CN107195462A - A kind of preparation method and applications of photosensitizer nano composite material - Google Patents
A kind of preparation method and applications of photosensitizer nano composite material Download PDFInfo
- Publication number
- CN107195462A CN107195462A CN201710408573.1A CN201710408573A CN107195462A CN 107195462 A CN107195462 A CN 107195462A CN 201710408573 A CN201710408573 A CN 201710408573A CN 107195462 A CN107195462 A CN 107195462A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- sio
- preparation
- aurosol
- nano
- 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.)
- Granted
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
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- 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
A kind of preparation method and applications of photosensitizer nano composite material, belong to technical field of solar batteries, and the present invention has synthesized Au@SiO using hydro-thermal method2@CeO2:Yb/Er nano composite materials, 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, so as to reduce electronics and in solution reduce electricity to contact, dark current can be reduced, be conducive to being lifted the open-circuit voltage of battery, the output of increase electric current and improvement 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 is novel, and particle diameter is in 100nm or so, and method is simple and convenient, and crystal formation 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 technology
The existence of the mankind and the development of social economy be unable to do without the energy, the green energy resource that new energy can especially regenerate
Development and utilization is the significant problem for being related to a national final and decisive juncture, because the environment that the application of a large amount of fossil fuels is caused is dirty
Dye and ecological disruption and greenhouse effects, are obvious to all, also result in the great attention of countries in the world, while in new energy
Substantial amounts of manpower and materials 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, be that the mankind consume gross energy every year tens of thousands of times.
One of primary study object of conversion and storage of solar energy is solar cell.The broad-band gaps such as titanium dioxide are partly led
The ability that body captures sunshine in itself is excessively poor, but by appropriate Dye Adsorption to semiconductor surface, can by means of dyestuff pair
See the strong absorption of light, but DSSC can not effectively absorb near-infrared and infrared light, limit the light of battery
Son-electronics conversion efficiency, as the dye photoactivation agent of battery core part, the long wavelength threshold of absorption spectrum does not surpass typically
750 nm are crossed, and have more than 55% 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 DSSC
Efficiency must just expand the spectral response range of battery, have special surface plasmon resonance effect to carry using noble metal
High up-conversion luminescent material is converted near infrared light the effect of visible ray.Therefore, research one kind has special construction and will
Up-conversion, which is applied to light anode material, important application value to DSSC.
There is also certain defect for DSSC prior art：Stability need improve, efficiency need after
It is continuous to improve, apply the semi-conducting material in DSSC also limited.
The content of the invention
It is simple the invention aims to provide a kind of technique, it is easy to operate, up-conversion fluorescence can be effectively improved, from
And improve the Au@SiO of solar cell photoelectric conversion efficiency2@CeO2:The preparation method of Yb/Er nano composite materials.
The present invention comprises the following steps：
1）By 100 DEG C of ultra-pure water and HAuCl4The aqueous solution and trisodium citrate aqueous solution mixing back flow reaction, back flow reaction knot
Shu Hou, room temperature is cooled to by reaction solution；
2）Above-mentioned reaction solution is mixed with the stirring of polyvinylpyrrolidone (PVP) aqueous solution, is then centrifuged for, solid phase gold is obtained molten
Glue, aurosol is scattered in deionized water, obtain the water dispersant of aurosol；
3）Under ultrasound condition, by water dispersant and ammoniacal liquor, the H of aurosol2TEOS is added under O, ethanol mixing, stirring condition,
After stirring, wash, dry through washing, alcohol after acquirement solid phase elder generation, obtain Au SiO2；
4）By Au@SiO2, the cerous nitrate aqueous solution, the ytterbium nitrate aqueous solution, the erbium nitrate aqueous solution and hexa (HMT) ultrasound
Mix laggard water-filling thermal response；
5）Hydro-thermal reaction terminates, and reaction solution is centrifuged, and takes solid phase to dry, calcine, obtains Au@SiO2@CeO2:Yb/Er nanometers multiple
Condensation material.
