CN104966618B - A kind of dye-sensitized solar cell anode and preparation method thereof - Google Patents
A kind of dye-sensitized solar cell anode and preparation method thereof Download PDFInfo
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- CN104966618B CN104966618B CN201510470503.XA CN201510470503A CN104966618B CN 104966618 B CN104966618 B CN 104966618B CN 201510470503 A CN201510470503 A CN 201510470503A CN 104966618 B CN104966618 B CN 104966618B
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- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a kind of dye-sensitized solar cell anode and preparation method thereof, it is characterised in that：It is with rear-earth-doped up-conversion luminescent material and TiO2Composite as light anode material；During preparation, first so that rear-earth-doped up-conversion luminescent material and titanium dioxide are carried out into physical mixed, doping β NaYF are obtained4:Er3+,Yb3+TiO2Slurry；Then slurry is printed on FTO electro-conductive glass and calcined using silk screen print method, form β NaYF4:Er3+,Yb3+@TiO2Composite photo-anode film；Dyestuff is finally adsorbed, that is, obtains light anode.There is high open-circuit voltage and short-circuit current density with battery prepared by the light anode of the present invention, the efficiency of battery is obtained up to more than 9%, efficiency improves more than 55% than pure titinium dioxide, and preparation technology is simple, it is repeated good, cost is cheap, can be also used for the fields such as photocatalysis, light sensitive material.
Description
First, technical field
The invention belongs to technical field of solar batteries, is related to a kind of dye-sensitized solar cell anode and its preparation
Method.
2nd, background technology
The utilization of regenerative resource are the primary solutions for solving fossil fuel crisis and global warming.To current
Untill, in numerous regenerative resources, solar energy is a kind of inexhaustible, nexhaustible, clean reproducible energy, is had only
Special advantage and huge developing and utilizingpotentiality, it is the new energy of following most development prospect.Since 1991 by Glan Ze ErProfessor etc. is prepared for the DSSC (Dye- of poriferous titanium dioxide nano material for the first time
Sensitized Solar Cell, hereinafter referred to as DSSC) since, due to its have higher photoelectric transformation efficiency, it is cheap into
This and simple preparation method and be considered as the most promising solar cell in field of renewable energy.Generally, one
The light anode of the DSSC of standard includes dye-sensitized nanocrystalline titanium dioxide perforated membrane, to electrode and electrolysis
Matter.
Light anode plays very important effect in DSSC, is the carrier of photosensitizer, and
Collect electronics and transmit the medium of electronics.In order to improve the photoelectric transformation efficiency of DSSC, researcher
Employ different technology and method, such as control titanium dioxide photo anode various nanostructured morphologies, and improve dyestuff
To effective absorbability of visible ray and near infrared light etc..The dyestuff adsorbed on poriferous titanium dioxide surface is absorbing sunshine
Aspect plays an important role.But DSSC can not effectively absorb near-infrared and infrared light, limit electricity
The photon-electron conversion efficiency in pond.In order to overcome this deficiency, the up-conversion that infrared light can be changed into visible ray draws
Enter DSSC, it is considered to be most potential solution, and have been used for the battery.Generally acknowledge at present
The rear-earth-doped up-conversion luminescent material of efficiency highest be β-NaYF4:Er3+,Yb3+.Although on β-NaYF4:Er3+,Yb3+
Application in DSSC has had many reports, but existing method is in the complexity and product of technique
Gratifying degree can not be reached in performance.3rd, the content of the invention
The present invention is to avoid the weak point present in above-mentioned prior art, there is provided a kind of technique is simple, can more added with
It is positive that effect improves the opto-electronic conversion performance of battery, the DSSC light for the photoelectric transformation efficiency for improving solar cell
Pole and preparation method thereof.
The present invention solves technical problem and adopted the following technical scheme that：
Dye-sensitized solar cell anode of the present invention, its feature are：It is with rear-earth-doped up-conversion luminescent material
With TiO2Composite as light anode material.Wherein, the rear-earth-doped up-conversion luminescent material is β-NaYF4:Er3+,
Yb3+Up-conversion.TiO is accounted in composite middle rare earth doping up-conversion luminescent material2The 2.5~20% of quality.
