CN101794670A - Preparation method of photo anode of dye-sensitized solar cell with optical gradient - Google Patents
Preparation method of photo anode of dye-sensitized solar cell with optical gradient Download PDFInfo
- Publication number
- CN101794670A CN101794670A CN 201010139950 CN201010139950A CN101794670A CN 101794670 A CN101794670 A CN 101794670A CN 201010139950 CN201010139950 CN 201010139950 CN 201010139950 A CN201010139950 A CN 201010139950A CN 101794670 A CN101794670 A CN 101794670A
- Authority
- CN
- China
- Prior art keywords
- preparation
- dye
- tio
- solar cell
- optical gradient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 238000007650 screen-printing Methods 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000004528 spin coating Methods 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 3
- 239000011521 glass Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 238000002231 Czochralski process Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 238000005266 casting Methods 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 16
- 239000010408 film Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Images
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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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)
Abstract
The invention relates to a preparation method of photo anode of dye-sensitized solar cell with optical gradient, comprising the following steps: (1), adding sodium hydroxide or ammonia water into the inorganic titanium slat used as the precursor to generate the precipitation, washing the precipitation with water to acquire solid in the gel manner, peptizing the same to prepare the pale yellow transparent solution, diluting the prepared solution, and performing hydro-thermal process on the same so as to prepare the transparent TiO2 solution of anatase phase; (2), depositing a TiO2 compact layer on a conductive substrate by spin-coating, dipping/coating or casting method; (3), depositing a layer of porous TiO2 film on the TiO2 compact layer by screen printing, blade coating method or spray coating method; and (4), calcining the film with two structure so as to form the photo anode with optical gradient. In the invention, the colloidal sol for preparing the transparent compact layer does not contain any organic matter and other impurities; the high temperature sintering is not required; the blocking layer formed between the conductive layer and the porous film blocks the corrosion of electrolyte on the substrate; and the preparation method has excellent application foreground.
Description
Technical field
The invention belongs to dye-sensitized solar cell anode and make field, particularly a kind of preparation method with dye-sensitized solar cell anode of optical gradient.
Background technology
1991,
Deng having prepared a kind of novel solar battery that is similar to the photosynthesis of plant principle, be called dye sensitized nano crystal salar battery (DSSCs).Because its cost is low, preparation technology is simple, electricity conversion is higher, causes the extensive concern of researcher to low-cost photovoltaic battery.
DSSC mainly contains the porous nano titanium oxide film of electro-conductive glass, absorption monolayer dyestuff, the electro-conductive glass and the electrolyte of platinum plating formed.Different with traditional silica-based solar cell, dye sensitization can battery be by means of the strong absorption of dyestuff to light very much, and luminous energy is converted into electric energy, and the absorption of electronics is carried out with transporting to separate.Core component light anode as DSSC is the emphasis that the researcher studies always, comprises that different nanostructures is to the cell photoelectric Effect on Performance.The present general problem that exists with the light anode of powder coated method preparation is not strong with the adhesion of electro-conductive glass substrate, porous membrane comes off from conductive glass surface easily, and electrolyte directly contacts with electro-conductive glass easily, not only influence the derivation of light induced electron, increased I in light induced electron and the electrolyte
3 -Compound probability.And electrolyte can corrode conductive substrates, had a strong impact on the electricity conversion and the stability of battery, hindered the commercial applications of battery.
Usually use the TiCl of 40mm
4The aqueous solution is handled electro-conductive glass, and the nano-titanium oxide film of preparation one deck densification reduces back of the body electronics and electrolytical compound, stops the corrosion of electrolyte to substrate simultaneously, finally also can improve the photoelectric current of battery.The problem that this method exists is TiCl
4As a kind of a kind of material of very easily hydrolysis, itself electro-conductive glass there is certain corrosion, discharge acidic materials after the heat treatment.And introduced Cl in the cell preparation process
-
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method with dye-sensitized solar cell anode of optical gradient.The prepared colloidal sol of the present invention approaches neutrality, do not contain any organic substance and other impurity, do not need through high temperature sintering, the barrier layer that between conductive layer and porous membrane, forms, stopped the corrosion of electrolyte to substrate, the final photoelectric current that also can improve battery has a good application prospect.