In the present invention, trisodium citrate is by AuCl4 -Au nano particles are reduced into, PVP prevents Au nanometers as protective agent
Grain aggregation.SiO2Formation is the process of TEOS hydrolysis and condensation, and kinetics simple equation is：
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, and Au@SiO have been synthesized using hydro-thermal method2@CeO2:Yb/Er
Nano composite material, the plasma resonance effect of noble metal is mutually tied with the advantageous property of the up-conversion luminescence of rare earth ion
Close, realize being kept completely separate for electronics and electrolyte, thus reduce electronics with reduced in solution electricity to contact, dark electricity can be reduced
Stream, is conducive to being lifted the open-circuit voltage of battery, the output of increase electric current and improvement output characteristics, as far as possible inspires all dyestuffs
Electronics move to conductive layer rapidly and be collected into external circuit, and improve the utilization rate of light.Synthetic material structure structure is new
Grain husk, particle diameter is in 100nm or so, and method is simple and convenient, and crystal formation is preferable.
Further, step 1 of the present invention）In, the HAuCl4HAuCl in the 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.
The step 3）In, aurosol and the TEOS volume ratio that feeds intake are 4: 1 in the water dispersant of the aurosol.This
Rate of charge can make it that the thickness of silica is optimal, and optimum thickness is 30nm, and Fluorescence Increasing effect is best.
The step 4）In, the cerous nitrate aqueous solution, the ytterbium nitrate aqueous solution, the erbium nitrate aqueous solution are according to the volume ratio that feeds intake
For 96.7: 0.3: 3, the Au@SiO2With the mixing being made up of the cerous nitrate aqueous solution, the ytterbium nitrate aqueous solution and the erbium nitrate aqueous solution
The rate of charge of solution is 8mg: 5mL.This rate of charge causes ceria to be preferably coated on outside silica, and pattern is equal
One.
The step 4）In, the environment temperature of the hydro-thermal reaction is the material grain synthesized under 180 DEG C, this hydrothermal temperature
Footpath is homogeneous, and covered effect is best.
The step 5）In, the centrifugation rate is 5000r/min, and calcining heat is 1100 DEG C, and calcination time is 2h.From
Heart speed is 5000r/min, will preferably synthesize into material washes clean and then separate drying, and calcining heat is fluorescence at 1100 DEG C
Effect is most strong.
Another object of the present invention is then to propose that composite prepared by above method is positive in DSSC light
Application in extremely.
Nano titania slurry is first coated in FTO glass surfaces, the titanium deoxide slurry bed of material is formed, 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 lucifuge
Sealing is soaked in after N719 dyestuffs, and taking-up is rinsed well with absolute ethyl alcohol, obtains dye-sensitized solar cell anode material.
The present invention is using FTO glass as carrier, using each layer of screen-printing deposition, reduces surface defect, and result in
Less size has large specific surface area, is adsorbed so as 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, opto-electronic conversion
Efficiency improves more than 17.8% than pure titinium dioxide, and hydro-thermal method synthesis, preparation technology is simple, easy to operate, and raw material is cheap, system
It is novel for the nano composite material structure gone out, it is adaptable to area of solar cell.
In addition, the grain diameter of nano titanium oxide described above is the nm of 25 nm ± 10；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 nano composite materials 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 cause the increase of semiconductor titanium dioxide thickness, there is big specific surface area to adsorb
Enough dyestuffs, will so produce substantial amounts of light induced electron, and ultimately resulting in battery has larger short circuit current flow.
The sealing soak time is 48h, dyestuff is more attracted on semi-conducting material, if soak time is oversize
Film layer can be caused to come off, influence battery efficiency.
Brief description of the drawings
The Au@SiO that Fig. 1 synthesizes for the present invention2@CeO2:The Flied emission transmission electron microscope TEM figures of Yb/Er nano composite materials.
The Au@SiO that Fig. 2 synthesizes for the present invention2@CeO2:The field emission scanning electron microscope SEM figures of Yb/Er nano composite materials.
The Au@SiO that Fig. 3 synthesizes for the present invention2@CeO2:Yb/Er nano composite materials, Au@CeO2:Yb/Er and Au@SiO2
X-ray diffraction XRD.
The Au@SiO that Fig. 4 synthesizes for the present invention2@CeO2:Yb/Er nano composite materials, SiO2@CeO2:Yb/Er and Au@
SiO2Up-conversion fluorescence spectrogram.
