550A (en) Preparation method and application of composite up-conversion luminescent material
CN104402234A (en) Glass powder for crystalline silicon solar cells' front silver paste and preparation method thereof
CN109574062A (en) Na5Yb9F32: Ho3+Up-conversion and preparation method thereof, photo-anode film and preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160511

WD01 Invention patent application deemed withdrawn after publication