CN110136963A - Based on SnO2@Air@TiO2The dye-sensitized solar cells and preparation method of double hollow nucleocapsid sea urchin microballoons - Google Patents
Based on SnO2@Air@TiO2The dye-sensitized solar cells and preparation method of double hollow nucleocapsid sea urchin microballoons Download PDFInfo
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- CN110136963A CN110136963A CN201910224782.XA CN201910224782A CN110136963A CN 110136963 A CN110136963 A CN 110136963A CN 201910224782 A CN201910224782 A CN 201910224782A CN 110136963 A CN110136963 A CN 110136963A
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 241000257465 Echinoidea Species 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 101
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 50
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 50
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 50
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 50
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 22
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- 238000003756 stirring Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 206010070834 Sensitisation Diseases 0.000 claims description 10
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
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- 238000001354 calcination Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 230000001154 acute effect Effects 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 51
- 239000000463 material Substances 0.000 description 23
- 239000010410 layer Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 13
- 239000010936 titanium Substances 0.000 description 12
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- 229910052719 titanium Inorganic materials 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
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- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 210000000232 gallbladder Anatomy 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 230000005622 photoelectricity Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
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- 241000186216 Corynebacterium Species 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
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- 229910001432 tin ion Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/2036—Light-sensitive devices comprising an oxide semiconductor electrode comprising mixed oxides, e.g. ZnO covered TiO2 particles
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to technical field of solar batteries, disclose a kind of based on SnO2@Air@TiO2The dye-sensitized solar cells and preparation method of double hollow nucleocapsid sea urchin microballoons prepare SnO using one step hydro thermal method2Hollow spherical structure；By SiO2SnO is coated in as transition zone2Surface, then coat the sea urchin shape TiO of one layer of different-thickness2Structure；Highly basic washes away SiO2Form SnO2And TiO2Hollow layer between shell；Slurry is made in SATS microballoon powder and P25 powder；The photo-anode film of preparation is immersed into the N719 solution that concentration is 0.5mmol/L, impregnates for 24 hours, dye molecule is made sufficiently to be adsorbed on film surface.With pure TiO2Or SnO2DSSC is compared, and the DSSC based on SATS improves photovoltaic performance, and PCE value is 6.88% in tested battery.Influence by the different optical anode materials of different comparisons and structure to battery performance.
Description
Technical field
The invention belongs to technical field of solar batteries, more particularly to one kind to be based on SnO2@Air@TiO2Double hollow nucleocapsid seas
The dye-sensitized solar cells and preparation method of gallbladder microballoon.
Background technique
The dye-sensitized solar cells (DSSCs) that Gratzel and O'Regan was put forward for the first time in 1991 has production stream
The advantages that journey is simple, at low cost, photoelectric conversion efficiency is high, if becoming area of solar cell expert extensive discussions in recent years
Topic.In order to promote the performance of DSSCs as far as possible, researcher is dedicated to the porous TiO of nanoscale2Material is applied in light
Anode, and significant effect has been harvested, the reason is that TiO2With non-toxic, suitable forbidden bandwidth, good photoelectric characteristic, change
The advantages such as stability and reserves are big.Due to TiO2The photoelectric conversion efficiency of base DSSCs theoretically can exceed that 10%, study people
Member has been devoted to TiO2The research of chemical synthesis, microstructure and the photovoltaic characterization of material etc..Typical DSSCs is by contaminating
Expect molecule sensitization light anode, electrolyte and to electrode form.As a part most important in DSSCs, light anode is in photon
It collects and plays extremely important effect in electron-transport.The dye molecule being adsorbed in light anode fully absorbs photon, shape
At the electron hole pair of excitation state and electronics is inserted into light anode conduction band.In addition, the structure of light anode also greatly affects
The photoelectric properties of DSSCs.Light anode structure type of the nanostructure of classifying as current most advantage, generally has specific surface
The advantages that product is big, photon equilibrium state ability is strong, electron transfer rate is fast, to improve power conversion efficiency (PCE).
Currently, the immediate prior art: it has been developed that many different TiO2Structure, as with rough surface
Microballoon, hollow sphere, core-shell particles, mesoporous aggregation and other special constructions.Due to their own specific surface with higher
Long-pending and light scattering ability, these TiO2Structure has successfully improved the photoelectric conversion efficiency of DSSCs.For example, prepared by Fang et al.
The TiO of core-shell structure out2Microballoon (YSHSs), wherein the surface of shell be made of single crystal nanoplate (nanometer sheet is about 150nm,
With a thickness of 4-7nm), and directly this structure is used as the light anode of DSSCs.TiO2Core-shell particles (YSHSs) are a kind of effective
Improve the ideal graded structure of photoelectric properties.Porous and coarse shell is capable of increasing specific surface area, and then absorbs more
Dyestuff, while hollow structure can increase reflection path of the photon inside spherical shell, absorb photon by dyestuff as far as possible.
Problem of the existing technology is: TiO2Have the shortcomings that electron mobility is lower and surface state is more, single TiO2
Material will limit light induced electron and transmit in conduction band, promote electronics and hole (including oxidation state dye molecule and oxidation state I3 -) multiple
It closes.
It solves the scheme of above-mentioned technical problem: (1) can use the TiO of one-dimensional nano structure2Material (receive by such as nano wire
Rice stick, nanofiber etc.) and TiO2Core-shell particles combine, and construct bilayer film to improve electronic conduction ability, reduce dark current；
(2) other conductor oxidates and TiO are utilized2The mode of Material cladding, such as ZnO, SnO2And Fe2O3Deng, enhancing light anode it is whole
The electronic conduction ability of body inhibits itself and oxidation state dyestuff and oxidation state I3 -It is compound.Wherein, SnO2Have in DSSCs application
Advantage in two self performances.On the one hand, SnO2Electron mobility (100-200cm2V-1S-1) it is higher than TiO2(0.1-
1.0cm2V-1S-1), illustrate SnO2With better electric conductivity.On the other hand, SnO2Band gap (3.6eV) be greater than TiO2Band gap
(3.2eV) can promote the stability of DSSCs since the oxidation hole generated in valence band is less.The present invention mainly uses second
The design of scheme progress DSSCs photo-anode film.
Solve the difficulty of above-mentioned technical problem: SnO2Conduction band edge relative to TiO2There is the positive-displacement of 300mV, it can shadow
Ring SnO2The light sensitive characteristic of material, while isopotential point is lower, acidic carboxypolymer is fewer to the absorption of dye molecule.Therefore, how
Effectively absorb SnO2And TiO2Respective advantage study and construct reasonable graded structure, while how to be effectively shielded from
SnO2And TiO2Respective disadvantage promotes the power conversion efficiency of DSSCs to the greatest extent.
