CN107170584B - The preparation method of compound nucleocapsid nano-hollow ball and its application in dye-sensitized solar cells - Google Patents
The preparation method of compound nucleocapsid nano-hollow ball and its application in dye-sensitized solar cells Download PDFInfo
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- 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
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- H—ELECTRICITY
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- 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
- H01G9/2045—Light-sensitive devices comprising a semiconductor electrode comprising elements of the fourth group of the Periodic System (C, Si, Ge, Sn, Pb) with or without impurities, e.g. doping materials
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- Y02E10/542—Dye sensitized solar cells
Abstract
The preparation method of compound nucleocapsid nano-hollow ball and its application in dye-sensitized solar cells, belong to technical field of solar batteries, hydro-thermal reaction is carried out after seven water cerous chlorates are mixed with trisodium citrate, ytterbium nitrate, erbium nitrate aqueous solution, aqueous hydrogen peroxide solution, obtains double-layer structure CeO2: Yb/Er hollow sphere nanosphere disperses the nanosphere in isopropanol, then mixes with ammonium hydroxide, tetraethyl orthosilicate and carry out water-bath, obtains the double-deck CeO2:Yb/Er@SiO2Hollow sphere nanosphere, then reacted with the mixing of polyvinylpyrrolidone, ethylene glycol, silver nitrate and sodium borohydride aqueous solution, obtain double-layer structure CeO2:Yb/Er@SiO2The compound nucleocapsid nano-hollow ball of@Ag.The material is coated in nano titania slurry surface and obtains dye-sensitized solar cell anode material after being calcined, being soaked in N719 dyestuff.
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
With the sharp deterioration of energy dangerization and environmental problem, people are more and more to the concern of new cleaning fuel.Too
Sun can be a kind of clean energy resource of rich reserves.The reasonable solar energy that develops and utilizes will dramatically improve people's lives.
Solar battery realizes and directly converts the solar into electric energy, and people utilize one of the basic mode of solar energy.Dyestuff
The one kind of sensitization solar battery as solar battery has many advantages, such as cheap, stable, efficient, easy production, therefore has
Boundless development prospect.
Efficient dye-sensitized solar cells is obtained, the nano material for constituting light anode there must be high specific surface
Product, can sufficiently contact with sensitizer, and sensitizer absorption is more, contact is more abundant, and the photogenerated current density of battery is also bigger.Although
Titanium dioxide nanocrystalline battery obtains preliminary success, but simple titanium dioxide nanocrystalline film is lacked there is also many
Point.On the one hand serious surface recombination limits the promotion of battery open circuit voltage, and affects the output characteristics of battery, makes battery
Fill factor it is not high.On the other hand, the titanium dioxide little particle of simple nanometer, is unfavorable for the scattering of light.
Dye-sensitized solar cells cannot effectively absorb near-infrared and infrared light, and the photon-electron for limiting battery turns
Efficiency is changed, as the dye photoactivation agent of battery core component part, the long wavelength threshold of absorption spectrum is generally no more than 750 nm,
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 pair
Full wave solar energy can not overall absorption.So thinking that the efficiency for fundamentally improving dye-sensitized solar cells just must
The spectral response range that battery must be expanded, is converted to visible light near infrared light using up-conversion luminescent material.Therefore, one is studied
Kind have special construction and by up-conversion luminescent material be applied to light anode have to dye-sensitized solar cells it is important
Application value.
The dye-sensitized solar cells prior art also suffers from certain drawbacks: although incident photon-to-electron conversion efficiency breaks through 11%,
It is intended to continue to improve to apply the semiconductor material in dye-sensitized solar cells also limited there are certain difficulty.
Summary of the invention
It is easy to operate the invention aims to provide a kind of simple process, dye-sensitized solar cells light can be used as
Anode material, and effectively improve the sensitizing dyestuff of photoelectric conversion efficiency --- double-layer structure CeO2:Yb/Er@SiO2@Ag complex nucleus
The preparation method of shell nano-hollow ball.
