CN107195462B - A kind of preparation method and applications of photosensitizer nanocomposite - Google Patents
A kind of preparation method and applications of photosensitizer nanocomposite Download PDFInfo
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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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
A kind of preparation method and applications of photosensitizer nanocomposite, belong to technical field of solar batteries, and the present invention has synthesized Au@SiO using hydro-thermal method2@CeO2: Yb/Er nanocomposite, the advantageous property of the up-conversion luminescence of the plasma resonance effect of noble metal and rare earth ion is combined, realize being kept completely separate for electronics and electrolyte, to the contact for reducing electronics with restoring electricity pair in solution, it can reduce dark current, be conducive to the open-circuit voltage for promoting battery, increase electric current output and improve output characteristics, the electronics for as far as possible inspiring all dyestuffs moves to rapidly conductive layer and is collected into external circuit, and improves the utilization rate of light.Synthetic material structure structure novel, for partial size in 100nm or so, method is simple and convenient, and crystal form is preferable.
Description
Technical field
The invention belongs to technical field of solar batteries, and in particular to the system of dye-sensitized solar cell anode material
Preparation Method.
Background technique
The existence of the mankind and the development of social economy be unable to do without the energy, and new energy especially can be with regenerated green energy resource
Development and utilization is to be related to the significant problem of a national final and decisive juncture, and the environment as caused by the application of a large amount of fossil fuels is dirty
Dye with ecological disruption and greenhouse effects, be it is obvious to all, also result in the great attention of countries in the world, while in new energy
A large amount of manpower and material resources have been put into terms of the R and D in source.Solar energy is a kind of pollution-free and inexhaustible energy,
It is about every year 5.4 × 10 to the energy of earth irradiation24J is tens of thousands of times that the mankind consume gross energy every year.
The primary study object of transformation and the storage of solar energy first is that solar battery.The broad-band gaps such as titanium dioxide are partly led
The ability that body itself captures sunlight is excessively poor, but by Dye Adsorption to semiconductor surface appropriate, by means of dyestuff to can
Light-exposed strong absorption, but dye-sensitized solar cells cannot effectively absorb near-infrared and infrared light, limit the light of battery
Son-electronics transfer efficiency, as the dye photoactivation agent of battery core component part, the long wavelength threshold of absorption spectrum does not surpass generally
750 nm are crossed, and have 55% or more the near infrared region being distributed in outside 750 nm in solar spectrum, so that dye-sensitized solar cells
Light anode can not overall absorption to full wave solar energy.So thinking fundamentally to improve dye-sensitized solar cells
Efficiency must just expand the spectral response range of battery, have special surface plasmon resonance effect that can mention using noble metal
Near infrared light is converted to the effect of visible light by high up-conversion luminescent material.Therefore, studying one kind has special construction and incites somebody to action
Up-conversion is applied to optical anode material and has important application meaning to dye-sensitized solar cells.
The dye-sensitized solar cells prior art also suffers from certain drawbacks: stability needs to improve, efficiency need after
It is continuous to improve, apply the semiconductor material in dye-sensitized solar cells also limited.
Summary of the invention
It is easy to operate the invention aims to provide a kind of simple process, up-conversion fluorescence can be effectively improved, from
And improve the Au@SiO of solar cell photoelectric transfer efficiency2@CeO2: the preparation method of Yb/Er nanocomposite.
The present invention the following steps are included:
1) by 100 DEG C of ultrapure water and HAuCl4Aqueous solution and trisodium citrate aqueous solution mix back flow reaction, and reflux is anti-
After answering, reaction solution is cooled to room temperature；
2) above-mentioned reaction solution and polyvinylpyrrolidone (PVP) aqueous solution are stirred, are then centrifuged for, obtain solid phase
Aurosol in deionized water by aurosol dispersion obtains the water dispersant of aurosol；
3) under ultrasound condition, by the water dispersant of aurosol and ammonium hydroxide, H2O, ethyl alcohol mixes, and adds under stirring condition
TEOS after stirring, obtains solid phase and successively washes, dries through washing, alcohol, obtain Au SiO2；
4) by Au@SiO2, cerous nitrate aqueous solution, ytterbium nitrate aqueous solution, erbium nitrate aqueous solution and hexa (HMT)
Hydro-thermal reaction is carried out after ultrasonic mixing；
5) hydro-thermal reaction terminates, and reaction solution is centrifuged, and takes solid phase drying, calcining, obtains Au@SiO2@CeO2: Yb/Er nanometers
Composite material.
