CN100356586C - Large area internal series dye sensitization nano thin film solar cell and producing method thereof - Google Patents
Large area internal series dye sensitization nano thin film solar cell and producing method thereof Download PDFInfo
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- CN100356586C CN100356586C CNB2004100144555A CN200410014455A CN100356586C CN 100356586 C CN100356586 C CN 100356586C CN B2004100144555 A CNB2004100144555 A CN B2004100144555A CN 200410014455 A CN200410014455 A CN 200410014455A CN 100356586 C CN100356586 C CN 100356586C
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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
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- 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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Abstract
The present invention relates to a large area internal series dye sensitization nano thin film solar cell and a producing method thereof. The solar cell is provided with an upper transparent base plate and a lower transparent base plate. The peripheries of transparent base plates are sealed into a cavity body which is provided with electrolyte. The transparent base plates are provided with transparent conductive films which are arranged on the transparent base plates at intervals, wherein a transparent conductive film of one transparent base plate is provided with a catalyst layer, and the transparent conductive film of the other transparent base plate is provided with nano porous semiconductor material blocks which are arranged at intervals. Dye is dipped in nano porous semiconductor material. The transparent conductive films of the two staggered transparent base plates are connected in series through electrode material. The present invention can be used for making series electrodes in the cell for obtaining the needed output current of the solar cell. The cell has the advantage of good sealing function, and the operating long-term stability of the cell is ensured. The technique and the method of the present invention have the advantages of simple and easy operation, low price and stable cell performance.
Description
Technical field
The present invention relates to semi-conducting material, macromolecular material, organic material, inorganic material, regenerative resource and solar cell and make the field, specifically relate to large tracts of land internal series-connection dye-sensitized nano film solar battery and preparation method thereof.
Technical background
The M.Gr tzel of the Institute of Technology such as Lausanne, SUI height in 1991 professor laboratory Nature (O ' Regan, B.; Gr tzel.M, 1991,353,737) go up the achievement in research of a kind of brand-new dye-sensitized nano film solar battery of report, obtain extensive concern and attention in the world immediately.From 1991 was international research focus so far always.Its cheap and production cost and the technology that is easy to suitability for industrialized production, and wide application prospect have attracted numerous scientists and enterprise to drop into.
Dye-sensitized nano film solar battery is that the compound system that utilizes the organic photosensitive functional molecular to combine with half semiconductor nano material carries out opto-electronic conversion to solar energy, it combines the function and the characteristics of organic and inorganic photoelectric material: the collection optical property of utilizing the organic photosensitive dye efficient, the rapid electric charge of semi-conducting material shifts and separates advantage, in conjunction with the porousness of semiconductor nano-crystal thin-film and high specific area, make full use of the flexibility of design of organic molecule and some new features that are different from the body material of nanometer semiconductor structure material.
Dye-sensitized nano film solar battery mainly is made up of following components: the light anode, dye photoactivation agent, electrolyte and counterelectrode and the encapsulant that contain nano porous semiconductor film.Because the circumstance complication of the internal physical of dye-sensitized nano film solar battery and chemistry, electronics is accompanied by complicated course of reaction in the process transmission of electrolyte, these are all had higher requirement to encapsulant and electrode material, and to have enough sealing intensities to prevent the volatilization and the leakage of electrolyte, this is the basic demand that reaches a long-life dye-sensitized nano film solar battery.
At present this battery at small size (less than 1cm
2) high conversion efficiency reached about 11%, but at area battery and assembly thereof, owing to fail on the key issues such as cell sealing to solve, hindered the extensive use of this solar cell always.
Summary of the invention
The purpose of this invention is to provide the preparation method who is suitable for preparation of industrialization large tracts of land, high efficiency dye-sensitized nano film solar battery.This method not only technology is simple, and battery is more stable, can reach long-life purpose.
