CN102496479A - Method for preparing titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for dye-sensitized solar cell - Google Patents

Method for preparing titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for dye-sensitized solar cell Download PDF

Info

Publication number
CN102496479A
CN102496479A CN2011103998463A CN201110399846A CN102496479A CN 102496479 A CN102496479 A CN 102496479A CN 2011103998463 A CN2011103998463 A CN 2011103998463A CN 201110399846 A CN201110399846 A CN 201110399846A CN 102496479 A CN102496479 A CN 102496479A
Authority
CN
China
Prior art keywords
dye
tio
shell structure
dmf solution
solution
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
Application number
CN2011103998463A
Other languages
Chinese (zh)
Other versions
CN102496479B (en
Inventor
杜平凡
熊杰
宋立新
席珍强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
Original Assignee
Zhejiang Sci Tech University ZSTU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Sci Tech University ZSTU filed Critical Zhejiang Sci Tech University ZSTU
Priority to CN 201110399846 priority Critical patent/CN102496479B/en
Publication of CN102496479A publication Critical patent/CN102496479A/en
Application granted granted Critical
Publication of CN102496479B publication Critical patent/CN102496479B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • Y02E10/549—Organic PV cells

Abstract

The invention discloses a method for preparing a titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for a dye-sensitized solar cell. A photo-anode film is a core part of the dye-sensitized solar cell. The performance of the dye-sensitized solar cell can be improved by performing physical and chemical modification such as surface coating on the photo-anode film and developing a novel nano structure photo-anode film. The TiO2/Nb2O5 core-shell structure nano-fiber film for the photo-anode of the dye-sensitized solar cell is prepared by using a unique coaxial electrostatic spinning technology. By the method, a quasi-one-dimensional nano structure can be formed, and shell coating treatment for inhibiting charge recombination can be realized. A small quantity of grain boundaries having the quasi-one-dimensional nano structure is generated, charge recombination is inhibited, and a short-circuit current Isc of a battery is improved. By introduction of a shell, an open-circuit voltage Voc of the battery is improved. Correspondingly, the overall photoelectric conversion efficiency eta of the battery is improved by 24 percent to 33 percent.