In the present invention, trisodium citrate is by AuCl4 -It is reduced into Au nano particle, PVP prevents Au nanometers as protective agent
Grain aggregation.SiO2Formation is the process of hydrolysis and the condensation of TEOS, kinetics simple equation are as follows:
Si—OR + HOH → Si—OH + ROH
Si—OR + HO—Si → Si—O—Si + ROH
Si—OH + HO—Si → Si—O—Si + HOH
Main raw material(s) of the present invention is widely used rare earth oxide, has synthesized Au@SiO using hydro-thermal method2@CeO2:
Yb/Er nanocomposite, by the advantageous property of the up-conversion luminescence of the plasma resonance effect of noble metal and rare earth ion
Combine, realize being kept completely separate for electronics and electrolyte, thus reduce electronics with the contact of electricity pair is restored in solution, can reduce
Dark current is conducive to the open-circuit voltage for promoting battery, increases electric current output and improves output characteristics, as far as possible swashs all dyestuffs
The electronics of sending moves to rapidly conductive layer and is collected into external circuit, and improves the utilization rate of light.Synthetic material structure knot
Structure is novel, and for partial size in 100nm or so, method is simple and convenient, and crystal form is preferable.
Further, in step 1) of the present invention, the HAuCl4HAuCl in aqueous solution4And trisodium citrate aqueous solution
The molar ratio of middle trisodium citrate is 100: 63.Using the ratio, trisodium citrate is just by AuCl4 -It is reduced into Au nanometers
Particle.
In the step 3), the volume ratio that feeds intake of aurosol and TEOS are 4: 1 in the water dispersant of the aurosol.This
Feed ratio can make the thickness of silica best, optimum thickness 30nm, and fluorescence enhancement effect is best.
In the step 4), the cerous nitrate aqueous solution, ytterbium nitrate aqueous solution, erbium nitrate aqueous solution are according to the volume ratio that feeds intake
It is 96.7: 0.3: 3, the Au@SiO2With the mixing being made of cerous nitrate aqueous solution, ytterbium nitrate aqueous solution and erbium nitrate aqueous solution
The feed ratio of solution is 8mg: 5mL.This feed ratio is coated on ceria preferably outside silica, and pattern is equal
One.
In the step 4), the environment temperature of the hydro-thermal reaction is 180 DEG C, the material grain synthesized under this hydrothermal temperature
Diameter is uniform, and covered effect is best.
In the step 5), the centrifugation rate is 5000r/min, and calcination temperature is 1100 DEG C, calcination time 2h.From
Heart rate is 5000r/min, preferably then synthesis is separated drying at material washes clean, calcination temperature is fluorescence at 1100 DEG C
Effect is most strong.
Another object of the present invention is then to propose the composite material of above method preparation in dye-sensitized solar cells light sun
Application in extremely.
Nano titania slurry is first coated in FTO glass surface, forms the titanium deoxide slurry bed of material, then will be described compound
Material is coated in nano titania slurry layer surface using method for printing screen, after 450 DEG C of high-temperature calcinations, under the conditions of being protected from light
Sealed soak after N719 dyestuff, rinsed well with dehydrated alcohol by taking-up, obtains dye-sensitized solar cell anode material.
The present invention, using each layer of screen-printing deposition, reduces surface defect using FTO glass as carrier, and can obtain
Lesser size has large specific surface area, is adsorbed to effectively improve dye molecule in photoanode surface.Institute of the present invention
The dye-sensitized solar cell anode material photoelectric properties for stating preparation are good, the enhancing of up-conversion fluorescence effect, photoelectric conversion
Efficiency improves 17.8% or more than pure titinium dioxide, and hydro-thermal method synthesis, preparation process is simple, and easy to operate, raw material is cheap, system
Standby nanocomposite structure novel out, is suitable for area of solar cell.