The preparation method of above-mentioned dye-sensitized solar cell anode, its feature are to carry out as follows：
A, doping β-NaYF are prepared4:Er3+,Yb3+TiO2Slurry：
By β-NaYF4:Er3+,Yb3+Up-conversion is mixed with titanium dioxide and ground uniformly, is sequentially added acetic acid and is gone
Ionized water, stir；Sequentially add absolute ethyl alcohol, terpinol and ethyl cellulose, last magnetic agitation, ultrasonic disperse,
Revolving, obtain doping β-NaYF4:Er3+,Yb3+TiO2Slurry；
Titanium dioxide in step a, acetic acid, deionized water, absolute ethyl alcohol, the amount ratio of terpinol and ethyl cellulose are：
0.5g：0.1mL：50μL：50mL：1.8g：0.25g；β-the NaYF4:Er3+,Yb3+The quality of up-conversion accounts for titanium dioxide
The 2.5~20% of quality.
B, β-NaYF are prepared4:Er3+,Yb3+@TiO2Composite photo-anode film
FTO electro-conductive glass is immersed in TiCl4TiCl is carried out in the aqueous solution4Pretreatment, then in Muffle furnace 500 DEG C forge
Burn 30min；β-NaYF will be adulterated using silk screen print method made from step a4:Er3+,Yb3+TiO2Slurry is printed in FTO conductions
On glass, stand, dry, then put and calcine 30min at 500 DEG C in Muffle furnace；After being naturally cooling to room temperature, then it is immersed in
TiCl4TiCl is carried out in the aqueous solution4Post processing, is again placed in calcining 30min at 500 DEG C in Muffle furnace after taking-up, i.e., is led in FTO
Electric glass surface forms β-NaYF4:Er3+,Yb3+@TiO2Composite photo-anode film；
C, dye-sensitized solar cell anode is prepared
Surface is formed with β-NaYF in stepb4:Er3+,Yb3+@TiO2The FTO conduction glass of composite photo-anode film
When glass is cooled to 100-120 DEG C, it is immersed in N719 dyestuffs, is rinsed, dried up with absolute ethyl alcohol after taking-up, that is, obtains and mixed with rare earth
Miscellaneous up-conversion luminescent material and TiO2Dye-sensitized solar cell anode of the composite as light anode material.
The preparation method of above-mentioned dye-sensitized solar cell anode is preferably：
A, doping β-NaYF are prepared4:Er3+,Yb3+TiO2Slurry：
P25 powder 0.5g are taken, by β-NaYF4:Er3+,Yb3+Up-conversion mixes with P25 powder and grinds uniform mixture
Material；With 10 μ L addition every time, point 10 addition 0.1mL acetic acid into mixed material, 3min is ground after adding acetic acid every time；
50 μ L deionized waters are added into mixed material with 10 μ L addition every time, points 5 times again, are ground after adding deionized water every time
3min；10mL absolute ethyl alcohols are added dropwise into the mixed material again, and grinds and stirs；Finally again into the mixed material
40mL absolute ethyl alcohols are added, obtain mixed liquor；
The mixed liquor is moved into beaker, magnetic agitation 20min, then alternately ultrasonic disperse and magnetic agitation each 20
It is secondary, each 1min；Then 1.8g terpinols, alternately ultrasonic disperse and magnetic agitation each 20 are added into the mixed liquor
It is secondary, each 1min；0.25g ethyl celluloses are added into the mixed liquor again, alternately ultrasonic disperse and magnetic agitation is each
20 times, each 1min；Finally by mixed liquor in Rotary Evaporators rotary distillation 1.5-2 hours at 50-55 DEG C, obtain doping β-
NaYF4:Er3+,Yb3+TiO2Slurry；
B, β-NaYF are prepared4:Er3+,Yb3+@TiO2Composite photo-anode film
FTO electro-conductive glass is immersed in 0.5mM TiCl4In the aqueous solution, 70 DEG C of holding 30min, TiCl is carried out4Pretreatment,
Then 500 DEG C of calcining 30min in Muffle furnace；Using silk screen print method, the silk screen with 300-450 mesh will be mixed made from step a
Miscellaneous β-NaYF4:Er3+,Yb3+TiO2Slurry is printed on FTO electro-conductive glass, stands 3min, 125 DEG C of dry 6min, repeats to print
Brush, stand and dry, the number repeated is according to required β-NaYF4:Er3+,Yb3+@TiO2Composite photo-anode film
Thickness determines；
Then put and calcine 30min at 500 DEG C in Muffle furnace；After being naturally cooling to room temperature, then it is immersed in 0.5mM's
TiCl4In the aqueous solution, 30min is kept at 70 DEG C, carries out TiCl4Post processing, is again placed in forging at 500 DEG C in Muffle furnace after taking-up
30min is burnt, i.e., forms β-NaYF in FTO conductive glass surfaces4:Er3+,Yb3+@TiO2Composite photo-anode film；
C, dye-sensitized solar cell anode is prepared
Surface is formed with β-NaYF in stepb4:Er3+,Yb3+@TiO2The FTO conduction glass of composite photo-anode film
When glass is cooled to 100-120 DEG C, it is put into the ethanol solution for the N719 dyestuffs that concentration is 50mM and soaks 12-24 hours, take
The dyestuff of remained on surface is washed off after going out with absolute ethyl alcohol, is finally dried up, that is, is obtained with rear-earth-doped up-conversion luminescent material
With TiO2Dye-sensitized solar cell anode of the composite as light anode material.