Use this method can prepare large tracts of land internal series-connection dye-sensitized nano film solar battery, overcome preparation technical barrier that large-area dye-sensitized nano film solar battery brought and material and select difficulty, and make this kind battery pass through internal series-connection by this method, the output voltage that acquisition is higher than single battery has been avoided stability problem that series connection brings and industrialization technology problem by outside batteries.
Technical scheme of the present invention is as follows:
Large tracts of land internal series-connection dye-sensitized nano film solar battery, include, following two sides transparency carrier, the transparency carrier periphery is sealed to cavity, electrolyte is arranged in the cavity, nesa coating is arranged on the transparency carrier, it is characterized in that described nesa coating is intervally arranged on transparency carrier, wherein there is catalyst layer to be intervally arranged on the nesa coating of a transparency carrier, there is the nano porous semiconductor material block to be intervally arranged on the nesa coating of another piece transparency carrier, be impregnated with dyestuff in the nano porous semiconductor material, connect by electrode material between the nesa coating that staggers mutually on two transparency carriers.
Described solar cell is characterized in that described electrode material is coated with macromolecular material or high polymer binder or glass material or ceramic material.
Described solar cell is characterized in that mixing mutually with the macromolecule binding material with metal dust, as inside battery series connection electrode material, or with metal paste as the inside battery electrode material of connecting.
Described solar cell is characterized in that the transparency carrier material is a clear glass, or transparent plastic, transparent polymer material.
The manufacture method of aforesaid solar cell is characterized in that may further comprise the steps:
(1), on transparency carrier, cover nesa coating, and cut apart disconnection,
(2), system electrode slurry: adopt silica gel, or epoxy glue, or ultraviolet cured adhesive, or macromolecular material solidify glue and catalyst according to a certain percentage with conductive powder, metallic nickel powder or ti powder or bronze end or silver powder, the ratio of metal dust and used glue between 1: 1 to 1: 10, and add the one thousandth to ten thousand of total weight/ platinum catalyst, after mixing, as the electrode material of internal series-connection battery; Or with metal paste as the inside battery electrode material of connecting,
(3), on each piece nesa coating of a transparency carrier, at interval printing, or spraying, or method such as sputter prepares nanometer or semiconductor porous film material and sintering, makes the uniform dyestuff of absorption in nanometer or the semiconductor porous film by dipping,
(4), on each piece nesa coating of another piece transparency carrier, printing, or spraying, or sputtering method prepares Catalytic Layer and sintering,
(5), utilize silk screen printing, or extruder, or distributor, or other method, with the electrode slurry of preparation in the even moulding of an end of conducting film, after two substrates are closed, the electrode slurry conducting film of the staggered positions on two substrates that is connected in series, and be heating and curing and seal
(6), the periphery of two substrates also solidifies with encapsulant and constitutes cavity, and injects electrolyte.
The manufacture method of described solar cell is characterized in that nanometer or semiconductor porous film material are meant nano-TiO
2Perforated membrane or nano-ZnO perforated membrane or other nano semiconductor material, film thickness can be a transparent conducting glass as substrate between 0.1 micron to 1 millimeter, sintering temperature is 450 to 600 degrees centigrade, sintering 30 to 200 minutes.
The manufacture method of described solar cell, it is characterized in that Catalytic Layer is meant the solution of platiniferous or method plating one deck platinum layer of jel print or spraying or sputter, or other catalytic specie, film thickness can be between 0.001 micron to 1 millimeter, as substrate is transparent conducting glass, sintering temperature is 450 to 600 degrees centigrade, sintering 30 to 200 minutes; 350 to 550 degrees centigrade of sintering 20 to 120 minutes.
The manufacture method of described solar cell, it is characterized in that (5) step was to utilize silk screen printing, or distributor, or the method for extrusion modling, electrode slurry silver paste, copper slurry or other metal and alloy pulp moulding on conducting film, 50 to 150 degrees centigrade of oven dry, and then outside electrocondution slurry printing and sealing with slurry glass paste, ceramic size, after two substrates are closed, the electrode slurry conducting film of the staggered positions on two substrates that is connected in series, and be heating and curing and seal.