Fig. 5 is the I-V characteristic curve map of each DSSC.
Embodiment
First, Au@SiO are prepared2@CeO2:Yb/Er nano composite materials：
Example 1：
（1）Take 30mL ultra-pure waters to be placed in 100mL single necked round bottom flask and be heated to boiling, it is 180mM's to be separately added into concentration
HAuCl4Aqueous solution 0.4mL and concentration are 38mM trisodium citrate aqueous solution 3mL, and reflux time is 0.5h.
（2）Above-mentioned reaction solution is cooled to after room temperature, polyvinylpyrrolidone (PVP) water that concentration is 1.28mM is added
Solution 150uL, stirring reaction 12h.Negate mixture after answering and be placed in centrifugation three times in the centrifuge that rotating speed is 11000r/min, close
And the solid phase that centrifuging and taking is obtained（That is aurosol）And be dispersed in 8mL deionized waters, obtain the water dispersant of aurosol.
（3）Take the water dispersant of 2mL aurosols to be placed in 50 mL single necked round bottom flask, after ultrasonic 5min, add ammoniacal liquor
1mL, ultra-pure water 6mL, ethanol 10mL are placed in after stirring at room temperature, add 0.5 mL TEOS, low whipping speed is 700r/
Reacted under the conditions of min after 6h, take each solid phase to be washed, alcohol is washed each three times, dried, obtain 50mg Au@SiO2。
（4）The sour cerium of configuration, ytterbium nitrate and erbium nitrate mixed aqueous solution：Take the sour cerium aqueous solution, nitric acid that concentration is 0.1M
The ytterbium aqueous solution and the erbium nitrate aqueous solution, with 96.7：0.3：3 volume ratio mixing, obtains sour cerium, ytterbium nitrate and erbium nitrate mixing water-soluble
Liquid.
Take Au@SiO2Sample 8mg and 5mL cerous nitrate, ytterbium nitrate and erbium nitrate mixed aqueous solution, 30mg hexa-methylenes four
Amine (HMT) is mixed, after ultrasonic disperse 30min, is moved to hydrothermal reaction kettle and is carried out hydro-thermal reaction, 4h is reacted under the conditions of 180 DEG C.
（5）Hydro-thermal reaction terminates, by reaction solution with 5000r/min centrifugal treatings three times, merges the solid phase that centrifuging and taking obtains and does
2h is calcined under the conditions of 1100 DEG C are placed in after dry 12h, Au SiO are obtained2@CeO2:Yb/Er nano composite materials 0.1g.
Example 2：
（1）Take 60mL ultra-pure waters to be placed in 200mL single necked round bottom flask and be heated to boiling, it is 180mM's to be separately added into concentration
HAuCl4Aqueous solution 0.8mL and concentration are 38mM trisodium citrate aqueous solution 6mL, and reflux time is 0.5h.
（2）Above-mentioned reaction solution is cooled to room temperature, concentration is added water-soluble for 1.28mM polyvinylpyrrolidone (PVP)
Liquid 300uL, mixing time is 12h.Negate mixture after answering and be placed in centrifugation three times in the centrifuge that rotating speed is 11000r/min, close
And the solid phase that obtains of centrifuging and taking and be dispersed in 16mL deionized waters, obtain the water dispersant of aurosol.
（3）The water dispersant of 4mL aurosols is taken to be placed in 50 mL single necked round bottom flask, ultrasonic 5min adds ammoniacal liquor
2mL, ultra-pure water 12mL, ethanol 20mL are placed in after stirring at room temperature, add 1 mL TEOS, and mixing speed is 700r/min's
After speed stirring 6h, take each solid phase to be washed, alcohol is washed each three times, dry, obtain 100mg Au@SiO2。
（4）The sour cerium of configuration, ytterbium nitrate and erbium nitrate mixed aqueous solution：Take the sour cerium aqueous solution, nitric acid that concentration is 0.1M
The ytterbium aqueous solution and the erbium nitrate aqueous solution, with 96.7：0.3：3 volume ratio mixing, obtains sour cerium, ytterbium nitrate and erbium nitrate mixing water-soluble
Liquid.
