CN105070510A - Flexible dye-sensitized solar cell and preparation method thereof - Google Patents
Flexible dye-sensitized solar cell and preparation method thereof Download PDFInfo
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- CN105070510A CN105070510A CN201510530646.5A CN201510530646A CN105070510A CN 105070510 A CN105070510 A CN 105070510A CN 201510530646 A CN201510530646 A CN 201510530646A CN 105070510 A CN105070510 A CN 105070510A
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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
- 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
Abstract
The invention relates to a flexible dye-sensitized solar cell comprising a flexible silver nano-wire polymer composite conductive substrate layer, a photoanode layer, an electrolyte layer, and a counter electrode layer. The layers are successively laminated. The flexible silver nano-wire polymer composite conductive substrate layer contains a silver nano-wire thin-film layer and a polymer layer covering the silver nano-wire thin-film layer. The flexible dye-sensitized solar cell has the following advantages: firstly, the silver nano-wire thin-film layer is used for replacing the existing ITO thin film and thus environment-friendly and cost-saving characteristics are realized; secondly, in-situ polymerization of macro-molecule prepolymers on the silver nano-wire thin-film layer is carried out to obtain the flexible silver nano-wire polymer composite conductive substrate layer based on one-stage forming and the conductive thin film and the polymer substrate are combined closely; and the resistivity is low and the light transmittance is high, and the photoelectric conversion efficiency of the solar cell is improved well; and thirdly, because the silver nano-wire thin-film layer can be prepared by means of silk-screen printing, large-area industrial production can be realized and the preparation process can be modulated and controlled easily.
Description
Technical field
The present invention relates to solar cell manufacture technology field, specifically a kind of flexible dye-sensitized solar cell and preparation method thereof.
Background technology
Dye-sensitized solar cells (DSSC) is subject to the close attention of scientific and technological circle because of its with low cost and simple feature of preparation technology, be described as the third generation solar cell; And flexible solar cell is prepared on flexible substrates, there is the feature of light, the portable and bend resistance of quality, can be used for solar telephone, solar sailor, solar energy knapsack are first-class, and particularly important for the realization of BIPV.
In the material of current DSSC flexible optoelectronic pole, polymer flexibility substrate is mutually compatible with traditional preparation technology because of cheap, the good mechanical performance of polymer substrate that adopts, has higher light transmission rate simultaneously, is considered to have practical and some commercial potential most; But traditional DSSC mostly adopts and covers including transparent conducting oxide layer tin indium oxide (ITO) or the electro-conductive glass of fluorine oxide tin (FTO) is underlayer electrode, it is hard, frangible, quality heavily etc. shortcoming limit the application of DSSC.
On market, the substrate of some polymer flexibility substrate adopts PETG (PET), PEN (PEN) and polyimides (PI), then on substrate, prepares ito thin film.Because polymer substrate can be no more than 180 DEG C by tolerable temperature, therefore device layers and ito thin film all require to prepare under cryogenic, higher to the requirement of apparatus for preparation, complex process, and cost is high; Because indium is rare precious metals, make ITO expensive; Moreover indium has severe toxicity, indium and tin easily penetrate in adjacent material in Synthesis and applications process, have a negative impact to device efficiency and life-span; The cost recovery of ITO Waste ammunition is high, is unfavorable for environmental protection.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the invention is to obtain the flexible conductive substrates layer of low-resistivity, high transmission rate by in-situ polymerization macromolecule prepolymer one-shot forming on nano silver wire, and prepare flexible solar cell as substrate, thus obtain environmental protection, flexible dye-sensitized solar cell that cost is low.
According to a kind of flexible dye-sensitized solar cell provided by the invention, comprise stack gradually flexible nano silver wire polymer composite conducting substrate layer, light anode layer, dielectric substrate, to electrode layer;
Described flexible polymer composite conducting substrate comprises: nano silver wire thin layer and the polymeric layer covered on described nano silver wire thin layer.
A preparation method for flexible dye-sensitized solar cell, comprises the steps:
S1, choose rigid substrate, rigid substrate is prepared flexible nano silver wire polymer composite conducting substrate layer;
S2, the described flexible nano silver wire polymer composite conducting substrate layer prepared in step S1 prepare oxide porous rete, then described oxide porous rete is immersed in dye solution, dries after cleaning and obtain light anode layer;
S3, to make electrode layer on described flexible nano silver wire polymer composite conducting substrate layer surface;
S4, described smooth anode layer and described to electrode layer between pour into electrolyte dyestuff, form described dielectric substrate.