Description

Dye-sensitized cell is with the preparation method of titanium dioxide-niobium pentaoxide nuclear shell structure nano tunica fibrosa
Technical field
The present invention relates to solar cell manufacturing technology field, particularly a kind of dye-sensitized cell is with the preparation method of titanium dioxide-niobium pentaoxide nuclear shell structure nano tunica fibrosa.
Background technology
Along with society, sustainable development of economy, non-renewable energy resources such as oil, coal etc. are exhausted day by day, and human existence and development are being faced with unprecedented challenge.Searching cleaning, regenerative resource have become global problem.It is estimated that the energy that earth every year obtains from solar irradiation is about 100,000 times of human annual energy-output ratio, therefore, the development and use of solar energy are the key subjects of new energy field.The solar cell of based semiconductor silicon pn knot principle is technological at present the most ripe electrooptical device, and in recent years, the paces that the silicon solar cell scale is used are just progressively accelerated.Yet expensive still is the reality that can't avoid of photovoltaic generation.For this reason, the effort of development of new photovoltaic device does not stop all the time in the global range.
Last century Mo, along with the rise of nanometer technology, one type of novel solar cell is that dye-sensitized solar cells (DSSC) arises at the historic moment.1991, Gr tzel reported first be the semiconductor nano thin film solar cell of sensitizer with the ruthenium complex dyestuff, its photoelectric conversion efficiency is higher than 7%, causes scientific circles' extensive concern, is regarded as third generation solar cell.Make great efforts after deliberation, the high conversion efficiency of small size DSSC has reached 11%, and with being on close level of amorphous silicon membrane battery, and cost is less than 1/5 of silion cell.Rely on tangible cost advantage and easy manufacture craft, DSSC or will in following photovoltaic industry development, become the strong competitor of silion cell, application potential is huge.
DSSC is made up of electrode nano structure membrane light anode, FTO electro-conductive glass matrix, sensitizing dyestuff, electrolyte and platinum plating.Its operation principle is following: sensitizing dyestuff absorbs luminous energy, electronics by ground state transition to excitation state; The last anode film of FTO is accepted the excitation state electronics as electron acceptor, and simultaneously, dye molecule loses electronics and is oxidation state; I -/ I 3 -I in the electrolyte -Electronics is provided and with its reducing/regenerating as electron donor to the oxidation state dye molecule, I 3 -Be diffused into and electrode is obtained electronics be reduced, thereby accomplish the Optical Electro-Chemistry reaction cycle.
Wherein, photo-anode film is core and the primary study object of DSSC, and its effect is that the dye molecule electrons excited is received and transmits.Conventional photo-anode film is usually with titanium dioxide (TiO 2) nanocrystalline be raw material.Nearly 20 years, a large amount of researchers carried out continuing deep research to nanocrystalline photo-anode film, had formed ripe relatively Experiment Preparation technology gradually.But this photo-anode film also exists some inherent shortcomings; Reason is that a large amount of crystal boundaries is arranged between nanocrystal; Specific area is huge, and surperficial dangling bonds play the trap effect of capturing light induced electron, and they can make the life-span of electronics and diffusion length reduce; Recombination probability increases, and is restricting the raising of battery efficiency.Therefore, nanocrystalline photo-anode film is carried out physical chemistry modifying, and to come this skin effect of passivation be the important channel of improving the DSSC performance, mainly comprises doping, TiCl 4Methods such as processing, surface coating.
In above-mentioned three kinds of means, the above two are relatively easy.But, doping is more limited to the raising of battery efficiency.TiCl 4Though the effect of handling receives certainly, it is ripe that technology is tending towards.And the coating method is in mechanism and technical all complicated, but the raising of performance is had more potentiality, and the selection of coating has diversity, thereby attracted more research.Because the nano-crystal film surface density of states is high, causes TiO 2Electron acceptor is compound serious in conduction band electron and oxidation state dyestuff or the electrolyte.And charge recombination restricts the principal element that DSSC efficient improves just.For this reason, some research trials reduce compound in thin layer