Take Au@SiO2Sample 16mg and 10mL acid cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution, 60mg hexas
(HMT) mix, after ultrasonic disperse 30min, move to hydrothermal reaction kettle and carry out hydro-thermal reaction, 4h is reacted under the conditions of 180 DEG C.
（5）Hydro-thermal reaction terminates, and reaction solution is centrifuged three times with 5000r/min, merges the solid phase drying 12h that centrifuging and taking is obtained
After be placed in 1100 DEG C under the conditions of calcine 2h, obtain Au SiO2@CeO2:Yb/Er nano composite materials 0.2g.
Example 3：
（1）The sour cerium of configuration, ytterbium nitrate and erbium nitrate mixed aqueous solution：Take the sour cerium aqueous solution, ytterbium nitrate water that concentration is 0.1M
Solution and the erbium nitrate aqueous solution, with 96.7：0.3：3 volume ratio mixing, obtains sour cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution.
Take SiO2Sample 8mg and 5mL acid cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution, 30mg hexas (HMT)
After mixing, ultrasonic disperse 30min, move to hydrothermal reaction kettle and carry out hydro-thermal reaction, 4h is reacted under the conditions of 180 DEG C.
（2）Hydro-thermal reaction terminates, and reaction solution is centrifuged three times with 5000r/min, merges the solid phase drying 12h that centrifuging and taking is obtained
After be placed in 1100 DEG C under the conditions of calcine 2h, take sodium hydroxide solution that drying sample is 0.1M with concentration to soak 3h, obtain CeO2:
Yb/Er nano composite materials 0.1g.
Example 4：
（1）Take 30mL ultra-pure waters to be placed in 100mL single necked round bottom flask and be heated to boiling, it is 180mM's to be separately added into concentration
HAuCl4Aqueous solution 0.4mL and concentration are 38mM trisodium citrate aqueous solution 3mL, and reflux time is 0.5h.
（2）Above-mentioned reaction solution is cooled to after room temperature, polyvinylpyrrolidone (PVP) water that concentration is 1.28mM is added
Solution 150uL, stirring reaction 12h.Negate mixture after answering and be placed in centrifugation three times in the centrifuge that rotating speed is 11000r/min, close
And the solid phase that obtains of centrifuging and taking and be dispersed in 8mL deionized waters, obtain the water dispersant of aurosol.
（3）Take the water dispersant of 2mL aurosols to be placed in 50 mL single necked round bottom flask, after ultrasonic 5min, add ammoniacal liquor
1mL, ultra-pure water 6mL, ethanol 10mL are placed in after stirring at room temperature, add 0.5 mL TEOS, low whipping speed is 700r/
Reacted under the conditions of min after 6h, take each solid phase to be washed, alcohol is washed each three times, dried, obtain 50mg Au@SiO2。
（4）The sour cerium of configuration, ytterbium nitrate and erbium nitrate mixed aqueous solution：Take the sour cerium aqueous solution, nitric acid that concentration is 0.1M
The ytterbium aqueous solution and the erbium nitrate aqueous solution, with 96.7：0.3：3 volume ratio mixing, obtains sour cerium, ytterbium nitrate and erbium nitrate mixing water-soluble
Liquid.
Take Au@SiO2Sample 8mg and 5mL sour cerium, ytterbium nitrate and erbium nitrate mixed aqueous solution, 30mg hexas
(HMT) mix, after ultrasonic disperse 30min, move to hydrothermal reaction kettle and carry out hydro-thermal reaction, 4h is reacted under the conditions of 180 DEG C.
（5）Hydro-thermal reaction terminates, by reaction solution with 5000r/min centrifugal treatings three times, merges the solid phase that centrifuging and taking obtains and does
2h is calcined under the conditions of 1100 DEG C are placed in after dry 12h, Au SiO are obtained2@CeO2:Yb/Er nano composite materials 0.1g.