Compared with the prior art, the present invention has the beneficial effect that：
1st, the photo-anode film that the present invention is prepared using rear-earth-doped up-conversion luminescent material with composite titania material
Contact that good, film surface is smooth with FTO electro-conductive glass, by changing the doping of rear-earth-doped up-conversion luminescent material, realize pair
Effective control of the absorption spectrum of composite light anode, specific surface area, voidage etc., has widened absorption spectrum ranges, has made light
Electronics can be scattered effectively in photo-anode film, improved the utilization rate of light, significantly improved current density and open-circuit voltage, obtain
The efficiency of battery improves more than 55% up to more than 9%, than pure titinium dioxide, significantly improves the photoelectric conversion of battery
Energy, improve the photoelectric transformation efficiency of solar cell.
2nd, preparation technology of the present invention is simple, and repeatability is good, and cost is cheap, and the utilization rate of light and the efficiency of battery carry significantly
Height, DSSC material is can be applied not only to, can also be applied in fields such as photocatalysis, senser elements.
4th, illustrate
Fig. 1 be doping different quality than β-NaYF4:Er3+,Yb3+TiO2The XRD of slurry.
Fig. 2 is β-NaYF4:Er3+,Yb3+Luminous spectrum under the conditions of 980nm laser pump (ing)s.
Fig. 3 a are β-NaYF4:Er3+,Yb3+TEM figure；Fig. 3 b are doping β-NaYF prepared by embodiment 64:Er3+,Yb3+
TiO2The TEM figures of slurry, β-NaYF4:Er3+,Yb3+Addition be TiO2The 15% of quality.
Fig. 4 a and b are respectively β-NaYF prepared by embodiment 64:Er3+,Yb3+@TiO2Composite photo-anode film is not
With the surface FE-SEM figures under multiplication factor, β-NaYF4:Er3+,Yb3+Addition be TiO2The 15% of quality.
Fig. 5 is the I-V for the DSSC that the dye-sensitized solar cell anode prepared by embodiment 2,4,6,8,9 is assembled into
Figure.
5th, embodiment
Embodiment 1：
A, doping β-NaYF are prepared4:Er3+,Yb3+TiO2Slurry：
P25 powder 0.5g are taken, are TiO by quality22.5% β-NaYF4:Er3+,Yb3+Up-conversion and TiO2Mixing
And grind uniform mixed material；Meanwhile 0.1mL acetic acid are added into mixed material with 10 μ L addition every time, points 10 times,
3min is ground after adding acetic acid every time；Add 50 μ L deionization into mixed material with 10 μ L addition every time, points 5 times again
Water, 3min is ground after adding deionized water every time；10mL absolute ethyl alcohols are added dropwise into mixed material from as little as more ground again, often add one
Secondary absolute ethyl alcohol grinds 3min；40mL absolute ethyl alcohols are finally added, obtain mixed liquor；
Mixed liquor is moved into beaker, after magnetic agitation 20min, then alternately ultrasonic disperse and magnetic agitation each 20
It is secondary, each 1min；Then 1.8g terpinols, alternately each 20 times of ultrasonic disperse and magnetic agitation are added into mixed liquor, often
Secondary 1min；0.25g ethyl celluloses, alternately each 20 times of ultrasonic disperse and magnetic agitation are added into mixed liquor again, every time
1min；Finally by mixed liquor in Rotary Evaporators rotary distillation 2 hours at 50 DEG C, obtain the doping β available for silk-screen printing-
NaYF4:Er3+,Yb3+TiO2Slurry, it is designated as slurry U1.