Solve the meaning of above-mentioned technical problem: for the photo-anode film of DSSCs, the adsorbance of dyestuff, photon dissipate
Penetrate ability and electron transfer rate all play the role of to the photoelectric properties of battery it is vital.Therefore, photo-anode film
Material selection and structure design affect Dye Adsorption amount, photon equilibrium state ability and the electron-transport speed of DSSCs to a certain extent
Rate.The present invention is by by SnO2And TiO2It is compound, and a kind of reasonable graded structure is constructed, not only maintain good dye
Expect adsorbance and photon equilibrium state ability, also solves TiO2The low problem of electron mobility facilitates the photoelectricity for promoting DSSCs
Performance.
Summary of the invention
In view of the problems of the existing technology, the present invention provides one kind to be based on SnO2@Air@TiO2Double hollow nucleocapsid sea urchins
The dye-sensitized solar cells and preparation method of microballoon.
The invention is realized in this way a kind of be based on SnO2@Air@TiO2The dye sensitization of double hollow nucleocapsid sea urchin microballoons is too
The preparation method of positive energy battery, it is described to be based on SnO2@Air@TiO2The dye-sensitized solar cells of double hollow nucleocapsid sea urchin microballoons
Preparation method the following steps are included:
The first step prepares SnO using one step hydro thermal method2Hollow spherical structure, particle size size be 200-300nm；
By way of collosol and gel, by SiO2SnO is coated in as transition zone2Surface, then coat the sea urchin shape of one layer of different-thickness
TiO2Structure；Highly basic washes away SiO2Form SnO2And TiO2Hollow layer between shell；
Slurry is made in SATS microballoon powder and P25 powder by second step；Before scratching slurry, FTO substrate is carried out clear
It washes and pre-processes；By treated, FTO substrate is fixed in the grinding tool of groove and posts adhesive tape controls the thickness of photo-anode film
Degree, makes effective glazed area 0.2cm2；Coated film is uniformly scraped with 45° angle scraper method；Successively scratch the P25 of the appropriate number of plies
Slurry and SATS microsphere slurries；Often scraping coated primary photo-anode film will heat 15 minutes in an oven, and maintain 125 DEG C
Constant temperature, and need nature to be down to room temperature after taking out, just scratched next time；Maintain 450 DEG C of calcining at constant temperature 30min, heating rate
For 1 DEG C/min, cooled to room temperature repeats the process of FTO substrate pre-treatment, obtains the multilayer photo-anode of SATS+P25
Film；
The photo-anode film of preparation is immersed the N719 solution that concentration is 0.5mmol/L, impregnates for 24 hours, make to contaminate by third step
Material molecule is adsorbed on film surface sufficiently to get to the photo-anode film after dye sensitization；It is thin to be cut out suitable PVC plastic
Piece, and be tightly attached on the conducting surface of FTO substrate；With two drop electrolyte I of syringe drop-/I3 -To film surface, after will clean
Pt electrode presses to the other side from FTO electro-conductive glass side, until whole air are discharged.
Further, the first step includes: that the preparation of optical anode material includes:
(1)SnO2The preparation of hollow microsphere: SnO is prepared using the hydro-thermal method of improvement2Hollow microsphere；Firstly, by 0.8mL salt
Acid solution 36wt% is added in the mixed solution of 33mL, and the volume ratio of dehydrated alcohol and deionized water is 10:1, lasting to stir
5min；Then by bis- hydrated stannous chloride SnCl of 0.263g22H2O is added above-mentioned mixed solution, and along with continuous ultrasound and
It stirs energetically；Continue after stirring 1h, mixed solution is transferred in the autoclave of the polytetrafluoroethylliner liner of 45mL and is sealed,
Hydro-thermal 12h at 200 DEG C.After cooled to room temperature, white depositions are collected by centrifugation with 9000r/min revolving speed, with anhydrous second
Pure and mild deionized water is respectively washed 3 times；Finally, sample is dried overnight at 60 DEG C；
(2)SnO2@SiO2The preparation of microballoon: using improvedMethod synthesizes SnO2@SiO2Microballoon is similar to colloidal sol
Gel method；In typical SiO2Under the uniform deposition mode of nano particle, first by 100mg SnO2It is dispersed in dehydrated alcohol
140ml and deionized water 35ml) mixed solution in, and energetically stir 30 minutes；Then, concentration is the ammonium hydroxide 2ml of 26wt%
It is added dropwise in above-mentioned solution with ethyl orthosilicate 0.3ml, after being ultrasonically treated 10min, continuously stirs 8h at room temperature.With
White depositions are collected by centrifugation in 8000r/min revolving speed, rear to use washes of absolute alcohol 4 times, and sediment is dried overnight at 60 DEG C,
Maintain 300 DEG C finally to calcine 2h, heating rate is 3 DEG C/min；
(3)SnO2@SiO2@TiO2The preparation of microballoon: the diethylentriamine of 0.05mL is well dispersed in isopropanol 40mL
In, 100mg SnO is added after being vigorously stirred2@SiO2Microballoon；X is respectively set to 0.1,0.3,0.5 and 0.7, corresponding product
It is respectively labeled as SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7；Mixing is added in the isopropyl titanate TIP of X mL
It quickly stirs in solution, until forming four kinds of different uniform suspension solutions, is sealed in the autoclave of polytetrafluoroethylliner liner,
Hydro-thermal is for 24 hours at 200 DEG C；It is cooled to room temperature taking-up naturally to water heating kettle, after high speed centrifugation, is cleaned and obtained repeatedly with dehydrated alcohol
Sample, be transferred in drying box, 8 hours of 60 DEG C of dryings obtain four kinds of different powder products；
(4)SnO2@Air@TiO2The preparation of microballoon: first by four kinds of SnO2@SiO2@TiO2100 mg of microballoon is scattered in respectively
In NaOH aqueous solution 120ml, 1.0M, continuous heating 1h in water-bath is put at 50 DEG C, and be stirred continuously；With 10000r/min
Sediment is collected by centrifugation in revolving speed, after with concentration be product is cleaned multiple times to acidity in 0.2mol/L nitric acid solution, use deionized water
Being cleaned multiple times to product is neutrality, ion presumable in product is washed away, and will be after product cleaning to neutrality；Four kinds are precipitated
Object is dried overnight at 60 DEG C, by product SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7 respectively in 450 DEG C of air
2h is calcined, heating rate is 3 DEG C/min.
Another object of the present invention is to provide one kind to be based on SnO by described2@Air@TiO2Double hollow nucleocapsid sea urchin microballoons
Dye-sensitized solar cells preparation method preparation dye-sensitized solar cells.
Another object of the present invention is to provide a kind of electric cars for being equipped with the dye-sensitized solar cells.
Another object of the present invention is to provide a kind of solar energy power accumulatings for being equipped with the dye-sensitized solar cells
Pond.
