CN105244172A - Preparation method and application of dye-sensitized solar battery photoanode - Google Patents

Preparation method and application of dye-sensitized solar battery photoanode Download PDF

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CN105244172A
CN105244172A CN201510717101.5A CN201510717101A CN105244172A CN 105244172 A CN105244172 A CN 105244172A CN 201510717101 A CN201510717101 A CN 201510717101A CN 105244172 A CN105244172 A CN 105244172A
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heterostructure
tio
dye
ybf
sensitized solar
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CN105244172B (en
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杨玉林
俞佳
范瑞清
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention discloses a preparation method and application of a dye-sensitized solar battery photoanode, and relates to a reparation method and application of a dye-sensitized solar battery photoanode, for solving the problems of little utilization of energy of a near infrared area by a dye-sensitized solar battery prepared in the prior art and low battery efficiency caused by compounding of interface photo-induced carriers. The method comprises the following steps: 1, preparing Ho(NO3)3 and Yb(NO3)3; 2, preparing YbF3-Ho; 3, uniformly mixing the YbF3-Ho with TiO2, and obtaining upconversion powder of a heterostructure through high-temperature calcining; and 4, preparing the photoanode. According to the invention, the upconversion photoanode dye-sensitized solar battery of the heterostructure is prepared by taking the dye-sensitized solar battery photoanode as an anode.

Description

A kind of preparation method of dye-sensitized solar cell anode and application thereof
Technical field
The present invention relates to a kind of preparation method and application thereof of dye-sensitized solar cell anode.
Background technology
The Energy harvesting of conventional dyes sensitization solar battery to near-infrared region is few, the absorption spectrum of battery is not mated with solar spectrum, limits the lifting of battery efficiency.
Rare earth up-conversion can utilize near infrared light, and convert thereof into visible ray, therefore being used for by rare earth up-conversion can by the photoresponse expanded range of battery near infrared region in DSSC, improve battery to the utilance of sunlight, thus improve the photoelectric conversion efficiency of battery.But, because the conductivity of upper conversion 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 the problem that battery efficiency that the DSSC compound that is few to near-infrared region Energy harvesting and interface photo-generated carrier prepared to solve prior art causes is low, and provides a kind of preparation method and application thereof of dye-sensitized solar cell anode.
A kind of preparation method of dye-sensitized solar cell anode specifically carries out according to the following steps:
One, by Yb 2o 3and Ho 2o 3mixing, obtains mixture, mixture is joined HNO 3in, be then heating for dissolving 15min ~ 45min under the condition of 50 DEG C ~ 90 DEG C in temperature, then under the condition of temperature 90 DEG C ~ 150 DEG C, dry 4h ~ 10h, obtain Yb (NO 3) 3with Ho (NO 3) 3; Described Ho 2o 3with Yb 2o 3mol ratio is 1:(40 ~ 100); The quality of described mixture and HNO 3volume ratio be 1g:(1 ~ 7) mL;
Two, by NH 4hF 2be dissolved in deionized water, obtain NH 4hF 2solution, Yb (the NO that step one is obtained 3) 3with Ho (NO 3) 3be dissolved in deionized water, obtain mixed liquor, then with the speed of 50/min ~ 80 droplet/min, mixed liquor is added dropwise to NH 4hF 2in solution, adopt HF adjust ph to be 1 ~ 7 after mixing completely, obtain synthetic product, synthetic product is transferred in water heating kettle and carry out hydro-thermal reaction, hydrothermal temperature is 150 DEG C ~ 200 DEG C, the hydro-thermal time is 12h ~ 24h, hydrothermal product is obtained after hydro-thermal, hydrothermal product is naturally cooled to room temperature, then centrifugation is carried out with the speed of 3000rpm ~ 15000rpm, obtain white depositions, deionized water white depositions is first adopted to wash 2 ~ 5 times, adopt washes of absolute alcohol again 2 ~ 5 times, obtain cleaning postprecipitation thing, cleaning postprecipitation thing being placed in temperature is after the dry 1h ~ 5h of vacuum drying chamber of 100 DEG C, being placed in temperature is again that 0.5h ~ 4h calcined by the Muffle furnace of 300 DEG C ~ 600 DEG C, naturally cool to room temperature, obtain changing YbF 3-Ho nano particle, described NH 4hF 2quality and the volume ratio of deionized water be 1g:(10 ~ 50) mL,
Three, upper conversion YbF step 2 obtained 3-Ho nano particle and TiO 2mixing, being then placed in temperature is that 0.5h ~ 5h calcined by the Muffle furnace of 100 DEG C ~ 600 DEG C, naturally cools to room temperature, obtains YbF 3-Ho/TiO 2powder changed by heterostructure; The upper conversion YbF that described step 2 obtains 3-Ho nano particle and TiO 2mass ratio be 1:(3 ~ 20);
Four, YbF step 3 obtained 3-Ho/TiO 2heterostructure is changed powder, ethyl cellulose, terpinol and ethanol to uniformly mix, make slurry, 250 order silk screens are used to carry out silk screen printing to slurry, with the heating rate of 1 DEG C/min, temperature is risen to 200 DEG C ~ 700 DEG C from room temperature, then at the temperature of 200 DEG C ~ 700 DEG C, be incubated 0.5h ~ 5h, obtain dye-sensitized solar cell anode; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethyl cellulose into 1:(0.1 ~ 0.5); The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and terpinol into 1:(2 ~ 7); The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethanol into 1:(2 ~ 5).