B, β-NaYF are prepared4:Er3+,Yb3+@TiO2Composite photo-anode film：
FTO electro-conductive glass is cleaned by ultrasonic 20min with liquid detergent, alcohol, acetone successively, rinsed well with deionized water,
After drying, electro-conductive glass is immersed in 0.5mM TiCl4In the aqueous solution, 30min is kept at 70 DEG C, carries out TiCl4Pretreatment；So
500 DEG C of calcining 30min in Muffle furnace afterwards；Using silk screen print method, slurry U1 made from step a is printed with the silk screen of 400 mesh
Brush on electro-conductive glass, stand 3min, keep 6min at 125 DEG C in drying box, repeat print, stand and dry 4 times；It is placed in horse
Not sintered in stove：150 DEG C of sintering 10min；325 DEG C of sintering 5min, 375 DEG C of sintering 5min, 450 DEG C of sintering 15min, 500 DEG C are burnt
Tie 30min；After being naturally cooling to room temperature, then it is immersed in 0.5mM TiCl4TiCl is carried out in the aqueous solution4Post processing, at 70 DEG C
Keep 30min；Finally it is again placed in Muffle furnace, calcines 30min in 500 DEG C in air atmosphere, formed in FTO conductive glass surfaces
Mass ratio is 2.5% β-NaYF4:Er3+,Yb3+@TiO2Composite photo-anode film.
C, β-NaYF are prepared4:Er3+,Yb3+@TiO2The process of composite light anode is：
Treat that surface is formed with β-NaYF in step b4:Er3+,Yb3+@TiO2The FTO conduction glass of composite photo-anode film
When glass cools to 120 DEG C, it is put into the 50mM ethanol solution of N719 dyestuffs, at room temperature closing immersion 24h；Take out,
The dyestuff of remained on surface is washed away with absolute ethyl alcohol, drying is obtained with rear-earth-doped up-conversion luminescent material and TiO2Composite wood
Expect the dye-sensitized solar cell anode as light anode material, be kept in dark place to be packaged.
N719 dyestuffs are cis-two (different thiocyanate)-two (4- carboxylic acids, 4 '-carboxylic acid tetrabutylammonium bipyridyls) in embodiment
Close the ethanol solution of ruthenium (II).
Embodiment 2：
The preparation method of the present embodiment is with embodiment 1, the difference is that β-NaYF4:Er3+,Yb3+The addition of up-conversion
For TiO2The 5% of quality, the slurry available for silk-screen printing obtained in step a, is designated as slurry U2.
Embodiment 3：
The preparation method of the present embodiment is with embodiment 1, the difference is that β-NaYF4:Er3+,Yb3+The addition of up-conversion
For TiO2The 7.5% of quality, the slurry available for silk-screen printing obtained in step a, is designated as slurry U3.
Embodiment 4：
The preparation method of the present embodiment is with embodiment 1, the difference is that β-NaYF4:Er3+,Yb3+The addition of up-conversion
For TiO2The 10% of quality, the slurry available for silk-screen printing obtained in step a, is designated as slurry U4.
Embodiment 5：
The preparation method of the present embodiment is with embodiment 1, the difference is that β-NaYF4:Er3+,Yb3+The addition of up-conversion
For TiO2The 12.5% of quality, the slurry available for silk-screen printing obtained in step a, is designated as slurry U5.
Embodiment 6：
The preparation method of the present embodiment is with embodiment 1, the difference is that β-NaYF4:Er3+,Yb3+The addition of up-conversion
For TiO2The 15% of quality, the slurry available for silk-screen printing obtained in step a, is designated as slurry U6.
Embodiment 7：
The preparation method of the present embodiment is with embodiment 1, the difference is that β-NaYF4:Er3+,Yb3+The addition of up-conversion
For TiO2The 17.5% of quality, the slurry available for silk-screen printing obtained in step a, is designated as slurry U7.