In described step S1, the preparation process of flexible nano silver wire polymer composite conducting substrate layer comprises: 1., by the nano silver wire dispersion soln of configuration be prepared in rigid substrate surface, makes nano silver wire thin layer; 2. the nano silver wire thin layer, by step 1. obtained dries rear covering one layer of polymeric monomer, removes rigid substrate, obtain flexible nano silver wire polymer composite conducting substrate layer after forming polymeric layer.
A kind of flexible dye-sensitized solar cell of the present invention and preparation method thereof, its advantage is:
1, replace existing ito thin film by nano silver wire thin layer, there is environmental friendliness, the feature such as cost-saving;
2, flexible nano silver wire polymer composite conducting substrate layer is by in-situ polymerization macromolecule prepolymer on nano silver wire thin layer, one-shot forming obtains, the combination of conductive film and polymeric substrates is tightr, and there is low-resistivity and high transmission rate, be conducive to the photoelectric conversion efficiency improving solar cell;
3, because nano silver wire thin layer can adopt the mode of silk screen printing to prepare, large area, suitability for industrialized production can be realized, easily preparation technology is regulated and controled.
Accompanying drawing explanation
Fig. 1 is flexible dye-sensitized solar cell structural representation of the present invention;
In above-mentioned figure:
1, flexible nano silver wire polymer composite conducting substrate layer, 11, nano silver wire thin layer, 12, polymeric layer;
2, light anode layer, 21, oxide porous rete, 22, dye coating;
3, dielectric substrate;
4, to electrode layer.
Embodiment
A kind of flexible dye-sensitized solar cell, comprise stack gradually flexible nano silver wire polymer composite conducting substrate layer 1, light anode layer 2, dielectric substrate 3, to electrode layer 4;
Preferably, described flexible nano silver wire polymer composite conducting substrate layer 1 comprises: nano silver wire thin layer 11 and the polymeric layer 12 covered on described nano silver wire thin layer 11.Described nano silver wire thin layer 11 by diameter be 25-50nm, length is that the nano silver wire of 10 μm-30 μm is formed, and its thickness is 0.025 μm ~ 1 μm; The thickness of described polymeric layer 12 is 10 μm ~ 1000 μm, is be polymerized by the polymer monomer of light or chemistry initiation; Described polymer monomer is the low molecule raw material having polymerizing power further, as acrylate monomer; Described nano silver wire thin layer 11 as the design of the conductive substrate layer of disposal molding with described polymeric layer 12, enhances the light transmittance of solar cell, reduces resistivity simultaneously.
Preferably, described smooth anode layer 2 comprises: oxide porous rete 21 and be adsorbed on the dye coating 22 on described oxide porous rete 21 surface, and described oxide porous rete 21 covers on described nano silver wire thin layer 11; Preferably, described oxide porous rete 21 is obtained by conductive oxide slurry, and the thickness of described oxide porous rete 21 is 5 μm-30 μm; Preferably, the oxide used in described conductive oxide slurry is titanium oxide, zinc oxide or tin oxide; Described dye coating 22 is made up of dye solution, when dye solution is the dye sensitizing agent of mineral-type, selected material is metal multi-pyridine ligand two-tetrabutylammonium-bis-(isothiocyano) two (2 of ruthenium, 2'-bipyridine-4,4'-dicarboxyl) ethanolic solution of ruthenium (II), or be inorganic-quantum-dot, as cadmium sulfide, CdSe quantum dots; When dye solution is organic dye sensitized dose, selected material is as natural dye chlorophyll.
Preferably, described dielectric substrate 3 is formed by acetonitrile solution, and wherein, the content proportioning of acetonitrile solution is 0.6M1-propyl group-3-methylpyridinium iodide imidazole salts, 0.5M3-tert .-butylpyridine, 0.3MLiI and 0.05MI
2; There is the effect that oxidationreduction is right, complete the circular regeneration of oxidation state dye molecule; Interpolation ionic liquid propyl group-3-methylpyridinium iodide imidazole salts and 3-tert .-butylpyridine, to suppress dark current, improve the photoelectric conversion efficiency of battery; Preferably, the thickness 30 μm-100 μm of described dielectric substrate 3.
