CN107039190B - A kind of dye-sensitized solar cells comprising titanium dioxide hollow ball structure - Google Patents
A kind of dye-sensitized solar cells comprising titanium dioxide hollow ball structure Download PDFInfo
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- CN107039190B CN107039190B CN201710267798.XA CN201710267798A CN107039190B CN 107039190 B CN107039190 B CN 107039190B CN 201710267798 A CN201710267798 A CN 201710267798A CN 107039190 B CN107039190 B CN 107039190B
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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
- 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
This application involves a kind of dye-sensitized solar cells comprising titanium dioxide hollow ball structure, including light anode, dye sensitizing agent, redox electrolyte and to electrode, which includes FTO substrate, ZnO microsphere layer and TiO2Hollow layers of balls, wherein the ZnO microsphere layer is set to FTO substrate surface, the TiO2Hollow layers of balls is set to ZnO microsphere layer surface.
Description
Technical field
This application involves field of dye-sensitized solar cells more particularly to a kind of comprising titanium dioxide hollow ball structure
Dye-sensitized solar cells.
Background technique
The energy is the important material base of national economy and social development, currently, relying primarily on petroleum, coal, natural gas
Equal traditional energies, but bring environmental problem is got worse in the finiteness and development process of traditional energy, seriously constrain through
The development of Ji and society.And solar energy is inexhaustible, nexhaustible clean energy resource, is well positioned to meet the mankind to the energy
Demand, but with regard to the high cost of current solar battery be always solar battery promote the use of bottleneck and solar-electricity
The prerequisite that can pond promote the use of on a large scale.
Dye-sensitized solar cells (DSSC), with its abundant raw materials, at low cost, nontoxic, relatively simple production work
The advantages that skill, has attracted the extensive concern of educational circles, industry, currently, finding it is most be based on TiO2The small area of film contaminates
Expect sensitization solar battery, many because being known as of DSSC photoelectric conversion efficiency is influenced, including light anode, to electrode, dyestuff
Sensitizer, redox electrolyte, cell package etc., especially light anode have the photoelectric conversion efficiency of battery heavy to closing
The influence wanted.In order to improve light anode, people are exploring always different approach, including the nanometer material for preparing different-shape
Material.
Summary of the invention
The present invention is intended to provide a kind of dye-sensitized solar cells comprising titanium dioxide hollow ball structure, on solving
State proposition problem.
A kind of dye-sensitized solar cells comprising titanium dioxide hollow ball structure is provided in the embodiment of the present invention,
Including light anode, dye sensitizing agent, redox electrolyte and to electrode, the light anode include FTO substrate, ZnO microsphere layer and
TiO2Hollow layers of balls, wherein the ZnO microsphere layer is set to FTO substrate surface, the TiO2Hollow layers of balls is set to ZnO microsphere layer surface.
The technical solution that the embodiment of the present invention provides can include the following benefits:
Dye-sensitized solar cells of the invention includes light anode, dye sensitizing agent, redox electrolyte and to electricity
Pole, the light anode include FTO substrate, ZnO microsphere layer and TiO2Hollow layers of balls, wherein the ZnO microsphere layer is set to FTO substrate table
Face, the TiO2Hollow layers of balls is set to ZnO microsphere layer surface；In above-mentioned ZnO microsphere, TiO2Under the synergistic effect of hollow sphere, so that this
The light anode of application has biggish mention in terms of Dye Adsorption performance, specific surface area, light scattering property, electronic transmission performance
Height effectively increases photoelectric conversion efficiency.
The additional aspect of the application and advantage will be set forth in part in the description, and will partially become from the following description
It obtains obviously, or recognized by the practice of the application.It should be understood that above general description and following detailed description are only
Be it is exemplary and explanatory, the application can not be limited.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawings, but the embodiment in attached drawing is not constituted to any limit of the invention
System, for those of ordinary skill in the art, without creative efforts, can also obtain according to the following drawings
Other attached drawings.
Fig. 1 is the structural schematic diagram of dye-sensitized solar cells of the present invention.
