CN105551834A - Low-temperature and low-pressure preparation method of flexible dye-sensitized solar cell - Google Patents
Low-temperature and low-pressure preparation method of flexible dye-sensitized solar cell Download PDFInfo
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- CN105551834A CN105551834A CN201610111198.XA CN201610111198A CN105551834A CN 105551834 A CN105551834 A CN 105551834A CN 201610111198 A CN201610111198 A CN 201610111198A CN 105551834 A CN105551834 A CN 105551834A
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- dye
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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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 provides a low-temperature and low-pressure preparation method of a flexible dye-sensitized solar cell. The low-temperature and low-pressure preparation method comprises the steps of a, producing an oxide porous membrane on a flexible polymer conductive substrate; b, after drying the oxide porous membrane, applying a pressure of 0.3MPa-2MPa to the oxide porous membrane at 20-30 DEG C for 1d-7d; c, soaking the oxide porous membrane obtained from the step b in a dye solution, cleaning and drying to obtain a flexible photo-anode layer; and d, producing a flexible counter electrode layer on the flexible photo-anode layer, and pouring electrolyte between the flexible photo-anode layer and the flexible counter electrode layer to form an electrolyte layer. The low-temperature and low-pressure preparation method of the flexible dye-sensitized solar cell is different from a traditional instant high-pressure applying way; in the low-temperature and low-pressure preparation method, as the oxide porous membrane layer is at a relatively low pressure, a solvent is evaporated gradually to form a compact structure; and the low-temperature and low-pressure preparation method has the advantages of operation convenience and low cost.
Description
Technical field
The invention belongs to solar cell manufacture technology field, particularly relate to a kind of low-temp low-pressure preparation method of flexible dye-sensitized solar cell.
Background technology
In recent years, market increases the need of photovoltaic, and flexible dye-sensitized solar cells device becomes one of the study hotspot in solar cell field.The structure of flexible dye-sensitized solar cell comprises: the oxide porous film prepared on flexible conductive substrates, dyestuff, electrolyte, flexibility are to electrode.Wherein, oxide porous film and dyestuff form light anode, and the performance of soft-light anode has conclusive impact for the preparation of flexible solar cell and the performance of battery device.In the flexible conductive substrates that soft-light anode adopts, what have practical and economization prospect most is substrate based on polymer, the maximum problem of current polymer substrate is that the temperature that can tolerate is no more than 180 DEG C, and therefore device layers all requires to prepare under cryogenic.In addition, the oxide porous rete of conventional dyes sensitization solar cell need at high temperature be prepared, to obtain the good semiconductive thin film of crystal property.Be limited to cryogenic conditions, prepare the method for the oxide porous film film of fine and close continuous print at present at low temperatures, effect is it is preferred that standby by mechanical pressurization legal system under the pressure of 20M-200M, but preparation technology's relative complex, cost are higher.
To sum up, traditional dye-sensitized solar cells device need at high temperature be prepared, and polymer substrate can tolerable temperature lower, traditional method is difficult to the requirement meeting low temperature, the method preparing dye-sensitized solar cells at present at low temperatures need complete under higher pressure, but complex process cost is high.
Summary of the invention
In view of this, the invention provides a kind of method preparing flexible dye-sensitized solar cell under low-temp low-pressure, be different from the mode of traditional instantaneous applying high pressure, in the present invention, oxide porous rete is in lower pressure, solvent evaporates gradually, form structure closely, there is the advantage that operation is convenient, with low cost.
A low-temp low-pressure preparation method for flexible dye-sensitized solar cell, step comprises:
A, in flexible polymer conductive substrates, prepare oxide porous film;
B, by after oxide porous film drying, oxide porous film is applied at 20-60 DEG C to the pressure of 0.3MPa-2MPa, exert pressure duration 1d-7d;
C, the oxide porous film of step b gained is immersed in dye solution, after cleaning-drying, obtains soft-light anode layer;
D, on soft-light anode layer preparation flexible to electrode layer, and pour into electrolyte between described soft-light anode layer and flexibility are to electrode layer, form dielectric substrate.