The sodium hydroxide solution immersion for being 0.1M with concentration by composite, obtains Au@CeO2:Yb/Er nano materials
0.5g。
2nd, Au@SiO2@CeO2:The sign of Yb/Er nano composite materials：
Fig. 1 illustrates Au@SiO prepared by the present invention2@CeO2:The Flied emission transmission electron microscope TEM figures of Yb/Er nano composite materials,
As can be seen from the figure this material is spherical, and particle diameter is in below 100nm nano composite material, and particle diameter 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 nano composite materials
Figure, as can be seen from the figure this material morphology is homogeneous, is homogeneous spherical structure.
Fig. 3 illustrates Au@SiO prepared by the present invention2@CeO2:Yb/Er nano composite materials, Au@CeO2:Yb/Er and Au@
SiO2X-ray diffraction XRD.Wherein curve A is Au@SiO2The XRD curves of nanosphere, curve B is Au@SiO2@CeO2:Yb/
The XRD curves of Er nano composite materials, figure C is Au@CeO2:The XRD curves of Yb/Er nano composite materials.
By contrasting XRD standard card PDF#33-0831, this product X RD collection of illustrative plates is consistent with standard spectrum,（111）、（200）、
（220）、（311）、（222）、（400）、（331）Crystallographic plane diffraction peak matches with the standard diffraction peak of ceria, illustrates this material
Expect for ceria.It is consistent with standard spectrum by contrasting XRD standard cards PDF#47-1144 this product X RD collection of illustrative plates,（011）It is brilliant
Face diffraction maximum matches with the standard diffraction peak of silica, illustrates that this material contains silica.By contrasting XRD standard cards
Piece PDF#04-0784 this product X RD collection of illustrative plates is consistent with standard spectrum,（111）(200) (220) crystallographic plane diffraction peak and golden nanometer particle
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 nano composite materials2Thickness 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.Silicon dioxide thickness can be seen that 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 light utilization efficiency highest.
3rd, dye-sensitized solar cell anode material is prepared：
1st, substrate is cleaned：
FTO glass is cut into long 5 cm, wide 10 cm size, respectively with sequentially ultrasound is clear in acetone, ethanol, deionized water
20 min are washed, taking-up after having cleaned, oven for drying is standby.
2、TiO2It is prepared by slurry：1g titanium dioxide is taken, stirring plus ultrasonic one day night in 20 mL absolute ethyl alcohols is dispersed in,
Take 2mL（5% ethyl cellulose terpinol）Above-mentioned reaction solution is added, 24h is stirred, then 70 DEG C of rotary evaporations, by ethanol therein
Evaporating completely is fallen, and obtains uniform and stable nano titania slurry.
Present example：
Using silk-screen printing, nano titania slurry is printed on FTO glass, drying at room temperature, is put into tube furnace and calcines,
450 DEG C are raised to 10 DEG C/min heating rate, 30 min, Temperature fall are calcined.In this approach, apply one layer and burn one layer, be painted with 6
~8 layers.Then silk-screen printing, then the Au@SiO that embodiment 1 is prepared are used2@CeO2:Yb/Er nano composite materials are coated in two
The upper surface of titania slurry layer, is subsequently placed in high-temperature calcination stove, using heating rate as 10 DEG C/min, furnace temperature is risen into 450
DEG C, taken out after 30min high-temperature calcinations.Sample is immersed in N719 dyestuffs again, 48h is placed after sealing under the conditions of lucifuge
Afterwards, taking-up is rinsed well with absolute ethyl 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 and calcines,
450 DEG C are raised to 10 DEG C/min heating rate, 30 min, Temperature fall are calcined.In this approach, apply one layer and burn one layer, be painted with 6
~8 layers.It is then placed in N719 dyestuffs and soaks 48 h, rinsed well with absolute ethyl alcohol, obtains DSSC light sun
Pole.
Comparison example 2：
Using silk-screen printing, nano titania slurry is printed on FTO glass, drying at room temperature, is put into tube furnace and calcines,
450 DEG C are raised to 10 DEG C/min heating rate, 30 min, Temperature fall are calcined.In this approach, apply one layer and burn one layer, be 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 the titanium deoxide slurry bed of material
Upper surface, is subsequently placed in high-temperature calcination stove, using heating rate as 10 DEG C/min, furnace temperature is risen into 450 DEG C, through 30min high temperature
Taken out after calcining.Sample is immersed in N719 dyestuffs again, after placing 48h under the conditions of lucifuge after sealing, anhydrous second is used in taking-up
Alcohol is rinsed well, obtains dye-sensitized solar cell anode material.
