CN100379033C - Mathod for preparing new hybridized electrode - Google Patents
Mathod for preparing new hybridized electrode Download PDFInfo
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- CN100379033C CN100379033C CNB2004100608437A CN200410060843A CN100379033C CN 100379033 C CN100379033 C CN 100379033C CN B2004100608437 A CNB2004100608437 A CN B2004100608437A CN 200410060843 A CN200410060843 A CN 200410060843A CN 100379033 C CN100379033 C CN 100379033C
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- titanium dioxide
- layer
- electrode
- film
- nanometer crystal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The present invention discloses a preparation method for a novel hybridized electrode used for dye sensitization nanometer crystal thin-film solar cells. The hybridized electrode comprises a sputtering settled layer and a nanometer crystal titanium dioxide layer, wherein the sputtering settled layer is deposited on a conductive layer of conductive glass through a reaction direct-current magnetron sputtering method and has favorable roughness. The traditional powder coating method is used for preparing a nanometer crystal titanium dioxide film layer. The method is favourable for increasing photoelectric parameters of the dye sensitization nanometer crystal solar cells, and is an effective method for increasing the photoelectric conversion efficiency of the solar cells. In addition, the method has the advantages of simple production process and low cost.
Description
Technical field
The present invention relates to a kind of preparation method of novel hybride electrode, particularly relate to a kind of preparation method who is used for the novel hybride electrode of dye sensitized nano crystal thin-film solar cells, belong to field of nanometer material technology, also belong to new energy field.
Background technology
The dye sensitized nano crystal salar battery of Gr tzel and colleague's exploitation thereof has noticeable feature on energy conversion efficiency and low cost.Since have good stable, the low-cost and simple course of processing, and titanium dioxide is widely used on the dye sensitized nano crystal salar battery.In fact, the photoelectric parameter of this battery is made up the influence of the structure of the method for nanocrystalline electrode and electrode thereof strongly.Up to now, the film of using the photovoltaic aspect usually generally adopts the preparation of powder coated method, has the porous film electrode of high surface area in order to preparation.But the contact area between the nano-titanium dioxide film that is formed by titania powder and the conductive film of electro-conductive glass is less, thus between the two in conjunction with firm inadequately.If the size of the titanium dioxide powder particles of using is big slightly, nano-titanium dioxide film just is easy to split away off from the conductive film of electro-conductive glass.In addition, bad if the nano titanium dioxide powder particle combines with on every side titanium dioxide powder particles, thus make the excitation electron in these titanium dioxide powder particles be difficult to be sent on the conductive film of electro-conductive glass.Also have, owing to space in the nano-titanium dioxide film that utilizes the preparation of powder coated method is a lot, the conductive film of electro-conductive glass not necessarily all can be covered by nano-titanium dioxide film, electrolyte might directly contact with the conductive film of electro-conductive glass by the space of nano-titanium dioxide film, thereby cause the electronics on the conductive film directly to be caught by electrolyte, rather than first being sent to by load is sent on the electrolyte after on the electrode again, thereby cause the partial short circuit of battery, reduced the photoelectric conversion efficiency of solar cell.In order to obtain better solar cell parameter, usefulness 4-butyl-pyridinium such as Gr tzel are handled the membrane electrode that has adsorbed dyestuff, and are the open circuit photoelectricity voltage that has obtained under 1.5 the sunlight greater than 720mV at the simulation air mass (AM); Bach etc. have designed a kind of titanium dioxide membrane electrode provided that is used for the sandwich structure on the dye-sensitized nanocrystalline titanium dioxide solar cell, this electrode has added one deck compact titanium dioxide layer by sol-gel process between electro-conductive glass and nano-crystalline titanium dioxide layer, and has obtained higher photoelectric conversion efficiency.Owing to covering one deck 4-butyl-pyridinium on the nano-crystalline titanium dioxide film or between conductive glass layer and nano-crystalline titanium dioxide film layer, adding one deck compacted zone, so dark current is suppressed on semiconductor titanium dioxide layer and electrolytical interface, thereby improved the solar cell parameter.
Recently, the reaction direct current magnetron sputtering process is used to be deposited on the preparation of photocatalysis titanium dioxide film on glass.Hagfeldt etc. have reported a kind of with reaction direct current magnetron sputtering process deposition of titanium oxide membrane electrode, and have obtained photoelectric conversion efficiency and be approximately 7% dye-sensitized cell.This sputtered film has represented a kind of feathery structure, has very large apparent surface area, and with electro-conductive glass between have good electricity and contact.Yet, with the titanium dioxide membrane electrode provided dyestuff adsorbance that makes of reaction direct current magnetron sputtering process still less than the dyestuff adsorbance of the nano-crystalline titanium dioxide film of same thickness.On the other hand, compare with sol-gal process, the film of reaction direct current magnetron sputtering process preparation demonstrates better mechanical stability, high photocatalytic activity, and favorable uniformity.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of novel hybride electrode is provided, it has the mechanical stability height and significantly improves the advantage of the parameter of solar cell.