In addition, the grain diameter of nano-titanium dioxide described above is ± 10 nm of 25 nm；The nano titanium dioxide paste
The number of plies of material coating is 6~8 layers, the Au@SiO2@CeO2: the number of plies of Yb/Er nanocomposite coating is 1~2 layer.This
The film of the particle composition of titanium dioxide in particle size range has 50~60% empty structure, and surface area ratio planar film is big
Nearly 2000 times.And the method for multiple coating can make semiconductor titanium dioxide thickness increase, and have big specific surface area to adsorb
Enough dyestuffs will generate a large amount of light induced electron in this way, and eventually leading to battery has biggish short circuit current.
The sealed soak time is 48h, is attracted to dyestuff more on semiconductor material, if soaking time is too long
It will lead to film layer to fall off, influence battery efficiency.
Detailed description of the invention
Fig. 1 is the Au@SiO that the present invention synthesizes2@CeO2: the Flied emission transmission electron microscope TEM figure of Yb/Er nanocomposite.
Fig. 2 is the Au@SiO that the present invention synthesizes2@CeO2: the field emission scanning electron microscope SEM figure of Yb/Er nanocomposite.
Fig. 3 is the Au@SiO that the present invention synthesizes2@CeO2: Yb/Er nanocomposite, Au@CeO2: Yb/Er and Au@SiO2
X-ray diffraction XRD diagram.
Fig. 4 is the Au@SiO that the present invention synthesizes2@CeO2: Yb/Er nanocomposite, SiO2@CeO2: Yb/Er and Au@
SiO2Up-conversion fluorescence spectrogram.
Fig. 5 is the I-V characteristic curve graph of each dye-sensitized solar cells.
Specific embodiment
One, Au@SiO is prepared2@CeO2: Yb/Er nanocomposite:
Example 1:
(1) it takes 30mL ultrapure water to be placed in 100mL single necked round bottom flask to be heated to boiling, being separately added into concentration is 180mM
HAuCl4Aqueous solution 0.4mL and concentration are 38mM trisodium citrate aqueous solution 3mL, reflux time 0.5h.
(2) after being cooled to room temperature above-mentioned reaction solution, polyvinylpyrrolidone (PVP) water that concentration is 1.28mM is added
Solution 150uL, is stirred to react 12h.It negates mixture after answering and is placed in revolving speed to be centrifuged in the centrifuge of 11000r/min three times, close
And solid phase (i.e. aurosol) that centrifuging and taking obtains and be dispersed in 8mL deionized water, obtain the water dispersant of aurosol.
(3) it takes the water dispersant of 2mL aurosol to be placed in 50 mL single necked round bottom flask, after ultrasonic 5min, adds ammonium hydroxide
After 1mL, ultrapure water 6mL, ethyl alcohol 10mL are placed in stirring at room temperature, the TEOS of 0.5 mL, low whipping speed 700r/ are added
After reacting 6h under the conditions of min, each solid phase is taken to be washed, alcohol is washed each three times, drying obtains the Au@SiO of 50mg2。
(4) configure sour cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution: taking concentration is sour cerium aqueous solution, the nitric acid of 0.1M
Ytterbium aqueous solution and erbium nitrate aqueous solution are mixed with the volume ratio of 96.7:0.3:3, and it is water-soluble to obtain sour cerium, ytterbium nitrate and erbium nitrate mixing
Liquid.
Take Au@SiO2Cerous nitrate, ytterbium nitrate and erbium nitrate mixed aqueous solution, the 30mg hexa-methylene four of sample 8mg and 5mL
Amine (HMT) mixes, and after ultrasonic disperse 30min, moves to hydrothermal reaction kettle and carries out hydro-thermal reaction, react 4h under the conditions of 180 DEG C.
(5) hydro-thermal reaction terminates, and three times with 5000r/min centrifugal treating by reaction solution, it is dry to merge the solid phase that centrifuging and taking obtains
Dry 12h calcines 2h under the conditions of being placed on 1100 DEG C, obtains Au@SiO2@CeO2: Yb/Er nanocomposite 0.1g.