4th, performance test：
Used as dye-sensitized solar cell photo-anode made from above present example and comparative example 1,2 is made into DSSC steps such as
Under：Assembled battery first, uses platinum electrode for electrode, by the conduction of working electrode up, and to electrode conduction directed downwardly
Face is picked up to press from both sides into sandwich structure, then inject electrolyte, progress DSSC between electrodes with clip
I-V curve test.
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 map.
Curve c is represented：Present example obtains dye-sensitized solar cell anode material I-V characteristic curve map.
Following table is as the photoelectric properties contrast table of the DSSC packaged by the light anode prepared by each example：
| Short-circuit current density (mA/ cm2) | Voltage (V) | Factor of influence | Photoelectric transformation 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 |
It was found from the data in table 1 and Fig. 5, dye-sensitized solar cell anode made from each example is used as work more than
Electrode, is assembled into DSSC.Compared with comparison example 1,2, the short-circuit current density of present example（Jsc）And photoelectric transformation efficiency
（η）All strengthen.Short-circuit current density（Jsc）Up to 15.45 mA/cm2, factor of influence（FF）Reach 69%, photoelectricity
Conversion efficiency（η）Up to 7.42%, the dominance structure of this material is novel, and similar structures are not reported temporarily, precious metal surface
Plasma resonance significantly improves the non-radiative decay rate between fluorogen, so that fluorescent effect strengthens, improves opto-electronic conversion effect
Rate.
These test result indicates that：The Au@SiO being made of the inventive method2@CeO2:Yb/Er nano composite material energy
Effectively increase photoelectric transformation efficiency.
Claims (9)
1. a kind of preparation method of photosensitizer nano composite material, it is characterised in that comprise the following steps：
1）By 100 DEG C of ultra-pure water and HAuCl4The aqueous solution and trisodium citrate aqueous solution mixing back flow reaction, back flow reaction terminate
Afterwards, reaction solution is cooled to room temperature；
2）Above-mentioned reaction solution is mixed with aqueous povidone solution stirring, is then centrifuged for, solid phase aurosol is obtained, will
Aurosol is scattered in deionized water, obtains the water dispersant of aurosol；
3）Under ultrasound condition, by water dispersant and ammoniacal liquor, the H of aurosol2TEOS is added under O, ethanol mixing, stirring condition, is stirred
After mixing, wash, dry through washing, alcohol after acquirement solid phase elder generation, obtain Au SiO2；
4）By Au@SiO2, the cerous nitrate aqueous solution, the ytterbium nitrate aqueous solution, the erbium nitrate aqueous solution and hexa (HMT) ultrasound
Mix laggard water-filling thermal response；
5）Hydro-thermal reaction terminates, and reaction solution is centrifuged, and takes solid phase to dry, calcine, obtains Au@SiO2@CeO2:Yb/Er is nano combined
Material.
2. the preparation method of material according to claim 1, it is characterised in that the step 1）In, the HAuCl4The aqueous solution
Middle HAuCl4Molar ratio with trisodium citrate in trisodium citrate aqueous solution is 100: 63.
3. the preparation method of material according to claim 1, it is characterised in that the step 3）In, the moisture of the aurosol
Aurosol and the TEOS volume ratio that feeds intake are 4: 1 in powder.
4. the preparation method of material according to claim 1, it is characterised in that the step 4）In, the cerous nitrate is water-soluble
Liquid, the ytterbium nitrate aqueous solution, the erbium nitrate aqueous solution are 96.7: 0.3: 3, the Au@SiO according to the volume ratio that feeds intake2With by cerous nitrate
The rate of charge of the mixed solution of the aqueous solution, the ytterbium nitrate aqueous solution and erbium nitrate aqueous solution composition is 8mg: 5mL.
5. the preparation method of material according to claim 1 or 4, it is characterised in that the step 4）In, the hydro-thermal reaction
Environment temperature be 180 DEG C.