of metal oxide formation nuclear-shell (Core-shell) structure that the nanocrystal surface coating has higher conduction band position.Promptly with TiO 2For nuclear, with other oxide (ZnO, Nb 2O 5, Al 2O 3, MgO etc.) be the structure of shell.Research is thought, can form energy barrier at shell after coating is handled and suppress TiO 2Conduction band electron and dye well are electrolytical compound, or form the injection efficiency that dipole layer improves electronics at the interface at nucleocapsid.In the above-mentioned coating, Nb 2O 5Be that effect is a kind of preferably.Like A. Zaban etc. with immersion method to TiO 2The nanocrystalline Nb that is 2O 5Coat and handle, usefulness gel-sol methods such as A.F. Nogueira are carried out identical coating, and the efficient of DSSC all is improved significantly.
Meanwhile, the novel nano structure also is the important directions of DSSC photo-anode film research.If replace nanocrystalline with one-dimensional nano structures such as nano wire, nanometer rods, nanotubes; Because their crystal boundary is less; Can effectively reduce wherein surface state to the capturing of light induced electron, suppress charge recombination meanwhile, the novel nano structure also is the important directions of DSSC photo-anode film research.If replace nanocrystalline with one-dimensional nano structures such as nano wire, nanometer rods, nanotubes; Because their crystal boundary is less, can effectively reduce wherein surface state trap to the capturing of light induced electron, suppress charge recombination; Accelerate collection, the transmission rate of electronics, and then improve the performance of battery.
Except that one-dimensional nano structure, the accurate one dimension TiO that makes by electrostatic spinning 2Nano fibrous membrane also begins to be used for DSSC light anode in recent years.In theory, this photo-anode film will be obtained and the similar effect of above-mentioned one-dimensional nano structure film.Related work mainly concentrates on the S. Ramakrishna of Singapore, several groups such as S. Shiratori of the D.Y. Kim of Korea S and Japan.Normally with TiO 2Precursor solution spin composite nano-fiber membrane directly be deposited on the FTO matrix, form the light anode through sintering.What deserves to be mentioned is to also have a special coaxial electrically spun technology in the electrostatic spinning technique, promptly utilize coaxial spinneret orifice to prepare the different nuclear-shell of inside and outside composition (or claiming skin-core) structure nano fiber.At present, this technology more is the preparation that is used for high polymer co-axial nano fiber.When it is used for the coaxial fiber production of inorganic matter, need consider two processes of spinning and sintering simultaneously, technology is complicated more than the former, thereby studies lessly, only has and counts few reports, electricity spinning LiCoO fully such as typical as D.R. Chen 2/ MgO co-axial nano fiber is promptly realized anode material of lithium battery LiCoO with MgO 2Coating modification.And the TiO of their preparation 2/ SiO 2The co-axial nano fiber be used for photocatalysis research.Infer in view of the above,, estimate also can form with TiO by coaxial electrically spun and sintering 2Be core, with Nb 2O 5Be the nanofiber of shell, realize surface coated effect, but have no the report of this respect at present.
Summary of the invention
The purpose of this invention is to provide the preparation method of a kind of dye-sensitized cell with titanium dioxide-niobium pentaoxide nuclear shell structure nano tunica fibrosa.
The technical scheme that the present invention adopts:
1) preparation high polymer PVAc (polyvinyl acetate) quality percentage composition is the DMF (N of 15wt.%; Dinethylformamide) solution; With volume is the surfactant Triton X-100 (TritonX) of DMF solution 25%; 2 times of TiP of quality (isopropyl titanate) to PVAc, and 1.5 times of quality are to the C of PVAc 10H 25NbO 5(ethoxy alcohol niobium) joins in the DMF solution, obtains TiO through magnetic agitation 8h 2/ Nb 2O 5Composite precursor spin coating liquid, and it is spin-coated on the FTO electro-conductive glass spin-coated layer that forms one deck with the spin coating appearance, spin coating appearance rotating speed is 2000rmin -1, the spin coating time is 30s;