Preferably, described dielectric substrate 3 plays instrumentality in charge-exchange, and its kind can be liquid state, solid-state or accurate solid-state;
Preferably, the described thickness to electrode layer 4 is 0.4 μm ~ 30 μm, and by metal material layer, metal material layer selects the metal materials such as gold, platinum, Graphene to make.
A preparation method for flexible dye-sensitized solar cell, comprises the steps:
S1, choose rigid substrate, rigid substrate is prepared flexible nano silver wire polymer composite conducting substrate layer 1;
S2, the described flexible nano silver wire polymer composite conducting substrate layer 1 prepared in step S1 prepare described oxide porous rete 21, then described oxide porous rete 21 is immersed in dye solution, dries after cleaning and obtain light anode layer 2;
S3, to make electrode layer 4 on described flexible nano silver wire polymer composite conducting substrate layer 1 surface;
S4, described smooth anode layer 2 and described to electrode layer 4 between pour into electrolyte dyestuff, form described dielectric substrate 3.
In described step S1, the preparation process of flexible nano silver wire polymer composite conducting substrate layer 1 comprises: 1., by the nano silver wire dispersion soln of configuration be prepared in rigid substrate surface, makes nano silver wire thin layer 11; 2. the nano silver wire thin layer 11, by step 1. obtained dries rear covering one layer of polymeric monomer, removes rigid substrate, obtain flexible nano silver wire polymer composite conducting substrate layer 1 after forming polymeric layer 12.
Preferably, described rigid substrate can select glass substrate.
In step S2, in the preparation process of light anode layer 2, be by conductive oxide slurry, under cryogenic, adopt knife coating or method of spin coating or silk screen print method to prepare oxide porous rete 21 on flexible nano silver wire polymer composite conducting substrate layer 1;
Below in conjunction with specific embodiment, the present invention is further illustrated:
Embodiment one:
The preparation of S1, flexible nano silver wire polymer composite conducting substrate layer 1: choose glass substrate and clean up, at room temperature configure the isopropyl alcohol dispersion soln of nano silver wire, wherein the mass concentration of isopropyl alcohol is 0.1%-1%, the glass substrate surface after cleaning is coated with scraping inker, obtained thickness is the nano silver wire thin layer 11 of 0.7 μm, and the transmitance of described nano silver wire thin layer 11 is up to 83%; Be that the acrylate monomer rotary coating of the light trigger of 1 ~ 5% is in the surface of nano silver wire thin layer 11 by adding mass concentration, under subsequently the nano silver wire thin layer 11 scribbling acrylate monomer being placed in uviol lamp, initiating methacrylates monomer polymerization, obtain the polymeric layer 12 that thickness is 300 μm, remove glass substrate after cooling, obtain flexible nano silver wire polymer composite conducting substrate layer 1;
The preparation of S2, light anode layer 2: by the TiO that market is buied
2colloidal solution, silk screen print method is adopted to be prepared on the obtained flexible nano silver wire polymer composite conducting substrate layer 1 of step 1 under room temperature, after to be dried, the pressure of 100Mpa is applied with pressure-like machine, prepare the oxide porous rete 21 that thickness is 15 μm, then obtained oxide porous rete 21 is immersed in two-tetrabutylammonium-bis-(isothiocyano) two (2 of 0.5mm, 2'-bipyridine-4,4'-dicarboxyl) in ruthenium (II) ethanolic solution, form dye coating 22, take out after lucifuge leaves standstill 2h and dry, namely obtain light anode layer 2;
S3, preparation to electrode layer 4: obtain after blade coating platinum slurry, drying on light anode layer 2 thickness be 13 μm to electrode layer 4;
The preparation of S4, dielectric substrate 3: the mixing acetonitrile solution of configuration 0.6M1-propyl group-3-methylpyridinium iodide imidazole salts, 0.5M3-tert .-butylpyridine, 0.3MLiI and 0.05MI2, then acetonitrile solution is poured in light anode layer 2 and between electrode layer 4, wire is adopted to be connected with load, form external loop, the thickness of described dielectric substrate 3 is 50 μm.