Wherein, 1- light anode, 3- redox electrolyte, 4- is to electrode, 11-FTO substrate, 12-ZnO microballoon layer, 13-
TiO2Hollow layers of balls.
Specific embodiment
Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to
When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment
Described in embodiment do not represent all embodiments consistented with the present invention.On the contrary, they be only with it is such as appended
The example of device and method being described in detail in claims, some aspects of the invention are consistent.
Embodiments herein is related to a kind of dye-sensitized solar cells comprising titanium dioxide hollow ball structure, the dye
Material sensitization solar battery includes light anode 1, dye sensitizing agent, redox electrolyte 3 and to electrode 4, wherein light sun
Pole 1 includes titanium dioxide hollow ball structure.
It is to be printed with platinum in the upper surface of FTO substrate to electrode 4；Dye sensitizing agent is N719 ruthenium dye；Redox electricity
The component for solving matter 3 is the tert-butyl of the 1- butyl -3- methylimidazole salt compounded of iodine of 0.6mol/l, the iodine of 0.03mol/l, 0.5mol/l
Pyridine, the guanidine thiocyanate of 0.1mol/l, 0.05mol/l lithium iodide acetonitrile solution.
The light anode 1 includes FTO substrate 11, ZnO microsphere layer 12 and TiO2Hollow layers of balls 13, wherein the ZnO microsphere layer 12
Set on 11 surface of FTO substrate, the TiO2Hollow layers of balls 13 is set to 12 surface of ZnO microsphere layer, and specific structure is as shown in Figure 1.
In the light anode 1, including TiO2Hollow layers of balls 13, wherein the TiO2Hollow layers of balls 13 is with a thickness of 30 μm, TiO2
Hollow bulb diameter is 10 μm, the TiO2Hollow sphere is prepared by template of pollen, the TiO2The spherical shell layer of hollow sphere be by
TiO2It is nanocrystalline to reunite.
In the light anode of the application, different from TiO under normal circumstances2Particle, and use TiO2Hollow ball structure, at this
TiO2It in hollow sphere, is prepared by template of pollen, therefore, spherical shell layer surface exhibits are that the hole of the opening of similar pollen is netted
Structure, and the spherical shell layer is by TiO2It is nanocrystalline to reunite, under this kind of structure, in addition to biggish specific surface area
It can adsorb outside more dyestuff, additionally it is possible to effectively improve the scattering property of light.
In the light anode 1, in FTO substrate 11 and TiO2It is additionally provided with ZnO microsphere layer 12 between hollow layers of balls 13, the ZnO
Microballoon layer 12 is with a thickness of 30 μm, and the diameter of the ZnO microsphere is 2 μm, and above-mentioned ZnO microsphere is formed by ZnO nano particle agglomeration
, which is 30nm.
In the light anode of the application, different from TiO under normal circumstances2Particle, in FTO substrate and TiO2Hollow layers of balls it
Between be equipped with ZnO microsphere layer, zinc oxide is a kind of semiconductor material with multiple functions, in gas sensor, field-causing electron
The fields such as transmitting, which have, to be widely applied, and zinc oxide material and titanic oxide material are combined as to the technical solution of optical anode material
Seldom, in the application, since zinc oxide and titanium dioxide have similar forbidden bandwidth and electron affinity, TiO2Hollow sphere with
ZnO microsphere combines, so that the absorption of dyestuff greatly increases.
In above-mentioned ZnO microsphere, TiO2Under the synergistic effect of hollow sphere, so that the light anode of the application is in Dye Adsorption
It is greatly improved in terms of energy, specific surface area, light scattering property, electronic transmission performance, effectively increases photoelectric conversion efficiency.