The present invention the following steps are included:
1) urea is dispersed in ultrapure water under ultrasound condition, is then blended into trisodium citrate aqueous solution, obtain lemon
The urea dispersing agent of sour trisodium；
2) by after the urea dispersant of seven water cerous chlorates and trisodium citrate, ytterbium nitrate aqueous solution and nitre are added
Sour erbium aqueous solution, then aqueous hydrogen peroxide solution is added dropwise, seven water cerous chlorates can be oxidized to ceria, stirring obtains yellowish
Mixture of colours solution；
3) faint yellow mixed solution is placed in autoclave and carries out hydro-thermal reaction；
4) mixture after hydro-thermal reaction is cooled to room temperature, then is dispersed with water and ethyl alcohol, through centrifuging and taking solid formation, then dried
It is dry, obtain double-layer structure CeO2: Yb/Er hollow sphere nanosphere；
5) under ultrasound condition, by double-layer structure CeO2: Yb/Er hollow sphere nanosphere is scattered in isopropanol, then with by ammonia
The mixed solution mixing of water and tetraethyl orthosilicate (TEOS) composition carries out water-bath；It is centrifuged after reaction, solid this is taken to dry,
Calcining, obtains the double-deck CeO2:Yb/Er@SiO2Hollow sphere nanosphere；
6) by double-layer structure CeO2:Yb/Er@SiO2Hollow sphere nanosphere mixes with polyvinylpyrrolidone (PVP) and is placed in second
It in glycol, adds silver nitrate aqueous solution and sodium borohydride aqueous solution is reacted, be centrifuged after reaction, take solid phase dry,
Obtain double-layer structure CeO2:Yb/Er@SiO2The compound nucleocapsid nano-hollow ball of@Ag.
Main raw material(s) of the present invention is cheap and widely used rare earth oxide, and precious metal surface has surface plasma
Then resonance effects coats one layer of SiO2It can protect its original double-deck pattern, while having adjusted fluorogen and noble metal
Distance.The CeO of double-layer structure is formed after silver nanoparticles loaded2:Yb/Er@SiO2@Ag hollow sphere nanometer realizes up-conversion fluorescence
Function, near infrared light and infrared light are converted to visible light.Spectral region is widened, the utilization rate of light is improved, can reduce dark
Electric current is conducive to the open-circuit voltage for promoting battery, increases electric current output and improves output characteristics, as far as possible excites all dyestuffs
Electronics out moves to rapidly conductive layer and is collected into external circuit.Synthetic material structure is the double-deck nucleocapsid composite hollow ball, partial size
In 500nm~700nm or so, structure novel, method is simple and convenient, and up-conversion fluorescence is greatly improved.
Further, in step 1) of the present invention, the concentration for mixed trisodium citrate aqueous solution is 10mM/L；
The mixing ratio of urea and trisodium citrate aqueous solution is 1g: 80 mL, manufactured product pattern can be made most uniform, crystal form is best.
In the step 2, the mass ratio that feeds intake of urea is in the urea dispersing agent of seven water cerous chlorates and trisodium citrate
1.2:1；The concentration of ytterbium nitrate aqueous solution is 0.1M, and the concentration of erbium nitrate aqueous solution is 0.1M, seven water cerous chlorates, ytterbium nitrate
The volume ratio that feeds intake of aqueous solution and erbium nitrate aqueous solution is 96.7: 0.3: 3；For hydrogen peroxide in the hydrogenperoxide steam generator of dropwise addition
Mass percent be 30%, the feed ratio of urea is in the urea dispersing agent of the aqueous hydrogen peroxide solution and trisodium citrate
1mL: 1g, it can be just fully oxidized at ceria by cerous chlorate.
In the step 3), when the hydrothermal temperature is 180 DEG C, and the reaction time is 20h, react more abundant,
Obtained double-layer structure CeO2: Yb/Er nano-hollow ball pattern is the most considerable, and partial size is the most uniform, and ensure that the double-deck knot
Structure.
In the step 4), the temperature environment of the drying is 80 DEG C.Ethyl alcohol evaporating completely can be fallen, obtain drying
The double-deck CeO2: Yb/Er nano-hollow ball.