6. the preparation method of material according to claim 1, it is characterised in that the step 5）In, the centrifugation rate is
5000r/min, calcining heat is 1100 DEG C, and calcination time is 2h.
7. the application of composite prepared by method as claimed in claim 1 in dye-sensitized solar cell anode, its
It is characterised by：Nano titania slurry is first coated in FTO glass surfaces, the titanium deoxide slurry bed of material is formed, then will be described multiple
Condensation material is coated in nano titania slurry layer surface using method for printing screen, after 450 DEG C of high-temperature calcinations, lucifuge condition
Lower sealing is soaked in after N719 dyestuffs, and taking-up is rinsed well with absolute ethyl alcohol, obtains dye-sensitized solar cell anode material
Material.
8. application according to claim 7, it is characterised in that：The grain diameter of the nano titanium oxide 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 materials of Yb/Er
The number of plies of material coating is 1~2 layer.
9. the application according to claim 7 or 8, it is characterised in that：The sealing soak time is 48h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408573.1A CN107195462B (en) | 2017-06-02 | 2017-06-02 | A kind of preparation method and applications of photosensitizer nanocomposite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710408573.1A CN107195462B (en) | 2017-06-02 | 2017-06-02 | A kind of preparation method and applications of photosensitizer nanocomposite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107195462A true CN107195462A (en) | 2017-09-22 |
| CN107195462B CN107195462B (en) | 2019-03-29 |
Family
ID=59876985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710408573.1A Active CN107195462B (en) | 2017-06-02 | 2017-06-02 | A kind of preparation method and applications of photosensitizer nanocomposite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107195462B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108022758A (en) * | 2017-11-28 | 2018-05-11 | 东莞理工学院 | Carbon coating ceria hollow ball and preparation method thereof |
| CN108587601A (en) * | 2018-05-29 | 2018-09-28 | 洛阳理工学院 | A kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials and preparation and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807351A (en) * | 2005-12-14 | 2006-07-26 | 吉林大学 | Method for prehydrolysis preparing core-envelope type inorganic nanocrystalline - silicon dioxide composite grain |
| CN102127444A (en) * | 2010-12-10 | 2011-07-20 | 吉林大学 | Nanogold modified enhanced up-conversion luminescence composite material and preparation method thereof |
| CN104810157A (en) * | 2015-02-13 | 2015-07-29 | 江汉大学 | Double-shell composite material, and preparation method and application thereof |
| CN105586039A (en) * | 2016-03-11 | 2016-05-18 | 扬州大学 | Hollow-structure CeO2:Er3+/Yb3+ up-conversion luminescent material and application thereof |
| CN106566550A (en) * | 2016-11-15 | 2017-04-19 | 扬州大学 | Preparation method and application of composite up-conversion luminescent material |
| CN106620702A (en) * | 2017-02-14 | 2017-05-10 | 扬州大学 | Preparation method of gold/nitrogen-doped hollow carbon nanosphere core-shell material |
-
2017
- 2017-06-02 CN CN201710408573.1A patent/CN107195462B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807351A (en) * | 2005-12-14 | 2006-07-26 | 吉林大学 | Method for prehydrolysis preparing core-envelope type inorganic nanocrystalline - silicon dioxide composite grain |
| CN102127444A (en) * | 2010-12-10 | 2011-07-20 | 吉林大学 | Nanogold modified enhanced up-conversion luminescence composite material and preparation method thereof |
| CN104810157A (en) * | 2015-02-13 | 2015-07-29 | 江汉大学 | Double-shell composite material, and preparation method and application thereof |
| CN105586039A (en) * | 2016-03-11 | 2016-05-18 | 扬州大学 | Hollow-structure CeO2:Er3+/Yb3+ up-conversion luminescent material and application thereof |
| CN106566550A (en) * | 2016-11-15 | 2017-04-19 | 扬州大学 | Preparation method and application of composite up-conversion luminescent material |
| CN106620702A (en) * | 2017-02-14 | 2017-05-10 | 扬州大学 | Preparation method of gold/nitrogen-doped hollow carbon nanosphere core-shell material |