The solar cell effective area adopting said method obtained is 0.16cm
2battery be 100mW/cm in radiant illumination
2the photoelectric conversion efficiency recorded under simulated solar irradiation is 0.6%.
Embodiment 2:
The preparation of S1, flexible nano silver wire polymer composite conducting substrate layer 1: choose glass substrate and clean up, at room temperature configure the isopropyl alcohol dispersion soln of nano silver wire, wherein the mass concentration of isopropyl alcohol is 0.1%-1%, by silk screen print method, the dispersion soln of configuration is prepared in the glass substrate surface after cleaning, obtained thickness is the nano silver wire thin layer 11 of 0.5 μm, and the transmitance of described nano silver wire thin layer 11 is up to 90%; Then be that the acrylate monomer of the light trigger of 1 ~ 5% drips the surface being applied to nano silver wire thin layer 11 by adding mass concentration, under subsequently the nano silver wire thin layer 11 scribbling acrylate monomer being placed in uviol lamp, initiating methacrylates monomer polymerization, obtain the polymeric layer 12 that thickness is 500 μm, remove glass substrate after cooling, obtain flexible nano silver wire polymer composite conducting substrate layer 1;
The preparation of S2, light anode layer 2: by the TiO that market is buied
2colloidal solution, knife coating is adopted to be prepared on the obtained flexible nano silver wire polymer composite conducting substrate layer 1 of step 1 under room temperature, after to be dried, the pressure of 100Mpa is applied with pressure-like machine, prepare the oxide porous rete 21 that thickness is 12 μm, then obtained oxide porous rete 21 is immersed in two-tetrabutylammonium-bis-(isothiocyano) two (2 of 0.5mm, 2'-bipyridine-4,4'-dicarboxyl) in ruthenium (II) ethanolic solution, form dye coating 22, take out after lucifuge leaves standstill 2h and dry, namely obtain light anode layer 2;
S3, preparation to electrode layer 4: on light anode layer 2, sputter the platinum that thickness is 1 μm, obtain electrode layer 4;
The preparation process of S4, dielectric substrate 3 is with embodiment one, and configuration mixing acetonitrile solution, is then poured in light anode layer 2 by acetonitrile solution and between electrode layer 4, adopt wire to be connected with load, the thickness forming dielectric substrate 3 described in external loop is 62 μm.
The solar cell effective area adopting said method obtained is 0.16cm
2battery be 100mW/cm in radiant illumination
2the photoelectric conversion efficiency recorded under simulated solar irradiation is 0.4%.
A kind of flexible dye-sensitized solar cell of the present invention and preparation method thereof, its advantage is:
1, replace existing ito thin film by nano silver wire thin layer, there is environmental friendliness, the feature such as cost-saving;
2, flexible nano silver wire polymer composite conducting substrate layer is by in-situ polymerization macromolecule prepolymer on nano silver wire thin layer, one-shot forming obtains, the combination of conductive film and polymeric substrates is tightr, and there is low-resistivity and high transmission rate, be conducive to the photoelectric conversion efficiency improving solar cell;
3, because nano silver wire thin layer can adopt the mode of silk screen printing to prepare, large area, suitability for industrialized production can be realized, easily preparation technology is regulated and controled.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a flexible dye-sensitized solar cell, is characterized in that: comprise stack gradually flexible nano silver wire polymer composite conducting substrate layer (1), light anode layer (2), dielectric substrate (3), to electrode layer (4);
Described flexible nano silver wire polymer composite conducting substrate layer (1) comprising: nano silver wire thin layer (11) and the polymeric layer (12) covered on described nano silver wire thin layer (11).
2. flexible dye-sensitized solar cell according to claim 1, is characterized in that: described nano silver wire thin layer (11) is made up of nano silver wire.
3. flexible dye-sensitized solar cell according to claim 1, is characterized in that: described polymeric layer (12) is polymerized by the polymer monomer of light or chemistry initiation.
4. flexible dye-sensitized solar cell according to claim 3, is characterized in that: described polymer monomer is acrylate monomer.