Example 2:
(1) it takes 60mL ultrapure water to be placed in 200mL single necked round bottom flask to be heated to boiling, being separately added into concentration is 180mM
HAuCl4Aqueous solution 0.8mL and concentration are 38mM trisodium citrate aqueous solution 6mL, reflux time 0.5h.
(2) above-mentioned reaction solution is cooled to room temperature, it is water-soluble that the polyvinylpyrrolidone (PVP) that concentration is 1.28mM is added
Liquid 300uL, mixing time 12h.It negates mixture after answering and is placed in revolving speed to be centrifuged in the centrifuge of 11000r/min three times, close
And the solid phase that obtains of centrifuging and taking and be dispersed in 16mL deionized water, obtain the water dispersant of aurosol.
(3) water dispersant of 4mL aurosol is taken to be placed in 50 mL single necked round bottom flask, ultrasonic 5min adds ammonium hydroxide
After 2mL, ultrapure water 12mL, ethyl alcohol 20mL are placed in stirring at room temperature, the TEOS of 1 mL is added, mixing speed is 700r/min's
After speed stirs 6h, each solid phase is taken to be washed, alcohol is washed each three times, drying obtains the Au@SiO of 100mg2。
(4) configure sour cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution: taking concentration is sour cerium aqueous solution, the nitric acid of 0.1M
Ytterbium aqueous solution and erbium nitrate aqueous solution are mixed with the volume ratio of 96.7:0.3:3, and it is water-soluble to obtain sour cerium, ytterbium nitrate and erbium nitrate mixing
Liquid.
Take Au@SiO2Sample 16mg and 10mL acid cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution, 60mg hexa
(HMT) it mixes, after ultrasonic disperse 30min, moves to hydrothermal reaction kettle and carry out hydro-thermal reaction, react 4h under the conditions of 180 DEG C.
(5) hydro-thermal reaction terminates, and reaction solution is centrifuged to the dry 12h of solid phase for merging that centrifuging and taking obtains three times with 5000r/min
2h is calcined under the conditions of being placed on 1100 DEG C, obtains Au@SiO2@CeO2: Yb/Er nanocomposite 0.2g.
Example 3:
(1) configure sour cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution: taking concentration is sour cerium aqueous solution, the nitric acid of 0.1M
Ytterbium aqueous solution and erbium nitrate aqueous solution are mixed with the volume ratio of 96.7:0.3:3, and it is water-soluble to obtain sour cerium, ytterbium nitrate and erbium nitrate mixing
Liquid.
Take SiO2Sample 8mg and 5mL acid cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution, 30mg hexa (HMT)
It mixes, after ultrasonic disperse 30min, moves to hydrothermal reaction kettle and carry out hydro-thermal reaction, react 4h under the conditions of 180 DEG C.
(2) hydro-thermal reaction terminates, and reaction solution is centrifuged to the dry 12h of solid phase for merging that centrifuging and taking obtains three times with 5000r/min
2h is calcined under the conditions of being placed on 1100 DEG C, takes drying sample to impregnate 3h with the sodium hydroxide solution that concentration is 0.1M, obtains CeO2:
Yb/Er nanocomposite 0.1g.
Example 4:
(1) it takes 30mL ultrapure water to be placed in 100mL single necked round bottom flask to be heated to boiling, being separately added into concentration is 180mM
HAuCl4Aqueous solution 0.4mL and concentration are 38mM trisodium citrate aqueous solution 3mL, reflux time 0.5h.
(2) after being cooled to room temperature above-mentioned reaction solution, polyvinylpyrrolidone (PVP) water that concentration is 1.28mM is added
Solution 150uL, is stirred to react 12h.It negates mixture after answering and is placed in revolving speed to be centrifuged in the centrifuge of 11000r/min three times, close
And the solid phase that obtains of centrifuging and taking and be dispersed in 8mL deionized water, obtain the water dispersant of aurosol.