In the step 5), the isopropanol and CeO2: the feed ratio of Yb/Er sample is 2ml:1mg.Isopropanol, ammonium hydroxide
The volume ratio that feeds intake with TEOS is 8:1:0.14.The temperature environment of drying is 80 DEG C, and calcination temperature is 1100 DEG C, and calcination time is
2h。SiO2Preferably packet is in outer layer, the SiO of cladding2Layer is the most uniform.
In the step 6), the concentration of the silver nitrate aqueous solution is 0.047M, and the concentration of sodium borohydride aqueous solution is
120mM；The double-layer structure CeO2:Yb/Er@SiO2The throwing of hollow sphere nanosphere and polyvinylpyrrolidone, silver nitrate aqueous solution
Material is than being 1mg:1.3mg:0.125ml；The volume ratio that feeds intake of silver nitrate aqueous solution and sodium borohydride aqueous solution is 1.25:1；Reaction
Temperature condition be 90 DEG C；The temperature environment of drying is 70~80 DEG C.PVP is as dressing agent, silver nitrate aqueous solution and hydroboration
The volume ratio that feeds intake of sodium water solution is 1.25:1, and temperature condition provides an optimum temperature, lucky boron hydrogen for 90 DEG C for reaction
Changing sodium for silver nitrate reduction is silver nano-grain.The temperature environment of drying, which is 70~80 DEG C, can dry sample.
Another object of the present invention is proposed using double-layer structure CeO made of above method2:Yb/Er@SiO2@Ag is compound
Application of the core-shell nano hollow sphere in dye-sensitized solar cell anode.
Nano titania slurry is first coated in FTO glass surface, then by double-layer structure CeO2:Yb/Er@SiO2@Ag
Compound nucleocapsid nano-hollow ball is coated in nano titania slurry surface using method for printing screen, through 450 DEG C of high-temperature calcinations
Afterwards, sealed soak after N719 dyestuff, rinsed well with dehydrated alcohol by taking-up under the conditions of being protected from light, and obtains dye sensitization of solar electricity
Pond optical 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 up-conversion fluorescence effect for stating preparation is good, improves the utilization rate of light, photo electric
Can be good, photoelectric conversion efficiency improves 33% or more than pure titinium dioxide, and synthetic method is simple, and raw material is cheap, and it is easy to operate,
The nucleocapsid hollow nano-material structure novel prepared is suitable for area of solar cell.
Further, the number of plies of the nano titania slurry coating is 6~8 layers, the double-layer structure CeO2It is hollow
The number of plies of ball nano material coating is 1~2 layer.The method of multiple coating can make semiconductor titanium dioxide thickness increase, and have big
Specific surface area adsorb enough dyestuffs, a large amount of light induced electron will be generated in this way, eventually lead to battery have it is biggish short
Road electric current.
The grain diameter of the nano-titanium dioxide is 25nm ± 10nm.The particle of titanium dioxide in this particle size range
The film of composition has 50~60% empty structure, and greatly nearly 2000 times of surface area ratio planar film.
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. 1,2 are respectively the double-layer structure CeO for inventing synthesis2:Yb/Er@SiO2The field of the compound nucleocapsid nano-hollow ball of@Ag
Transmission Electronic Speculum TEM figure.
Fig. 3 is double-layer structure CeO of the present invention2:Yb/Er@SiO2The Flied emission of the compound nucleocapsid nano-hollow ball of@Ag scans electricity
Mirror SEM figure.
Fig. 4 is double-layer structure CeO of the present invention2:Yb/Er@SiO2The compound nucleocapsid nano-hollow ball of@Ag, CeO2:Yb/Er@
SiO2Nano-hollow ball and CeO2: the X-ray diffraction XRD diagram of Yb/Er nano-hollow ball.
Fig. 5 is double-layer structure CeO of the present invention2:Yb/Er@SiO2The compound nucleocapsid nano-hollow ball of@Ag, CeO2:Yb/Er@
SiO2Nano-hollow ball and CeO2: the up-conversion fluorescence spectrogram of Yb/Er nano-hollow ball.