Another object of the present invention is to provide a kind of mobile phones for being equipped with the dye-sensitized solar cells.
Advantages of the present invention and good effect are as follows: the present invention is using easy and continuous hydro-thermal/collosol and gel/solvent heat
Method has been sequentially prepared SnO2、SnO2@SiO2、SnO2@SiO2@TiO2、SnO2@Air@TiO2, finally obtained double hollow nucleocapsids
Sea urchin microballoon (SATS) not only has excellent photon equilibrium state ability and Dye Adsorption ability, but also there is quick electronics to pass
Defeated rate.By SnO2And TiO2Respectively characteristic outstanding combines semiconductor material, and the microscopic appearance structure for arranging in pairs or groups special.Cause
This, with pure P25 or TiO2The DSSC of core-shell particles (YSHSs) is compared, and the DSSC based on SATS improves photovoltaic performance, in quilt
It surveys PCE value in battery and is up to 6.87%.Influence by the different optical anode materials of different comparisons and structure to battery performance,
The development of following photo-anode film can more preferably be instructed.The present invention and prior art TiO2Core-shell particles (YSHSs) it is various
Photoelectric properties parameter comparison is as follows:
According to the above important parameter comparison analysis, with prior art TiO2Core-shell particles (YSHSs) photo-anode film phase
Than double hollow nucleocapsid sea urchin microballoon (SATS) photo-anode films of the invention are in specific surface area, short-circuit current density, fill factor
There is apparent advantage with incident photon-to-electron conversion efficiency etc., therefore, SATS DSSCs prepared by the present invention has outstanding photoelectricity
Performance.
Detailed description of the invention
Fig. 1 is provided in an embodiment of the present invention based on SnO2@Air@TiO2The dye sensitization of double hollow nucleocapsid sea urchin microballoons is too
The preparation method flow chart of positive energy battery.
Fig. 2 is SnO provided in an embodiment of the present invention2、SnO2@SiO2、SnO2@SiO2@TiO2To SnO2@Air@TiO2Microballoon
Synthesis process schematic diagram.
Fig. 3 is SnO provided in an embodiment of the present invention2Microballoon (a), SnO2@SiO2Microballoon (b) and SATS-0.5 microballoon (c-
D) SEM figure.
Fig. 4 is SATS-0.1 (a), SATS-0.3 (b), SATS-0.5 (c) and SATS-0.7 provided in an embodiment of the present invention
(d) the TEM figure of microballoon；E is TiO2The fringe region of club shaped structure and the lattice distance figure of 0.238nm；F, g, h are respectively Ti
(f), the distribution diagram of element of O (g), Sn (h) element in single SATS microballoon.
Fig. 5 is SnO provided in an embodiment of the present invention2The XRD spectrum schematic diagram of hollow sphere and SATS microballoon.
Fig. 6 is the J-V curve synoptic diagram of five kinds of DSSCs provided in an embodiment of the present invention.
Fig. 7 is the diffusing reflection spectrum schematic diagram that five kinds of photo-anode films provided in an embodiment of the present invention are not impregnated with dyestuff.
Fig. 8 is diffusing reflection (a) and absorption (b) light of five kinds of photo-anodes film immersion dyestuff provided in an embodiment of the present invention
Compose schematic diagram.
Fig. 9 is that incident photon-current conversion efficiency (IPCE) curve of five kinds of DSSCs provided in an embodiment of the present invention shows
It is intended to.
Figure 10 is five kinds of DSSCs provided in an embodiment of the present invention Nyquist figure as obtained by EIS measurement, and illustration is impedance
The equivalent circuit simulation drawing of spectrum.
Figure 11 is the electron diffusion coefficient and electron lifetime schematic diagram of five kinds of DSSCs provided in an embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
For TiO2Electron mobility is lower and surface state more than disadvantage, single TiO2Material will limit light induced electron and exist
It is transmitted in conduction band, promotes electronics and hole (including oxidation state dye molecule and oxidation state I3 -) compound problem.The present invention is successively
It is prepared for SnO2、SnO2@SiO2、SnO2@SiO2@TiO2、 SnO2@Air@TiO2Microballoon is finally obtained in a manner of successively constructing
Double hollow nucleocapsid sea urchin microballoons (SATS).By the bis- hollow nucleocapsids of SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7
Sea urchin micro-sphere material is combined with P25.
Application principle of the invention is explained in detail with reference to the accompanying drawing.
As shown in Figure 1, provided in an embodiment of the present invention be based on SnO2@Air@TiO2The dyestuff of double hollow nucleocapsid sea urchin microballoons
The preparation method of sensitization solar battery the following steps are included:
S101: SnO is prepared using one step hydro thermal method2Hollow spherical structure, particle size size is about 200-300nm；
By way of collosol and gel, by SiO2SnO is coated in as transition zone2Surface, then coat the sea urchin shape of one layer of different-thickness
TiO2Structure；Last highly basic washes away SiO2Form SnO2And TiO2Hollow layer between shell；
S102: slurry is made in SATS microballoon powder and P25 powder；Before scratching slurry, to FTO substrate carry out cleaning and
Pretreatment；By treated, FTO substrate is fixed in the grinding tool of groove and posts adhesive tape controls the thickness of photo-anode film, is made
Effective glazed area is 0.2cm2；Coated film is uniformly scraped with 45° angle scraper method；Successively scratch the P25 slurry of the appropriate number of plies
With SATS microsphere slurries；Often scraping coated primary photo-anode film will heat 15 minutes in an oven, and maintain 125 DEG C of perseverances
Temperature, and need nature to be down to room temperature after taking out, it can just be scratched next time；Maintain 450 DEG C of calcining at constant temperature 30min, heating speed
Rate is 1 DEG C/min, and cooled to room temperature repeats the process of FTO substrate pre-treatment, obtains the multilayer light anode of SATS+P25
Film；
S103: the photo-anode film of preparation is immersed into the N719 solution that concentration is 0.5mmol/L, impregnates for 24 hours, makes dyestuff point
Son is adsorbed on film surface sufficiently to get to the photo-anode film after dye sensitization；It is cut out suitable PVC plastic thin slice, and
It is tightly attached on the conducting surface of FTO substrate；With two drop electrolyte (I of syringe drop-/I3 -) arrive film surface, after the Pt that will clean
Electrode presses to the other side from FTO electro-conductive glass side, until whole air are discharged.
Application effect of the invention is described in detail below with reference to experiment.