The manufacture method of described solar cell, it is characterized in that conducting film is cut apart is to utilize laser grooving and scribing or other mechanical scratching or water under high pressure delineation need be divided into certain size to the conducting film on the transparency carrier by design, and cleans up stand-by; The nano-porous film absorbing dye is to instigate dyestuff to circulate in battery, treat that dyestuff evenly is adsorbed in the porous membrane after, stop the dyestuff circulation, remove surplus solution in the dry film; The injection electrolyte is meant and utilizes vacuum or manual method to inject electrolyte solution in solar cell, and hermetic electrolyte matter is injected aperture.
The manufacture method of described solar cell is characterized in that metal paste is silver paste or copper slurry, or other metal and alloy pulp.
Described solar cell manufacture method, it is characterized in that described series connection electrode material is an electrode slurry: adopt silica gel, or epoxy glue, or ultraviolet cured adhesive, or macromolecular material solidify glue and catalyst according to a certain percentage with conductive powder, more corrosion resistant metal dusts such as metallic nickel powder or ti powder or bronze end mix, as electrode material.
The periphery of two transparent substrates is by macromolecular material or high polymer binder or glass material or ceramic material curing.
Each electrode of two transparent substrates can cover or not cover macromolecular material or high polymer binder or glass material or ceramic material.
Can design the quantity of inside battery Series Sheet batteries arbitrarily according to the numerical value of designer's needs output voltage by all connecting in the battery.
Utilize single battery conductive electrode material to pass through inner the connection, finish the inside battery series connection.
The series connection electrode slurry can by the printing or methods such as extrusion modling or coating, electrode slurry by designing requirement moulding on the nesa coating of selecting for use, as the internal series-connection electrode.
Dye-sensitized nano film solar battery is to be electrode with the transparent conductive film material, with dye-sensitized nano semiconductor porous film material is the light anode, to contain the catalyst film layer is photocathode, with the liquid electrolyte system of iodine/iodide ion solution, bromine/halogens such as bromide ion solution/halide ion electrolyte composition; With organic high molecular compound, as: the gelling liquid that the copolymer of APEO (PEO), polyacrylonitrile (PAN), epoxychloropropane and oxirane etc. are formed is electrolytical, with the organic molecule gelling agent, as: form the quaternary ammonium salt reaction and in organic liquid, form gel network structure and make liquid electrolyte solidify by amine and halogenated hydrocarbons, and the gelling liquid electrolyte that obtains; With ion liquid medium as: organic cation is alkyl ammonium cation, alkyl imidazole cation and alkyl pyridine cation etc., and common inorganic anion is BF
4 -, AlCl
4 -, PF
6 -, AsF
6 -, SbF
6 -, F (HF)
n -, CF
3SO
3 -, CF
3(CF
2)
3SO
3 -, (CF
3SO
2)
2N
-, CF
3COO
-, CF
3(CF
2)
2COO
-Deng, be the sol-gel electrolyte on basis; With the organic hole transferring material mainly is OMeTAD, P
3HT, P
3OT, PDTI, PTPD etc. replace the solid electrolyte system that the derivative of triphen amine and the polymer of aromatic heterocycle analog derivatives such as polymer, thiophene and pyrroles etc. are the basis; With inorganic p-N-type semiconductor N material, as: the solid electrolyte system that CuI and CuSCN etc. form.The present invention utilizes the method in this kind solar cell internal production electrode or employing guard electrode, makes inside battery series connection electrode, uses the present invention can make the inner any series connection of this kind solar cell, obtains needed this solar cell output voltage.The present invention has good cell sealing function simultaneously, has guaranteed the long-time stability of battery operation.The present invention has broken through the difficult point that large-area dye-sensitized nano film solar battery is made, and crucial effect is played in the making and the realization of area battery.Operation is simple for technology of the present invention and method, cheap, and battery performance is stable.