Non-Patent Citations (3)
| Title |
|---|
| 崔天蜂: ""Au@SiO2@LaF3:Eu纳米核壳结构的制备及其发光性能"", 《材料科学与工程学报》 * |
| 杨扬: ""Er和Yb共掺杂稀土氧化物上转换纳米材料的制备及性能研究"", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
| 程彦敏: ""Color tunable upconversion emission in CeO2:Yb,Er three-dimensional ordered macroporous materials"", 《JOURAL OF RARE EARTHS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108022758A (en) * | 2017-11-28 | 2018-05-11 | 东莞理工学院 | Carbon coating ceria hollow ball and preparation method thereof |
| CN108022758B (en) * | 2017-11-28 | 2020-07-24 | 东莞理工学院 | Carbon-coated cerium dioxide hollow sphere and preparation method thereof |
| CN108587601A (en) * | 2018-05-29 | 2018-09-28 | 洛阳理工学院 | A kind of rear-earth-doped Au@TiO2Core-shell structured nanomaterials and preparation and application |
| CN108587601B (en) * | 2018-05-29 | 2020-08-11 | 洛阳理工学院 | Rare earth doped Au @ TiO2Core-shell structure nano material, preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107195462B (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Savari et al. | Development of photo-anodes based on strontium doped zinc oxide-reduced graphene oxide nanocomposites for improving performance of dye-sensitized solar cells | |
| CN104538192B (en) | A kind of loose structure hybrid perovskite battery and preparation method thereof | |
| CN101770869B (en) | Method for preparing titanium dioxide films for dye-sensitized solar battery | |
| CN106277023A (en) | The preparation method and applications of double-decker CeO2 nano-hollow ball | |
| CN105336862A (en) | Integrated stack double-junction perovskite solar cell and preparation method thereof | |
| CN107170584B (en) | The preparation method of compound nucleocapsid nano-hollow ball and its application in dye-sensitized solar cells | |
| CN105044180A (en) | Preparation method and application of heterojunction photoelectrode | |
| Wang et al. | Enhancing photovoltaic performance of dye-sensitized solar cells by rare-earth doped oxide of SrAl2O4: Eu3+ | |
| CN105586039A (en) | Hollow-structure CeO2:Er3+/Yb3+ up-conversion luminescent material and application thereof | |
| Akhtar et al. | Synthesis and characterization of ZnO nanorods and balls nanomaterials for dye sensitized solar cells | |
| Yu et al. | Pt/Y 2 O 3: Eu 3+ composite nanotubes: Enhanced photoluminescence and application in dye-sensitized solar cells | |
| Zhang et al. | A synergistic effect of NaYF4: Yb, Er@ NaGdF4: Nd@ SiO2 upconversion nanoparticles and TiO2 hollow spheres to enhance photovoltaic performance of dye-sensitized solar cells | |
| Ran et al. | Positive effects in perovskite solar cells achieved using down-conversion NaEuF4 nanoparticles | |
| Yao et al. | Improving the photovoltaic performance of dye sensitized solar cells based on a hierarchical structure with up/down converters | |
| CN107195462B (en) | A kind of preparation method and applications of photosensitizer nanocomposite | |
| CN110349753A (en) | Rear-earth-doped upper conversion titanium dioxide nanostructure complex light anode of one kind and its preparation method and application | |
| CN107731538B (en) | A kind of novel light anode and its preparation method and application of Er doping carbon quantum dot auxiliary | |
| CN112642456B (en) | Preparation method of composite photocatalyst | |
| CN107537458B (en) | Preparation method of oxide quantum dot modified graphene/zinc oxide photocatalytic material | |
| CN105244172B (en) | A kind of preparation method and applications of dye-sensitized solar cell anode | |
| CN103903860A (en) | Single-layer ternary nanocrystal titanium dioxide film photo-anode and manufacturing method thereof | |
| CN106566550A (en) | Preparation method and application of composite up-conversion luminescent material | |
| CN110841686A (en) | Carbon-coated titanium suboxide composite carbon nitride composite material and preparation method and application thereof | |
| CN107680817B (en) | A kind of two-way light conversion agent GdBO3:Yb3+/Tb3+Light anode of auxiliary and its preparation method and application | |
| CN105869897B (en) | A kind of hollow material CeO2@TiO2Preparation method and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |