CN102709067B - Method for preparing permutable multi-dye absorption layer co-sensitized thin film by electrochemical desorption method - Google Patents
Method for preparing permutable multi-dye absorption layer co-sensitized thin film by electrochemical desorption method Download PDFInfo
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- CN102709067B CN102709067B CN201210164924.6A CN201210164924A CN102709067B CN 102709067 B CN102709067 B CN 102709067B CN 201210164924 A CN201210164924 A CN 201210164924A CN 102709067 B CN102709067 B CN 102709067B
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- dyestuff
- dye
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- thin film
- desorption
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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
- Y02E10/549—Organic PV cells
Abstract
The invention relates to a method for preparing a permutable multi-dye absorption layer co-sensitized thin film by an electrochemical desorption method, which comprises the following steps of: (1) preparing a nano porous semiconductor thin film on a conductive glass substrate; (2) dipping the nano porous semiconductor thin film in the solution of dye a so that the thin film completely absorbs the solution of the dye a; (3) using the nano porous semiconductor thin film which absorbs the dye a as a work electrode and a platinum sheet as a desorption electrode; (4) dipping the semiconductor thin film containing a dye blank layer into a second dye b so that the dye blank layer absorbs the dyes to obtain the co-sensitized thin film containing two dye absorption layers; and (5) repeating the steps (3) and (4) to obtain the co-sensitized thin film containing the multi-dye absorption layer. The invention has the advantages that the contradiction among dye absorption time, dye absorption amount and the dye blank layer thickness in original method for preparing the co-sensitized thin film only by dye absorption can be solved; and the thickness of each dye absorption layer is adjusted and controlled by controlling the depth of potential distribution.
Description
Technical field
The invention belongs to the crossing domain of electrochemistry and nano material, particularly relate to and can arrange the method that polychromatophilia material adsorption layer is total to sensitization film a kind of preparation by electrochemistry desorption method.
Background technology
1991
novel photovoltaic device-dye-sensitized solar cells that professor develops opens a frontier for human use's solar power generation.Unique structural design and uncommon photoelectric conversion mode make dye-sensitized solar cells attract wide attention.Dye-sensitized solar cells is a kind of Multi-phase light electrochemical system, primarily of electro-conductive glass, nano porous semiconductor film, dyestuff, electrolyte and platinum to electrode composition " sandwich " structure.In these parts, thickness only has the semiconductive thin film of about 10 μm adsorption dyestuffs (sensitization film) to be the core component that battery realizes photoelectric energy conversion.The important photoelectric energy conversion processes such as photoelectronic generation, transmission and compound all betide this, and the dynamics speed of these processes decides the height of cell photoelectric transformation efficiency.How to obtain high performance sensitization film is Focal point and difficult point problem in dye-sensitized solar cells field always.Absorption spectrum is the key factor affecting dye-sensitized solar cells performance, and semiconductive thin film only absorbs the ultraviolet portion in solar spectrum, so the dyestuff performance on absorption semiconductive thin film surface determines absorption region and the intensity of sensitization film.The light in particular range of wavelengths can only be absorbed due to a kind of dyestuff, also there is no absorption that a kind of dyestuff can be stronger at present from visible region until the light of infrared light district scope.Such as conventional N719 dyestuff absorbs in 400 ~ 600 nm shortwave districts comparatively strong and absorbs more weak in the long-wave band of 600 ~ 900 nm.So incident light major parts more than 600 nm wave bands by absorbing directly through sensitization film, can not cause the direct losses of luminous energy thus.If increase a kind of dyestuff that the absorption of the long-wave band of 600 ~ 900 nm is stronger the absorption of 400 ~ 600 nm shortwave districts is more weak, the common sensitization film that so these two kinds of dyestuffs are formed improves absorbing light greatly by 400 ~ 900 nm wave bands, and battery efficiency also will get a promotion.The method of sensitization can make full use of existing dyestuff altogether, several different types of Dye Adsorption is realized on same film dye absorber to have complementary advantages, widen dye-sensitized solar cells absorption spectrum, improve electricity conversion, now become one, dye-sensitized solar cells field study hotspot.