Description of drawings:
Fig. 1 is the internal structural map of dye-sensitized nano film solar battery.
101-glass 102-conducting film 103-nano porous semiconductor film 104-organic dyestuff adsorption layer 105-encapsulant 106-electrolyte 107-load
Fig. 2 is the dye-sensitized nano film solar battery structural representation.
The nano-porous film 204-catalyst layer 205-encapsulant 206-electrolyte 207-series connection electrode of 201-transparent substrates material 202-nesa coating 203-absorbing dye
Fig. 3 is another structural representation of dye-sensitized nano film solar battery.
The nano-porous film 304-catalyst layer 305-encapsulant 306-electrolyte 307-electrode protection of 301-transparent substrates material 302-nesa coating 303-absorbing dye and encapsulant 308-series connection electrode
Embodiment
Embodiment 1
Referring to Fig. 1, Fig. 3.
1. the preparation of transparency conductive electrode material: transparency carrier 301, as: transparent conducting glass, or conductive plastics, or electrically conducting transparent macromolecular material, cover one deck conducting film 302 thereon, utilize the delineation of laser grooving and scribing or other mechanical scratching or water under high pressure need be divided into certain size to the conducting film on the electro-conductive glass 302 by design, and clean up stand-by.
2. light anode preparation (negative electrode): on the electro-conductive glass 301, printing, or spraying, or method such as sputter prepares nanometer (or porous) film 303 (as nano-TiO
2Perforated membrane or nano-ZnO perforated membrane), film thickness can be between 0.1 micron to 1 millimeter, and carry out sintering and processing (as: is that substrate prepares battery with the transparent conducting glass, this step can 450 to 600 degrees centigrade of sintering 30 to 200 minutes) according to the material self character.
3. photocathode preparation (positive electrode): on another piece electro-conductive glass 301, printing, or spraying, or method such as sputter prepares Catalytic Layer 304 (as method plating one deck platinum layer of the solution printing of platiniferous or spraying, sputter, or other catalytic specie), film thickness can be between 0.001 micron to 1 millimeter, and it is stand-by to carry out sintering and processing (as: is the preparation battery of substrate with the transparent conducting glass, this step can 350 to 550 degrees centigrade of sintering 20 to 120 minutes) according to the material self character.
4. utilize silk screen printing, or distributor, or the method for extrusion modling, the moulding on conducting film 302 of conduction sintered electrode slurry 308 (as silver paste, copper slurry or other metal and alloy pulp), 50 to 150 degrees centigrade of oven dry, by designing requirement printing and sealing slurry 307 (as glass paste, ceramic size etc.), above print thickness can be made needs according to battery and be decided then.
5. clear glass 301 respectively is stacked together, also can add certain pressure, between the nesa coating 302 that staggers mutually on two transparency carriers 301 by electrode slurry 308 series connection, make encapsulant 305 sealed transparent glass 301 peripheries, and by the requirement sintering of internal series-connection electrode material and encapsulant.
6. utilize the method and apparatus of circulation that dyestuff is circulated in battery, after treating that dyestuff evenly is adsorbed in the porous membrane 303, stop the dyestuff circulation, remove surplus solution in the dry film, and injection electrolyte solution 306, utilize vacuum or manual method to inject electrolyte, and hermetic electrolyte matter injection aperture, this kind internal series-connection dye-sensitized nano film solar battery manufacturing process finished.
Embodiment 2
Referring to Fig. 2.The light anode that is printed with nano-porous film is put into dye solution soak more than one hour, make the uniform dyestuff of absorption in the semiconductor porous film, can select to utilize specific solution to clean, make the place that does not have film not have the absorption of dyestuff.Get 100 grams, 200 purpose titanium valves, 30 gram silica gel and 0.1 gram Platium-Divinyltetramethyl-Disiloxrane Complex mix as electrode material, and electrode material is printing and sealing slurry no longer outward.All the other are with example 1.