(3) it takes the water dispersant of 2mL aurosol to be placed in 50 mL single necked round bottom flask, after ultrasonic 5min, adds ammonium hydroxide
After 1mL, ultrapure water 6mL, ethyl alcohol 10mL are placed in stirring at room temperature, the TEOS of 0.5 mL, low whipping speed 700r/ are added
After reacting 6h under the conditions of min, each solid phase is taken to be washed, alcohol is washed each three times, drying obtains the Au@SiO of 50mg2。
(4) configure sour cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution: taking concentration is sour cerium aqueous solution, the nitric acid of 0.1M
Ytterbium aqueous solution and erbium nitrate aqueous solution are mixed with the volume ratio of 96.7:0.3:3, and it is water-soluble to obtain sour cerium, ytterbium nitrate and erbium nitrate mixing
Liquid.
Take Au@SiO2Sour cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution, the 30mg hexa of sample 8mg and 5mL
(HMT) it mixes, after ultrasonic disperse 30min, moves to hydrothermal reaction kettle and carry out hydro-thermal reaction, react 4h under the conditions of 180 DEG C.
(5) hydro-thermal reaction terminates, and three times with 5000r/min centrifugal treating by reaction solution, it is dry to merge the solid phase that centrifuging and taking obtains
Dry 12h calcines 2h under the conditions of being placed on 1100 DEG C, obtains Au@SiO2@CeO2: Yb/Er nanocomposite 0.1g.
Composite material is impregnated with the sodium hydroxide solution that concentration is 0.1M, obtains Au@CeO2: Yb/Er nano material
0.5g。
Two, Au@SiO2@CeO2: the characterization of Yb/Er nanocomposite:
Fig. 1 illustrates Au@SiO prepared by the present invention2@CeO2: the Flied emission transmission electron microscope TEM of Yb/Er nanocomposite
Figure, as can be seen from the figure this material is spherical shape, and partial size is in 100nm nanocomposite below, and partial size is than more uniform.
Fig. 2 illustrates Au@SiO prepared by the present invention2@CeO2: the field emission scanning electron microscope SEM of Yb/Er nanocomposite
Figure, as can be seen from the figure this material morphology is uniform, is uniform spherical structure.
Fig. 3 illustrates Au@SiO prepared by the present invention2@CeO2: Yb/Er nanocomposite, Au@CeO2: Yb/Er and Au@
SiO2X-ray diffraction XRD diagram.Wherein curve A is Au@SiO2The XRD curve of nanosphere, curve B are Au@SiO2@CeO2:Yb/
The XRD curve of Er nanocomposite, figure C are Au@CeO2: the XRD curve of Yb/Er nanocomposite.
By comparing XRD standard card PDF#33-0831, this product X RD map is consistent with standard spectrum, (111), (200),
(220), (311), (222), (400), (331) crystallographic plane diffraction peak match with the standard diffraction peak of ceria, illustrate this material
Material is ceria.Consistent with standard spectrum by comparison XRD standard card PDF#47-1144 this product X RD map, (011) is brilliant
Face diffraction maximum matches with the standard diffraction peak of silica, illustrates that this material contains silica.By comparing XRD standard card
Piece PDF#04-0784 this product X RD map is consistent with standard spectrum, (111) (200) (220) crystallographic plane diffraction peak and gold nanoparticle
Standard diffraction peak match, illustrate that this material contains gold nano grain.
Fig. 4 illustrates Au@SiO prepared by the present invention2@CeO2: the different SiO of Yb/Er nanocomposite2Thickness and
CeO2: the up-conversion fluorescence spectrogram that Yb/Er is inquired into as fluorescence intensity, thickness be respectively 0nm, 10nm, 20nm, 30nm, 40nm,
50nm.It can be seen that silicon dioxide thickness in 30nm by up-conversion fluorescence spectrogram, up-conversion fluorescence effect is most strong.Explanation
When the spacing distance of noble metal and illuminophore is 30nm, composite material light utilization efficiency highest.