2) preparing PVA c quality percentage composition is the DMF solution of 11.5wt.%; With volume is the surfactant Triton X-100 of DMF solution 15%, and 1.5 times of quality are to the C of PVAc 10H 25NbO 5Join in the DMF solution, obtain Nb through magnetic agitation 8h 2O 5(niobium pentaoxide) presoma spinning solution; Preparing PVA c quality percentage composition is the DMF solution of 11.5wt.%; With volume is the surfactant Triton X-100 of DMF solution 15%; Volume is the HAc (glacial acetic acid) of DMF solution 10%, and 2 times of TiP to PVAc of quality join in the DMF solution, obtains TiO through magnetic agitation 8h 2The presoma spinning solution; With Nb 2O 5, TiO 2Two kinds of presoma spinning solutions are respectively charged in two syringes; Between coaxial spinning head and receiving system, add high voltage; Charged drop overcomes self under effect of electric field surface tension forms the injection thread, is controlled the rate of extrusion of two kinds of presoma spinning solutions respectively by two micro-injection pumps; Along with solvent evaporates, spray the fiber that thread solidify to form nucleocapsid structure, directly be collected on the FTO of spin-coat process electro-conductive glass with disordered state and form composite cellulosic membrane, FTO glass is fixed by receiving system;
3) (film thickness behind the corresponding sintering is about 10 μ m, the i.e. effective thickness of photo-anode film) behind the spinning 30min is with putting into the Muffle furnace sintering after the composite cellulosic membrane drying of collecting, with 1 °Cmin -1Speed be warming up to 500 °Be incubated 1h behind the C, obtain the TiO of nucleocapsid structure 2/ Nb 2O 5Nano fibrous membrane.
Use TiO 2/ Nb 2O 5Nuclear shell structure nano tunica fibrosa and TiO 2Nano fibrous membrane, N719 sensitizing dyestuff, I -/ I 3 -Standard electrolyte and plating Pt carry out relevant characterization and test to electrode assembled battery, and compare the performance difference between two types of batteries, and test mainly comprises I-VCharacteristic curve and photoelectric current action spectrum. I-VThe curve test macro is made up of the xenon lamp of simulated solar light source, digital source table etc.Through I-VCurve, can obtain battery open circuit voltage ( V Oc ), short circuit current ( I Sc ), fill factor, curve factor ( FF) and conversion efficiency ( η) four parameters, wherein, conversion efficiency ηBe the basic parameter of estimating the solar cell performance, be defined as the battery peak power output ( P Max ) and input power ( P In ) ratio, can calculate through following formula: η= P Max / P In =( FF * I Sc * V Oc )/ P In The photoelectric current action spectrum is the relation curve between IPCE and the lambda1-wavelength, measures through the QE/IPCE measuring system.So-called IPCE is the monochromatic photon of incident-electronics transformation efficiency, is defined as the light induced electron number that produces in the unit interval NeWith incident monochromatic light subnumber NpRatio, the photoelectricity that is battery at the different wave length place of reflection transforms situation, also is to influence short circuit current I Sc The most critical factor.IPCE can be expressed as the product of three factors, i.e. IPCE (λ)= LHE (λ) * Φ Inj * Φ c , wherein LHE (λ)The capture rate of expression light, Φ Inj The injection efficiency of expression electronics, Φ c It then is the collection efficiency of electronics.
The beneficial effect that the present invention has is:
Address before the background technology part, photo-anode film is carried out physical chemistry modifyings such as surface coating, and the nanostructure anode film of development of new, all be the important channel of realizing that the DSSC performance improves.The present invention adopts unique coaxial electrically spun technology to prepare the TiO that is used for DSSC light anode 2/ Nb 2O 5The nuclear shell structure nano tunica fibrosa.This technology can realize two kinds of processes of shell coating processing that quasi-one dimensional nanostructure forms and suppresses charge recombination simultaneously.The crystal boundary of quasi-one dimensional nanostructure is less, less conduction band electron and oxidation state sensitizing dyestuff and electrolyte electron acceptor I 3 -Between compound, promptly increased the collection efficiency of electronics Φ c , improved IPCE and short circuit current I Sc The open circuit voltage of battery V Oc Depend on TiO 2Quasi-Fermi level and electrolyte oxidation reduction are poor to electromotive force, Nb 2O 5TiO has been raised in the introducing of shell 2The quasi-Fermi level of nano fibrous membrane means battery V Oc Improved.Correspondingly, the total conversion efficiency of battery ηAlso be improved.It is thus clear that the synergy of the two can improve the performance of battery better.
Description of drawings
Fig. 1 is the sketch map of electrostatic spinning process.Among the figure: 1, TiO 2The presoma spinning solution, 2, Nb 2O 5The presoma spinning solution, 3, syringe, 4, syringe, 5, coaxial spinning head, 6, receiving system, 7, high voltage source, 8, micro-injection pump, 9, micro-injection pump, 10, electro-conductive glass, 11, composite cellulosic membrane.
The TiO that Fig. 2 makes for embodiment 1 2/ Nb 2O 5The SEM of nuclear shell structure nano tunica fibrosa (ESEM) photo.
Fig. 3 executes the TiO that example 1 makes 2/ Nb 2O 5The xps energy spectrum figure of nuclear shell structure nano tunica fibrosa and TEM (transmission electron microscope) photo.
Fig. 4 executes the TiO that example 1 makes 2/ Nb 2O 5Nuclear shell structure nano tunica fibrosa and TiO 2The IPCE photoelectric current action spectrum contrast of the DSSC of nano fibrous membrane assembling.
Fig. 5 executes the TiO that example 1 makes 2/ Nb 2O 5Nuclear shell structure nano tunica fibrosa and TiO 2The DSSC's of nano fibrous membrane assembling I-VThe characteristic curve contrast.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described further.
Embodiment 1:
0.68g PVAc joined in the 4ml DMF organic solvent to form the quality percentage composition be the solution of 15wt.%, in this solution, add 1ml Triton X-100,1.36g TiP, and 1.02g C 10H 25NbO 5, through the TiO of magnetic agitation 8h acquisition clarification, thickness 2/ Nb 2O 5Composite precursor spin coating liquid; And it being spin-coated on the FTO electro-conductive glass of acetone and absolute ethyl alcohol ultrasonic cleaning the spin-coated layer that forms one deck with the spin coating appearance, spin coating appearance rotating speed is 2000rmin -1, the used spin coating time is 30s.
0.52g PVAc joined among the 4ml DMF to form the quality percentage composition be the solution of 11.5wt.%, two parts of same solution preparations, ie in solution I and solution II; In the solution I, add 0.6ml Triton X-100 and 0.78g C 10H 25NbO 5, magnetic agitation 8h obtains Nb 2O 5Presoma spinning solution 1.In the solution II, add 0.6ml Triton X-100,0.4ml HAc, and 1.04g TiP, magnetic agitation 8h obtains TiO 2Presoma spinning solution 2.With Nb 2O 5Presoma spinning solution 1 and TiO 2 Presoma spinning solution 2 is respectively charged in two syringes 3 and 4; At coaxial spinning head 5 and 6 high voltages that add 16KV of receiving system; Spinning head is 12cm to the distance of dash receiver, and charged drop overcomes self under effect of electric field surface tension forms the injection thread.Control the rate of extrusion of two syringes respectively by two micro-injection pumps 8 and 9, wherein the shell rate of extrusion is 0.7ml/h, and the rate of extrusion of stratum nucleare is 0.4ml/h; Along with solvent evaporates, spray the fiber that thread solidify to form nucleocapsid structure, directly be collected in disordered state and on the FTO of spin-coat process electro-conductive glass 10, form composite cellulosic membrane 11, as shown in Figure 1; Behind the spinning 30min, with putting into the Muffle furnace sintering after the composite cellulosic membrane of collecting 11 dryings, with 1 °Cmin -1Speed be warming up to 500 °Be incubated 1h behind the C, obtain TiO 2/ Nb 2O 5The nuclear shell structure nano tunica fibrosa.The TiO that Fig. 2 makes for this embodiment 2/ Nb 2O 5The stereoscan photograph of nuclear shell structure nano tunica fibrosa.
Use TiO 2/ Nb 2O 5Nuclear shell structure nano tunica fibrosa and TiO 2Nano fibrous membrane, N719 sensitizing dyestuff, I -/ I 3 -Standard electrolyte and plating Pt carry out relevant characterization and test to electrode assembled battery, and compare the performance difference between two types of batteries.Fig. 3 is the xps energy spectrum figure and the transmission electron microscope photo of gained nano fibrous membrane, has confirmed TiO 2/ Nb 2O 5The formation of nucleocapsid structure; Fig. 4 is for the contrast of the photoelectric current action spectrum of two types of DSSC of assembling, based on TiO 2/ Nb 2O 5The IPCE of the DSSC of anode film is higher than pure TiO 2The DSSC of film; Fig. 5 is two types of DSSC of assembling I-VThe characteristic curve contrast.Pure TiO 2Film DSSC's V Oc =0.78V, I Sc =7.4mAcm -2, FF=61%, η=3.5%; And Nb 2O 5After shell coats V Oc =0.85V, I Sc =8 mAcm -2, FF=66%, η=4.5%.Wherein, the photoelectric conversion efficiency of most critical brings up to 4.5% from 3.5%, has improved 28%.
Embodiment 2:
0.68g PVAc joined in the 4ml DMF organic solvent to form the quality percentage composition be the solution of 15wt.%, in this solution, add 1ml Triton X-100,1.36g TiP, and 1.02g C 10H 25NbO 5, through the TiO of magnetic agitation 8h acquisition clarification, thickness 2/ Nb 2O 5Composite precursor spin coating liquid; And it being spin-coated on the FTO electro-conductive glass of acetone and absolute ethyl alcohol ultrasonic cleaning the spin-coated layer that forms one deck with the spin coating appearance, spin coating appearance rotating speed is 2000rmin -1, the used spin coating time is 30s.
0.52g PVAc joined among the 4ml DMF to form the quality percentage composition be the solution of 11.5wt.%, two parts of same solution preparations, ie in solution I and solution II; In the solution I, add 0.6ml Triton X-100 and 0.78g C 10H 25NbO 5, magnetic agitation 8h obtains Nb 2O 5Presoma spinning solution 1.In the solution II, add 0.6ml Triton X-100,0.4ml HAc, and 1.04g TiP, magnetic agitation 8h obtains TiO 2Presoma spinning solution 2.With Nb 2O 5Presoma spinning solution 1 and TiO 2 Presoma spinning solution 2 is respectively charged in two syringes 3 and 4; At coaxial spinning head 5 and 6 high voltages that add 16KV of receiving system; Spinning head is 12cm to the distance of dash receiver, and charged drop overcomes self under effect of electric field surface tension forms the injection thread.Control the rate of extrusion of two syringes respectively by two micro-injection pumps 8 and 9, wherein the shell rate of extrusion is 0.6ml/h, and the rate of extrusion of stratum nucleare is 0.5ml/h; Along with solvent evaporates, spray the fiber that thread solidify to form nucleocapsid structure, directly be collected in disordered state and on the FTO of spin-coat process electro-conductive glass 10, form composite cellulosic membrane 11, as shown in Figure 1; Behind the spinning 30min, with putting into the Muffle furnace sintering after the composite cellulosic membrane of collecting 11 dryings, with 1 °Cmin -1Speed be warming up to 500 °Be incubated 1h behind the C, obtain TiO 2/ Nb 2O 5The nuclear shell structure nano tunica fibrosa.The TiO that Fig. 2 makes for this embodiment 2/ Nb 2O 5The stereoscan photograph of nuclear shell structure nano tunica fibrosa.
Use TiO 2/ Nb 2O 5Nuclear shell structure nano tunica fibrosa and TiO 2Nano fibrous membrane, N719 sensitizing dyestuff, I -/ I 3 -Standard electrolyte and plating Pt carry out relevant characterization and test to electrode assembled battery, and compare the performance difference between two types of batteries.Characterize with the process of performance test and result and embodiment 1 in similar, related data and picture are not listed as.Wherein, the photoelectric conversion efficiency of most critical brings up to 4.66% from 3.5%, has improved 33%.
Embodiment 3:
0.68g PVAc joined in the 4ml DMF organic solvent to form the quality percentage composition be the solution of 15wt.%, in this solution, add 1ml Triton X-100,1.36g TiP, and 1.02g C 10H 25NbO 5, through the TiO of magnetic agitation 8h acquisition clarification, thickness 2/ Nb 2O 5Composite precursor spin coating liquid; And it being spin-coated on the FTO electro-conductive glass of acetone and absolute ethyl alcohol ultrasonic cleaning the spin-coated layer that forms one deck with the spin coating appearance, spin coating appearance rotating speed is 2000rmin -1, the used spin coating time is 30s.
0.52g PVAc joined among the 4ml DMF to form the quality percentage composition be the solution of 11.5wt.%, two parts of same solution preparations, ie in solution I and solution II; In the solution I, add 0.6ml Triton X-100 and 0.78g C 10H 25NbO 5, magnetic agitation 8h obtains Nb 2O 5Presoma spinning solution 1.In the solution II, add 0.6ml Triton X-100,0.4ml HAc, and 1.04g TiP, magnetic agitation 8h obtains TiO 2Presoma spinning solution 2.With Nb 2O 5Presoma spinning solution 1 and TiO 2 Presoma spinning solution 2 is respectively charged in two syringes 3 and 4; At coaxial spinning head 5 and 6 high voltages that add 16KV of receiving system; Spinning head is 12cm to the distance of dash receiver, and charged drop overcomes self under effect of electric field surface tension forms the injection thread.Control the rate of extrusion of two syringes respectively by two micro-injection pumps 8 and 9, wherein the shell rate of extrusion is 0.5ml/h, and the rate of extrusion of stratum nucleare is 0.6ml/h; Along with solvent evaporates, spray the fiber that thread solidify to form nucleocapsid structure, directly be collected in disordered state and on the FTO of spin-coat process electro-conductive glass 10, form composite cellulosic membrane 11, as shown in Figure 1; Behind the spinning 30min, with putting into the Muffle furnace sintering after the composite cellulosic membrane of collecting 11 dryings, with 1 °Cmin -1Speed be warming up to 500 °Be incubated 1h behind the C, obtain TiO 2/ Nb 2O 5The nuclear shell structure nano tunica fibrosa.The TiO that Fig. 2 makes for this embodiment 2/ Nb 2O 5The stereoscan photograph of nuclear shell structure nano tunica fibrosa.
Use TiO 2/ Nb 2O 5Nuclear shell structure nano tunica fibrosa and TiO 2Nano fibrous membrane, N719 sensitizing dyestuff, I -/ I 3 -Standard electrolyte and plating Pt carry out relevant characterization and test to electrode assembled battery, and compare the performance difference between two types of batteries.Characterize with the process of performance test and result and embodiment 1 in similar, related data and picture are unlisted.Wherein, the photoelectric conversion efficiency of most critical brings up to 4.34% from 3.5%, has improved 24%.

Claims (4)

1. a dye-sensitized cell is characterized in that with the preparation method of titanium dioxide-niobium pentaoxide nuclear shell structure nano tunica fibrosa the step of this method is following:
1) preparing PVA c quality percentage composition is the DMF solution of 15wt.%, is the surfactant Triton X-100 of DMF solution 25% with volume, and 2 times of quality are to the TiP of PVAc, and 1.5 times of quality are to the C of PVAc 10H 25NbO 5Join in the DMF solution; Obtain TiO through magnetic agitation 8h 2/ Nb 2O 5Composite precursor spin coating liquid, and it is spin-coated on the FTO electro-conductive glass spin-coated layer that forms one deck with the spin coating appearance;
2) preparing PVA c quality percentage composition is the DMF solution of 11.5wt.%, is the surfactant Triton X-100 of DMF solution 15% with volume, and 1.5 times of quality are to the C of PVAc 10H 25NbO 5Join in the DMF solution, obtain Nb through magnetic agitation 8h 2O 5Presoma spinning solution (1); Preparing PVA c quality percentage composition is the DMF solution of 11.5wt.%; With volume is the surfactant Triton X-100 of DMF solution 15%; Volume is the HAc of DMF solution 10%, and 2 times of TiP to PVAc of quality join in the DMF solution, obtains TiO through magnetic agitation 8h 2Presoma spinning solution (2); Presoma spinning solution (1) and (2) are respectively charged in syringe (3) and (4); Between coaxial spinning head (5) and receiving system (6), add high voltage (7); Charged drop overcomes self under effect of electric field surface tension forms the injection thread, is controlled the rate of extrusion of (3) and (4) respectively by micro-injection pump (8) and (9); Along with solvent evaporates, spray the fiber that thread solidify to form nucleocapsid structure, directly be collected in through the FTO of spin-coat process electro-conductive glass (10) with disordered state and go up formation composite cellulosic membrane (11), FTO glass (10) is fixing by receiving system (6);
3) behind the spinning 30min, with putting into the Muffle furnace sintering after the tunica fibrosa of collecting (11) drying, with 1 °Cmin -1Speed be warming up to 500 °Be incubated 1h behind the C, obtain the TiO of nucleocapsid structure 2/ Nb 2O 5Nano fibrous membrane.
2. a kind of dye-sensitized cell according to claim 1 is characterized in that with the preparation method of titanium dioxide-niobium pentaoxide nuclear shell structure nano tunica fibrosa: the spin coating appearance rotating speed that adopts in the said step 1) is 2000rmin -1, the spin coating time is 30s.
3. a kind of dye-sensitized cell according to claim 1 is with the preparation method of titanium dioxide-niobium pentaoxide nuclear shell structure nano tunica fibrosa; It is characterized in that: micro-injection pump (8) is that the rate of extrusion of shell is 0.5 ~ 0.7 ml/h said step 2), and micro-injection pump (9) is that the rate of extrusion of stratum nucleare is 0.4 ~ 0.6 ml/h.
4. a kind of dye-sensitized cell according to claim 1 is characterized in that: TiO with the preparation method of titanium dioxide-niobium pentaoxide nuclear shell structure nano tunica fibrosa 2/ Nb 2O 5The DSSC and the TiO of the assembling of nuclear shell structure nano tunica fibrosa 2The DSSC of nano fibrous membrane assembling compares photoelectric conversion efficiency ηImproved 24% ~ 33%.
CN 201110399846 2011-12-06 2011-12-06 Method for preparing titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for dye-sensitized solar cell Expired - Fee Related CN102496479B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110399846 CN102496479B (en) 2011-12-06 2011-12-06 Method for preparing titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for dye-sensitized solar cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110399846 CN102496479B (en) 2011-12-06 2011-12-06 Method for preparing titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for dye-sensitized solar cell