The invention has the beneficial effects as follows:
1, flexible dye-sensitized solar cell is prepared by low-pressure process at low temperatures, the oxide porous rete of battery device is in lower pressure, solvent evaporates gradually, the close structure formed, there is the advantage that operation is convenient, with low cost, there is the features such as handling safety, cost-saving and energy consumption simultaneously, be convenient to large area, suitability for industrialized production;
2, adopt the method for low-temp low-pressure to prepare flexible battery, be convenient to the integrated of battery device and other facilities, have more practical advantage, and each function admirable of flexible dye-sensitized solar cell battery obtained.
Accompanying drawing explanation
Fig. 1 is flexible dye-sensitized solar cell structural representation of the present invention, and wherein, 1 is flexible polymer conductive substrate layer; 2 is light anode layer, and 21 is oxide porous rete, and 22 is dye coating; 3 is dielectric substrate; 4 is to electrode layer; 5 is external circuit.
Embodiment
The invention provides a kind of low-temp low-pressure preparation method of flexible dye-sensitized solar cell, step comprises:
A, in flexible polymer conductive substrates, prepare oxide porous film;
B, by after oxide porous film drying, oxide porous film is applied at 20-30 DEG C to the pressure of 0.3MPa-2MPa, exert pressure duration 1d-7d;
C, the oxide porous film of step b gained is immersed in dye solution, after cleaning-drying, obtains soft-light anode layer;
D, on soft-light anode layer preparation flexible to electrode layer, and pour into electrolyte between described soft-light anode layer and flexibility are to electrode layer, form dielectric substrate.
Preferably, flexible polymer conductive substrates described in step a comprises polymer/ITO substrate, polymer/silver nano wire substrate.
Be more preferably, described polymer comprises polyacrylate, PEN (PEN), polyethylene terephthalate (PET), polyimides (PI).Specifically, conducting polymer substrate optimization polypropylene acid esters/nano silver wire substrate, PEN/ITO substrate.
Preferably, the oxide that the oxide porous rete described in step a adopts comprises titanium oxide, zinc oxide, tin oxide.Oxide porous rete is by conductive oxide slurry, under cryogenic, adopts knife coating or method of spin coating or silk screen print method to be prepared from flexible polymer conductive substrate layer.
Be more preferably, the oxide porous thicknesses of layers described in step a is 5 μm-30 μm.
Preferably, dye solution described in step c comprises the multi-pyridine ligand of ruthenium, phthalocyanine and cyanine type dye, cadmiumsulfide quantum dot, CdSe quantum dots, nanometer particle material II-VI compounds of group, IV-VI compounds of group, III-V compounds of group, as cadmium sulfide, cadmium selenide, cadmium telluride, vulcanized lead, lead selenide, indium phosphide quantum dot, when dye solution is organic dye sensitized dose, selected material is as natural dye chlorophyll.
Preferably, electrolyte described in steps d is for including 1-propyl group-3-methylpyridinium iodide imidazole salts, 3-tert .-butylpyridine, LiI, I
2acetonitrile solution, or Na
2sO
4/ Na
2s system or Br
2/ Br
-system or [Fe (CN)
6]
3 -/ [Fe (CN)
6]
4 -system solution.Add LiI, I
2have 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.Dielectric substrate plays instrumentality in charge-exchange, and the form of its material can be liquid state, solid-state or accurate solid-state.
Be more preferably, the concentration of the concentration of described 1-propyl group-3-methylpyridinium iodide imidazole salts to be the concentration of 0.6M, 3-tert .-butylpyridine be 0.5M, LiI is 0.3M, I
2concentration be 0.05M.
As adopted inorganic-quantum-dot dyestuff, electrolyte described in steps d should select Na
2sO
4/ Na
2s system solution.Preferably, adopt electrolyte solvent be methyl alcohol and pure water by volume 7:3 mix, add 0.5MNa
2s, 0.125M sulphur powder and 0.2MKCl.
Preferred further, the thickness of dielectric substrate described in steps d is 30 μm-100 μm.
Preferably, described in steps d, flexibility comprises gold, platinum, Graphene to electrode layer material therefor, and flexible is 5 μm ~ 50 μm to the thickness of electrode layer.
