CN105551834B - 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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- CN105551834B CN105551834B CN201610111198.XA CN201610111198A CN105551834B CN 105551834 B CN105551834 B CN 105551834B CN 201610111198 A CN201610111198 A CN 201610111198A CN 105551834 B CN105551834 B CN 105551834B
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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, more particularly to a kind of flexible dye-sensitized solar cell it is low
Warm low pressure preparation method.
Background technology
In recent years, market increases to the need persistence of photovoltaic, and flexible dye-sensitized solar cells device becomes sun electricity
One of the study hotspot in pond field.The structure of flexible dye-sensitized solar cell includes：The oxygen prepared on flexible conductive substrates
Compound perforated membrane, dyestuff, electrolyte, flexibility are to electrode.Wherein, oxide porous film and dyestuff constitute light anode, flexible light sun
The performance of pole has conclusive impact for the preparation of flexible solar cell and the performance of battery device.Soft-light anode is adopted
Flexible conductive substrates in, most practical and economization prospect is substrate based on polymer, current polymer substrate
Maximum problem is that tolerable temperature is less than 180 DEG C, therefore device layers are required to prepare under cryogenic.Separately
Outward, the oxide porous film layer of conventional dyes sensitization solar cell need to be prepared at high temperature, and good to obtain crystal property half
Conductor thin film.Cryogenic conditions are limited to, the method for preparing fine and close continuous oxide porous film thin film at present at low temperature, effect
Most preferably prepared with mechanical pressurization method under the pressure of 20M-200M, but preparation technology is relative complex, relatively costly.
To sum up, traditional dye-sensitized solar cells device need to be prepared at high temperature, and the tolerable temperature of polymer substrate
Degree is relatively low, and traditional method is difficult to the requirement for meeting low temperature, and the method for preparing dye-sensitized solar cells at present at low temperature is needed
Complete under higher pressure, but complex process high cost.
The content of the invention
In view of this, the invention provides a kind of method that flexible dye-sensitized solar cell is prepared under low-temp low-pressure,
Different from the mode of traditional instantaneous applying high pressure, in the present invention, oxide porous film layer is in relatively low pressure, solvent by
Gradually evaporate, form close structure, have the advantages that operation is convenient, with low cost.
A kind of low-temp low-pressure preparation method of flexible dye-sensitized solar cell, step include：
A, oxide porous film is prepared in flexible polymer conductive substrates；
B, by oxide porous film be dried after, apply the pressure of 0.3MPa-2MPa to oxide porous film at 20-60 DEG C
By force, press duration 1d-7d；
C, the oxide porous film obtained by step b is immersed in dye solution, after cleaning-drying, obtains soft-light anode
Layer；
D, on soft-light anode layer prepare flexibility to electrode layer, and the soft-light anode layer with flexibility to electrode layer
Between irrigate electrolyte, form dielectric substrate.
The invention has the beneficial effects as follows：
1st, flexible dye-sensitized solar cell is prepared with low-pressure process at low temperature, the oxide porous film layer of battery device is in
Under relatively low pressure, solvent gradually evaporates, the close structure of formation, has the advantages that operation is convenient, with low cost, while having
The features such as safe operation, cost-effective and energy consumption, it is easy to large area, industrialized production；
2nd, flexible battery is prepared using the method for low-temp low-pressure, is easy to battery device integrated with other facilities, more in fact
With changing advantage, and each function admirable of obtained flexible dye-sensitized solar cell battery.
Description of the drawings
Fig. 1 is the flexible dye-sensitized solar cell structural representation of the present invention, wherein, 1 is flexible polymer conductive liner
Bottom；2 is light anode layer, and 21 is oxide porous film layer, and 22 is dye coating；3 is dielectric substrate；4 is to electrode layer；5 is outer
Circuit.
Specific embodiment
The invention provides a kind of low-temp low-pressure preparation method of flexible dye-sensitized solar cell, step includes：
A, oxide porous film is prepared in flexible polymer conductive substrates；
B, by oxide porous film be dried after, apply the pressure of 0.3MPa-2MPa to oxide porous film at 20-30 DEG C
By force, press duration 1d-7d；
C, the oxide porous film obtained by step b is immersed in dye solution, after cleaning-drying, obtains soft-light anode
Layer；
D, on soft-light anode layer prepare flexibility to electrode layer, and the soft-light anode layer with flexibility to electrode layer
Between irrigate electrolyte, form dielectric substrate.
Preferably, flexible polymer conductive substrates described in step a include polymer/ITO substrates, polymer/silver nano wire
Substrate.
More preferred, the polymer includes polyacrylate, PEN (PEN), gathers to benzene two
Formic acid second diester (PET), polyimides (PI).Specifically, the preferred polyacrylate of conducting polymer substrate/nano silver wire lining
Bottom, PEN/ITO substrates.