Claims (10)
1, large tracts of land internal series-connection dye-sensitized nano film solar battery, include, following two sides transparency carrier, the transparency carrier periphery is sealed to cavity, electrolyte is arranged in the cavity, nesa coating is arranged on the transparency carrier, it is characterized in that described nesa coating is intervally arranged on transparency carrier, wherein on the nesa coating of a transparency carrier catalyst layer is arranged and be intervally arranged with respect to substrate with nesa coating, the nano porous semiconductor material block is arranged on the nesa coating of another piece transparency carrier and with nesa coating with respect to being intervally arranged, be impregnated with dyestuff in the nano porous semiconductor material, connect by electrode material between the nesa coating that staggers mutually on two transparency carriers.
2, solar cell as claimed in claim 1 is characterized in that described electrode material is coated with macromolecular material or high polymer binder or glass material or ceramic material.
3, solar cell as claimed in claim 1 is characterized in that mixing mutually with the macromolecule binding material with full genus powder, as inside battery series connection electrode material.
4, solar cell as claimed in claim 1 is characterized in that the transparency carrier material is a clear glass, or transparent plastic, transparent polymer material.
5, the manufacture method of solar cell as claimed in claim 1 is characterized in that may further comprise the steps:
(1), on transparency carrier, cover nesa coating, and cut apart disconnection,
(2), system electrode slurry: adopt silica gel, or epoxy glue, or ultraviolet cured adhesive, or macromolecular material solidify glue and catalyst according to a certain percentage with conductive powder, metallic nickel powder or ti powder or bronze end or silver powder, the ratio of metal dust and used glue between 1: 1 to 1: 10, and add the one thousandth to ten thousand of total weight/ platinum catalyst, after mixing, as the electrode material of internal series-connection battery; Or with metal paste as the inside battery electrode material of connecting,
(3), on each piece nesa coating of a transparency carrier, at interval printing or spraying, or sputtering method prepares nanometer or semiconductor porous film material and sintering, makes the uniform dyestuff of absorption in nanometer or the semiconductor porous film by dipping,
(4), on each piece nesa coating of another piece transparency carrier, printing, or spraying, or sputtering method prepares Catalytic Layer and sintering,
(5), utilize silk screen printing, or extruder, or distributor, or other method, with the electrode slurry of preparation in the even moulding of an end of nesa coating, after two substrates are closed, the electrode slurry nesa coating of the staggered positions on two substrates that is connected in series, and be heating and curing and seal
(6), the periphery of two substrates also solidifies with encapsulant and constitutes cavity, and injects electrolyte.
6, the manufacture method of solar cell as claimed in claim 5 is characterized in that nanometer or semiconductor porous film material are meant nano-TiO
2Perforated membrane or nano-ZnO perforated membrane or other nano semiconductor material, film thickness can be a transparent conducting glass as substrate between 0.1 micron to 1 millimeter, sintering temperature is 450 to 600 degrees centigrade, sintering 30 to 200 minutes.
7, the manufacture method of solar cell as claimed in claim 5, it is characterized in that Catalytic Layer is meant the solution of platiniferous or method plating one deck platinum layer of jel print or spraying or sputter, or other catalytic specie, film thickness can be between 0.001 micron to 1 millimeter, as substrate is transparent conducting glass, sintering temperature is 450 to 600 degrees centigrade, sintering 30 to 200 minutes; 350 to 500 degrees centigrade of sintering 20 to 120 minutes.
8, the manufacture method of solar cell as claimed in claim 5, it is characterized in that (5) step was to utilize silk screen printing, or distributor, or the method for extrusion modling, electrode slurry silver paste, copper slurry or other metal and alloy pulp moulding on conducting film, 50 to 150 degrees centigrade of oven dry, and then outside electrocondution slurry printing and sealing with slurry glass paste, ceramic size, after two substrates are closed, the electrode slurry conducting film of the staggered positions on two substrates that is connected in series, and be heating and curing and seal.