Altogether sensitization film preparation difficult point is that the semiconductive thin film blanket layer that how thickness can be provided controlled for often kind of dyestuff can not sacrifice again the adsorbance of dyestuff simultaneously.Semiconductive thin film soaks the main preparation methods that dyestuff mode is common sensitization film, the method is the absorption of passive control dyestuff, not only cause Dye Adsorption time, contradiction between adsorbance and adsorption deeply, and be difficult to by the common sensitization film of the method preparation containing more than 2 Dye Adsorption layers.Sensitization preparation method restricts the optimization of its structure altogether.Because current preparation method is difficult to change Dye Adsorption layer thickness, adsorption layer position, Dye Adsorption amount and Dye Adsorption layer order freely, so that deeply can not optimize adsorbed layer structure, cause film sensitization poor effect altogether, limit widening further of common sensitization film absorption spectrum.Therefore, present stage is found preparation and is total to the top priority that sensitization new film method is still this field.Prepared by the present invention contains more than 2 Dye Adsorption layers and layer thickness controllable, layer position can select the sequencable wide spectral of order between layer to be total to sensitization film can be provided one strong " heart " for dye-sensitized solar cells, and cell photoelectric conversion efficiency is further enhanced.
Summary of the invention
The invention provides a kind of method that can be arranged polychromatophilia material adsorption layer altogether sensitization film by the preparation of electrochemistry desorption method, be intended to obtain containing multiple Dye Adsorption layer and each adsorbent layer thickness can regulate and control, the common sensitization film that adsorption layer position can arrange.
The present invention prepares common sensitization film and comprises the steps:
Method is:
(1) in electro-conductive glass substrate, nano porous semiconductor film is prepared;
(2) immersed by nano porous semiconductor film in dyestuff a solution, make the complete absorbing dye a of film, the time that nano porous semiconductor film immerses dye solution is generally 10-20 hour, and temperature is 25 degrees Celsius;
(3) with the nano porous semiconductor film of absorbing dye a for work electrode, platinized platinum is as desorption electrode, saturated calomel electrode forms four electrode systems as reference electrode and platinum loop as auxiliary electrode and carries out dyestuff desorption, by controlling to apply the size of negative potential, position and duration, negative potential is only existed film is inner in certain distance, exist in the region of electromotive force, the formation one of getting off of dyestuff desorption does not have the blanket layer (dyestuff desorption layer) of Dye Adsorption;
(4) semiconductive thin film containing dyestuff blanket layer is immersed the second dyestuff b, make dyestuff blanket layer absorbing dye obtain containing the common sensitization film of 2 Dye Adsorption layers;
(5) the common sensitization film that step (3) and (4) can obtain containing polychromatophilia material adsorption layer is repeated.
The optimum thickness of described nano porous semiconductor film is at 10-15 micron, and battery performance is best.
Described dyestuff has N719, N3, black dyestuff, Z907, Z910, Z955, K8, K19, K51, K73, HRS-1 ruthenium pyridines complex, osmium pyridines complex, merocyanine, porphyrin metal class complex, indolin derivatives, coumarin derivative organic dyestuff, often kind of dyestuff is dissolved in separately in acetonitrile or ethanol, and concentration is about 1.0 × 10
-3-5.0 × 10
-4m, forms a kind of dye solution.
Compared with existing preparation altogether sensitization thin film technique, advantage of the present invention is:
[1] solve depended merely on Dye Adsorption preparation in the past and existed in sensitization film process altogether the Dye Adsorption time, contradiction between Dye Adsorption amount and dyestuff blanket layer thickness;
[2] thickness of each Dye Adsorption layer can be regulated and controled by controlling the Potential Distributing degree of depth;
[3] apply by changing electromotive force the position that position just can change dyestuff desorption layer;
[4] order by regulating sensitization order just can arrange each dye coating;
[5] the common sensitization film containing more than 2 Dye Adsorption layers can be prepared.