1. experimental section
The preparation of 1.1 optical anode materials
(1)SnO2The preparation of hollow microsphere: SnO is prepared using the hydro-thermal method of improvement2Hollow microsphere.Firstly, by 0.8mL salt
Acid solution (36wt%) is added in the mixed solution of 33mL (volume ratio of dehydrated alcohol and deionized water is 10:1), lasting to stir
5min.Then by bis- hydrated stannous chloride (SnCl of 0.263g22H2O it) is slowly added to above-mentioned mixed solution, and along with continuous
Ultrasound and stir energetically.Continue after stirring 1h, mixed solution is transferred to close in the autoclave of the polytetrafluoroethylliner liner of 45mL
Envelope, the hydro-thermal 12h at 200 DEG C.After cooled to room temperature, white depositions are collected by centrifugation with 9000r/min revolving speed, with nothing
Water-ethanol and deionized water are respectively washed 3 times.Finally, sample is dried overnight at 60 DEG C.
(2)SnO2@SiO2The preparation of microballoon: using improvedMethod synthesizes SnO2@SiO2Microballoon is similar to colloidal sol
Gel method.In typical SiO2Under the uniform deposition mode of nano particle, first by 100mg SnO2It is dispersed in dehydrated alcohol
In (140ml) and the mixed solution of deionized water (35ml), and stir 30 minutes energetically.Then, concentration is the ammonium hydroxide of 26wt%
(2ml) and ethyl orthosilicate (0.3ml) are added dropwise in above-mentioned solution, after being ultrasonically treated 10min, are continuously stirred at room temperature
8h.White depositions are collected by centrifugation with 8000r/min revolving speed, it is rear to use washes of absolute alcohol 4 times, by sediment in 60 DEG C of dryings
Overnight, 300 DEG C are maintained finally to calcine 2h, heating rate is 3 DEG C/min.
(3)SnO2@SiO2@TiO2The preparation of microballoon: the diethylentriamine of 0.05mL is well dispersed in isopropanol (40mL)
In, 100mg SnO is added after being vigorously stirred2@SiO2Microballoon.In order to study the various dose of precursor liquid isopropyl titanate (TIP) to production
X is respectively set to 0.1,0.3,0.5 and 0.7 by the influence of the form and property of object, and corresponding product is respectively labeled as SATS-
0.1, SATS-0.3, SATS-0.5 and SATS-0.7.Therefore, the isopropyl titanate (TIP) of X mL is added fast in mixed solution
Speed stirring seals, at 200 DEG C until forming four kinds of different uniform suspension solutions in the autoclave of polytetrafluoroethylliner liner
Lower hydro-thermal is for 24 hours.It is cooled to room temperature taking-up naturally to water heating kettle, after high speed centrifugation, the sample cleaned repeatedly with dehydrated alcohol,
It is transferred in drying box, 8 hours of 60 DEG C of dryings obtain four kinds of different powder products.
(4)SnO2@Air@TiO2The preparation of microballoon: first by four kinds of SnO2@SiO2@TiO2Microballoon (100 mg) is uniform respectively
It is scattered in NaOH aqueous solution (120ml, 1.0M), continuous heating 1h in water-bath is put at 50 DEG C, and be stirred continuously.With
Sediment is collected by centrifugation in 10000r/min revolving speed, after with concentration be that product is cleaned multiple times to acidity in 0.2mol/L nitric acid solution,
It is neutral for being cleaned multiple times with deionized water to product, ion presumable in product is washed away, and will be after product cleaning to neutrality.
Four kinds of sediments are dried overnight at 60 DEG C, product SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7 are existed respectively
2h is calcined in 450 DEG C of air, heating rate is 3 DEG C/min.In order to which SnO is more clearly understood2@Air@TiO2The conjunction of microballoon
At details, SnO is depicted2Hollow microsphere, SnO2@SiO2Microballoon, SnO2@SiO2@TiO2Microballoon is until SnO2@Air@TiO2Microballoon
Specific synthesis process schematic diagram, be illustrated in fig. 2 shown below.
The preparation of 1.2 multilayer photo-anode films
Slurry is made in SATS microballoon powder (SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7) and P25 powder
Material.Pay attention to before scratching slurry, FTO substrate need to be cleaned and be pre-processed.By treated, FTO substrate is fixed on groove
In grinding tool and adhesive tape is posted to control the thickness of photo-anode film, makes effective glazed area 0.2cm2.Then, 45° angle is used
Scraper method uniformly scrapes coated film.The P25 slurry and SATS microsphere slurries for successively scratching the appropriate number of plies, make to be assembled into DSSCs's
Photoelectric characteristic is best, it is therefore desirable to multiple comparative experiments.Often scraping coated primary photo-anode film will heat in an oven
15 minutes, and 125 DEG C of constant temperature are maintained, and need nature to be down to room temperature after taking out, it can just be scratched next time.Scrape coated film
The sliminess of number and slurry has codetermined the thickness of film and the photoelectric characteristic of battery.Finally, 450 DEG C of constant temperature is maintained to forge
30min is burnt, heating rate is 1 DEG C/min, and cooled to room temperature repeats the process of FTO substrate pre-treatment to get SATS+ is arrived
The multilayer photo-anode film of P25.For the needs of experiment, the photo-anode film of pure P25 has been obtained with same preparation method
The assembling of 1.3DSSCs
The photo-anode film of preparation is immersed into the N719 solution that concentration is 0.5mmol/L, impregnates for 24 hours, fills dye molecule
Film surface point is adsorbed on to get to the photo-anode film after dye sensitization.It is cut out suitable PVC plastic tab, and is close to
On the conducting surface of FTO substrate.With two drop electrolyte (I of syringe drop-/I3 -) arrive film surface, after the Pt electrode that will clean
The other side is pressed to from FTO electro-conductive glass side, until whole air are discharged.Two electrodes finally are clamped with clip, can be obtained
SnO2/TiO2Laminated film DSSCs, so that it may carry out photoelectric characteristic and test.
2 results
2.1 material characterization
(1)SnO2@Air@TiO2The SEM of double hollow nucleocapsid sea urchin microballoons is characterized
Electron scanning Electronic Speculum (SEM) is irradiated to the sample products of each step experiment, is detailed in order to be carried out to SATS microballoon
The characterization of thin structure and pattern.As in Fig. 3 a it can be seen that, SnO2The favorable dispersibility of microballoon, spherome surface bumps are not
It is flat, while there is certain homogeneity, but be also not excluded for the partial size of certain microballoons and other microballoons compare it is bigger than normal.Microspherulite diameter is big
About 250 ± 50nm.Therefore, next collosol and gel and solvent heat are tested, the SnO2Microballoon is good spherical template.
By in Fig. 4 a it can clearly be seen that SnO2Microballoon is by a large amount of SnO2It is anti-by hydro-thermal made of the accumulation of nanometer little particle and fusion
The influence of time, temperature and the acid-base property answered, tin ion are hydrolyzed into nano particle and complete the process of self assembly.Regrettably,
SEM Electronic Speculum did not photograph SnO2The hollow structure of microballoon can observe hollow structure by transmission electron microscope (TIM).