Below in conjunction with specific embodiment, the low-temp low-pressure preparation method to flexible dye-sensitized solar cell provided by the invention is further described.
Embodiment one
The present embodiment adopts the method for low-temp low-pressure to prepare flexible dye-sensitized solar cell, and as shown in Figure 1, concrete preparation process is as follows for the structure of gained battery:
The preparation of S1, flexibility " polymer/silver nano wire " conductive substrate layer 1: choose glass substrate and clean up, the isopropyl alcohol dispersion soln of nano silver wire is configured at room temperature 25 DEG C, 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 of 0.7 μm, and the transmitance of described nano silver wire thin layer 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 by adding mass concentration, under subsequently the nano silver wire thin layer scribbling acrylate monomer being placed in uviol lamp, initiating methacrylates monomer polymerization, obtain the polymeric layer 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, soft-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 S1 at room temperature 25 DEG C, after to be dried, with the smooth iron block pressure of 2.5KG thereon, the pressure that iron block applies is about 0.4MPa, removed after 1 week, obtain 15 μm of thick oxide porous retes 21, 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 12h and dry, namely soft-light anode layer 2 is obtained,
S3, preparation to electrode layer 4: obtain after the upper blade coating platinum slurry of flexible conductive substrates " polymer/silver nano wire ", drying thickness be 43 μm to electrode layer 4;
The preparation of S4, dyestuff dielectric substrate 3: configuration 0.6M1-propyl group-3-methylpyridinium iodide imidazole salts, 0.5M3-tert .-butylpyridine, 0.3MLiI and 0.05MI
2mixing acetonitrile solution, then acetonitrile solution is poured in soft-light anode layer 2 and between electrode layer 4, adopts wire to be connected with load, formation 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 0.2%.
Embodiment two
The present embodiment adopts the method for low-temp low-pressure to prepare flexible dye-sensitized solar cell, and as shown in Figure 1, concrete preparation process is as follows for the structure of gained battery:
Choosing of S1, flexibility " polymer/ITO " conductive substrate layer 1: choose commercially available PEN/ITO substrate, 15ohm/square square resistance, light transmittance 81%;
The preparation of S2, light anode layer 2: by the TiO that market is buied
2colloidal solution, knife coating is adopted to be prepared in the flexible polymer conductive substrate layer 1 of step 1 at room temperature 28 DEG C, after to be dried, be placed on smooth heater, with the smooth iron block pressure of 3.5KG thereon, the pressure that iron block applies is about 2MPa, set temperature 60 DEG C, keep removing after 72 hours, 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 24h and dry, namely soft-light anode layer 2 is obtained,
S3, preparation to electrode layer 4: in flexible PEN/ITO conductive substrate layer 1, sputter the platinum that thickness is 100 μm, obtain electrode layer 4;
The preparation process of S4, dielectric substrate 3 is with embodiment one, configuration mixing acetonitrile solution, then acetonitrile solution is poured in soft-light anode layer 2 and between electrode layer 4, adopts wire to be connected with load, described in formation external loop, the thickness of dyestuff dielectric substrate 3 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 0.3%.
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 (10)
1. a low-temp low-pressure preparation method for flexible dye-sensitized solar cell, step comprises:
A, in flexible polymer conductive substrates, prepare oxide porous film;
B, by after oxide porous film drying, oxide porous film is applied at 20-30 DEG C to the pressure of 0.3MPa-2MPa, exert pressure duration 1d-7d;
C, the oxide porous film of step b gained is immersed in dye solution, after cleaning-drying, obtains soft-light anode layer;
D, on soft-light anode layer preparation flexible to electrode layer, and pour into electrolyte between described soft-light anode layer and flexibility are to electrode layer, form dielectric substrate.
2. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 1, is characterized in that: flexible polymer conductive substrates described in step a comprises polymer/ITO substrate, polymer/silver nano wire substrate.
3. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 2, is characterized in that: described polymer comprises polyacrylate, polyethylene terephthalate, PEN, polyimides.
4. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 1, is characterized in that: the oxide that the oxide porous film described in step a adopts comprises titanium oxide, zinc oxide, tin oxide.
5. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 4, is characterized in that: the oxide porous film thickness described in step a is 5 μm-30 μm.
6. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 1, is characterized in that: dye solution described in step c comprises the multi-pyridine ligand of ruthenium, phthalocyanine and cyanine type dye, nanometer particle material II-VI compounds of group, IV-VI compounds of group, III-V compounds of group, natural dye.
7. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 1, is characterized in that: electrolyte described in steps d is for including 1-propyl group-3-methylpyridinium iodide imidazole salts, 3-tert .-butylpyridine, LiI, I
2acetonitrile solution, or Na
2sO
4/ Na
2s system or Br
2/ Br
-system or [Fe (CN)
6]
3 -/ [Fe (CN)
6]
4 -system solution.
8. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 7, is characterized in that: the concentration of the concentration of described 1-propyl group-3-methylpyridinium iodide imidazole salts to be the concentration of 0.6M, 3-tert .-butylpyridine be 0.5M, LiI is 0.3M, I
2concentration be 0.05M.
9. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 8, is characterized in that: the thickness of dielectric substrate described in steps d is 30 μm-100 μm.
10. the low-temp low-pressure preparation method of flexible dye-sensitized solar cell as claimed in claim 1, is characterized in that: described in steps d, flexibility comprises gold, platinum, Graphene to electrode layer material therefor, flexible is 5 μm ~ 50 μm to the thickness of electrode layer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107086124A (en) * | 2016-11-03 | 2017-08-22 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN110136964A (en) * | 2019-04-23 | 2019-08-16 | 长江大学 | Flexibility for dye-sensitized solar cells is to electrode |
| CN110648852A (en) * | 2019-10-09 | 2020-01-03 | 温州大学 | Counter electrode and quantum dot sensitized solar cell |
| CN113797970A (en) * | 2020-06-01 | 2021-12-17 | 中国科学院理化技术研究所 | Multi-pyridine iron complex photocatalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531362A (en) * | 2012-07-02 | 2014-01-22 | 华东师范大学 | High-efficiency flexible dye-sensitized solar cell and preparation method thereof |
| CN103762084A (en) * | 2014-01-13 | 2014-04-30 | 华东师范大学 | Dye-sensitized solar cell and low-temperature preparation method of photo-anode of dye-sensitized solar cell |
-
2016
- 2016-02-29 CN CN201610111198.XA patent/CN105551834B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531362A (en) * | 2012-07-02 | 2014-01-22 | 华东师范大学 | High-efficiency flexible dye-sensitized solar cell and preparation method thereof |
| CN103762084A (en) * | 2014-01-13 | 2014-04-30 | 华东师范大学 | Dye-sensitized solar cell and low-temperature preparation method of photo-anode of dye-sensitized solar cell |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107086124A (en) * | 2016-11-03 | 2017-08-22 | 武汉市三选科技有限公司 | DSSC and its manufacture method |
| CN110136964A (en) * | 2019-04-23 | 2019-08-16 | 长江大学 | Flexibility for dye-sensitized solar cells is to electrode |
| CN110648852A (en) * | 2019-10-09 | 2020-01-03 | 温州大学 | Counter electrode and quantum dot sensitized solar cell |
| CN110648852B (en) * | 2019-10-09 | 2021-02-26 | 温州大学 | Counter electrode and quantum dot sensitized solar cell |
| CN113797970A (en) * | 2020-06-01 | 2021-12-17 | 中国科学院理化技术研究所 | Multi-pyridine iron complex photocatalyst and preparation method and application thereof |
| CN113797970B (en) * | 2020-06-01 | 2023-08-04 | 中国科学院理化技术研究所 | Polypyridine iron complex photocatalyst and preparation method and application thereof |
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Effective date of registration: 20180314 Address after: 100007 Beijing, Dongzhimen, North Street, No. 9, No. Co-patentee after: Yangtze University Patentee after: China Petroleum & Natural Gas Co., Ltd. Address before: 434023 Jingzhou South Road, Hubei, No. 1 Patentee before: Yangtze University |