A kind of application of dye-sensitized solar cell anode is as the upper convert light anode DSSC of anode for the preparation of heterostructure using dye-sensitized solar cell anode; The photoelectric conversion efficiency of the upper convert light anode DSSC of described heterostructure is 8.2% ~ 8.4%; The short circuit current of the upper convert light anode DSSC of described heterostructure is 19.4mAcm 2~ 20.2mAcm 2.
Beneficial effect of the present invention:
The present invention has prepared a kind of dye-sensitized solar cell anode, and preparation method is simple.The upper convert light anode DSSC of the heterostructure that the dye-sensitized solar cell anode adopting the present invention to prepare prepares has following advantage compared with traditional light anode dye-sensitized cell:
1, photoelectric respone is created near infrared light, improve the utilance of battery to sunlight.
2, YbF 3the upper conversion nano particle of-Ho can pass through YbF 3-Ho and TiO 2heterogeneous interface directly by excitation state electron injection TiO 2in conduction band, improve the short circuit current of battery;
3, through YbF 3-Ho/TiO 2the visible ray that heterostructure powder converts to can be sensitized agent N719 and absorb, and improves the short circuit current of battery;
4, the YbF of this heterostructure 3-Ho/TiO 2tiO can be promoted 2the separation of middle photo-generate electron-hole, extends electron lifetime, is conducive to the raising of cell photoelectric performance.
5, YbF 3-Ho/TiO 2the above advantage of heterostructure powder makes this based on YbF 3-Ho/TiO 2on heterostructure, the DSSC of the light anode composition of conversion nano powder has less transmission resistance, is conducive to the fast transport of electronics; In battery, the life-span of light induced electron increases, and makes the photoelectric conversion efficiency of battery relative to existing TiO 2p25 light anode cell improves 27%, and short circuit current improves 28%.
Accompanying drawing explanation
Fig. 1 is the YbF obtained in embodiment one step 3 3-Ho/TiO 2heterostructure is changed the scanning electron microscope (SEM) photograph of powder;
Fig. 2 is the YbF obtained in embodiment one step 3 3-Ho/TiO 2heterostructure is changed the transmission electron microscope picture of powder;
Fig. 3 is the YbF obtained in embodiment one step 3 3-Ho/TiO 2heterostructure is changed the fluorescent spectrum curve comparison diagram of powder respectively in ethanol and N719 ethanolic solution, wherein 1 is fluorescent spectrum curve in ethanol, and 2 is the fluorescent spectrum curve in N719 ethanolic solution;
Fig. 4 is the TiO without sensitizer N719 sensitization 2the short circuit current of the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC obtains with the embodiment two without sensitizer N719 sensitization and open circuit voltage correlation curve, wherein 1 is the upper convert light anode DSSC of the heterostructure obtained without the embodiment two of sensitizer N719 sensitization, 2 be without sensitizer N719 sensitization TiO 2p25 light anode cell;
Fig. 5 is TiO 2the transient state spectrum correlation curve of the upper convert light anode DSSC of the heterostructure that P25 light anode cell and embodiment two obtain, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC;
Fig. 6 is TiO 2the open circuit voltage attenuation verses curve of the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC and embodiment two obtain, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC;
Fig. 7 is TiO under illumination condition 2the AC impedance of the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC and embodiment two obtain contrasts collection of illustrative plates, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC;
Fig. 8 is TiO 2the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC and embodiment two obtain under the condition simulating 1.5G sunlight under short circuit current and open circuit voltage correlation curve, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC.