The preparation process of herein described dye-sensitized solar cells is as follows:
A, ZnO microsphere layer is prepared
A1, the two water zinc acetates of the methanol solution of 500ml and 8g are stirred evenly under magnetic stirring；
A2, then the FTO substrate cleaned up is put into the methanol solution, conductive face-up, 60 DEG C of constant temperature reactions
For 24 hours, then FTO substrate is taken out, cleans, dries；
A3, the FTO substrate calcined to 70min at 350 DEG C, heating rate is 6 DEG C/min, Temperature fall after calcining,
ZnO microsphere layer is obtained in FTO substrate；
B, TiO is prepared2Hollow sphere
B1, firstly, filter out 10 μm of diameter of rape petal pollen, take 6g to be rinsed with alcohol, be dry；
Ti (the SO of 3g is added into the deionized water of 150ml by b2, then4)2, 20min is stirred, then to above-mentioned deionization
The ammonium fluoride of 0.42g and the urea of 1.2g are added in water, stirs 30min, then 6g pollen is added into above-mentioned deionized water, stirring
Then above-mentioned deionized water is transferred in water heating kettle by 10min, by it in 180 DEG C of hydro-thermal reaction 15h, after reaction, collect
White precipitate in water heating kettle, and cleaned up, TiO is obtained after dry 10h at 80 DEG C in drying box2Hollow sphere；
C, light anode is prepared
C1, TiO obtained above is taken2Hollow sphere 2g, terpinol 7g, 10% ethyl cellulose ethanol solution 9g, will be upper
It states substance to be put into the ethanol solution of 30ml, continuous magnetic agitation, until ethyl alcohol volatilization becomes viscous syrup, obtains TiO2
Hollow sphere slurry；
C2, a small amount of TiO is taken2Hollow sphere slurry is coated in FTO substrate surface obtained in a3, dries, then by the FTO base
Anneal 1h in Muffle furnace at bottom, and annealing temperature is 440 DEG C, then again in 480 DEG C of annealing 1h, wherein heating rate be 1 DEG C/
Min after annealing, obtains the light anode of the application；
D, dyestuff is adsorbed
The above-mentioned light anode prepared is put into the ethanol solution of 50mmol/L N719 ruthenium dye and is impregnated for 24 hours,
Dye sensitizing agent remained on surface is washed away with dehydrated alcohol after taking-up, is kept in dark place after drying；
E, preparation is to electrode
One layer of platinum slurry is printed in the FTO substrate beating an aperture in advance and cleaning up, 420 DEG C in Muffle furnace
Lower sintering 30min, obtain load have platinum electrode to electrode；
F, it encapsulates
By the light anode obtained above for being adsorbed with dyestuff with to electrode, to folded, encapsulation injects electrolyte, seals aperture,
It is assembled into dye-sensitized solar cells.
It is tested using Keithley2400 digital power table and solar simulator (xenon lamp of light source 500W, AM=1.5)
The I-V indicatrix of obtained battery 1~3 obtains the open-circuit voltage V of dye cell from test resultocFor 0.97V, short circuit
Current density, JscFor 20.04mA/cm2, photoelectric conversion efficiency η is 11.5%, it can be seen that the dye sensitization of solar of the application
In battery, preferable photoelectric conversion efficiency is showed.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of dye-sensitized solar cells comprising titanium dioxide hollow ball structure, including light anode, dye sensitizing agent, oxygen
Change goes back original electrolyte and to electrode, which is characterized in that the light anode includes FTO substrate, ZnO microsphere layer and TiO2Hollow layers of balls,
Wherein, which is set to FTO substrate surface, the TiO2Hollow layers of balls is set to ZnO microsphere layer surface；The dyestuff is quick
The preparation process for changing solar battery is as follows:
A, ZnO microsphere layer is prepared
A1, the two water zinc acetates of the methanol solution of 500ml and 8g are stirred evenly under magnetic stirring；
A2, then the FTO substrate cleaned up is put into the methanol solution, conductive face-up, 60 DEG C of constant temperature are reacted for 24 hours, so
FTO substrate is taken out afterwards, cleans, dry；