9, the manufacture method of solar cell as claimed in claim 5, it is characterized in that conducting film is cut apart is to utilize laser grooving and scribing or other mechanical scratching or water under high pressure delineation need be divided into certain size to the conducting film on the transparency carrier by design, and cleans up stand-by; The nano-porous film absorbing dye is to instigate dyestuff to circulate in battery, treat that dyestuff evenly is adsorbed in the porous membrane after, stop the dyestuff circulation, remove surplus solution in the dry film; The injection electrolyte is meant and utilizes vacuum or manual method to inject electrolyte solution in solar cell, and hermetic electrolyte matter is injected aperture.
10, the manufacture method of solar cell as claimed in claim 5 is characterized in that metal paste is silver paste or copper slurry or other metal and alloy pulp.
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| CNB2004100144555A CN100356586C (en) | 2004-03-23 | 2004-03-23 | Large area internal series dye sensitization nano thin film solar cell and producing method thereof |
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| CNB2004100144555A CN100356586C (en) | 2004-03-23 | 2004-03-23 | Large area internal series dye sensitization nano thin film solar cell and producing method thereof |
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| CN100356586C true CN100356586C (en) | 2007-12-19 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4932852B2 (en) * | 2007-06-06 | 2012-05-16 | 株式会社フジクラ | Dye-sensitized solar cell module and manufacturing method thereof |
| CN101877282B (en) * | 2009-04-30 | 2012-12-12 | 中国科学院物理研究所 | Dye-sensitized solar cell module and preparation method thereof |
| CN101916669B (en) * | 2010-02-09 | 2012-07-18 | 南京大学 | Dye adsorption method of working electrodes of dye-sensitized solar cell |
| CN102468054A (en) * | 2010-11-15 | 2012-05-23 | 海洋王照明科技股份有限公司 | Large-area dye-sensitized solar cell and preparation method thereof |
| CN106158384B (en) * | 2015-03-27 | 2019-02-01 | 凯惠科技发展(上海)有限公司 | Dye-sensitized solar cells and preparation method thereof |
| CN106876143A (en) * | 2015-12-11 | 2017-06-20 | 天津榛发科技有限责任公司 | A kind of Graphene DSSC |
Citations (4)
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|---|---|---|---|---|
| CN2205991Y (en) * | 1994-10-14 | 1995-08-23 | 李毅 | Solar noncrystalline silicon cell |
| US6495067B1 (en) * | 1999-03-01 | 2002-12-17 | Fuji Photo Film Co., Ltd. | Liquid crystal compound, liquid crystal mixture or composition, electrolyte comprising the same, electrochemical cell and photo-electrochemical cell containing the electrolyte |
| JP2003086258A (en) * | 2001-06-28 | 2003-03-20 | Toshiba Corp | Material kit for electrolyte composition, electrolyte composition, and photo-sensitizing type solar cell |
| CN1412861A (en) * | 2001-10-12 | 2003-04-23 | 拜尔公司 | Photoelectric assembly with thermoplastic hotmelt adhesive layer, and its producing method |
-
2004
- 2004-03-23 CN CNB2004100144555A patent/CN100356586C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2205991Y (en) * | 1994-10-14 | 1995-08-23 | 李毅 | Solar noncrystalline silicon cell |
| US6495067B1 (en) * | 1999-03-01 | 2002-12-17 | Fuji Photo Film Co., Ltd. | Liquid crystal compound, liquid crystal mixture or composition, electrolyte comprising the same, electrochemical cell and photo-electrochemical cell containing the electrolyte |
| JP2003086258A (en) * | 2001-06-28 | 2003-03-20 | Toshiba Corp | Material kit for electrolyte composition, electrolyte composition, and photo-sensitizing type solar cell |
| CN1412861A (en) * | 2001-10-12 | 2003-04-23 | 拜尔公司 | Photoelectric assembly with thermoplastic hotmelt adhesive layer, and its producing method |
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