Fig. 6 is the I-V characteristic curve graph of each dye-sensitized solar cells.
Specific embodiment
One, double-layer structure CeO2:Yb/Er@SiO2The preparation of the compound nucleocapsid nano hollow sphere material of@Ag:
Example 1:
1. double-layer structure CeO2: the preparation of Yb/Er:
(1) under ultrasound condition, 1g urea is thoroughly dispersed in 170mL ultrapure water, obtains urea dispersion liquid, then to urea
80 mL of trisodium citrate aqueous solution that concentration is 10mM/L is added in dispersion liquid, is vigorously stirred 15min, obtains trisodium citrate
Urea dispersing agent.
(2) seven water cerous chlorate of 1.2g is dissolved in 32mL water, is configured to the solution that concentration is 0.1M and 23.8mL is taken to be added to
In the urea dispersing agent of above-mentioned trisodium citrate, stir 15min after, be added 74uL concentration be 0.1M ytterbium nitrate solution and
740uL concentration is the Nitrate Solution of 0.1M.With vigorous stirring, then be added dropwise concentration be 30%(mass percent) peroxidating
Hydrogen solution 1mL obtains faint yellow mixed solution after 45min.
(3) obtained faint yellow mixed solution is gone into hydro-thermal reaction in autoclave, sets reaction temperature as 180
DEG C, carry out hydro-thermal reaction, time 20h.
(4) after hydro-thermal reaction, it is cooled to room temperature, the product of hydro-thermal reaction is taken out, water-dispersible rear centrifugal treating
Three times, solid formation is isolated, for the centrifugal rotational speed used for 4000~5000 r/min, centrifugation time is 5~10 min.
Then, centrifugal treating three times, isolates solid formation after being dispersed with ethyl alcohol, and the centrifugal rotational speed used is 1500~2500
R/min, centrifugation time are 5~10 min.Finally, solid formation is dried 12h at a temperature of 80 DEG C, double-layer structure CeO is obtained2:
The compound nucleocapsid nano-hollow ball 0.5g of Yb/Er.
2. double-layer structure CeO2:Yb/Er@SiO2Preparation:
Take double-layer structure CeO2: the compound nucleocapsid nano-hollow ball 20mg of Yb/Er is added in 40mL isopropanol, ultrasonic disperse
30min is separately added into 10mL ultrapure water, 5mL ammonium hydroxide, 70uL TEOS under 40 DEG C of water bath conditions.It is stirred with the revolving speed of 500r/min
Mix 2h.Sample is washed 3 times, ethyl alcohol is washed 3 times, 70 DEG C of dry 12h.1100 DEG C of calcining 2h, acquirement in Muffle furnace by sample
CeO2:Yb/Er@SiO2Hollow sphere.
3. double-layer structure CeO2:Yb/Er@SiO2Preparation:
(1) CeO is taken2:Yb/Er@SiO2Hollow sphere 10mg is added 13mg polyvinylpyrrolidone (PVP), and 10mL second is added
Glycol is placed in 90 DEG C of stirred in water bath 20min.Take the silver nitrate aqueous solution 1.25mL that concentration is 0.047M that above-mentioned mixture is added
In system, 3min is stirred.
(2) it is 120mM NaBH that 1mL concentration, which is added,4Solution stirs 1h.Sample 5000r/min centrifugation is washed 3 times, second
Alcohol is washed 3 times, and 70 DEG C of dry 12h obtain double-layer structure CeO2:Yb/Er@SiO2。
Example 2:
1. double-layer structure CeO2: the preparation of Yb/Er:
(1) under ultrasound condition, 2g urea is thoroughly dispersed in 340mL ultrapure water, obtains urea dispersion liquid, then to urea
160 mL of trisodium citrate aqueous solution that concentration is 10mM is added in dispersion liquid, is vigorously stirred 15min, obtains trisodium citrate
Urea dispersing agent.