5. flexible dye-sensitized solar cell according to claim 1, it is characterized in that: described smooth anode layer (2) comprising: oxide porous rete (21) and be adsorbed on described oxide porous rete (21) surface dye coating (22), described oxide porous rete (21) covers on described nano silver wire thin layer (11).
6. flexible dye-sensitized solar cell according to claim 5, is characterized in that: the thickness of described oxide porous rete (21) is 5 μm-30 μm.
7. flexible dye-sensitized solar cell according to claim 1, is characterized in that: described dielectric substrate (3) is formed by acetonitrile solution.
8. the preparation method of the flexible dye-sensitized solar cell as described in claim 1 to 7, is characterized in that: comprise the steps:
S1, choose rigid substrate, rigid substrate is prepared flexible nano silver wire polymer composite conducting substrate layer (1);
S2, the described oxide porous rete (21) of the upper preparation of described flexible nano silver wire polymer composite conducting substrate layer (1) of preparing in step S1, then described oxide porous rete (21) is immersed in dye solution, dries after cleaning and obtain light anode layer (2);
S3, to make electrode layer (4) on described flexible nano silver wire polymer composite conducting substrate layer (1) surface;
S4, described smooth anode layer (2) and described to electrode layer (4) between pour into electrolyte dyestuff, form described dielectric substrate (3);
In described step S1, the preparation process of flexible nano silver wire polymer composite conducting substrate layer (1) comprising: 1., by the nano silver wire dispersion soln of configuration be prepared in rigid substrate surface, makes nano silver wire thin layer (11); 2. the nano silver wire thin layer (11), step 1. obtained dries rear covering one layer of polymeric monomer, form polymeric layer (12) and remove rigid substrate afterwards, obtain flexible nano silver wire polymer composite conducting substrate layer (1).
9. the preparation method of flexible dye-sensitized solar cell according to claim 8, it is characterized in that: in step S2 as claimed in claim 8, in the preparation process of light anode layer (2), by conductive oxide slurry, under cryogenic, adopt knife coating or method of spin coating or silk screen print method flexible nano silver wire polymer composite conducting substrate layer (1) the oxide porous rete of upper preparation (21).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054282A (en) * | 2017-11-27 | 2018-05-18 | 济南大学 | Zinc doping nickel oxide nanoparticle hole transmission layer inverts perovskite solar cell and preparation method |
| CN110136964A (en) * | 2019-04-23 | 2019-08-16 | 长江大学 | Flexibility for dye-sensitized solar cells is to electrode |
| RU2776427C2 (en) * | 2018-05-16 | 2022-07-19 | Эксегер Оперейшнз Аб | Photoelectric device |
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| CN101292362A (en) * | 2005-08-12 | 2008-10-22 | 凯博瑞奥斯技术公司 | Nanowires-based transparent conductors |
| CN102243921A (en) * | 2010-05-14 | 2011-11-16 | 福盈科技化学股份有限公司 | Dye sensitized solar cell with metal line layer and electrodes thereof |
| CN103871751A (en) * | 2014-03-31 | 2014-06-18 | 宋旭 | Novel flexible dye-sensitized solar cell |
| CN204946727U (en) * | 2015-08-26 | 2016-01-06 | 长江大学 | Flexible dye-sensitized solar cell |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101292362A (en) * | 2005-08-12 | 2008-10-22 | 凯博瑞奥斯技术公司 | Nanowires-based transparent conductors |
| CN102243921A (en) * | 2010-05-14 | 2011-11-16 | 福盈科技化学股份有限公司 | Dye sensitized solar cell with metal line layer and electrodes thereof |
| CN103871751A (en) * | 2014-03-31 | 2014-06-18 | 宋旭 | Novel flexible dye-sensitized solar cell |
| CN204946727U (en) * | 2015-08-26 | 2016-01-06 | 长江大学 | Flexible dye-sensitized solar cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108054282A (en) * | 2017-11-27 | 2018-05-18 | 济南大学 | Zinc doping nickel oxide nanoparticle hole transmission layer inverts perovskite solar cell and preparation method |
| RU2776427C2 (en) * | 2018-05-16 | 2022-07-19 | Эксегер Оперейшнз Аб | Photoelectric device |
| CN110136964A (en) * | 2019-04-23 | 2019-08-16 | 长江大学 | Flexibility for dye-sensitized solar cells is to electrode |
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