Embodiment
Embodiment one: the preparation method of a kind of dye-sensitized solar cell anode of present embodiment specifically carries out according to the following steps:
One, by Yb 2o 3and Ho 2o 3mixing, obtains mixture, mixture is joined HNO 3in, be then heating for dissolving 15min ~ 45min under the condition of 50 DEG C ~ 90 DEG C in temperature, then under the condition of temperature 90 DEG C ~ 150 DEG C, dry 4h ~ 10h, obtain Yb (NO 3) 3with Ho (NO 3) 3; Described Ho 2o 3with Yb 2o 3mol ratio is 1:(40 ~ 100); The quality of described mixture and HNO 3volume ratio be 1g:(1 ~ 7) mL;
Two, by NH 4hF 2be dissolved in deionized water, obtain NH 4hF 2solution, Yb (the NO that step one is obtained 3) 3with Ho (NO 3) 3be dissolved in deionized water, obtain mixed liquor, then with the speed of 50/min ~ 80 droplet/min, mixed liquor is added dropwise to NH 4hF 2in solution, adopt HF adjust ph to be 1 ~ 7 after mixing completely, obtain synthetic product, synthetic product is transferred in water heating kettle and carry out hydro-thermal reaction, hydrothermal temperature is 150 DEG C ~ 200 DEG C, the hydro-thermal time is 12h ~ 24h, hydrothermal product is obtained after hydro-thermal, hydrothermal product is naturally cooled to room temperature, then centrifugation is carried out with the speed of 3000rpm ~ 15000rpm, obtain white depositions, deionized water white depositions is first adopted to wash 2 ~ 5 times, adopt washes of absolute alcohol again 2 ~ 5 times, obtain cleaning postprecipitation thing, cleaning postprecipitation thing being placed in temperature is after the dry 1h ~ 5h of vacuum drying chamber of 100 DEG C, being placed in temperature is again that 0.5h ~ 4h calcined by the Muffle furnace of 300 DEG C ~ 600 DEG C, naturally cool to room temperature, obtain changing YbF 3-Ho nano particle, described NH 4hF 2quality and the volume ratio of deionized water be 1g:(10 ~ 50) mL,
Three, upper conversion YbF step 2 obtained 3-Ho nano particle and TiO 2mixing, being then placed in temperature is that 0.5h ~ 5h calcined by the Muffle furnace of 100 DEG C ~ 600 DEG C, naturally cools to room temperature, obtains YbF 3-Ho/TiO 2powder changed by heterostructure; The upper conversion YbF that described step 2 obtains 3-Ho nano particle and TiO 2mass ratio be 1:(3 ~ 20);
Four, YbF step 3 obtained 3-Ho/TiO 2heterostructure is changed powder, ethyl cellulose, terpinol and ethanol to uniformly mix, make slurry, 250 order silk screens are used to carry out silk screen printing to slurry, with the heating rate of 1 DEG C/min, temperature is risen to 200 DEG C ~ 700 DEG C from room temperature, then at the temperature of 200 DEG C ~ 700 DEG C, be incubated 0.5h ~ 5h, obtain dye-sensitized solar cell anode; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethyl cellulose into 1:(0.1 ~ 0.5); The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and terpinol into 1:(2 ~ 7); The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethanol into 1:(2 ~ 5).
TiO described in present embodiment 2be mixed to get by the rutile titanium dioxide of the anatase titanium dioxide of 80 percent and 20 percent.
HNO described in this city execution mode step one 3concentration be 98%.
Present embodiment has prepared a kind of dye-sensitized solar cell anode, and preparation method is simple.The upper convert light anode DSSC of the heterostructure that the dye-sensitized solar cell anode adopting present embodiment to prepare prepares has following advantage compared with traditional light anode dye-sensitized cell:
1, photoelectric respone is created near infrared light, improve the utilance of battery to sunlight.
2, YbF 3the upper conversion nano particle of-Ho can pass through YbF 3-Ho and TiO 2heterogeneous interface directly by excitation state electron injection TiO 2in conduction band, improve the short circuit current of battery;
3, through YbF 3-Ho/TiO 2the visible ray that heterostructure powder converts to can be sensitized agent N719 and absorb, and improves the short circuit current of battery;
4, the YbF of this heterostructure 3-Ho/TiO 2tiO can be promoted 2the separation of middle photo-generate electron-hole, extends electron lifetime, is conducive to the raising of cell photoelectric performance.