(2) seven water cerous chlorate of 2.4g is dissolved in 64mL water, is configured to the solution that concentration is 0.1M and 47.6mL is taken to be added to
In the urea dispersing agent of above-mentioned trisodium citrate, stir 15min after, be added 148uL concentration be 0.1M ytterbium nitrate solution and
1.48mL concentration is the Nitrate Solution of 0.1M.With vigorous stirring, then be added dropwise concentration be 30%(mass percent) peroxidating
Hydrogen solution 2mL obtains faint yellow mixed solution after 45min.
(3) the faint yellow mixed solution of obtained acquirement is gone into hydro-thermal reaction in autoclave, set reaction temperature as
180 DEG C, reaction time 20h.
(4) after hydro-thermal reaction, it is cooled to room temperature, the product of hydro-thermal reaction is taken out, water-dispersible rear centrifugal treating
Three times, solid formation is isolated, for the centrifugal rotational speed used for 4000~5000 r/min, centrifugation time is 5~10 min.
Then, centrifugal treating three times, isolates solid formation after being dispersed with ethyl alcohol, and the centrifugal rotational speed used is 1500~2500
R/min, centrifugation time are 5~10 min.Finally, solid formation is dried 12h at a temperature of 80 DEG C, double-layer structure CeO is obtained2:
The compound nucleocapsid nano-hollow ball 1g of Yb/Er.
2. double-layer structure CeO2:Yb/Er@SiO2Preparation:
Take double-layer structure CeO2: the compound nucleocapsid nano-hollow ball 40mg of Yb/Er is added in 80mL isopropanol, ultrasonic disperse
30min is separately added into 20mL ultrapure water, 10mL ammonium hydroxide, 140uL TEOS under 40 DEG C of water bath conditions.With the revolving speed of 500r/min
Stir 2h.Sample is washed 3 times, ethyl alcohol is washed 3 times, 70 DEG C of dry 12h.By sample in Muffle furnace 1100 DEG C of calcining 2h, obtain
CeO2:Yb/Er@SiO2Hollow sphere.
3. double-layer structure CeO2:Yb/Er@SiO2Preparation:
(1) CeO is taken2:Yb/Er@SiO2Hollow sphere 20mg is added 26mg polyvinylpyrrolidone (PVP), and 20mL second is added
Glycol is placed in 25ml round-bottomed flask, in 90 DEG C of stirred in water bath 20min.Taking concentration is the silver nitrate aqueous solution of 0.047M
2.5mL is added in above-mentioned mixed system, stirs 3min.
(2) it is 120mM NaBH that 2mL concentration, which is added,4Solution stirs 1h.Sample 5000r/min centrifugation is washed 3 times, second
Alcohol is washed 3 times, and 70 DEG C of dry 12h obtain double-layer structure CeO2:Yb/Er@SiO2。
Example 3:
1. double-layer structure CeO2: the preparation of Yb/Er:
(1) under ultrasound condition, 10 g urea are thoroughly dispersed in 1.7 L ultrapure waters, obtain urea dispersion liquid, then to urine
800 mL of trisodium citrate aqueous solution that concentration is 10mM/L is added in plain dispersion liquid, is vigorously stirred 15min, obtains citric acid three
The urea dispersing agent of sodium.
(2) seven water cerous chlorate of 12g is dissolved in 320mL water, is configured to the solution that concentration is 0.1M and 238mL is taken to be added to
It states in the urea dispersing agent of trisodium citrate, after stirring 15min, the ytterbium nitrate solution and 7.4ml that 740ul concentration is 0.1M is added
Concentration is the Nitrate Solution of 0.1M.With vigorous stirring, then be added dropwise concentration be 30%(mass percent) hydrogenperoxide steam generator
10mL obtains faint yellow mixed solution after 45min.
(3) the faint yellow mixed solution of obtained acquirement is gone into hydro-thermal reaction in autoclave, set reaction temperature as
180 DEG C, reaction time 20h.
(4) after hydro-thermal reaction, it is cooled to room temperature, the product of hydro-thermal reaction is taken out, water-dispersible rear centrifugal treating
Three times, solid formation is isolated, for the centrifugal rotational speed used for 4000~5000 r/min, centrifugation time is 5~10 min.
Then, centrifugal treating three times, isolates solid formation after being dispersed with ethyl alcohol, and the centrifugal rotational speed used is 1500~2500
R/min, centrifugation time are 5~10 min.Finally, solid formation is dried 12h at a temperature of 80 DEG C, double-layer structure CeO is obtained2:
The compound nucleocapsid nano-hollow ball 5g of Yb/Er.
2. double-layer structure CeO2:Yb/Er@SiO2Preparation:
Take the CeO prepared2: Yb/Er hollow sphere sample 200mg is added in 400mL isopropanol, ultrasonic disperse
30min is separately added into 100mL ultrapure water, 50mL ammonium hydroxide, 700uLTEOS under 40 DEG C of water bath conditions.With the revolving speed of 500r/min
Stir 2h.Sample is washed 3 times, ethyl alcohol is washed 3 times, 70 DEG C of dry 12h.1100 DEG C of calcining 2h, acquirement in Muffle furnace by sample
CeO2:Yb/Er@SiO2Hollow sphere.
3. double-layer structure CeO2:Yb/Er@SiO2Preparation:
(1) CeO is taken2:Yb/Er@SiO2Hollow sphere 100mg is added 130mg polyvinylpyrrolidone (PVP), and 10mL is added
Ethylene glycol is placed in 25mL round-bottomed flask, in 90 DEG C of stirred in water bath 20min.Taking concentration is the silver nitrate aqueous solution of 0.047M
12.5mL is added in above-mentioned mixed system, stirs 3min.
(2) it is 120mM NaBH that 10mL concentration, which is added,4Solution stirs 1h.Sample 5000r/min centrifugation is washed 3 times, second
Alcohol is washed 3 times, and 80 DEG C of dry 12h obtain double-layer structure CeO2:Yb/Er@SiO2。
Two, double-layer structure CeO2:Yb/Er@SiO2The characterization of the compound nucleocapsid nano-hollow ball of@Ag:
Fig. 1,2 illustrate double-layer structure CeO prepared by the present invention2:Yb/Er@SiO2The compound nucleocapsid nano-hollow ball material of@Ag
The Flied emission transmission electron microscope TEM of material schemes, and as can be seen from the figure this material is that the double-deck nucleocapsid is nano-hollow sphere structured, and partial size compares
Uniform, Ag nano particle is uniformly supported on SiO2Above, partial size is between 500~700 nm.
Fig. 3 illustrates double-layer structure CeO prepared by the present invention2:Yb/Er@SiO2The compound nucleocapsid nano hollow sphere material of@Ag
Flied emission transmission electron microscope SEM figure, as can be seen from the figure this material morphology is uniform, area load silver nano-grain.
Fig. 4 illustrates double-layer structure CeO prepared by the present invention2:Yb/Er@SiO2The compound nucleocapsid nano hollow sphere material of@Ag,
Double-layer structure CeO2:Yb/Er@SiO2Nano-hollow ball and double-layer structure CeO2: the X-ray diffraction XRD of Yb/Er nano-hollow ball
Figure.
By comparing XRD standard card PDF#33-0831 and standard card PDF#04-0783, this product X RD map and mark
Quasi- spectrum is consistent, (111), (200), (220), (311), (222), (400), (331) crystallographic plane diffraction peak and ceria standard
Diffraction maximum matches, and illustrates that this material is ceria.(111), the standard diffraction peak phase of (200) crystallographic plane diffraction peak and silver-colored simple substance
It coincide.
Fig. 5 illustrates double-layer structure CeO prepared by the present invention2:Yb/Er@SiO2The compound nucleocapsid nano hollow sphere material of@Ag,
CeO2:Yb/Er@SiO2Nano hollow sphere material and CeO2: the up-conversion fluorescence spectrogram of Yb/Er nano hollow sphere material.From figure
It is greatly improved it can be concluded that having loaded up-conversion fluorescence after silver nano-grain.
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 30 min, and taking-up after having cleaned, baking oven is dried for standby.
2、TiO2Slurry preparation:
1g titanium dioxide is taken, stirring plus ultrasonic one day night in 20 mL dehydrated alcohols is dispersed in, takes 2mL(5% ethyl cellulose
Plain terpinol) above-mentioned reaction solution is added, for 24 hours, then 70 DEG C of rotary evaporations, ethyl alcohol evaporating completely therein is fallen, is obtained for stirring
Uniform and stable nano titania slurry.
Comparison example of the present invention:
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 double-layer structure CeO that embodiment 1 is prepared are used2:Yb/Er@SiO2@Ag is hollow
Ball nano material 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 be 10 DEG C/
Furnace temperature is risen to 450 DEG C, taken out after 30min high-temperature calcination by min.Sample is immersed in N719 dyestuff again, is being kept away after sealing
After placing 48h under striation part, 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 double-layer structure CeO that embodiment 1 is prepared are used2: Yb/Er hollow sphere nanometer material
Material 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
450 DEG C are risen to, is taken out after 30min high-temperature calcination.Sample is immersed in N719 dyestuff again, is being protected from light condition decentralization after sealing
After setting 48h, taking-up is rinsed well with dehydrated alcohol, obtains dye-sensitized solar cell anode material.
Comparison example 3:
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 is used, then by bilayer CeO made of 1 method of embodiment2:Yb/Er@SiO2Hollow sphere nanometer
Material 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 rise is taken out after 30min high-temperature calcination to 450 DEG C.Sample is immersed in N719 dyestuff again, after sealing under the conditions of being protected from light
After placing 48h, taking-up is rinsed well with dehydrated alcohol, obtains dye-sensitized solar cell anode material.
Four, performance test:
By the above embodiment of the present invention and comparative example 1,2,3, dye-sensitized solar cell anode obtained is used as respectively
Steps are as follows by DSSC: assembled battery first, uses platinum electrode for electrode, up by the conduction of working electrode, and to electrode
Conducting surface directed downwardly is picked up to press from both sides into sandwich structure, then inject electrolyte between electrodes, carry out dye sensitization with clip
The I-V curve of solar battery is tested.
In Fig. 6, 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: comparison example 3 obtains dye-sensitized solar cell anode material I-V characteristic curve graph.
Curve d is represented: the embodiment of the present invention 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 | 13.42 | 0.70 | 0.67 | 6.31 |
| Comparison example 2 | 17.03 | 0.73 | 0.63 | 7.90 |
| Comparison example 3 | 17.13 | 0.73 | 0.63 | 7.91 |
| Comparison example of the present invention | 19.23 | 0.73 | 0.61 | 8.50 |
From the data in table 1 and Fig. 6 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 1,2,3, the short-circuit current density (Jsc) and light of comparison example of the present invention
Photoelectric transformation efficiency (η) is all enhanced.Short-circuit current density (Jsc) is up to 19.23 mA/cm2, impact factor (FF) reaches
To 73%, photoelectric conversion efficiency (η) is up to 8.5%.
These are the results showed that using double-layer structure CeO made of the method for the present invention2:Yb/Er@SiO2@Ag complex nucleus
Shell nano hollow sphere material effectively can convert visible light for near-infrared and infrared light, improve the utilization rate and photoelectric conversion of light
Efficiency.