As shown in Figure 4 b, SnO2Microballoon is located at SnO2@SiO2The center of microballoon, using the method for collosol and gel, by SiO2It receives
Rice grain is uniformly coated on SnO2Microsphere surface.SnO2@SiO2The diameter of microballoon increases to about 400 ± 50nm, while SiO2
The thickness of nano particle is about 80nm.It is shown from Fig. 3 b, SiO2After nano particle cladding, which is still presented good dispersibility
And size is relatively uniform.SnO2@SiO2Microsphere surface is very smooth, while SiO2Nano particle has good translucency.It is worth
It is noted that the microballoon of a small amount of and dispersion small particle appears in SEM figure, it may be possible to SiO have occurred2Nano particle from group
Dress, the SnO that can be coated2Microballoon has had reached saturation state.
In SnO2Hollow ball and TiO2Layer builds completion, and washes away SiO with highly basic2After nano particle, it is bis- to can be obtained SATS
Hollow nucleocapsid sea urchin micro-sphere structure.As shown in Figure 3c, the diameter of SATS microballoon increases to about 600nm, and partial size starts to become not
It is uniform.TiO2Nano particle is random on the surface of spherical shell and closely grows, and 24 hours solvent thermal reactions make TiO2Nanometer
Particle is grown along (001) crystal face, and forms the corynebacterium nanostructure of a large amount of length about 100nm, and microsphere surface is gradually
Become rough porous.Mutual winding and connection occur for the short bar structure of different SATS microsphere surfaces, although losing certain
Dispersibility, but this is very beneficial for transmitting effect of the light induced electron between SATS microballoon.It can be seen that a table in Fig. 4 d
The SATS microballoon of face rupture and its inside and outside microstructure.It is about 80nm that the position of rupture, which can see a thickness,
Hollow layer and a surface irregularity interior ball, it is sufficient to illustrate that NaOH aqueous solution has washed away SiO2Nano particle, because
SiO2Silicate may be generated under alkaline condition.
(2)SnO2@Air@TiO2The TEM of double hollow nucleocapsid sea urchin microballoons is characterized
In order to further study the bis- hollow nucleocapsid sea urchin microballoons of SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7
Nano structure, complete to the TEM of specimen material characterization, as shown in Figure 3.It was found that the SnO in core position2It is micro-
Ball color is deep, but its center shows certain translucency, therefore SnO2The hollow structure of microballoon is tested
Card.Although SnO2The size of hollow ball is not uniform enough, but surface relative smooth.It can be found from each TEM figure, SnO2It is hollow
Ball and TiO2There is the hollow layer of one fixed width, SnO in outer interlayer2Hollow ball can be in TiO2In the inner space of outer layer freely
Movement, illustrate SnO2The surface coated SiO of hollow ball2Nano particle is washed away by highly basic, while double hollow and extra large without destroying
The structure of gallbladder shape.With regard to TiO2For layer, TiO2Particle along the continuous crystalline growth of (101) crystal face, is formed fine and close on the surface of the microsphere
And irregular nanorod structure, the length of nanometer rods tips branch are about 30nm, advantageously form porous structure and increase ratio
Surface area, to promote dye molecule to adsorb.Between SATS microballoon, is contacted with each other or connected by nanorod structure, though it reduces
The dispersibility of structure, but the transmission rate of light induced electron is effectively promoted.In addition, from figure 3, it can be seen that with TiO2Content
Increase, TiO2The color of layer structure gradually deepens, and thickness is also being slowly increased.By micro- to the bis- hollow nucleocapsid sea urchins of SATS
The high-resolution TEM image of ball characterizes, to study the nanocrystalline structure of SATS microballoon.Such as Fig. 4 e it is found that some TiO2It is rodlike
The fringe region of structure and the lattice distance of 0.238nm are corresponding, are anatase TiO2(004) face illustrates that these nanometer rods are
It is grown along (004) direction, and TiO2Nanometer rods have good crystallinity.
In order to explore elemental distribution of Ti, O, Sn element in single SATS microballoon, complete based on electron scanning
The EDS of Electronic Speculum is characterized, as shown in Fig. 4 f- Fig. 4 h.With SATS-0.1, SATS-0.3, SATS-0.5 and SATS- of Fig. 4 a to Fig. 4 d
0.7 pair of hollow nucleocapsid sea urchin microballoon matches, it is found that the outer shell that SATS microballoon is distributed in Ti element set, Sn element mainly divide
Cloth is in the core position of SATS microballoon, and O Elemental redistribution is in entire SATS microballoon.In addition, being in the Sn element point set of outer shell
Not as good as more than Ti element and O number of elements and densely distributed, it is understood that there may be two kinds of reasons: one, in the effect of hydro-thermal reaction and calcining
Under, sub-fraction SnO2The same SnO of particle2After hollow ball separation, freely disperses and be adsorbed on TiO2Outer shell；Two, SnO2It is hollow
Ball is made sub-fraction SnO by alkali corrosion2Particle disintegrates and is dispersed in TiO2Outer shell.Therefore, SnO is further illustrated2
The same TiO of hollow ball2Shell exists together.
(3)SnO2@Air@TiO2The XRD characterization of double hollow nucleocapsid sea urchin microballoons
In order to further probe into the crystal structure of specimen material, to the SnO successively prepared2Hollow sphere and the bis- hollow cores of SATS
Shell sea urchin microballoon has carried out X ray diffracting spectrum characterization, and characterization situation is as shown in Figure 4.SnO2The diffraction maximum of hollow sphere all with
Cassiterite phase SnO2The characteristic peak of (JCPDS No.1-625) matches, and the intensity of diffraction maximum is very high and arranges, and illustrates SnO2
The good crystallinity of hollow sphere and orderly aligned, crystal face expose much.And the main diffraction maximum of SATS microballoon is at 2 θ=27.27 °
It is compared with standard anatase crystal face, corresponding (101) crystal face of the absorption peak, and the diffraction maximum is obviously sharp, illustrates that it has well
Crystallinity.By XRD spectrum it is found that other most of diffraction maximums of SATS microballoon all with cassiterite phase SnO2(JCPDS No.1-625)
Characteristic peak match, illustrate SnO2Hollow sphere is present in the kernel of SATS microballoon, not by the shadow of subsequent chemical reaction
It rings.It can be seen that SnO from the diffraction maximum state of SATS microballoon2And TiO2The diffraction maximum of nanocrystal may interact and produce
Raw obvious decrease, illustrates that the crystal structure of SATS microballoon is more complicated.
The characterization of 2.2DSSCs device performance
(1) J-V curve characterizes
In order to explore the bis- hollow optimal photoelectric properties of nucleocapsid sea urchin micro-sphere structure of this novel SATS, in third step packet
Cover TiO2In the experiment of nanocrystal, the different amounts of isopropyl titanate precursor liquid of 0.1ml, 0.3ml, 0.5ml and 0.7ml is measured and has made
Comparative experiments for reactant, for DSSCs.J-V curve contain open-circuit voltage, short-circuit current density, fill factor and
These four critical data (table 1) of incident photon-to-electron conversion efficiency, can effectively measure the output performance of DSSCs.This experiment uses number
Word source table (2400, Keithley), and the use of the xenon lamp of 1000W power is light source, so that its power density is reached 100mW/cm2,
If Fig. 5 is the J-V curve for being prepared into DSSCs and surveying under light illumination.
The photoelectric properties parameter of DSSCs under 1 different ratio of table
It will be appreciated from fig. 6 that the Jsc and η of the DSSCs of this SATS-0.5 proportion are respectively 13.72mA/cm2It, can with 6.87%
To find out that the DSSCs of the bis- hollow nucleocapsid sea urchin microballoons of SATS-0.5 is much higher than the photoelectric properties of the DSSCs of pure P25 nano particle,
It may be so that dye molecule is fully absorbed photon, simultaneously because its double hollow structure substantially increases the propagation path of photon
The specific surface area of increase increases the adsorbance of dye molecule, and the photoelectric properties of DSSCs are improved under collective effect.It is astonishing
, two significant datas of Jsc and η of the DSSCs of SATS-0.1 are below the DSSCs of P25.In SATS-0.1 microballoon,
TiO2Content far fewer than SnO2, with TiO2It compares, SnO2With better good conductivity but light sensitive characteristic it is not strong, and chemistry is steady
It is qualitative bad, excessive SnO2The photoelectric properties of battery can be weakened.And when the amount of isopropyl titanate increases to 0.7ml, SATS-0.7
DSSCs photoelectric properties be gradually reduced.Excessive TiO2The cladding and growth of nano particle, although helping to promote DSSCs's
Light sensitive characteristic, but increase TiO2The thickness of layer, increases the length of conduction band, to promote light induced electron and oxidation state dyestuff
With electrolyte I3 -It is compound.It is filled with for the factor, the FF of SATS-0.5 battery is maximum (69.1%), this is because optimal
SnO2@Air@TiO2Double hollow nucleocapsid sea urchin microballoons inhibit the compound of interface electronics and promote the transmission of electronics.In addition, hair
The open-circuit voltage of existing P25 battery is higher than SATS-X battery, is because of SnO2Band edge relative to TiO2There is the forward direction of 300mV
Displacement, will affect the photoelectric characteristic of battery.With pure TiO2It contaminates quick battery to compare, SnO2@TiO2Compound SATS-X DSSCs can be led
The forward migration for causing fermi level, may slow down the compound of interface electronics, make to capture density increase.
(2) reflection and absorption spectra characterization of the diffusing reflectance spectra and dip dyeing material of material are not disseminated
The diffusing reflection spectrum can reflect out the photon equilibrium state ability of thin-film material, and Fig. 7 shows the light sun of different ratio
Very thin films are in the diffusing reflection spectrum being not impregnated under dye conditions.Since the size of the bis- hollow nucleocapsid sea urchin microballoons of SATS is all in nanometer
Rank has reached highest photon reflectivity within the scope of the relatively small wavelength of 400-450nm.And when wavelength is more than 450nm, light
The scattering property of son gradually weakens, and illustrates that scattering power of the photon of longer wavelength in small size microballoon film is weak.In addition,
SATS-0.7 film shows strongest photon reflectivity in 400-450nm wave-length coverage, and as titanium source content is reduced, light
Sub- scattering power weakens, until being less than the reflectivity of P25, illustrates the TiO of special appearance2Outer layer potentially contributes to promote photon
Scattering power.
Fig. 8 be shown diffusing reflection spectrum (Fig. 8 a) of the photo-anode film of different ratio after impregnating N719 dyestuff and
Absorption spectrum (Fig. 8 b).It is worth noting that, diffusing reflection spectrum and the data of absorption spectrum are in symmetric relation.The suction of all films
The minimum of spectrum is received present in 550nm, it is strongest to illustrate that the dye molecule being adsorbed on film has the incident light of the wavelength
Sink effect.By Fig. 8 b it is found that the photonic absorption ability of SATS-0.5 film is all best on most of wave band, while
It can be seen that P25 film still remains higher photon reflectivity.But the photon equilibrium state ability of photo-anode film may be with
The photoelectric conversion efficiency (PCE) and monochromatic light ray photoelectric transformation efficiency (IPCE) of DSSCs has certain difference, because of PCE and IPCE
It is to be influenced by multiple performance parameter is common, represents the comprehensive photoelectric characteristic of battery, and diffusing reflection and absorption spectrum only reflect
The optical characteristics of film.
(3) monochromatic light ray photoelectric transformation efficiency (IPCE) characterizes
Fig. 9 is the DSSCs that the bis- hollow nucleocapsid sea urchin microballoons of the SATS of different ratio and P25 nano particle collectively constitute
Monochromatic light ray photoelectric transformation efficiency (IPCE) curve.The photo-anode film of this five kinds of DSSCs uses same N719 dyestuff,
Under the influence of the highest absorption peak of N719 dyestuff, strongest absorption peak is all shown in the position that natural optical wavelength is 525nm,
Therefore five kinds of batteries have obtained the peak of IPCE at 525nm.Compared with pure P25DSSCs, the SATS's of different ratio
DSSCs has bigger IPCE value in most spectral region, has in the wave-length coverage of 400nm-650nm more obvious
Promotion, main cause is promotion and the high-specific surface area of photon equilibrium state ability.The IPCE value of pure P25DSSCs is in most of light
All be in spectral limit it is minimum, because of TiO2Nano particle has simple microstructure, lacks the space of incident photon scattering,
And TiO2The specific surface area of nano particle is smaller, and the adsorbance of dye molecule is limited.As seen from the figure, in lambda1-wavelength
In the range of 400nm-650nm, with increasing for titanium elements content, IPCE value constantly increases.The IPCE of SATS-0.5DSSCs
Value reaches highest 70% in a length of 525nm of incident light wave.However, excessive titanium elements also result in the reduction of IPCE value, just
If the IPCE value of SATS-0.7DSSCs is both less than SATS-0.5DSSCs in most of wave-length coverage, excessive titanium elements increase
TiO is added2The thickness of shell, influences the scattering power of photon, while also limiting the absorption of dye molecule.
(4) AC impedance (EIS) characterizes
The ac impedance spectroscopy (EIS) of dark-state under the conditions of bias -0.8V is shown in Figure 10, and illustration is DSSCs
Equivalent circuit simulation drawing.The intensity of illumination of this experiment is 100mW/cm2, alternating voltage amplitude is 10mV, and frequency is in 0.1Hz-
Between 10KHz, further visited by the electrochemical impedance spectroscopy of the SATS-X DSSCs and pure P25 DSSCs of characterization different ratio
Study carefully the influence factor of DSSCs photoelectric properties.As Figure 10 Nyquist curve graph in, what small semicircle represented is electrolyte/Pt electricity
Electron-transport resistance between the interface of pole, and the electronics combined resistance between being dyestuff/electrolyte interface that large semicircle represents.It can by table 2
Know, the SATS DSSCs and pure P25DSSCs of four kinds of different ratios have used same electrolyte, N719 dyestuff, FTO conduction glass
Glass and Pt electrode, so the R inside the equivalent circuit simulation drawing of five kinds of batteries1And RsIt is identical.Utilize the equivalent electricity of illustration
Road carries out the Fitting Calculation of data, the composite impedance R of SATS-0.5DSSCs2It is more than other four kinds of SATS for 115.5 Ω
DSSCs and pure P25DSSCs.Therefore, the bis- hollow nucleocapsid sea urchin microballoons of this novel SATS can efficiently reduce dyestuff/electrolysis
Electronics between matter interface is compound, promotes the transmission of electronics, but excessive titanium elements also can make the structure go wrong and contain
The transmission of electronics.
The EIS parameter of DSSCs under 2 different ratio of table
(5) electron diffusion coefficient (Dn) and electron lifetime (τ e) characterization
The laser emitter that this experiment is adjustable with an intensity and wavelength constant is 600nm is light source, passes through and changes light
Open-circuit voltage (V is controlled according to intensityoc), and the electronics for influencing the SATS DSSCs and pure P25 DSSCs of four kinds of different ratios expands
Dissipate coefficient (Dn) and electron lifetime (τe), finally further probe into the photoelectric properties of five kinds of DSSCs.As shown in Figure 11, with open circuit
The increase of voltage, electron diffusion coefficient curve shows the trend of growth, and electron lifetime curve shows downward trend, because
Bigger for intensity of illumination, light induced electron is bigger along the kinetic energy that conduction band transmits, and then improves the quantity and speed of light induced electron diffusion
Rate.Importantly, electron diffusion coefficient (Dn) will receive photoanode thin film material microscopic appearance influence, and electron lifetime
(τe) but related with the structure of photo-anode film.
By observing electron diffusion coefficient curve, the D of the SATS DSSCs of four kinds of different ratiosnCurve is all pure
The top of P25DSSCs, and the D of SATS-0.5DSSCsnValue is maximum, illustrates that the electrons spread characteristic of SATS DSSCs is more preferable, can
It can be because this microballoon contacted with each other has better interface conductivity and high crystalline, and the P25 nanometer dispersed each other
Particle inhibits the transmission of light induced electron.And electron lifetime (τe) it is the important indicator for measuring the electron-transport efficiency of DSSCs.It is logical
Cross observation electron lifetime curve, the τ of the SATS DSSCs of four kinds of different ratioseCurve also all in the top of pure P25DSSCs, and
The electron lifetime of SATS-0.5DSSCs is maximum.Therefore, compared to nanoparticle structure, the electron lifetime of core-shell structure is longer,
The probability of recombination of the electron-hole pair of SATS DSSCs is smaller.In addition, increasing with titanium elements content, SATS DSSCs
Electron lifetime increasing, excessive titanium elements can inhibit the growth of electron lifetime instead, because of TiO2The thickness of shell is excessive,
Excessive crystal boundary can promote electronics compound.
A kind of easy and continuous hydro-thermal/collosol and gel/solvent heat method of major design of the present invention is sequentially prepared
SnO2、SnO2@SiO2、SnO2@SiO2@TiO2、SnO2@Air@TiO2Microballoon has been finally obtained double hollow in a manner of successively constructing
Nucleocapsid sea urchin microballoon (SATS).By the bis- hollow cores of SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7 of different ratio
Shell sea urchin micro-sphere material is combined with P25, completes a series of characterization of materials and DSSCs device performance.
First it is tin source with two hydrated stannous chlorides, has synthesized size uniformly and good dispersion using hydro-thermal method
SnO2Hollow mould cricket.Then smooth surface, the SnO of good dispersion have been synthesized with sol-gal process2@SiO2Microballoon, as mistake
Cross structure.Then using isopropyl titanate as titanium source, using solvent-thermal method, synthesized surface cover with it is fine and close and not regulation nanometer rods
SnO2@SiO2@TiO2Microballoon.Finally, with highly basic by SiO2Layer washes away, and forms SnO2@Air@TiO2Double hollow nucleocapsid sea urchins are micro-
Spherical structure.
SEM, TEM and XRD characterization are carried out to the material of preparation.By SEM and TIM figure it is found that double hollow structures can be promoted
Photon equilibrium state ability, TiO2The nanorod structure of layer growth can increase the specific surface area of material.The collective effect of various advantages
Under, it will the performance of battery is substantially improved.
Slurry is respectively prepared in the SATS microballoon and P25 of different ratio, when scraping coated film, by changing different layer ratios
(P25:SATS), effective test has been carried out respectively to the performance of these films, having obtained optimal layer than (P25:SATS) is
4:2.And when P25 particle and SATS microballoon collectively serve as optical anode material and layer compares for 4:2, the PCE of DSSC is up to
6.88%, the DSSCs (5.10%) far superior to based on P25 particle.In efficient DSSCs, the bis- hollow nucleocapsid sea urchins of SATS
Microballoon shows superior performance and enough potentiality, alternative traditional P25NPs.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (6)
1. one kind is based on SnO2@Air@TiO2The preparation method of the dye-sensitized solar cells of double hollow nucleocapsid sea urchin microballoons,
It is characterized in that, it is described to be based on SnO2@Air@TiO2The preparation method of the dye-sensitized solar cells of double hollow nucleocapsid sea urchin microballoons
The following steps are included:
The first step prepares SnO using one step hydro thermal method2Hollow spherical structure, particle size size be 200-300nm；By molten
The mode of glue gel, by SiO2SnO is coated in as transition zone2Surface, then coat the sea urchin shape TiO of one layer of different-thickness2Knot
Structure；Highly basic washes away SiO2Form SnO2And TiO2Hollow layer between shell；
Slurry is made in SATS microballoon powder and P25 powder by second step；Before scratching slurry, cleaning and pre- is carried out to FTO substrate
Processing；By treated, FTO substrate is fixed in the grinding tool of groove and posts adhesive tape controls the thickness of photo-anode film, makes to have
The glazed area of effect is 0.2cm2；Coated film is uniformly scraped with 45° angle scraper method；Successively scratch the appropriate number of plies P25 slurry and
SATS microsphere slurries；Often scraping coated primary photo-anode film will heat 15 minutes in an oven, and maintain 125 DEG C of constant temperature,
And need nature to be down to room temperature after taking out, just scratched next time；Maintaining 450 DEG C of calcining at constant temperature 30min, heating rate is 1 DEG C/
Min, cooled to room temperature repeat the process of FTO substrate pre-treatment, obtain the multilayer photo-anode film of SATS+P25；
The photo-anode film of preparation is immersed the N719 solution that concentration is 0.5mmol/L, impregnates for 24 hours, make dye molecule by third step
It is adsorbed on film surface sufficiently to get to the photo-anode film after dye sensitization；It is cut out suitable PVC plastic thin slice, and tight
It is attached on the conducting surface of FTO substrate；With two drop electrolyte I of syringe drop-/I3 -To film surface, after the Pt electrode that will clean
The other side is pressed to from FTO electro-conductive glass side, until whole air are discharged.