Publications (2)

Publication Number Publication Date
CN102496479A true CN102496479A (en) 2012-06-13
CN102496479B CN102496479B (en) 2013-07-17

Family

ID=46188290

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110399846 Expired - Fee Related CN102496479B (en) 2011-12-06 2011-12-06 Method for preparing titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for dye-sensitized solar cell

Country Status (1)

Country Link
CN (1) CN102496479B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060008942A1 (en) * 2004-07-07 2006-01-12 Nanosys, Inc. Systems and methods for harvesting and integrating nanowires
CN101244381A (en) * 2008-03-07 2008-08-20 东南大学 Process for producing TiO2-Al2O3composite nano-powder body material
CN101582332A (en) * 2009-06-29 2009-11-18 中国科学院等离子体物理研究所 Application of down-conversion luminescent material on dye-sensitized solar cells
CN101834068A (en) * 2009-03-13 2010-09-15 中国科学院福建物质结构研究所 Core-shell structure positive electrode for dye sensitization solar battery and preparation method thereof
CN102082031A (en) * 2009-11-27 2011-06-01 济南大学 Novel dye-sensitized solar cell photoanode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060008942A1 (en) * 2004-07-07 2006-01-12 Nanosys, Inc. Systems and methods for harvesting and integrating nanowires
CN101244381A (en) * 2008-03-07 2008-08-20 东南大学 Process for producing TiO2-Al2O3composite nano-powder body material
CN101834068A (en) * 2009-03-13 2010-09-15 中国科学院福建物质结构研究所 Core-shell structure positive electrode for dye sensitization solar battery and preparation method thereof
CN101582332A (en) * 2009-06-29 2009-11-18 中国科学院等离子体物理研究所 Application of down-conversion luminescent material on dye-sensitized solar cells
CN102082031A (en) * 2009-11-27 2011-06-01 济南大学 Novel dye-sensitized solar cell photoanode

Also Published As

Publication number Publication date
CN102496479B (en) 2013-07-17

Similar Documents

Publication Publication Date Title
CN102496471B (en) Method for preparing titanium dioxide-zinc oxide nuclear shell structure nanometer fiber membrane for dye sensitized battery
Li et al. Detachment and transfer of ordered TiO 2 nanotube arrays for front-illuminated dye-sensitized solar cells
CN101901693B (en) Graphene composite dye-sensitized solar cell light anode and preparation method thereof
CN101728083B (en) Heterostructure photoanode for dye-sensitized solar cell and manufacturing method thereof
US20150144199A1 (en) Dye-sensitized solar cell having carbon nano-web coated with graphene and method for manufacturing same
CN109065724B (en) Mo-titanium dioxide-AgNWs flexible perovskite solar cell and preparation method thereof
CN109252179A (en) A kind of double absorption layer light anode and preparation method for photocatalytic water
KR101431817B1 (en) Double device merged tandem solar cell and its production method
CN102496485B (en) Method for improving firmness of combination of dye-sensitized cell nanometer fibrous membrane and conductive glass
Wu et al. Anodic TiO2 nanotube arrays for dye-sensitized solar cells characterized by electrochemical impedance spectroscopy
Zhu et al. Facile fabrication of open-ended TiO2 nanotube arrays with large area for efficient dye-sensitized solar cells
CN104310794A (en) Porous TiO2 nanocrystalline thin film having three-dimensional nanorod floral structure as well as preparation method and application of porous TiO2 nanocrystalline thin film
Wang et al. Effects of low pressure plasma treatments on DSSCs based on rutile TiO2 array photoanodes
JP2015185836A (en) Composite self-supporting film, solar cell, method of producing composite self-supporting film
CN101697320B (en) Dye-sensitized solar cell photoanode and preparation method thereof
CN105702472A (en) Solar cell electrode, preparation method therefor, and solar cell
CN102751096B (en) A kind of transparent two sides dye-sensitized solar cell anode
CN102496478A (en) Method for improving performance of nanofiber membrane of dye-sensitized battery by synergistic action of carbon nanotubes and titanium tetrachloride
CN103972398B (en) A kind of organic inorganic hybridization solaode and preparation method thereof
CN102496479B (en) Method for preparing titanium dioxide (TiO2)/niobium pentoxide (Nb2O5) core-shell structure nano-fiber film for dye-sensitized solar cell
Arifin et al. Characteristics of ZnO nanofiber in double Layer (TiO2/ZnO) DSSC results of direct deposition electrospinning manufacturing: Variation of tip to collector distance
Khusaini et al. The influence of electrospinning flow rate parameter on ZnO nanofiber as photoanode of dye-sensitized solar cell
CN106847518B (en) A kind of dye-sensitized solar cell anode and preparation method thereof
CN103165292B (en) A kind of preparation method of thread dye-sensitized solar cell anode
Onwona-Agyeman et al. Photoelectrochemical solar cells made from SnO2/ZnO films sensitized with an indoline dye

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130717

Termination date: 20151206

EXPY Termination of patent right or utility model