A kind of preparation method of the present invention with dye-sensitized solar cell anode of optical gradient, comprise: (1) is presoma with the inorganic titanium salt of 0.4～1M, adding 0.1～4M NaOH or ammoniacal liquor down at 25～80 ℃ makes it produce precipitation, precipitation is through washing 4～5 times to neutrality, obtain gelatinous solid, with its dispergation 0.5～5 hour, obtain shallow yellow transparent solution, with 1～5 times of gained solution dilution, form the transparent anatase phase TiO that concentration is 0.1～5wt% after 2～50 hours with 100～200 ℃ of hydrothermal treatment consists
2Colloidal sol;
(2) the employing rotation applies on conductive substrates, dipping lifts or The tape casting deposition one deck anatase-phase nano crystalline substance TiO
2Compacted zone;
(3) by silk screen printing, blade coating or spraying process at TiO
2Deposition one deck porous TiO on the compacted zone
2Film;
(4) film that will have two kinds of structures is calcined the light anode that formation in 15～120 minutes has optical gradient at 400～550 ℃.
Inorganic titanium salt in the described step (1) is Ti (SO
4)
2, TiOSO
4, Ti (NO
3)
4Or TiCl
4
Dispergation method in the described step (1) for gelatinous solid with 1g: 1～10ml is dispersed in HNO
3Or H
2O
2In.
Conductive substrates in the described step (2) is the SnO of doped with fluorine
2Electro-conductive glass (SnO
2: F) be called for short FTO or indium tin oxide-coated glass and be called for short the ITO electro-conductive glass.
Spin coating process in the described step (2) is with TiO
2Colloidal sol drips to the conductive substrates that is fixed on the sol evenning machine, and even glue is 10～1000 seconds under the rotating speed of sol evenning machine is 50-2000 rev/min, with TiO
2Compacted zone air dry or in baking oven dry 0.1～10 hour, baking temperature is 25～100 ℃, repeats above operation 1 to 50 time.
Dipping czochralski process in the described step (2) is for to put into TiO with conductive substrates
2In the colloidal sol, flooded 1～100 minute, TiO
2Compacted zone air dry or in baking oven dry 0.1～10 hour, baking temperature is 25～100 ℃, repeats above operation 1～10 time.
The brilliant TiO of anatase-phase nano in the described step (2)
2Dense layer thickness is 0.1～5 micron.
Porous TiO in the described step (3)
2Film thickness is 5～20 microns.
TiO on the dye-sensitized solar cell anode base material of optical gradient of the present invention
2Film is made of two parts, and one deck is transparent TiO
2Nanocrystalline compacted zone, another layer are the titanium dioxide layer of porous.With high degree of dispersion anatase phase TiO
2Colloidal sol is raw material, forms transparent titanium dioxide nanocrystalline compacted zone by methods such as rotation coating, curtain coating or dipping lift on conductive substrates, and thickness is 0.1～5 micron, keeps 0.1～10 hour under 25～80 ℃ of conditions; Then by methods such as silk screen printing, blade coating, sprayings at nanocrystalline TiO
2Deposit the certain thickness porous titanium oxide film of one deck on the compacted zone again; Obtain having the dye-sensitized solar cell anode of optical gradient at last through calcining.
The present invention adopts the transparent TiO with high degree of dispersion
2Colloidal sol is raw material, has prepared a kind of dye-sensitized solar cell anode with optical gradient.The transparent anatase-phase nano crystalline substance thin film of titanium oxide of preparation one deck densification earlier under cryogenic conditions, and then the titanium deoxid film of deposition one deck porous form the light anode through Overheating Treatment at last.The advantage of this method is that this colloidal sol is to approach neutrality, and does not contain any organic substance and other impurity, does not need through high temperature sintering.The sol particle pattern is bar-shaped, even particle size distribution.The use of this novel optical gradient dye-sensitized solar cell anode has at first formed a barrier layer between conductive layer and porous membrane, completely cut off electrolyte and contacted with the direct of electro-conductive glass, has reduced I in light induced electron and the electrolyte
3 -Compound probability.By the I-V characteristic curve test shows of battery, improve a lot with the cell photoelectric stream of this smooth anode preparation.