Embodiment 8：
The preparation method of the present embodiment is with embodiment 1, the difference is that β-NaYF4:Er3+,Yb3+The addition of up-conversion
For TiO2The 20% of quality, the slurry available for silk-screen printing obtained in step a, is designated as slurry U8.
Embodiment 9：
The preparation method of the present embodiment is with embodiment 1, the difference is that being not added with β-NaYF4:Er3+,Yb3+, obtain in step a
Available for the slurry of silk-screen printing, slurry U0 is designated as.
The powder that the step b of embodiment 2,4,6,8, the 9 composite photo-anode films obtained are scraped off is successively in 150
DEG C 10min, 325 DEG C of 5min, 375 DEG C of 5min, 450 DEG C of 15min, 500 DEG C of 30min are sintered, and obtained powder is carried out respectively
XRD analysis, as a result as shown in Figure 1.Peak shown in U is the XRD diffraction maximums of rear-earth-doped up-conversion in Fig. 1；Remaining peak is two
Anatase (PDF No.21-1272) diffraction maximum of titanium oxide.Fig. 1 XRD analysis show the-NaYF containing β4:Er3+,Yb3+For 5-
TiO in 20% photo-anode film2All it is anatase structured, β-NaYF4:Er3+,Yb3+Addition not change TiO2Crystalline substance
Phase.This TiO obtained with SEM (FE-SEM) analysis2The diameter of particle is about that 15-40nm is consistent.
To β-NaYF4:Er3+,Yb3+Under conditions of 980nm laser pump (ing)s, its luminous spectrum is determined, as shown in Figure 2.By Fig. 2
It can be seen that rear-earth-doped upper conversion can launch 510~560nm green glow and 645~670nm feux rouges, wherein appear in 529nm,
Spectral peak at 541nm, 654nm corresponds to Er respectively3+H11/2→4I15/2、4S3/2→4I15/2、4F9/2→4I15/2The transition of energy level.This
A little emission spectras, particularly at 541nm, the light of the most effective wave band utilized with DSSC coincide, therefore it
Addition in dye-sensitized solar cell anode, the utilization rate of light can be strengthened, improve the efficiency of battery.
The U6 that the step a of embodiment 6 is obtained is analyzed on scanning projection electron microscope (TEM), by Fig. 3 a and figure
3b understands β-NaYF4:Er3+,Yb3+It is about 200-600nm blocks in irregular shape for size, its surface covers crystallization ratio
Preferable anatase TiO2Particle, effectively inhibit the compound of up-conversion and electrolyte, reduce dark current, significantly carry
The high efficiency of current density and battery.
Electron microscope (FE- is scanned to the surface of the step b of the embodiment 6 composite photo-anode films obtained
SEM), as a result as shown in Figure 4.Analyze obtained four layers of doping β-NaYF of printing4:Er3+,Yb3+TiO2Slurry, the film after sintering
About 8.33 μm of thickness.Composite photo-anode film relative coarseness, nano particle overall distribution are uniform as shown in Figure 4, and are formed
The network-like structure being connected to each other, in bigger block (for β-NaYF4:Er3+,Yb3+) around be distributed with it is smaller (for
TiO2) particle, the little particle not only adds β-NaYF4:Er3+,Yb3+With TiO2Effective connection between particle, while
Make β-NaYF4:Er3+,Yb3+Combination between electro-conductive glass is more firm；Larger block can play in light anode
Light scattering acts on.
Dye-sensitized solar cells light anode encapsulation prepared by embodiment 1-9 is prepared into DSSC, had
Body step is as follows：
Punch, clean on FTO electro-conductive glass, drying is stand-by.One layer of platinum slurry is printed on electro-conductive glass, in Muffle furnace
Middle sintering, keep 30min at 410 DEG C, obtain platinum to electrode.β-the NaYF respectively prepared by embodiment 1-94:Er3+,Yb3+@
TiO2Composite light anode and platinum are folded to electrode pair, the three-back-shaped heat-sealing film of upper 60 μ m-thick are padded between two electrodes, with heat-sealing
Machine carries out packaging by hot pressing at 130 DEG C, and hot pressing time is 20 seconds.By injecting (the 0.045M of electrolyte 1 to the aperture on electrode
LII, 0.032M I2, 0.5M TBP, volume ratio is 85/15 acetonitrile/valeronitrile solution), reusable heat sealer and slide seal small
Hole, battery is assembled into, obtains β-NaYF4:Er3+,Yb3+Addition is respectively 0%, 2.5%, 5%, 7.5%, 10%, 12.5%,
15%, 17.5% and 20% dye-sensitized solar cells, Cell 0, Cell 1, Cell 2, Cell3, Cell are designated as respectively
4, Cell 5, Cell 6, Cell 7, Cell 8.