2. being based on SnO as described in claim 12@Air@TiO2The dye-sensitized solar cells of double hollow nucleocapsid sea urchin microballoons
Preparation method, which is characterized in that the first step includes: that the preparation of optical anode material includes:
(1)SnO2The preparation of hollow microsphere: SnO is prepared using the hydro-thermal method of improvement2Hollow microsphere；Firstly, 0.8mL hydrochloric acid is molten
Liquid 36wt% is added in the mixed solution of 33mL, and the volume ratio of dehydrated alcohol and deionized water is 10:1, persistently stirs 5min；It connects
By bis- hydrated stannous chloride SnCl of 0.263g22H2Above-mentioned mixed solution is added in O, and stirs along with continuous ultrasound and energetically
It mixes；Continue after stirring 1h, mixed solution is transferred in the autoclave of the polytetrafluoroethylliner liner of 45mL and is sealed, at 200 DEG C
Hydro-thermal 12h；After cooled to room temperature, white depositions are collected by centrifugation with 9000r/min revolving speed, with dehydrated alcohol and go from
Sub- water is respectively washed 3 times；Finally, sample is dried overnight at 60 DEG C；
(2)SnO2@SiO2The preparation of microballoon: using improvedMethod synthesizes SnO2@SiO2Microballoon is similar to collosol and gel
Method；In typical SiO2Under the uniform deposition mode of nano particle, first by 100mg SnO2It is dispersed in dehydrated alcohol 140ml
It is stirred 30 minutes in the mixed solution of deionized water 35ml), and energetically；Then, concentration is the ammonium hydroxide 2ml and positive silicon of 26wt%
Acetoacetic ester 0.3ml is added dropwise in above-mentioned solution, after being ultrasonically treated 10min, continuously stirs 8h at room temperature；With 8000r/
White depositions are collected by centrifugation in min revolving speed, rear to use washes of absolute alcohol 4 times, sediment is dried overnight at 60 DEG C, finally ties up
300 DEG C are held to calcine 2h, heating rate is 3 DEG C/min；
(3)SnO2@SiO2@TiO2The preparation of microballoon: the diethylentriamine of 0.05mL is well dispersed in isopropanol 40mL, acute
100mg SnO is added after strong stirring2@SiO2Microballoon；X is respectively set to 0.1,0.3,0.5 and 0.7, corresponding product is marked respectively
It is denoted as SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7；The isopropyl titanate TIP of X mL is added in mixed solution
Quickly stirring seals, 200 until forming four kinds of different uniform suspension solutions in the autoclave of polytetrafluoroethylliner liner
Hydro-thermal is for 24 hours at DEG C；It is cooled to room temperature taking-up naturally to water heating kettle, after high speed centrifugation, the sample that is cleaned repeatedly with dehydrated alcohol
Product are transferred in drying box, and 8 hours of 60 DEG C of dryings obtain four kinds of different powder products；
(4)SnO2@Air@TiO2The preparation of microballoon: first by four kinds of SnO2@SiO2@TiO2Microballoon 100mg is scattered in NaOH respectively
In aqueous solution 120ml, 1.0M, continuous heating 1h in water-bath is put at 50 DEG C, and be stirred continuously；With 10000r/min revolving speed
Sediment is collected by centrifugation, after with concentration be that 0.2mol/L nitric acid solution is cleaned multiple times product to acidity, it is multiple with deionized water
Cleaning to product is neutrality, ion presumable in product is washed away, and will be after product cleaning to neutrality；Four kinds of sediments are existed
60 DEG C are dried overnight, and product SATS-0.1, SATS-0.3, SATS-0.5 and SATS-0.7 are calcined in 450 DEG C of air respectively
2h, heating rate are 3 DEG C/min.
3. one kind is based on SnO as described in claim 1~2 any one2@Air@TiO2The dyestuff of double hollow nucleocapsid sea urchin microballoons
The dye-sensitized solar cells of the preparation method preparation of sensitization solar battery.
4. a kind of electric car for being equipped with dye-sensitized solar cells described in claim 3.
5. a kind of solar storage battery for being equipped with dye-sensitized solar cells described in claim 3.
6. a kind of mobile phone for being equipped with dye-sensitized solar cells described in claim 3.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099052A (en) * | 2016-07-23 | 2016-11-09 | 合肥工业大学 | A kind of carbon cladding SnO2hollow nanospheres composite and preparation method thereof |
| CN107144607A (en) * | 2017-06-27 | 2017-09-08 | 中国科学院合肥物质科学研究院 | Hollow porous membrane gas sensor of tin oxide and preparation method thereof |
-
2019
- 2019-03-24 CN CN201910224782.XA patent/CN110136963B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099052A (en) * | 2016-07-23 | 2016-11-09 | 合肥工业大学 | A kind of carbon cladding SnO2hollow nanospheres composite and preparation method thereof |
| CN107144607A (en) * | 2017-06-27 | 2017-09-08 | 中国科学院合肥物质科学研究院 | Hollow porous membrane gas sensor of tin oxide and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JUN SONG CHEN等: "TiO2 and SnO2@TiO2 hollow spheres assembled from anatase TiO2 nanosheets with enhanced lithium storage properties", 《THE ROYAL SOCIETY OF CHEMISTRY 2010》 * |
| SUNG HOON AHN等: "Hierarchical Double-Shell Nanostructures of TiO 2 Nanosheets on SnO 2 Hollow Spheres for High-Effi ciency, Solid-State, Dye-Sensitized Solar Cells", 《ADV. FUNCT. MATER. 2014》 * |
| 强亮生: "《新型功能材料制备技术与分析表征方法》", 30 September 2017 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028185A (en) * | 2020-09-15 | 2020-12-04 | 赵玉平 | Mesoporous titanium oxide hollow microsphere electrode material |
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