Beneficial effect
(1) with the inorganic ti sources is presoma, do not add under the situation of any surfactant, adopt the synthetic transparent anatase phase oxidation titanium hydrosol of method of precipitation dispergation hydrothermal crystallizing,, therefore no longer need higher calcining heat to make its crystallization owing to be the anatase phase.And colloidal sol can not discharge harmful material in heat treatment process, not residual Cl
-Thin film of titanium oxide by in the densification of FTO conductive glass surface deposition one deck has not only reduced the I in suprabasil light induced electron of electro-conductive glass and the electrolyte
3 -Compound, stoped the corrosion of electrolyte simultaneously to electro-conductive glass.
(2) and TiCl
4Preliminary treatment is compared, and the film of the optical gradient that the compacted zone that uses colloidal sol to prepare constitutes has higher short circuit current and open circuit voltage.
Description of drawings
Fig. 1 is the X-ray diffractogram of anatase phase colloidal sol;
Fig. 2 is the transparent compacted zone of employing spin-coating method preparation and the comparison diagram of the transmitance of the electro-conductive glass of sky;
Fig. 3 is the structural representation of optical gradient dye-sensitized solar cell anode;
Fig. 4 is the compacted zone SEM surface topography map of optical gradient dye-sensitized solar cell anode;
Fig. 5 is the porous layer SEM surface topography map of optical gradient dye-sensitized solar cell anode;
Fig. 6 is the porous layer SEM sectional drawing of optical gradient dye-sensitized solar cell anode;
Fig. 7 is a different structure light anode preparation DSSC photovoltaic curve.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
After the 1M titanium sulfate solution is warming up to 60 ℃, drip the sodium hydroxide solution of 4M, be neutralized to the pH value and approximate 7, obtain white precipitate, use the distilled water cyclic washing, obtain gelatinous solid.Get in the hydrogen peroxide that moist precipitate 80 gram is dispersed in (containing about 12 grams of titanium dioxide) 100 milliliter 30%,, obtain shallow yellow transparent solution 60 ℃ of dispergation 2 hours.Get 10 milliliters of this clear solutions, be diluted to 40 milliliters, join water heating kettle, 120 ℃ of hydrothermal treatment consists are taken out after 12 hours and are formed vitreosol.Get the powder that 20 milliliters of colloidal sol vacuumizes obtain and carry out XRD analysis, X-ray diffraction (XRD) result shows that titanium dioxide wherein is the anatase phase, as shown in Figure 1, is pure anatase phase as can be seen, and grain size is the 7-8 nanometer.Compound concentration is 50 milliliters of 0.1wt% TiO 2 sols, is placed in 100 milliliters of empty glass beakers.After the cleaning of FTO electro-conductive glass process, be immersed in the TiO 2 sol 10 minutes, from beaker, take out electro-conductive glass then and put into baking oven, 50 ℃ of dryings 30 minutes, repeat above operation 2 times, on electro-conductive glass, form the fine and close transparent anatase-phase nano crystal layer of one deck.Through the electro-conductive glass behind the dipping, transmitance generation significant change useless.The microscopic appearance of nanocrystalline laminar surface as shown in Figure 4, as can be seen, the compacted zone surfacing, sol particle is deposited in together closely.Adopting method deposit thickness on compacted zone of silk screen printing then is the thin film of titanium oxide of 8um.At last this laminated film was calcined 30 minutes at 500 ℃, formed dye-sensitized solar cell anode with optical gradient.Have optical gradient DSSC the light anode structural representation as shown in Figure 3, be followed successively by conductive layer, compacted zone, porous film layer from the bottom up.
