CN102709067A - 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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- CN102709067A CN102709067A CN2012101649246A CN201210164924A CN102709067A CN 102709067 A CN102709067 A CN 102709067A CN 2012101649246 A CN2012101649246 A CN 2012101649246A CN 201210164924 A CN201210164924 A CN 201210164924A CN 102709067 A CN102709067 A CN 102709067A
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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, relate in particular to and to arrange the polychromatophilia material adsorption layer method of sensitization film altogether a kind of the preparation through the electrochemical de adsorption method.
Background technology
1991
Novel photovoltaic device-dye-sensitized solar cells that professor develops has been opened up a frontier for human use's solar power generation.Special structure design and uncommon photoelectric conversion mode make dye-sensitized solar cells cause extensive concern.Dye-sensitized solar cells is a kind of heterogeneous Optical Electro-Chemistry system, mainly by electro-conductive glass, nano porous semiconductor film, dyestuff, electrolyte and platinum electrode is formed " sandwich " structure.In these several parts, it is that battery is realized the core component that photoelectric energy transforms that thickness has only the semiconductive thin film (sensitization film) of 10 μ m left and right sides surface adsorption dyestuffs.Photoelectronic generation, transmission and important photoelectric energy conversion process such as compound all betide this, and the dynamics speed of this plurality of processes is determining the height of cell photoelectric transformation efficiency.How to obtain high performance sensitization film is emphasis and the difficult point problem in the dye-sensitized solar cells field always.Absorption spectrum is a key factor that influences the dye-sensitized solar cells performance, and semiconductive thin film only absorbs the ultraviolet portion in the solar spectrum, so the dyestuff performance on absorption semiconductive thin film surface has determined the absorption region and the intensity of sensitization film.Because a kind of dyestuff can only absorb the light in the particular range of wavelengths, also there is not absorption that a kind of dyestuff can be stronger at present from the light of visible region until infrared light district scope.N719 dyestuff for example commonly used absorbs strong and a little less than the long-wave band of 600～900 nm absorbs in 400～600 nm shortwave districts.So the above incident light major part of 600 nm wave bands can not be absorbed and directly see through the sensitization film, causes the direct losses of luminous energy thus.A kind ofly absorb more weak in 400～600 nm shortwave districts and long-wave bands 600～900 nm absorb stronger dyestuffs if increase; The common sensitization film that constitutes of these two kinds of dyestuffs will improve the absorbing of light at 400～900 nm wave bands greatly so, and battery efficiency also will get a promotion.The method of sensitization can make full use of existing dyestuff altogether; Several kinds of different types of dyestuffs are adsorbed on realization dyestuff absorption mutual supplement with each other's advantages on the same film; Widened the dye-sensitized solar cells absorption spectrum; Improve electricity conversion, become the research in dye-sensitized solar cells field focus at present.
Sensitization film preparation difficult point is how can not sacrifice the adsorbance of dyestuff simultaneously again for every kind of dyestuff provides the semiconductive thin film blanket layer of a controllable thickness altogether.It is the main preparation methods of common sensitization film that semiconductive thin film soaks the dyestuff mode; The method is the absorption of passive control dyestuff; Not only caused the contradiction between dyestuff adsorption time, adsorbance and the adsorption deeply, and be difficult to contain the common sensitization film of 2 above dyestuff adsorption layers through the method preparation.The sensitization preparation method restricts the optimization of its structure altogether.Because the preparation method is difficult to change freely dyestuff adsorbent layer thickness, adsorption layer position, dyestuff adsorbance and dyestuff adsorption layer order at present; So that can not deeply optimize adsorbed layer structure; Cause film sensitization poor effect altogether, limited further widening of common sensitization film absorption spectrum.Therefore, present stage is sought preparation and is total to the top priority that sensitization new film method is still this field.The present invention preparation contain 2 above dyestuff adsorption layers and layer thickness adjustable; Layer position can select and layer between the sequencable wide spectrum of order altogether the sensitization film can one strong " heart " be provided for dye-sensitized solar cells, the cell photoelectric conversion efficiency is further enhanced.
Summary of the invention
The present invention provides a kind of can arrange the polychromatophilia material adsorption layer method of sensitization film altogether through electrochemical de adsorption method preparation, is intended to obtain containing a plurality of dyestuff adsorption layers and each adsorbent layer thickness can be regulated and control, the common sensitization film that the adsorption layer position can be arranged.
The present invention prepares common sensitization film and comprises the steps:
Method is:
(1) in the electro-conductive glass substrate, prepares nano porous semiconductor film;
(2) nano porous semiconductor film is immersed in the dyestuff a solution, make the complete absorbing dye a of film, the time that nano porous semiconductor film immerses dye solution was generally 10-20 hour, and temperature is 25 degrees centigrade;
(3) nano porous semiconductor film with absorbing dye a is a work electrode; Platinized platinum is as the desorption electrode; Saturated calomel electrode is formed four electrode systems as reference electrode and platinum loop as auxiliary electrode and is carried out the dyestuff desorption; The size, position and the duration that apply negative potential through control make negative potential exist in certain distance inner of film, exist in the zone of electromotive force, and the dyestuff desorption gets off to form a blanket layer (dyestuff desorption layer) that does not have dyestuff absorption;
The semiconductive thin film that (4) will contain the dyestuff blanket layer immerses second kind of dyestuff b, makes dyestuff blanket layer absorbing dye obtain containing the common sensitization film of 2 dyestuff adsorption layers;
(5) repeating step (3) and (4) can obtain containing the common sensitization film of polychromatophilia material adsorption layer.
The optimum thickness of said nano porous semiconductor film is at the 10-15 micron, and battery performance is best.
Said 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; Every kind of dyestuff is dissolved in separately in acetonitrile or the ethanol, and concentration is about 1.0 * 10
-3-5.0 * 10
-4M constitutes a kind of dye solution.
Be total to the sensitization thin film technique with existing preparation and compare, advantage of the present invention is:
[1] solution was depended merely on dyestuff absorption preparation in the past and was total to the contradiction between dyestuff adsorption time, dyestuff adsorbance and the dyestuff blanket layer thickness that exists in the sensitization film process;
[2] can regulate and control the thickness of each dyestuff adsorption layer through controlling the Potential Distributing degree of depth;
[3] apply the position that the position just can change dyestuff desorption layer through changing electromotive force;
[4] through regulating the order that the sensitization order just can be arranged each dye coating;
[5] can prepare the common sensitization film that contains 2 above dyestuff adsorption layers.
Description of drawings
Fig. 1 dye-sensitized film desorption system.
Embodiment
Mode one: embedded preparation is the sensitization film altogether, and is as shown in Figure 1, with TiO
2Slurry is printed in conductive substrates 1 top, forms 15 μ m thickness nanoporous TiO in 30 minutes through 510 ℃ of sintering
2Film.Immerse and form single dye sensitization TiO that plants in the dyestuff a solution after 12 hours
2Film.TiO with absorbing dye a
2 Film 2 is as work electrode, and saturated calomel electrode 3 constitutes 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, is adsorbed on TiO
2Dyestuff a on the film 2 can be from conductive substrates 1 beginning desorption.After applying 10 minutes electromotive force time, obtain the adsorption layer of about 10 μ m dyestuff blanket layer and 5 μ m dyestuff a.Afterwards film is immersed and carry out the secondary sensitization among the dyestuff b, 10 μ m dyestuff blanket layer absorbing dye b obtain the b/a type and are total to the sensitization film for 2 layers; Carry out the dyestuff desorption step again; After applying 5 minutes electromotive force time; Obtain the adsorption layer of about 5 μ m dyestuff blanket layer, 5 μ m dyestuff b and the adsorption layer of 5 μ m dyestuff a, film is immersed carry out three sensitizations among the dyestuff c afterwards, can obtain the c/b/a type and be total to the sensitization film for 3 layers.
Mode two: the superposing type preparation is the sensitization film altogether, and is as shown in Figure 1, with TiO
2Slurry is printed in conductive substrates 1 top, forms 15 μ m thickness nanoporous TiO in 30 minutes through 510 ℃ of sintering
2Film.Immerse and form single dye sensitization TiO that plants in the dyestuff a solution after 12 hours
2Film.TiO with absorbing dye a
2 Film 2 is as work electrode, and saturated calomel electrode 3 constitutes 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 is contact TiO closely
2The rear end of film 2.After negative potential-1.5 V puts on platinized platinum 5, be adsorbed on TiO
2Dyestuff a on the film 2 can be from TiO
2 Film 2 rear ends begin desorption.After applying 10 minutes electromotive force time, obtain the adsorption layer of about 10 μ m dyestuff blanket layer and 5 μ m dyestuff a.Afterwards film is immersed and carry out the secondary sensitization among the dyestuff b, 10 μ m dyestuff blanket layer absorbing dye b obtain the a/b type and are total to the sensitization film for 2 layers; Carry out the dyestuff desorption step again; After applying 5 minutes electromotive force time; Obtain the adsorption layer of about 5 μ m dyestuff blanket layer, 5 μ m dyestuff b and the adsorption layer of 5 μ m dyestuff a, film is immersed carry out three sensitizations among the dyestuff c afterwards, can obtain the a/b/c type and be total to the sensitization film for 3 layers.
Mode three: the sandwich preparation is the sensitization film altogether, and is as shown in Figure 1, with TiO
2Slurry is printed in conductive substrates 1 top, forms 15 μ m thickness nanoporous TiO in 30 minutes through 510 ℃ of sintering
2Film.Immerse and form single dye sensitization TiO that plants in the dyestuff a solution after 12 hours
2Film.TiO with absorbing dye a
2 Film 2 is as work electrode, and saturated calomel electrode 3 constitutes 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 is contact TiO closely
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 the film 2 can be from TiO
2 Film 2 front-end and back-end begin desorption.After applying 5 minutes electromotive force time, obtain the adsorption layer of two about 5 μ m dyestuff blanket layer and 5 μ m dyestuff a.Afterwards film is immersed and carry out the secondary sensitization among the dyestuff b, two 5 μ m dyestuff blanket layer absorbing dye b obtain the b/a/b type and are total to the sensitization film for 3 layers.
Claims (3)
1. can arrange the polychromatophilia material adsorption layer method of sensitization film altogether through electrochemical de adsorption method preparation for one kind, it is characterized in that method is:
(1) in the electro-conductive glass substrate, prepares nano porous semiconductor film;
(2) nano porous semiconductor film is immersed in the dyestuff a solution, make the complete absorbing dye a of film, the time that nano porous semiconductor film immerses dye solution was generally 10-20 hour, and temperature is 25 degrees centigrade;
(3) nano porous semiconductor film with absorbing dye a is a work electrode; Platinized platinum is as the desorption electrode; Saturated calomel electrode is formed four electrode systems as reference electrode and platinum loop as auxiliary electrode and is carried out the dyestuff desorption; The size, position and the duration that apply negative potential through control make negative potential exist in certain distance inner of film, exist in the zone of electromotive force, and the dyestuff desorption gets off to form a blanket layer (dyestuff desorption layer) that does not have dyestuff absorption;
The semiconductive thin film that (4) will contain the dyestuff blanket layer immerses second kind of dyestuff b, makes dyestuff blanket layer absorbing dye obtain containing the common sensitization film of 2 dyestuff adsorption layers;
(5) repeating step (3) and (4) can obtain containing the common sensitization film of polychromatophilia material adsorption layer.
2. can arrange the polychromatophilia material adsorption layer method of sensitization film altogether 1 described the preparation through the electrochemical de adsorption method according to right, the optimum thickness that it is characterized in that nano porous semiconductor film is at the 10-15 micron, and battery performance is best.
3. can arrange the polychromatophilia material adsorption layer method of sensitization film altogether 1 described the preparation according to right through the electrochemical de adsorption method; It is characterized in that said 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, every kind of dyestuff is dissolved in separately in acetonitrile or the ethanol, and concentration is about 1.0 * 10
-3-5.0 * 10
-4M constitutes a kind of dye solution.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111161958A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing multilayer co-sensitized film by light control technology |
| CN111161956A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing co-sensitization film by bidirectional diffusion technology |
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| JP2008243753A (en) * | 2007-03-29 | 2008-10-09 | Tdk Corp | Photoelectric conversion electrode, manufacturing method of the same, and dye-sensitized solar cell |
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Patent Citations (2)
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| JP2008243753A (en) * | 2007-03-29 | 2008-10-09 | Tdk Corp | Photoelectric conversion electrode, manufacturing method of the same, and dye-sensitized solar cell |
| CN102024572A (en) * | 2010-12-09 | 2011-04-20 | 华中科技大学 | Method for preparing sulfide quantum dot co-sensitization porous titanium dioxide photoelectrode |
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| 方靖淮等: "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", 《太阳能学报》, vol. 18, no. 2, 30 April 1997 (1997-04-30) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111161958A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing multilayer co-sensitized film by light control technology |
| CN111161956A (en) * | 2020-01-03 | 2020-05-15 | 南昌航空大学 | Method for preparing co-sensitization film by bidirectional diffusion technology |
| 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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