Technical scheme provided by the invention is: a kind of preparation method of novel hybride electrode, it is characterized in that on electro-conductive glass, forming shaggy titanium dioxide sputtering depositing layer with the reaction direct current magnetron sputtering process, on sputtering depositing layer, prepare nano-crystalline titanium dioxide layer, absorbing dye then with the powder coated method again.
The present invention makes up one deck sputtering depositing layer and one deck nanometer crystal layer successively on electro-conductive glass, the hybrid electrode of forming a kind of brand-new sandwich structure, adopt the titanium deoxid film of reaction direct current magnetron sputtering process deposition, the mechanical stability height, surface roughness is big, can improve the parameter of DSSC significantly.Like this, this hybrid electrode had just both kept the high surface area performance of nano-crystalline film electrode, had taken into account conductive layer in the electro-conductive glass again and had contacted with good electrical between the magnetron sputtering layer.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described:
Embodiment
The hydridization titanium dioxide electrodes deposits sputtering depositing layer and nano-crystalline titanium dioxide layer by the following method respectively successively: sputtering depositing layer is to deposit 10～40 minutes under 150～350 ℃ on the conductive layer of electro-conductive glass by the reaction direct current magnetron sputtering process at underlayer temperature.Target is that diameter is that 6 centimetres, purity are 99.99% Titanium.The deposition rate of titanium deoxid film is approximately per minute 2 nanometers.The ratio of oxygen and argon gas is 1: 6～1: 12, and pressure is 0.8～2.0Pa.Scanning electron micrograph shows that sputtering depositing layer is that the particle of 500 nanometers is formed by crystal size, has demonstrated good roughening.On this basis, adopt the conventional powder cladding process to prepare the nano-crystalline titanium dioxide film layer of one deck 1～10 micron thickness.Afterwards hybrid electrode is immersed and dissolved in the straight alcohol of dyestuff N3, thereby cover one deck dyestuff N3 at the nano hybridization electrode surface.
As a comparison, adopt the conventional powder cladding process on electro-conductive glass, to prepare one deck same thickness nano-crystalline titanium dioxide film layer.Absorbing dye N3.
Respectively with the electrode of above preparation as negative electrode, as to electrode, adopt 0.5M LiI and 0.04M I with the platinum piece
2Propylene carbonate ester (PC) solution as redox electrolytes matter, assembled battery.In the standard atmosphere quality is that 1.5 (AM1.5), intensity are 98mW/cm
2Simulated solar irradiation under, the battery of hybrid electrode assembling: photoelectric conversion efficiency η=5.1%, fill factor, curve factor FF=0.5, closed circuit density of photocurrent J
Sc=15.4mA/cm
2, open circuit voltage V
Oc=615mV; And under the similarity condition, pure nano-crystalline titanium dioxide battery: photoelectric conversion efficiency η=1.5%, fill factor, curve factor FF=0.39, closed circuit density of photocurrent are J
Sc=7.9mA/cm
2, open circuit voltage V
Oc=471mV.Compare with pure nanocrystalline electrode, this hybrid electrode has improved 1 times nearly on short-circuit photocurrent density; Open circuit voltage has improved near 1/3rd.
Claims (1)
1. the preparation method of a hybrid electrode, it is characterized in that on electro-conductive glass, forming shaggy titanium dioxide sputtering depositing layer with the reaction direct current magnetron sputtering process, on sputtering depositing layer, prepare nano-crystalline titanium dioxide layer, absorbing dye then with the powder coated method again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100608437A CN100379033C (en) | 2004-09-13 | 2004-09-13 | Mathod for preparing new hybridized electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100608437A CN100379033C (en) | 2004-09-13 | 2004-09-13 | Mathod for preparing new hybridized electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1588651A CN1588651A (en) | 2005-03-02 |
| CN100379033C true CN100379033C (en) | 2008-04-02 |
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| CNB2004100608437A Expired - Fee Related CN100379033C (en) | 2004-09-13 | 2004-09-13 | Mathod for preparing new hybridized electrode |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1909261B (en) * | 2006-08-28 | 2011-10-26 | 清华大学 | Titanium dioxide crystallized light absorption enhancement thin film electrode and its preparation method |
| CN101452772B (en) * | 2009-01-04 | 2012-11-07 | 上海大学 | Dye sensitization solar cell electrode and method for making same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1411077A (en) * | 2001-09-26 | 2003-04-16 | 北京科技大学 | Nano titanium dioxide film and its manufacturing method |
| US6677516B2 (en) * | 2001-01-29 | 2004-01-13 | Sharp Kabushiki Kaisha | Photovoltaic cell and process for producing the same |
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2004
- 2004-09-13 CN CNB2004100608437A patent/CN100379033C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6677516B2 (en) * | 2001-01-29 | 2004-01-13 | Sharp Kabushiki Kaisha | Photovoltaic cell and process for producing the same |
| CN1411077A (en) * | 2001-09-26 | 2003-04-16 | 北京科技大学 | Nano titanium dioxide film and its manufacturing method |
Non-Patent Citations (1)
| Title |
|---|
| 孟庆铂，林原，戴松元.物理学与新能源材料专题，第3卷. 2004 * |
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| CN1588651A (en) | 2005-03-02 |
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