After the 1M titanium sulfate solution is warming up to 60 ℃, drip the ammonia spirit of 4M toward the 1M titanium sulfate solution, be neutralized to the pH value and approximate 7, obtain white precipitate, use the distilled water cyclic washing, obtain gelatinous solid, getting moist precipitate 80 gram (amounting to into titanium dioxide is 12 grams) is dispersed in it in 300 milliliter 30% the hydrogen peroxide, in 60 ℃ of dispergation 1 hour, obtain shallow yellow transparent solution, get 20 milliliters of this clear solutions, be diluted to 40 milliliters, join water heating kettle, 180 degree hydrothermal treatment consists are taken out after 12 hours and are formed vitreosol.Compound concentration is 50 milliliters of 1wt% TiO 2 sols, is placed in 100 milliliters of glass beakers, and is standby.The FTO electro-conductive glass through after cleaning, is immersed in the TiO 2 sol 30 minutes, took out drying at room temperature then 30 minutes, repeat above operation 2 times.Through the light anode behind the dipping, transmitance generation significant change useless still is transparent, and as shown in Figure 2, transmitance does not have to change substantially as can be seen, illustrates that compacted zone is transparent.Adopt the method for silk screen printing to prepare thin film of titanium oxide then on compacted zone, thickness is 10um, and the laminated film for preparing was 500 ℃ of sintering 30 minutes.The microstructure of porous membrane presents typical cellular as shown in Figure 5.The photovoltaic performance that assembles different structure behind the battery as shown in Figure 7, the DSSC density of photocurrent minimum of traditional as can be seen light anode preparation, the light anodic current density of handling with titanium tetrachloride secondly, two have the DSSC density of photocurrent maximum of optical gradient light anode preparation.
Embodiment 3
After the 0.85M titanium sulfate solution is warming up to 70 ℃, drip the sodium hydroxide solution of 4M toward the 0.85M titanium sulfate solution, be neutralized to the pH value and approximate 7, obtain white precipitate, use the distilled water cyclic washing, obtain gelatinous solid, getting moist precipitate 80 gram (amounting to into titanium dioxide is 12 grams) is dispersed in it in 200 milliliter 30% the hydrogen peroxide, obtain shallow yellow transparent solution, get 30 milliliters of this clear solutions, be diluted to 70 milliliters, join water heating kettle, 150 degree hydrothermal treatment consists are taken out after 24 hours and are formed vitreosol.Compound concentration is 50 milliliters of 2wt% TiO 2 sols, is placed in 100 milliliters of glass beakers, and is standby.The ITO electro-conductive glass through after cleaning, is immersed in the TiO 2 sol 50 minutes, takes out then and put into oven drying 30 minutes, baking temperature is 80 ℃.Through the light anode behind the dipping, transmitance generation significant change useless still is transparent.Adopt the method for silk screen printing to prepare thin film of titanium oxide then on compacted zone, thickness is 12um, and the laminated film for preparing was 400 ℃ of sintering 30 minutes.The microstructure of porous membrane is typical loose structure as shown in Figure 5 as can be seen, connects loose between the particle.
After the 1M titanium sulfate solution is warming up to 60 ℃, drip the ammonia spirit of 4M toward the 1M titanium sulfate solution, be neutralized to the pH value and approximate 7, obtain white precipitate, use the distilled water cyclic washing, obtain gelatinous solid, getting moist precipitate 80 gram (amounting to into titanium dioxide is 12 grams) is dispersed in it in 800 milliliter 30% the hydrogen peroxide, in 50 ℃ of dispergation 2 hours, obtain shallow yellow transparent solution, get 10 milliliters of this clear solutions, be diluted to 70 milliliters, join water heating kettle, 200 degree hydrothermal treatment consists are taken out after 10 hours and are formed vitreosol.Compound concentration is 50 milliliters of 5wt% TiO 2 sols, is placed in 100 milliliters of glass beakers, and is standby.The ITO electro-conductive glass through after cleaning, is placed on above the sol evenning machine, and rotary speed is 500 rpms.Rotational time is 30 seconds.Take out then and put into oven drying 20 minutes, baking temperature is 50 ℃, repeats above operation 4 times.Through the light anode after the rotation coating, transmitance generation significant change useless still is transparent.Adopt the method for silk screen printing to prepare thin film of titanium oxide then on compacted zone, thickness is 15um, and the laminated film for preparing was 500 ℃ of sintering 30 minutes.Have optical gradient DSSC the light anode structural representation as shown in Figure 6, can find out clearly that optical gradient light anode construction is a double-layer structure: one deck is the anatase phase titanium dioxide compacted zone, and one deck is the titanium dioxide layer of porous.