Claims (8)
1. a kind of preparation method of compound nucleocapsid nano-hollow ball, it is characterised in that the following steps are included:
1) urea is dispersed in ultrapure water under ultrasound condition, is then blended into trisodium citrate aqueous solution, obtain citric acid three
The urea dispersing agent of sodium；
2) by after the urea dispersant of seven water cerous chlorates and trisodium citrate, ytterbium nitrate aqueous solution and erbium nitrate are added
Aqueous solution, then aqueous hydrogen peroxide solution is added dropwise, stirring obtains faint yellow mixed solution；
3) faint yellow mixed solution is placed in autoclave and carries out hydro-thermal reaction；
4) mixture after hydro-thermal reaction is cooled to room temperature, then is dispersed with water and ethyl alcohol, through centrifuging and taking solid formation, then dried,
Obtain double-layer structure CeO2: Yb/Er hollow sphere nanosphere；
5) under ultrasound condition, by double-layer structure CeO2: Yb/Er hollow sphere nanosphere is scattered in isopropanol, the isopropanol and double
Layer structure C eO2: the feed ratio of Yb/Er hollow sphere nanosphere is 2mL: 1mg；It is mixed again with what is be made of ammonium hydroxide and tetraethyl orthosilicate
It closes solution mixing and carries out water-bath, the volume ratio that feeds intake of isopropanol, ammonium hydroxide and TEOS is 8: 1: 0.14；After reaction from
The heart takes solid phase drying, calcining, and dry temperature environment is 80 DEG C, and calcination temperature is 1100 DEG C, calcination time 2h；It obtains double-deck
CeO2:Yb/Er@SiO2Hollow sphere nanosphere；
6) by double-layer structure CeO2:Yb/Er@SiO2Hollow sphere nanosphere is mixed with polyvinylpyrrolidone to be placed in ethylene glycol, then
Silver nitrate aqueous solution is added and sodium borohydride aqueous solution is reacted, is centrifuged after reaction, takes solid phase dry, obtains double-layer structure
CeO2:Yb/Er@SiO2The compound nucleocapsid nano-hollow ball of@Ag.
2. preparation method according to claim 1, it is characterised in that in the step 1), be used for mixed trisodium citrate
The concentration of aqueous solution is 10mM/L；The mixing ratio of urea and trisodium citrate aqueous solution is 1g: 80 mL.
3. preparation method according to claim 1, it is characterised in that in the step 2, seven water cerous chlorates and citric acid
The mass ratio that feeds intake of urea is 1.2: 1 in the urea dispersing agent of trisodium；The concentration of ytterbium nitrate solution is 0.1M, Nitrate Solution
Concentration be 0.1M, seven water cerous chlorates, ytterbium nitrate solution and Nitrate Solution the volume ratio that feeds intake be 96.7: 0.3: 3；With
The mass percent of hydrogen peroxide is 30% in the aqueous hydrogen peroxide solution of dropwise addition, the aqueous hydrogen peroxide solution and citric acid
The feed ratio of urea is 1mL: 1g in the urea dispersing agent of trisodium.
4. preparation method according to claim 1, it is characterised in that in the step 3), the environment temperature of the hydro-thermal reaction
Degree is 180 DEG C, reaction time 20h.
5. preparation method according to claim 1, it is characterised in that in the step 4), the temperature environment of the drying is
80℃。
6. preparation method according to claim 1, it is characterised in that in the step 6), the silver nitrate aqueous solution it is dense
Degree is 0.047M, and the concentration of sodium borohydride aqueous solution is 120mM；The double-layer structure CeO2:Yb/Er@SiO2Hollow sphere nanosphere
Feed ratio with polyvinylpyrrolidone, silver nitrate aqueous solution is 1mg:1.3mg: 0.125ml；Silver nitrate aqueous solution and hydroboration
The volume ratio that feeds intake of sodium water solution is 1.25: 1；The temperature condition of reaction is 90 DEG C；The temperature environment of drying is 70~80 DEG C.
7. the double-layer structure CeO of method preparation as described in claim 12:Yb/Er@SiO2The compound nucleocapsid nano-hollow ball of@Ag exists
Application in dye-sensitized solar cell anode, it is characterised in that: nano titania slurry is first coated in FTO glass
Surface forms nano titania slurry layer, then by the double-layer structure CeO2:Yb/Er@SiO2The compound nucleocapsid nano-hollow of@Ag
Ball is coated in nano titania slurry layer surface using method for printing screen, and after 450 DEG C of calcinings, leaching is sealed under the conditions of being protected from light
It steeps after N719 dyestuff 48h, taking-up is rinsed well with dehydrated alcohol, obtains dye-sensitized solar cell anode material.
8. application according to claim 7, it is characterised in that: the grain diameter of the nano-titanium dioxide be 25 nm ±
The number of plies of 10 nm, the nano titania slurry coating are 6~8 layers, the double-layer structure CeO2:Yb/Er@SiO2@Ag is multiple
The number of plies of synkaryon shell nano-hollow ball coating is 1~2 layer.
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