5, YbF 3-Ho/TiO 2the above advantage of heterostructure powder makes this based on YbF 3-Ho/TiO 2on heterostructure, the DSSC of the light anode composition of conversion nano powder has less transmission resistance, is conducive to the fast transport of electronics; In battery, the life-span of light induced electron increases, and makes the photoelectric conversion efficiency of battery relative to existing TiO 2p25 light anode cell improves 27%, and short circuit current improves 28%.
Embodiment two: present embodiment and embodiment one are unlike Ho described in step one 2o 3with Yb 2o 3mol ratio is 1:50.76.Other steps and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are unlike the quality of mixture described in step one and HNO 3volume ratio be 1g:5.28mL.Other steps and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: be heating for dissolving 20min under the condition of 90 DEG C in temperature in step one.Other steps and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: under the condition of temperature 110 DEG C, dry 6h in step one.Other steps and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: transferred in water heating kettle by synthetic product in step 2 and carry out hydro-thermal reaction, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 18h.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 NH described in step 2 4hF 2quality and the volume ratio of deionized water be 1g:20.8mL.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 upper conversion YbF that the step 2 described in step 3 obtains 3-Ho nano particle and TiO 2mass ratio be 1:19.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 YbF that the step 3 described in step 4 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethyl cellulose into 1:0.27; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and terpinol into 1:4.68; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethanol into 1:2.98.Other steps and parameter identical with one of embodiment one to eight.
Embodiment ten: the application of a kind of dye-sensitized solar cell anode of present embodiment is as the upper convert light anode DSSC of anode for the preparation of heterostructure using dye-sensitized solar cell anode; The photoelectric conversion efficiency of the upper convert light anode DSSC of described heterostructure is 8.2% ~ 8.4%; The short circuit current of the upper convert light anode DSSC of described heterostructure is 19.4mAcm 2~ 20.2mAcm 2.
Beneficial effect of the present invention is verified by following examples:
Embodiment one: the preparation method of a kind of dye-sensitized solar cell anode of the present embodiment specifically carries out according to the following steps:
One, by Yb 2o 3and Ho 2o 3mixing, obtains mixture, mixture is joined HNO 3in, be then heating for dissolving 20min under the condition of 90 DEG C in temperature, then under the condition of temperature 110 DEG C, dry 6h, obtain Yb (NO 3) 3with Ho (NO 3) 3; Described Ho 2o 3with Yb 2o 3mol ratio is 1:50.76; The quality of described mixture and HNO 3volume ratio be 1g:5.28mL;
Two, by NH 4hF 2be dissolved in deionized water, obtain NH 4hF 2solution, Yb (the NO that step one is obtained 3) 3with Ho (NO 3) 3be dissolved in deionized water, obtain mixed liquor, then with the speed of 60/min, mixed liquor is added dropwise to NH 4hF 2in solution, adopt HF adjust ph to be 4 ~ 5 after mixing completely, obtain synthetic product, synthetic product is transferred in water heating kettle and carry out hydro-thermal reaction, hydrothermal temperature is 180 DEG C, the hydro-thermal time is 18h, hydrothermal product is obtained after hydro-thermal, hydrothermal product is naturally cooled to room temperature, then centrifugation is carried out with the speed of 12000rpm, obtain white depositions, deionized water white depositions is first adopted to wash 3 times, adopt washes of absolute alcohol again 3 times, obtain cleaning postprecipitation thing, cleaning postprecipitation thing being placed in temperature is after the dry 2h of vacuum drying chamber of 100 DEG C, being placed in temperature is again that 2h calcined by the Muffle furnace of 500 DEG C, naturally cool to room temperature, obtain changing YbF 3-Ho nano particle, described NH 4hF 2quality and the volume ratio of deionized water be 1g:20.8mL,
Three, upper conversion YbF step 2 obtained 3-Ho nano particle and TiO 2mixing, being then placed in temperature is that 2h calcined by the Muffle furnace of 500 DEG C, naturally cools to room temperature, obtains YbF 3-Ho/TiO 2powder changed by heterostructure; The upper conversion YbF that described step 2 obtains 3-Ho nano particle and TiO 2mass ratio be 1:19;
Four, YbF step 3 obtained 3-Ho/TiO 2heterostructure is changed powder, ethyl cellulose, terpinol and ethanol to uniformly mix, make slurry, 250 order silk screens are used to carry out silk screen printing to slurry, with the heating rate of 1 DEG C/min, temperature is risen to 500 DEG C from room temperature, then at the temperature of 500 DEG C, be incubated 0.5h, obtain dye-sensitized solar cell anode; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethyl cellulose into 1:0.27; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and terpinol into 1:4.68; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethanol into 1:2.98.