Three, dye-sensitized solar cell anode material is prepared:
1, substrate is cleaned:
FTO glass is cut into the size of long 5 cm, wide 10 cm, is sequentially surpassed in acetone, ethyl alcohol, deionized water respectively
Sound cleans 20 min, and taking-up after having cleaned, baking oven is dried for standby.
2、TiO2Slurry preparation: taking 1g titanium dioxide, is dispersed in stirring plus ultrasonic one day night in 20 mL dehydrated alcohols,
Take 2mL(5% ethyl cellulose terpinol) above-mentioned reaction solution is added, it stirs for 24 hours, then 70 DEG C of rotary evaporations, by ethyl alcohol therein
Evaporating completely is fallen, and uniform and stable nano titania slurry is obtained.
Present example:
Using silk-screen printing, nano titania slurry is printed on FTO glass, drying at room temperature is put into tube furnace
Calcining is raised to 450 DEG C with the heating rate of 10 DEG C/min, calcines 30 min, Temperature fall.In this approach, it applies one layer and burns one layer,
It is painted with 6~8 layers.Then silk-screen printing, then the Au@SiO that embodiment 1 is prepared are used2@CeO2: Yb/Er nanocomposite
It is coated in the upper surface of the titanium deoxide slurry bed of material, is subsequently placed in high-temperature calcination stove, with heating rate for 10 DEG C/min, by furnace temperature liter
To 450 DEG C, taken out after 30min high-temperature calcination.Sample is immersed in N719 dyestuff again, is placed under the conditions of being protected from light after sealing
After 48h, taking-up is rinsed well with dehydrated alcohol, obtains dye-sensitized solar cell anode material.
Comparison example 1:
Using silk-screen printing, nano titania slurry is printed on FTO glass, drying at room temperature is put into tube furnace
Calcining is raised to 450 DEG C with the heating rate of 10 DEG C/min, calcines 30 min, Temperature fall.In this approach, it applies one layer and burns one layer,
It is painted with 6~8 layers.It is then placed in N719 dyestuff and impregnates 48 h, rinsed well with dehydrated alcohol, obtain dye-sensitized solar cells
Light anode.
Comparison example 2:
Using silk-screen printing, nano titania slurry is printed on FTO glass, drying at room temperature is put into tube furnace
Calcining is raised to 450 DEG C with the heating rate of 10 DEG C/min, calcines 30 min, Temperature fall.In this approach, it applies one layer and burns one layer,
It is painted with 6~8 layers.Then silk-screen printing, then the SiO that embodiment 3 is prepared are used2@CeO2: Yb/Er is coated in titania slurry
The upper surface of layer, is subsequently placed in high-temperature calcination stove, with heating rate for 10 DEG C/min, furnace temperature is risen to 450 DEG C, through 30min
It is taken out after high-temperature calcination.Sample is immersed in N719 dyestuff again, after placing 48h under the conditions of being protected from light after sealing, nothing is used in taking-up
Water-ethanol is rinsed well, and dye-sensitized solar cell anode material is obtained.
Four, performance test:
Dye-sensitized solar cell anode made from the above present example and comparative example 1,2 is used as DSSC step
As follows: assembled battery first uses platinum electrode up by the conduction of working electrode to lead with to electrode is directed downwardly to electrode
Electric face is picked up to press from both sides into sandwich structure, then inject electrolyte between electrodes, carry out dye sensitization of solar electricity with clip
The I-V curve in pond is tested.
In Fig. 5, curve a is represented: comparison example 1 obtains dye-sensitized solar cell anode material I-V characteristic curve
Figure.
Curve b is represented: comparison example 2 obtains dye-sensitized solar cell anode material I-V characteristic curve graph.
Curve c is represented: present example obtains dye-sensitized solar cell anode material I-V characteristic curve graph.