Preferably, the oxide that the oxide porous film layer described in step a is adopted includes titanium oxide, Zinc Oxide, stannum oxide.
Oxide porous film layer is by conductive oxide slurry, under cryogenic, using knife coating or method of spin coating or silk screen
Print process is prepared from flexible polymer conductive substrate layer.
More preferred, the oxide porous thicknesses of layers described in step a is 5 μm -30 μm.
Preferably, dye solution described in step c includes multi-pyridine ligand, phthalocyanine and cyanine type dye, the cadmium sulfide amount of ruthenium
Sub- point, CdSe quantum dots, II-VI compounds of group of nanometer particle material, IV-VI compounds of group, such as III-V compounds of group, sulfur
Cadmium, cadmium selenide, cadmium telluride, vulcanized lead, lead selenide, indium phosphide quantum dot, when dye solution is organic dye sensitized dose, institute
The selection of material such as natural dye chlorophyll.
Preferably, electrolyte described in step d for include 1- propyl group -3- methylpyridinium iodide imidazole salts, 3- tert .-butylpyridines,
LiI、I2Acetonitrile solution, or Na2SO4/Na2S systems or Br2/Br-System or [Fe (CN)6]3 -/[Fe(CN)6]4 -System is molten
Liquid.Addition LiI, I2Effect with oxidation-reduction pair, completes the circular regeneration of oxidation state dye molecule, adds ionic liquid
Propyl group -3- methylpyridinium iodides imidazole salts and 3- tert .-butylpyridines improve the photoelectric transformation efficiency of battery to suppress dark current.Electrolyte
Layer plays instrumentality in charge-exchange, and the form of its material can be liquid, solid-state or quasi- solid-state.
More preferred, the concentration of the 1- propyl group -3- methylpyridinium iodide imidazole salts is 0.6M, the concentration of 3- tert .-butylpyridines
For 0.5M, the concentration of LiI is 0.3M, I2Concentration be 0.05M.
Inorganic-quantum-dot dyestuff is adopted such as, described in step d, electrolyte preferably selects Na2SO4/Na2S system solutions.Preferably,
It is methanol and pure water by volume 7 using electrolyte solvent:3 mix, and add 0.5M Na2S, 0.125M sulphur powder and
0.2M KCl。
It is further preferred that the thickness of dielectric substrate described in step d is 30 μm -100 μm.
Preferably, flexibility described in step d includes gold, platinum, Graphene, the flexible thickness to electrode layer to electrode layer material therefor
Spend for 5 μm～50 μm.
It is prepared by the low-temp low-pressure of the flexible dye-sensitized solar cell provided to the present invention below in conjunction with specific embodiment
Method is further described.
Embodiment one
The present embodiment is prepared for flexible dye-sensitized solar cell using the method for low-temp low-pressure, and the structure of gained battery is such as
Shown in accompanying drawing 1, specific preparation process is as follows：
The preparation of S1, flexibility " polymer/silver nano wire " conductive substrate layer 1：Choose glass substrate to clean up, in room temperature
The isopropanol dispersion soln of nano silver wire is configured at 25 DEG C, the wherein mass concentration of isopropanol is 0.1%-1%, is applied with inker is scraped
The glass substrate surface after cleaning is distributed in, prepared thickness is 0.7 μm of nano silver wire thin layer, the nano silver wire thin layer
Transmitance is up to 83%；The acrylate monomer rotary coating of the light trigger that mass concentration is 1～5% will be added in Yin Na
The surface of rice noodle thin layer, is subsequently placed on the nano silver wire thin film for scribbling acrylate monomer under uviol lamp, causes propylene
Acid ester monomer is polymerized, and obtains the polymeric layer that thickness is 300 μm, glass substrate is removed after cooling, obtains flexible nano silver wire and gathers
Compound composite conducting substrate layer 1；
The preparation of S2, soft-light anode layer 2：By the TiO buied on market2Colloid solution, adopts silk screen at 25 DEG C of room temperature
Print process is prepared on flexible nano silver wire polymer composite conducting substrate layer 1 obtained in step S1, it is to be dried after, use 2.5KG
Smooth iron block be pressed in thereon, iron block apply pressure about 0.4MPa, removed after 1 week, obtain the oxide porous of 15 μ m-thicks
Film layer 21, two-tetrabutylammonium-bis- (isothiocyanos) that obtained oxide porous film layer 21 is immersed in into 0.5mm then it is double (2,
2'- bipyridyl -4,4'- dicarboxyls) in ruthenium (II) ethanol solution, dye coating 22 is formed, lucifuge is taken out after standing 12h and is dried, i.e.,
Obtain soft-light anode layer 2；
S3, the preparation to electrode layer 4：Platinum slurry is scratched on the flexible conductive substrates " polymer/silver nano wire ", be dried after
It it is 43 μm to electrode layer 4 to thickness；
The preparation of S4, dyestuff dielectric substrate 3：Configuration 0.6M 1- propyl group -3- methylpyridinium iodide imidazole salts, the 0.5M 3- tert-butyl groups
Pyridine, 0.3M LiI and 0.05M I2Mixing acetonitrile solution, then by acetonitrile solution be poured in soft-light anode layer 2 with to electricity
Between pole layer 4, it is connected with load using wire, forms external loop, the thickness of the dielectric substrate 3 is 50 μm.