A3, the FTO substrate is calcined to 70min at 350 DEG C, heating rate is 6 DEG C/min, Temperature fall after calcining, in FTO base
ZnO microsphere layer is obtained on bottom；
B, TiO is prepared2Hollow sphere
B1, firstly, filter out 10 μm of diameter of rape petal pollen, take 6g to be rinsed with alcohol, be dry；
Ti (the SO of 3g is added into the deionized water of 150ml by b2, then4)2, 20min is stirred, then into above-mentioned deionized water
The ammonium fluoride of 0.42g and the urea of 1.2g is added, stirs 30min, then 6g pollen is added into above-mentioned deionized water, stirring
Then above-mentioned deionized water is transferred in water heating kettle by 10min, by it in 180 DEG C of hydro-thermal reaction 15h, after reaction, collect
White precipitate in water heating kettle, and cleaned up, TiO is obtained after dry 10h at 80 DEG C in drying box2Hollow sphere；
C, light anode is prepared
C1, TiO obtained above is taken2Hollow sphere 2g, terpinol 7g, 10% ethyl cellulose ethanol solution 9g, by above-mentioned substance
It is put into the ethanol solution of 30ml, continuous magnetic agitation, until ethyl alcohol volatilization becomes viscous syrup, obtains TiO2Hollow sphere
Slurry；
C2, a small amount of TiO is taken2Hollow sphere slurry is coated in FTO substrate surface obtained in a3, dries, then the FTO substrate exists
Anneal 1h in Muffle furnace, and annealing temperature is 440 DEG C, and then again in 480 DEG C of annealing 1h, wherein heating rate is 1 DEG C/min, is moved back
After fire, the light anode of the application is obtained；
D, dyestuff is adsorbed
The above-mentioned light anode prepared is put into the ethanol solution of 50mmol/L N719 ruthenium dye and is impregnated for 24 hours, after taking-up
Dye sensitizing agent remained on surface is washed away with dehydrated alcohol, is kept in dark place after drying；
E, preparation is to electrode
One layer of platinum slurry is printed in the FTO substrate beating an aperture in advance and cleaning up, and is burnt at 420 DEG C in Muffle furnace
Tie 30min, obtain load have platinum electrode to electrode；
F, it encapsulates
By the light anode obtained above for being adsorbed with dyestuff with to electrode, to folded, encapsulation injects electrolyte, seals aperture, assembles
At dye-sensitized solar cells.
2. dye-sensitized solar cells according to claim 1, which is characterized in that the TiO2Hollow sphere layer is with a thickness of 30 μ
m。
3. dye-sensitized solar cells according to claim 2, which is characterized in that the TiO2Hollow bulb diameter is 10 μm,
The TiO2Hollow sphere is prepared by template of pollen, the TiO2The spherical shell layer of hollow sphere is by TiO2It is nanocrystalline to reunite.
4. dye-sensitized solar cells according to claim 1, which is characterized in that in FTO substrate and TiO2Hollow layers of balls
Between be additionally provided with ZnO microsphere layer, the ZnO microsphere layer is with a thickness of 30 μm.
5. dye-sensitized solar cells according to claim 4, which is characterized in that the diameter of the ZnO microsphere is 2 μm,
ZnO microsphere is as made of ZnO nano particle agglomeration, which is 30nm.
6. dye-sensitized solar cells according to claim 1, which is characterized in that be in the upper of FTO substrate to electrode
Surface printing has platinum；Dye sensitizing agent is N719 ruthenium dye；The component of redox electrolyte is the 1- butyl -3- of 0.6mol/l
Methylimidazole salt compounded of iodine, the iodine of 0.03mol/l, the tert .-butylpyridine of 0.5mol/l, the guanidine thiocyanate of 0.1mol/l, 0.05mol/l
Lithium iodide acetonitrile solution.
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Effective date of registration: 20181205 Address after: 221600 in Anguo Town, Peixian County, Xuzhou City, Jiangsu Province Applicant after: Peixian Guoyuan Photovoltaic Power Co., Ltd. Address before: 200331 2264, room 5, 5, Liu Yuan Road, Putuo District, Shanghai. Applicant before: Shanghai ran Environmental Protection Technology Co., Ltd. |
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