Following table is the photoelectric properties contrast table of DSSC packaged by the light anode as prepared by each example:
| Short-circuit current density (mA/ cm2) | Voltage (V) | Impact factor | Photoelectric conversion efficiency (%) | |
| Comparison example 1 | 13.96 | 0.70 | 0.64 | 6.3 |
| Comparison example 2 | 14.45 | 0.69 | 0.6 | 6.86 |
| Present example | 15.45 | 0.70 | 0.69 | 7.42 |
From the data in table 1 and Fig. 5 it is found that using dye-sensitized solar cell anode conduct made from above each example
Working electrode is assembled into DSSC.Compared with comparison example 1,2, the short-circuit current density (Jsc) and photoelectric conversion of present example
Efficiency (η) is all enhanced.Short-circuit current density (Jsc) is up to 15.45 mA/cm2, impact factor (FF) reaches 69%,
Photoelectric conversion efficiency (η) is up to 7.42%, and the dominance structure of this material is novel, and similar structures are not reported temporarily, noble metal
Surface plasma resonance significantly improves the non-radiative decay rate between fluorogen, so that fluorescent effect enhances, improves photoelectricity and turns
Change efficiency.
These are the results showed that using Au@SiO made of the method for the present invention2@CeO2: Yb/Er nanocomposite energy
Effectively increase photoelectric conversion efficiency.
Claims (6)
1. a kind of preparation method of photosensitizer nanocomposite, it is characterised in that the following steps are included:
1) by 100 DEG C of ultrapure water and HAuCl4Aqueous solution and trisodium citrate aqueous solution mix back flow reaction, and back flow reaction terminates
Afterwards, reaction solution is cooled to room temperature；The HAuCl4HAuCl in aqueous solution4With trisodium citrate in trisodium citrate aqueous solution
Molar ratio be 100: 63；
2) above-mentioned reaction solution is stirred with aqueous povidone solution, is then centrifuged for, obtain solid phase aurosol, it will
Aurosol disperses in deionized water, to obtain the water dispersant of aurosol；
3) under ultrasound condition, by the water dispersant of aurosol and ammonium hydroxide, H2O, ethyl alcohol mixes, and adds TEOS under stirring condition, stirs
After mixing, obtains solid phase and successively wash, dry through washing, alcohol, obtain Au SiO2；
4) by Au@SiO2, cerous nitrate aqueous solution, ytterbium nitrate aqueous solution, erbium nitrate aqueous solution and hexa (HMT) ultrasound
Hydro-thermal reaction is carried out after mixing；
5) hydro-thermal reaction terminates, and reaction solution is centrifuged, and takes solid phase drying, calcining, and the centrifugation rate is 5000r/min, calcining
Temperature is 1100 DEG C, calcination time 2h；Obtain Au@SiO2@CeO2: Yb/Er nanocomposite.
2. the preparation method of material according to claim 1, it is characterised in that in the step 3), the moisture of the aurosol
The volume ratio that feeds intake of aurosol and TEOS are 4: 1 in powder.
3. the preparation method of material according to claim 1, it is characterised in that in the step 4), the cerous nitrate is water-soluble
Liquid, ytterbium nitrate aqueous solution, erbium nitrate aqueous solution are 96.7: 0.3: 3 according to the volume ratio that feeds intake, the Au@SiO2With by cerous nitrate
The feed ratio of the mixed solution of aqueous solution, ytterbium nitrate aqueous solution and erbium nitrate aqueous solution composition is 8mg: 5mL.
4. according to claim 1 or the preparation method of 3 materials, it is characterised in that in the step 4), the hydro-thermal reaction
Environment temperature be 180 DEG C.
5. application of the composite material of method preparation as described in claim 1 in dye-sensitized solar cell anode,
It is characterized in that: nano titania slurry being first coated in FTO glass surface, form the titanium deoxide slurry bed of material, then will be described multiple
Condensation material is coated in nano titania slurry layer surface using method for printing screen and is protected from light condition after 450 DEG C of high-temperature calcinations
Lower sealed soak after N719 dyestuff 48h, rinsed well with dehydrated alcohol, obtains dye-sensitized solar cell anode by taking-up
Material.
6. application according to claim 5, it is characterised in that: the grain diameter of the nano-titanium dioxide be 25 nm ±
10 nm；The number of plies of the nano titania slurry coating is 6~8 layers, the Au@SiO2@CeO2: the nano combined material of Yb/Er
The number of plies of material coating is 1~2 layer.
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