Solar cell effective area obtained in said method is adopted for 0.16cm2Battery radiant illumination be 100mW/cm2
The photoelectric transformation efficiency measured under simulated solar irradiation is 0.2%.
Embodiment two
The present embodiment is prepared for flexible dye-sensitized solar cell using the method for low-temp low-pressure, and the structure of gained battery is such as
Shown in accompanying drawing 1, specific preparation process is as follows：
The selection of S1, flexibility " polymer/ITO " conductive substrate layer 1：Choose commercially available PEN/ITO substrates, 15ohm/square
Square resistance, light transmittance 81%；
The preparation of S2, light anode layer 2：By the TiO buied on market2Colloid solution, using blade coating legal system at 28 DEG C of room temperature
It is standby in the flexible polymer conductive substrate layer 1 of step 1, it is to be dried after, be placed on smooth heater, it is flat with 3.5KG
Whole iron block is pressed in thereon, the pressure about 2MPa that iron block applies, and arranges temperature 60 C, removes after being kept for 72 hours, and preparing thickness is
Then obtained oxide porous film layer 21 is immersed in the two-tetrabutylammonium of 0.5mm-bis- by 12 μm of oxide porous film layer 21
In (isothiocyano) double (2,2'- bipyridyl -4,4'- dicarboxyls) ruthenium (II) ethanol solution, dye coating 22 is formed, lucifuge stands
Take out after 24h and dry, that is, obtain soft-light anode layer 2；
S3, the preparation to electrode layer 4：The platinum that thickness is 100 μm is sputtered in flexible PEN/ITO conductive substrate layers 1, is obtained
To electrode layer 4；
Then acetonitrile solution is irrigated by S4, the preparation process of dielectric substrate 3 with embodiment one, configuration mixing acetonitrile solution
In soft-light anode layer 2 and to, between electrode layer 4, being connected with load using wire, dyestuff dielectric substrate 3 described in external loop is formed
Thickness be 62 μm.
Solar cell effective area obtained in said method is adopted for 0.16cm2Battery radiant illumination be 100mW/cm2
The photoelectric transformation efficiency measured under simulated solar irradiation is 0.3%.
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (1)
1. the low-temp low-pressure preparation method of a kind of flexible dye-sensitized solar cell, it is characterised in that specifically include following steps：
The selection of S1, flexible polymer/ITO conductive substrate layers：PEN/ITO substrates are chosen, the sheet resistance value of the substrate is
15ohm/square, light transmittance are 81%；
The PEN is PEN；The ITO is indium tin oxide；
The preparation of S2, light anode layer：By TiO2Colloid solution, at 28 DEG C of room temperature using knife coating prepare S1 flexible polymer/
In ITO conductive substrate layers, it is to be dried after, be placed on smooth heater, be pressed in thereon with the smooth iron block of 3.5KG, iron block
The pressure 2MPa of applying, arranges temperature 60 C, removes, prepare the oxide porous film layer that thickness is 12 μm after being kept for 72 hours,
Then two-tetrabutylammonium-bis- (isothiocyanos) that obtained oxide porous film layer be immersed in into 0.5mm it is double (2,2'- bipyridyls-
4,4'- dicarboxyls) in ruthenium (II) ethanol solution, dye coating is formed, lucifuge is taken out after standing 24h and is dried, that is, obtain flexible light positive
Pole layer；
S3, the preparation to electrode layer：The platinum that thickness is 100 μm is sputtered in flexible PEN/ITO conductive substrate layers, is obtained to electrode
Layer；
The preparation of S4, dielectric substrate：Configuration 0.6M1- propyl group -3- methylpyridinium iodide imidazole salts, 0.5M3- tert .-butylpyridines,
0.3MLiI and 0.05MI2Mixing acetonitrile solution, then by acetonitrile solution be poured in soft-light anode layer with to electrode layer it
Between, it is connected with load using wire, forms external loop, the thickness of the dielectric substrate is 62 μm.
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| CN110136964A (en) * | 2019-04-23 | 2019-08-16 | 长江大学 | Flexibility for dye-sensitized solar cells is to electrode |
| CN110648852B (en) * | 2019-10-09 | 2021-02-26 | 温州大学 | Counter electrode and quantum dot sensitized solar cell |
| 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 |
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