Using Keithley2400 digital sourcemeters and solar simulator (light source 500W xenon lamp, AM=1.5, simulated light
Exposure intensity is 100W/m2) different battery Cell 0-8 I-V indicatrixes that test obtains, it thus can obtain opening for battery
Road voltage Voc, short-circuit current density Jsc, fill factor, curve factor FF, energy conversion efficiency η, it the results are shown in Table 1 and Fig. 5.
Table 1 shows, with β-NaYF4:Er3+,Yb3+The increase of content, open-circuit voltage slightly increase, and current density is substantially gradual
Increase, directly results in significantly increasing for battery efficiency.When doping is 15%, maximum short circuit current density reaches
19.82mA·cm-2, photoelectric transformation efficiency 9.37%.When doping is more than 15%, short-circuit current density is not further added by, efficiency
Also it is not further added by.
Table 1 is contrasted as the photoelectric properties of the DSSC packaged by the light anode of each embodiment
Claims (4)
- A kind of 1. dye-sensitized solar cell anode, it is characterised in that：It is with rear-earth-doped up-conversion luminescent material and TiO2 Composite as light anode material；The rear-earth-doped up-conversion luminescent material is β-NaYF4:Er3+,Yb3+Upper conversion material Material；In the composite, β-NaYF4:Er3+,Yb3+For size 200-600nm blocks in irregular shape, its surface Cover diameter 15-40nm anatase TiO2Particle；The preparation method of described dye-sensitized solar cell anode, it is to carry out as follows：A, doping β-NaYF are prepared4:Er3+,Yb3+TiO2Slurry：By β-NaYF4:Er3+,Yb3+Up-conversion is mixed with titanium dioxide and ground uniformly, sequentially adds acetic acid and deionization Water, stir；Sequentially add absolute ethyl alcohol, terpinol and ethyl cellulose, last magnetic agitation, ultrasonic disperse, revolving, Obtain doping β-NaYF4:Er3+,Yb3+TiO2Slurry；B, β-NaYF are prepared4:Er3+,Yb3+@TiO2Composite photo-anode filmFTO electro-conductive glass is immersed in TiCl4TiCl is carried out in the aqueous solution4Pretreatment, then 500 DEG C of calcinings in Muffle furnace 30min；β-NaYF will be adulterated using silk screen print method made from step a4:Er3+,Yb3+TiO2Slurry is printed in FTO conduction glass On glass, stand, dry, then put and calcine 30min at 500 DEG C in Muffle furnace；After being naturally cooling to room temperature, then it is immersed in TiCl4TiCl is carried out in the aqueous solution4Post processing, is again placed in calcining 30min at 500 DEG C in Muffle furnace after taking-up, i.e., is led in FTO Electric glass surface forms β-NaYF4:Er3+,Yb3+@TiO2Composite photo-anode film；C, dye-sensitized solar cell anode is preparedSurface is formed with β-NaYF in stepb4:Er3+,Yb3+@TiO2The FTO electro-conductive glass drop of composite photo-anode film When temperature is to 100-120 DEG C, it is immersed in N719 dyestuffs, is rinsed, dried up with absolute ethyl alcohol after taking-up, that is, obtains with rear-earth-doped Changing luminous material and TiO2Dye-sensitized solar cell anode of the composite as light anode material.
- 2. dye-sensitized solar cell anode according to claim 1, it is characterised in that：In the composite Rear-earth-doped up-conversion luminescent material accounts for TiO2The 2.5~20% of quality.
- 3. dye-sensitized solar cell anode according to claim 1, it is characterised in that：Titanium dioxide in step a, acetic acid, deionized water, absolute ethyl alcohol, the amount ratio of terpinol and ethyl cellulose are：0.5g： 0.1mL：50μL：50mL：1.8g：0.25g；β-the NaYF4:Er3+,Yb3+The quality of up-conversion accounts for titanium dioxide quality 2.5~20%.