Accompanying drawing explanation
Fig. 1 dye-sensitized film desorption system.
Embodiment
Mode one: embedded preparation is sensitization film altogether, as shown in Figure 1, by TiO
2slurry is printed in conductive substrates 1 top, within 30 minutes, forms 15 μm of thickness nanoporous TiO by 510 DEG C of sintering
2film.Immerse in dyestuff a solution and form single dye sensitization TiO after 12 hours
2film.With the TiO of absorbing dye a
2film 2 is as work electrode, and saturated calomel electrode 3 forms three electrode dyestuff desorption systems as reference electrode and platinum loop 4 as auxiliary electrode, and electrolyte is concentration 0.3 M TBAPF
6and LiClO
4acetonitrile solution.Negative potential-1.5 V puts on conductive substrates 1(and is defined as TiO
2the front end of film 2) after, be adsorbed on TiO
2dyestuff a on film 2 can from conductive substrates 1 desorption.After applying 10 minutes electromotive force time, obtain the adsorption layer of about 10 μm of dyestuff blanket layer and 5 μm of dyestuff a.Afterwards film is immersed in dyestuff b and carry out secondary sensitization, 10 μm of dyestuff blanket layer absorbing dye b, obtain 2 layers, b/a type sensitization film altogether; Carry out dyestuff desorption step again, after applying 5 minutes electromotive force time, obtain about 5 μm of dyestuff blanket layer, the adsorption layer of 5 μm of dyestuff b and the adsorption layer of 5 μm of dyestuff a, film is immersed in dyestuff c afterwards and carry out three sensitizations, 3 layers, c/b/a type sensitization film altogether can be obtained.
Mode two: superposing type preparation sensitization film altogether, as shown in Figure 1, by TiO
2slurry is printed in conductive substrates 1 top, within 30 minutes, forms 15 μm of thickness nanoporous TiO by 510 DEG C of sintering
2film.Immerse in dyestuff a solution and form single dye sensitization TiO after 12 hours
2film.With the TiO of absorbing dye a
2film 2 is as work electrode, and saturated calomel electrode 3 forms four electrode dyestuff desorption systems as auxiliary electrode and platinized platinum 5 as auxiliary desorption electrode as reference electrode, platinum loop 4, and electrolyte is concentration 0.3 M TBAPF
6and LiClO
4acetonitrile solution.Platinized platinum 5 close contact TiO
2the rear end of film 2.After negative potential-1.5 V puts on platinized platinum 5, be adsorbed on TiO
2dyestuff a on film 2 can from TiO
2film 2 rear end starts desorption.After applying 10 minutes electromotive force time, obtain the adsorption layer of about 10 μm of dyestuff blanket layer and 5 μm of dyestuff a.Afterwards film is immersed in dyestuff b and carry out secondary sensitization, 10 μm of dyestuff blanket layer absorbing dye b, obtain 2 layers, a/b type sensitization film altogether; Carry out dyestuff desorption step again, after applying 5 minutes electromotive force time, obtain about 5 μm of dyestuff blanket layer, the adsorption layer of 5 μm of dyestuff b and the adsorption layer of 5 μm of dyestuff a, film is immersed in dyestuff c afterwards and carry out three sensitizations, 3 layers, a/b/c type sensitization film altogether can be obtained.
Mode three: sandwich preparation sensitization film altogether, as shown in Figure 1, by TiO
2slurry is printed in conductive substrates 1 top, within 30 minutes, forms 15 μm of thickness nanoporous TiO by 510 DEG C of sintering
2film.Immerse in dyestuff a solution and form single dye sensitization TiO after 12 hours
2film.With the TiO of absorbing dye a
2film 2 is as work electrode, and saturated calomel electrode 3 forms four electrode dyestuff desorption systems as auxiliary electrode and platinized platinum 5 as auxiliary desorption electrode as reference electrode, platinum loop 4, and electrolyte is concentration 0.3 M TBAPF
6and LiClO
4acetonitrile solution.Platinized platinum 5 close contact TiO
2the rear end of film 2.Negative potential-1.5 V is adsorbed on TiO after putting on conductive substrates 1 and platinized platinum 5
2dyestuff a on film 2 can from TiO
2film 2 front-end and back-end start desorption.After applying 5 minutes electromotive force time, obtain the adsorption layer of two about 5 μm of dyestuff blanket layer and 5 μm of dyestuff a.Afterwards film is immersed in dyestuff b and carry out secondary sensitization, two 5 μm dyestuff blanket layer absorbing dye b, obtain 3 layers, b/a/b type sensitization film altogether.
Claims (3)
1. can arrange by the preparation of electrochemistry desorption method the method that polychromatophilia material adsorption layer is total to sensitization film, it is characterized in that method is:
(1) in electro-conductive glass substrate, nano porous semiconductor film is prepared;
(2) immersed by nano porous semiconductor film in dyestuff a solution, make the complete absorbing dye a of film, the time that nano porous semiconductor film immerses dye solution is 10-20 hour, and temperature is 25 degrees Celsius;
(3) with the nano porous semiconductor film of absorbing dye a for work electrode, platinized platinum is as desorption electrode, saturated calomel electrode forms four electrode systems as reference electrode and platinum loop as auxiliary electrode and carries out dyestuff desorption, by controlling to apply the size of negative potential, position and duration, negative potential is only existed film is inner in certain distance, exist in the region of electromotive force, the formation one of getting off of dyestuff desorption does not have the blanket layer of Dye Adsorption, i.e. dyestuff desorption layer;
(4) semiconductive thin film containing dyestuff blanket layer is immersed the second dyestuff b, make dyestuff blanket layer absorbing dye obtain containing the common sensitization film of two Dye Adsorption layers;
(5) the common sensitization film that step (3) and (4) can obtain containing polychromatophilia material adsorption layer is repeated.
2. can arrange the method that polychromatophilia material adsorption layer is total to sensitization film according to claim 1 preparation by electrochemistry desorption method, it is characterized in that the optimum thickness of nano porous semiconductor film is at 10-15 micron, battery performance is best.
3. can arrange the method that polychromatophilia material adsorption layer is total to sensitization film according to claim 1 preparation by electrochemistry desorption method, it is characterized in that described dyestuff has N719, N3, black dyestuff, Z907, Z910, Z955, K8, K19, K51, K73, HRS-1 ruthenium pyridines complex, osmium pyridines complex, merocyanine, porphyrin metal class complex, indolin derivatives, coumarin derivative organic dyestuff, often kind of dyestuff is dissolved in separately in acetonitrile or ethanol, and concentration is 1.0 × 10
-3-5.0 × 10
-4m, forms a kind of dye solution.
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| WO2016032266A1 (en) * | 2014-08-28 | 2016-03-03 | 주식회사 동진쎄미켐 | Novel ruthenium-based dye and method for preparing same |
| CN107687018A (en) * | 2017-07-25 | 2018-02-13 | 南昌航空大学 | A kind of method of sensitization solar battery light anode MAT'L recycling |
| CN108597884A (en) * | 2018-04-19 | 2018-09-28 | 南昌航空大学 | A method of it preparing stereo colour using conductive metal adhesive tape combination electrochemistry desorption and is sensitized film |
| CN111161956B (en) * | 2020-01-03 | 2021-06-22 | 南昌航空大学 | Method for preparing co-sensitization film by bidirectional diffusion technology |
| CN111161958B (en) * | 2020-01-03 | 2021-06-22 | 南昌航空大学 | Method for preparing multilayer co-sensitized film by light control technology |
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| 双染料共敏化的纳米晶二氧化钛多孔电极的光伏特性研究;方靖淮等;《太阳能学报》;19970430;第18卷(第2期);全文 * |
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