Claims (8)
1. preparation method with dye-sensitized solar cell anode of optical gradient comprises:
(1) be presoma with the inorganic titanium salt of 0.4～1M, adding 0.1～4M NaOH or ammoniacal liquor down at 25～80 ℃ makes it produce precipitation, precipitation is through washing 4～5 times to neutrality, obtain gelatinous solid, with it in 25～80 ℃ of dispergation 0.5～5 hour, obtain shallow yellow transparent solution,, form the transparent anatase phase TiO that concentration is 0.1～5wt% after 2～50 hours with 100～200 ℃ of hydrothermal treatment consists with 1～5 times of gained solution dilution
2Colloidal sol;
(2) the employing rotation applies on conductive substrates, dipping lifts or The tape casting deposition one deck anatase-phase nano crystalline substance TiO
2Compacted zone;
(3) by silk screen printing, blade coating or spraying process at TiO
2Deposition one deck porous TiO on the compacted zone
2Film;
(4) film that will have two kinds of structures is calcined the light anode that formation in 15～120 minutes has optical gradient at 400～550 ℃.
2. a kind of preparation method with dye-sensitized solar cell anode of optical gradient according to claim 1 is characterized in that: the inorganic titanium salt in the described step (1) is Ti (SO
4)
2, TiOSO
4, Ti (NO
3)
4Or TiCl
4
3. a kind of preparation method with dye-sensitized solar cell anode of optical gradient according to claim 1 is characterized in that: the dispergation in the described step (1) is meant gelatinous solid with 1g: 1～10ml is dispersed in HNO
3Or H
2O
2In handle.
4. a kind of preparation method with dye-sensitized solar cell anode of optical gradient according to claim 1 is characterized in that: the conductive substrates in the described step (2) is the SnO of doped with fluorine
2Electro-conductive glass (SnO
2: F) be called for short FTO or indium tin oxide-coated glass and be called for short the ITO electro-conductive glass.
5. a kind of preparation method with dye-sensitized solar cell anode of optical gradient according to claim 1 is characterized in that: the spin coating process in the described step (2) is with TiO
2Colloidal sol drips to the conductive substrates that is fixed on the sol evenning machine, and even glue is 10～1000 seconds under the rotating speed of sol evenning machine is 50-2000 rev/min, with TiO
2Compacted zone air dry or in baking oven dry 0.1～10 hour, baking temperature is 25～100 ℃, repeats above operation 1 to 50 time.
6. a kind of preparation method with dye-sensitized solar cell anode of optical gradient according to claim 1 is characterized in that: the dipping czochralski process in the described step (2) is for to put into TiO with conductive substrates
2In the colloidal sol, flooded 1～100 minute, TiO
2Compacted zone air dry or in baking oven dry 0.1～10 hour, baking temperature is 25～100 ℃, repeats above operation 1～10 time.
7. a kind of preparation method with dye-sensitized solar cell anode of optical gradient according to claim 1 is characterized in that: the brilliant TiO of the anatase-phase nano in the described step (2)
2Dense layer thickness is 0.1～5 micron.
8. a kind of preparation method with dye-sensitized solar cell anode of optical gradient according to claim 1 is characterized in that: the porous TiO in the described step (3)
2Film thickness is 5～20 microns.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101399504A CN101794670B (en) | 2010-04-06 | 2010-04-06 | Preparation method of photo anode of dye-sensitized solar cell with optical gradient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101399504A CN101794670B (en) | 2010-04-06 | 2010-04-06 | Preparation method of photo anode of dye-sensitized solar cell with optical gradient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101794670A true CN101794670A (en) | 2010-08-04 |
| CN101794670B CN101794670B (en) | 2012-01-04 |
Family
ID=42587281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101399504A Expired - Fee Related CN101794670B (en) | 2010-04-06 | 2010-04-06 | Preparation method of photo anode of dye-sensitized solar cell with optical gradient |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101794670B (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102136372A (en) * | 2011-01-22 | 2011-07-27 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell treated by ion implantation and preparation method thereof |
| CN102176387A (en) * | 2011-03-02 | 2011-09-07 | 东莞宏威数码机械有限公司 | Methods for preparing porous spherical titanium dioxide paste and sensitized photo-anode |
| CN102509623A (en) * | 2011-10-28 | 2012-06-20 | 奇瑞汽车股份有限公司 | Method for preparing photoanode coating of dye sensitized solar cell |
| CN102610395A (en) * | 2012-04-17 | 2012-07-25 | 东华大学 | Preparation method for photo-anode of dye-sensitized solar cell with flexible plastic substrate |
| CN102623186A (en) * | 2012-04-01 | 2012-08-01 | 东华大学 | Titanium-foil-based flexible dye-sensitized solar cell and preparation method thereof |
| CN102674706A (en) * | 2012-06-01 | 2012-09-19 | 天津大学 | Method for preparing titanium dioxide nano multi-level structure thin film on conductive glass |
| CN102983005A (en) * | 2012-12-04 | 2013-03-20 | 天津大学 | Preparation method for photo-anode with TiO2 compact layer |
| CN103198927A (en) * | 2013-04-07 | 2013-07-10 | 东华大学 | Preparation method of dye-sensitized solar cell titanium dioxide photo anode |
| CN103714975A (en) * | 2013-12-16 | 2014-04-09 | 华侨大学 | Method for preparing light anode barrier layer of sensitized solar cell |
| CN104966620A (en) * | 2015-05-15 | 2015-10-07 | 重庆大学 | Photo-anode based on active metal for flexible dye-sensitized solar cell |
| CN105493305A (en) * | 2013-08-23 | 2016-04-13 | 弗劳恩霍夫应用研究促进协会 | Photovoltaic elements having long-term stability that can be precipitated out of solutions, and in-situ method for producing said elements |
| CN105895378A (en) * | 2016-06-28 | 2016-08-24 | 郑州大学 | Fabrication method for dual-layer titanium dioxide photo anode of dye-sensitized solar cell |
| CN106206030A (en) * | 2015-05-08 | 2016-12-07 | 北京纳米能源与系统研究所 | Light anode, preparation method, battery and the photovoltaic device of fiber dyes sensitization |
| CN106206031A (en) * | 2015-05-08 | 2016-12-07 | 北京纳米能源与系统研究所 | Light anode, preparation method, battery and the photovoltaic device of fiber dyes sensitization |
| CN106587282A (en) * | 2016-12-08 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Difunctional multi-template molecularly imprinted type photoelectric anode material and preparation method and application |
| CN106816384A (en) * | 2015-11-30 | 2017-06-09 | 英飞凌科技股份有限公司 | Make the method and device of layer |
| CN108470623A (en) * | 2018-03-09 | 2018-08-31 | 三峡大学 | Used by dye sensitization solar battery silica and zinc oxide anti-reflection film and preparation method thereof |
| CN108823590A (en) * | 2018-06-19 | 2018-11-16 | 上海大学 | TiO is carried out using electron irradiation2The modified method and its application of nano-wire array |
| CN113751294A (en) * | 2021-09-09 | 2021-12-07 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing titanium-based nano anticorrosive film by taking titanium tetrachloride as titanium source |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101929A (en) * | 2006-07-07 | 2008-01-09 | 北京大学 | Dye-sensitized solar battery and structure of its work pole |
| CN101320631A (en) * | 2008-07-08 | 2008-12-10 | 西安交通大学 | Demixing-adsorption cooperated-sensitization wide optical spectrum dye sensitization solar battery |
-
2010
- 2010-04-06 CN CN2010101399504A patent/CN101794670B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101929A (en) * | 2006-07-07 | 2008-01-09 | 北京大学 | Dye-sensitized solar battery and structure of its work pole |
| CN101320631A (en) * | 2008-07-08 | 2008-12-10 | 西安交通大学 | Demixing-adsorption cooperated-sensitization wide optical spectrum dye sensitization solar battery |
Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102136372A (en) * | 2011-01-22 | 2011-07-27 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell treated by ion implantation and preparation method thereof |
| CN102136372B (en) * | 2011-01-22 | 2012-11-14 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell treated by ion implantation and preparation method thereof |
| CN102176387B (en) * | 2011-03-02 | 2012-09-26 | 东莞宏威数码机械有限公司 | Methods for preparing porous spherical titanium dioxide paste and sensitized photo-anode |
| CN102176387A (en) * | 2011-03-02 | 2011-09-07 | 东莞宏威数码机械有限公司 | Methods for preparing porous spherical titanium dioxide paste and sensitized photo-anode |
| CN102509623A (en) * | 2011-10-28 | 2012-06-20 | 奇瑞汽车股份有限公司 | Method for preparing photoanode coating of dye sensitized solar cell |
| CN102623186A (en) * | 2012-04-01 | 2012-08-01 | 东华大学 | Titanium-foil-based flexible dye-sensitized solar cell and preparation method thereof |
| CN102623186B (en) * | 2012-04-01 | 2015-05-13 | 东华大学 | Titanium-foil-based flexible dye-sensitized solar cell and preparation method thereof |
| CN102610395A (en) * | 2012-04-17 | 2012-07-25 | 东华大学 | Preparation method for photo-anode of dye-sensitized solar cell with flexible plastic substrate |
| CN102674706A (en) * | 2012-06-01 | 2012-09-19 | 天津大学 | Method for preparing titanium dioxide nano multi-level structure thin film on conductive glass |
| CN102983005A (en) * | 2012-12-04 | 2013-03-20 | 天津大学 | Preparation method for photo-anode with TiO2 compact layer |
| CN103198927A (en) * | 2013-04-07 | 2013-07-10 | 东华大学 | Preparation method of dye-sensitized solar cell titanium dioxide photo anode |
| CN105493305A (en) * | 2013-08-23 | 2016-04-13 | 弗劳恩霍夫应用研究促进协会 | Photovoltaic elements having long-term stability that can be precipitated out of solutions, and in-situ method for producing said elements |
| CN105493305B (en) * | 2013-08-23 | 2018-09-11 | 弗劳恩霍夫应用研究促进协会 | The photovoltaic element and its produced in situ method steady in a long-term that can be precipitated from solution |
| CN103714975A (en) * | 2013-12-16 | 2014-04-09 | 华侨大学 | Method for preparing light anode barrier layer of sensitized solar cell |
| CN106206031A (en) * | 2015-05-08 | 2016-12-07 | 北京纳米能源与系统研究所 | Light anode, preparation method, battery and the photovoltaic device of fiber dyes sensitization |
| CN106206030A (en) * | 2015-05-08 | 2016-12-07 | 北京纳米能源与系统研究所 | Light anode, preparation method, battery and the photovoltaic device of fiber dyes sensitization |
| CN104966620A (en) * | 2015-05-15 | 2015-10-07 | 重庆大学 | Photo-anode based on active metal for flexible dye-sensitized solar cell |
| CN104966620B (en) * | 2015-05-15 | 2018-02-13 | 重庆大学 | Flexible dye-sensitized solar battery light anode based on active metal |
| CN106816384A (en) * | 2015-11-30 | 2017-06-09 | 英飞凌科技股份有限公司 | Make the method and device of layer |
| CN105895378A (en) * | 2016-06-28 | 2016-08-24 | 郑州大学 | Fabrication method for dual-layer titanium dioxide photo anode of dye-sensitized solar cell |
| CN105895378B (en) * | 2016-06-28 | 2018-09-28 | 郑州大学 | The preparation method of dye-sensitized solar cells two-layer titanium dioxide light anode |
| CN106587282A (en) * | 2016-12-08 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Difunctional multi-template molecularly imprinted type photoelectric anode material and preparation method and application |
| CN106587282B (en) * | 2016-12-08 | 2020-02-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Double-functional multi-template molecularly imprinted photoelectric anode material and preparation and application thereof |
| CN108470623A (en) * | 2018-03-09 | 2018-08-31 | 三峡大学 | Used by dye sensitization solar battery silica and zinc oxide anti-reflection film and preparation method thereof |
| CN108470623B (en) * | 2018-03-09 | 2019-09-24 | 三峡大学 | Used by dye sensitization solar battery silica and zinc oxide anti-reflection film and preparation method thereof |
| CN108823590A (en) * | 2018-06-19 | 2018-11-16 | 上海大学 | TiO is carried out using electron irradiation2The modified method and its application of nano-wire array |
| CN113751294A (en) * | 2021-09-09 | 2021-12-07 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing titanium-based nano anticorrosive film by taking titanium tetrachloride as titanium source |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101794670B (en) | 2012-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101794670B (en) | Preparation method of photo anode of dye-sensitized solar cell with optical gradient | |
| CN101702377B (en) | Zinc oxide/titanium dioxide hybrid electrode and preparation method thereof | |
| CN101058483B (en) | Method for preparing nanometer porous titanium oxide thick film | |
| Jin et al. | Properties of TiO2 films prepared for use in dye-sensitized solar cells by using the sol-gel method at different catalyst concentrations | |
| CN101697321B (en) | Preparation method of titanium dioxide dense film for dye-sensitized solar cell | |
| CN104282847B (en) | Interruptible perovskite type organic halide thin-film solar cell photo-anode preparing method | |
| CN101697319B (en) | Dye-sensitized anode of solar battery light and preparation method thereof | |
| CN104518091A (en) | Preparation method of organic-inorganic perovskite solar battery | |
| WO2016026339A1 (en) | Synthesis method for tio2 nanocrystal | |
| CN101567270A (en) | Method for preparing meso-porous ZnO/TiO* composite film with high zinc content | |
| CN110828673B (en) | Method for preparing efficient perovskite solar cell by introducing sulfide additive | |
| Nien et al. | Investigation of Dye-Sensitized Solar Cell With Photoanode Modified by TiO₂-ZnO Nanofibers | |
| CN101439873B (en) | Method for titania film growth in fluorine-based aqueous solution | |
| CN102354606B (en) | Preparation method of photoanode of dye-sensitized solar cell | |
| CN104628262B (en) | Method for preparing matchstick-shaped TiO2 nanoparticle and nanorod composite array | |
| JP4842910B2 (en) | Method for producing titanium oxide airgel thin film or thick film used as electrode holder for transparent solar cell | |
| Pari et al. | Recent advances in SnO2 based photo anode materials for third generation photovoltaics | |
| CN101692411B (en) | Composite electrode of solar battery and preparation method thereof | |
| CN103972398B (en) | A kind of organic inorganic hybridization solaode and preparation method thereof | |
| CN103198927B (en) | A kind of preparation method of DSSC titanium dioxide photo anode | |
| CN102795665B (en) | Preparation method of titanium dioxide nanotube (rod) array | |
| Liu et al. | Enhanced photoelectrical performance of dye-sensitized solar cells with double-layer TiO 2 on perovskite SrTiO 3 substrate | |
| CN101814377B (en) | Preparation method of TiO2 film of dye-sensitized solar battery with high conversion efficiency under low light intensity | |
| CN103030304B (en) | Preparation method of titanium dioxide nano porous film material | |
| Chen et al. | Hydrothermal preparation of anatase TiO2 nanoparticles for dye-sensitized solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120104 Termination date: 20140406 |