Fig. 1 is the YbF obtained in embodiment one step 3 3-Ho/TiO 2heterostructure is changed the scanning electron microscope (SEM) photograph of powder; Fig. 2 is the YbF obtained in embodiment one step 3 3-Ho/TiO 2heterostructure is changed the transmission electron microscope picture of powder; The existence of heterogeneous interface in heterostructure can be confirmed from figure.
Fig. 3 is the YbF obtained in embodiment one step 3 3-Ho/TiO 2heterostructure is changed the fluorescent spectrum curve comparison diagram of powder respectively in ethanol and N719 ethanolic solution, wherein 1 is fluorescent spectrum curve in ethanol, and 2 is the fluorescent spectrum curve in N719 ethanolic solution; In N719 ethanolic solution, the remitted its fury of up-conversion fluorescence emission peak, demonstrates YbF 3-Ho/TiO 2up-conversion luminescence heterostructure being changed powder can be absorbed by N719, is conducive to the short circuit current improving battery.
Embodiment two: dye-sensitized solar cell anode embodiment one obtained is as the upper convert light anode DSSC of anode for the preparation of heterostructure.
Fig. 4 is the TiO without sensitizer N719 sensitization 2the short circuit current of the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC obtains with the embodiment two without sensitizer N719 sensitization and open circuit voltage correlation curve, wherein 1 is the upper convert light anode DSSC of the heterostructure obtained without the embodiment two of sensitizer N719 sensitization, 2 be without sensitizer N719 sensitization TiO 2p25 light anode cell; As can be seen from the figure YbF 3the upper conversion nano particle of-Ho can pass through YbF 3-Ho and TiO 2heterogeneous interface directly by excitation state electron injection TiO 2in conduction band, improve the short circuit current of battery.
Fig. 5 is TiO 2the transient state spectrum correlation curve of the upper convert light anode DSSC of the heterostructure that P25 light anode cell and embodiment two obtain, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC; As can be seen from the figure the YbF of this heterostructure 3-Ho/TiO 2tiO can be promoted 2the separation of middle light induced electron, extends electron lifetime.
Fig. 6 is TiO 2the open circuit voltage attenuation verses curve of the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC and embodiment two obtain, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC; As can be seen from the figure this based on YbF 3-Ho/TiO 2in the DSSC that on heterostructure, the light anode of conversion nano powder forms, the life-span of light induced electron increases.
Fig. 7 is TiO under illumination condition 2the AC impedance of the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC and embodiment two obtain contrasts collection of illustrative plates, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC; As can be seen from the figure this based on YbF 3-Ho/TiO 2on heterostructure, the DSSC of the light anode composition of conversion nano powder has less transmission resistance, is conducive to the fast transport of electronics.
Fig. 8 is TiO 2the upper convert light anode DSSC of the heterostructure that P25 light anode DSSC and embodiment two obtain under the condition simulating 1.5G sunlight under short circuit current and open circuit voltage correlation curve, wherein 1 is the upper convert light anode DSSC of the heterostructure that embodiment two obtains, and 2 is TiO 2p25 light anode DSSC; As can be seen from the figure this based on YbF 3-Ho/TiO 2on heterostructure, the DSSC of the light anode composition of conversion nano powder improves short circuit current and the open circuit voltage of battery, and the photoelectric conversion efficiency of battery is improved.