- 4. the preparation method of the dye-sensitized solar cell anode described in a kind of claim 1, it is characterised in that be specifically Carry out as follows：A, doping β-NaYF are prepared4:Er3+,Yb3+TiO2Slurry：P25 powder 0.5g are taken, by β-NaYF4:Er3+,Yb3+Up-conversion mixes with P25 powder and grinds uniform mixed material；With 10 μ L addition, point 10 addition 0.1mL acetic acid into mixed material every time, 3min is ground after adding acetic acid every time；Again with Every time 10 μ L addition, 50 μ L deionized waters are added into mixed material points for 5 times, ground after adding deionized water every time 3min；10mL absolute ethyl alcohols are added dropwise into the mixed material again, and grinds and stirs；Finally again into the mixed material 40mL absolute ethyl alcohols are added, obtain mixed liquor；The mixed liquor is moved into beaker, magnetic agitation 20min, then alternately each 20 times of ultrasonic disperse and magnetic agitation, Each 1min；Then 1.8g terpinols, alternately each 20 times of ultrasonic disperse and magnetic agitation are added into the mixed liquor, often Secondary 1min；0.25g ethyl celluloses, alternately each 20 times of ultrasonic disperse and magnetic agitation are added into the mixed liquor again, Each 1min；Finally by mixed liquor in Rotary Evaporators rotary distillation 1.5-2 hours at 50-55 DEG C, obtain doping β- NaYF4:Er3+,Yb3+TiO2Slurry；B, β-NaYF are prepared4:Er3+,Yb3+@TiO2Composite photo-anode filmFTO electro-conductive glass is immersed in 0.5mM TiCl4In the aqueous solution, 70 DEG C of holding 30min, TiCl is carried out4Pretreatment, then 500 DEG C of calcining 30min in Muffle furnace；Using silk screen print method, with the silk screen of 300-450 mesh will be adulterated made from step a β- NaYF4:Er3+,Yb3+TiO2Slurry is printed on FTO electro-conductive glass, is stood 3min, 125 DEG C of dry 6min, is repeated print, be quiet Put and dry, the number repeated is according to required β-NaYF4:Er3+,Yb3+@TiO2The thickness of composite photo-anode film comes Determine；Then put and calcine 30min at 500 DEG C in Muffle furnace；After being naturally cooling to room temperature, then it is immersed in 0.5mM TiCl4It is water-soluble In liquid, 30min is kept at 70 DEG C, carries out TiCl4Post processing, is again placed in calcining 30min at 500 DEG C in Muffle furnace after taking-up, β-NaYF are formed in FTO conductive glass surfaces4:Er3+,Yb3+@TiO2Composite photo-anode film；C, dye-sensitized solar cell anode is preparedSurface is formed with β-NaYF in stepb4:Er3+,Yb3+@TiO2The FTO electro-conductive glass drop of composite photo-anode film When temperature is to 100-120 DEG C, it is put into the ethanol solution for the N719 dyestuffs that concentration is 50mM and soaks 12-24 hours, after taking-up The dyestuff of remained on surface is washed off with absolute ethyl alcohol, is finally dried up, that is, obtain with rear-earth-doped up-conversion luminescent material with TiO2Dye-sensitized solar cell anode of the composite as light anode material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105514279B (en) * | 2016-01-26 | 2018-03-02 | 西安交通大学 | A kind of honeycomb sandwich Ca-Ti ore type solar cell and preparation method thereof |
| CN106449124B (en) * | 2016-12-20 | 2019-02-26 | 哈尔滨工业大学 | TiO2Microballoon and its TiO2The preparation method of base light anode dye-sensitized solar cells |
| CN107633949A (en) * | 2017-08-10 | 2018-01-26 | 广东工业大学 | A kind of erbium list mixes C 12 A 7 up-conversion dopant dye sensitization light anode and its preparation method and application |
| CN109603920B (en) * | 2018-12-18 | 2020-04-07 | 同济大学 | Visible light excited cellulose-TiO2Composite photocatalyst |
| CN111081478B (en) * | 2019-12-31 | 2022-05-17 | 黑龙江大学 | Rare earth trimesic acid complex/yttrium oxide/titanium dioxide composite photo-anode and construction method thereof |
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