Claims (10)

1. a preparation method for dye-sensitized solar cell anode, is characterized in that what the preparation method of dye-sensitized solar cell anode specifically carried out according to the following steps:
One, by Yb 2o 3and Ho 2o 3mixing, obtains mixture, mixture is joined HNO 3in, be then heating for dissolving 15min ~ 45min under the condition of 50 DEG C ~ 90 DEG C in temperature, then under the condition of temperature 90 DEG C ~ 150 DEG C, dry 4h ~ 10h, obtain Yb (NO 3) 3with Ho (NO 3) 3; Described Ho 2o 3with Yb 2o 3mol ratio is 1:(40 ~ 100); The quality of described mixture and HNO 3volume ratio be 1g:(1 ~ 7) mL;
Two, by NH 4hF 2be dissolved in deionized water, obtain NH 4hF 2solution, Yb (the NO that step one is obtained 3) 3with Ho (NO 3) 3be dissolved in deionized water, obtain mixed liquor, then with the speed of 50/min ~ 80 droplet/min, mixed liquor is added dropwise to NH 4hF 2in solution, adopt HF adjust ph to be 1 ~ 7 after mixing completely, obtain synthetic product, synthetic product is transferred in water heating kettle and carry out hydro-thermal reaction, hydrothermal temperature is 150 DEG C ~ 200 DEG C, the hydro-thermal time is 12h ~ 24h, hydrothermal product is obtained after hydro-thermal, hydrothermal product is naturally cooled to room temperature, then centrifugation is carried out with the speed of 3000rpm ~ 15000rpm, obtain white depositions, deionized water white depositions is first adopted to wash 2 ~ 5 times, adopt washes of absolute alcohol again 2 ~ 5 times, obtain cleaning postprecipitation thing, cleaning postprecipitation thing being placed in temperature is after the dry 1h ~ 5h of vacuum drying chamber of 100 DEG C, being placed in temperature is again that 0.5h ~ 4h calcined by the Muffle furnace of 300 DEG C ~ 600 DEG C, naturally cool to room temperature, obtain changing YbF 3-Ho nano particle, described NH 4hF 2quality and the volume ratio of deionized water be 1g:(10 ~ 50) mL,
Three, upper conversion YbF step 2 obtained 3-Ho nano particle and TiO 2mixing, being then placed in temperature is that 0.5h ~ 5h calcined by the Muffle furnace of 100 DEG C ~ 600 DEG C, naturally cools to room temperature, obtains YbF 3-Ho/TiO 2powder changed by heterostructure; The upper conversion YbF that described step 2 obtains 3-Ho nano particle and TiO 2mass ratio be 1:(3 ~ 20);
Four, YbF step 3 obtained 3-Ho/TiO 2heterostructure is changed powder, ethyl cellulose, terpinol and ethanol to uniformly mix, make slurry, 250 order silk screens are used to carry out silk screen printing to slurry, with the heating rate of 1 DEG C/min, temperature is risen to 200 DEG C ~ 700 DEG C from room temperature, then at the temperature of 200 DEG C ~ 700 DEG C, be incubated 0.5h ~ 5h, obtain dye-sensitized solar cell anode; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethyl cellulose into 1:(0.1 ~ 0.5); The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and terpinol into 1:(2 ~ 7); The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethanol into 1:(2 ~ 5).
2. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, is characterized in that Ho described in step one 2o 3with Yb 2o 3mol ratio is 1:50.76.
3. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, is characterized in that quality and the HNO of mixture described in step one 3volume ratio be 1g:5.28mL.
4. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, to is characterized in that in step one heating for dissolving 20min under temperature is the condition of 90 DEG C.
5. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, is characterized in that under the condition of temperature 110 DEG C, drying 6h in step one.
6. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, it is characterized in that being transferred in water heating kettle by synthetic product in step 2 carrying out hydro-thermal reaction, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 18h.
7. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, is characterized in that NH described in step 2 4hF 2quality and the volume ratio of deionized water be 1g:20.8mL.
8. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, is characterized in that the upper conversion YbF that the step 2 described in step 3 obtains 3-Ho nano particle and TiO 2mass ratio be 1:19.
9. the preparation method of a kind of dye-sensitized solar cell anode according to claim 1, is characterized in that the YbF that the step 3 described in step 4 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethyl cellulose into 1:0.27; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and terpinol into 1:4.68; The YbF that described step 3 obtains 3-Ho/TiO 2heterostructure is changed the mass ratio of powder and ethanol into 1:2.98.
10. the application of a kind of dye-sensitized solar cell anode as claimed in claim 1, it is characterized in that dye-sensitized solar cell anode as the upper convert light anode DSSC of anode for the preparation of heterostructure; The photoelectric conversion efficiency of the upper convert light anode DSSC of described heterostructure is 8.2% ~ 8.4%; The short circuit current of the upper convert light anode DSSC of described heterostructure is 19.4mAcm 2~ 20.2mAcm 2.
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