CN101540234B - Method for preparing dye-sensitized solar cell - Google Patents
Method for preparing dye-sensitized solar cell Download PDFInfo
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- CN101540234B CN101540234B CN2009101286575A CN200910128657A CN101540234B CN 101540234 B CN101540234 B CN 101540234B CN 2009101286575 A CN2009101286575 A CN 2009101286575A CN 200910128657 A CN200910128657 A CN 200910128657A CN 101540234 B CN101540234 B CN 101540234B
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- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 claims description 2
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- RVOWBUHHAGFJPC-UHFFFAOYSA-N dibutyl(naphthalen-1-yl)sulfanium Chemical class C1=CC=C2C([S+](CCCC)CCCC)=CC=CC2=C1 RVOWBUHHAGFJPC-UHFFFAOYSA-N 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/2068—Panels or arrays of photoelectrochemical cells, e.g. photovoltaic modules based on photoelectrochemical cells
- H01G9/2077—Sealing arrangements, e.g. to prevent the leakage of the electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
-
- 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
-
- 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
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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a method of manufacturing a dye-sensitized solar cell, and more particularly, to a method of manufacturing a dye-sensitized solar cell using a low melting point glass frit composition and a photocurable resin composition so as to enable low-temperature laser sintering to reduce damage to thermally unstable devices, and performing pre-sealing with a photocurable resin composition so as to improve the effectiveness of frit sealing and the effectiveness of treatment, thereby preventing an electrolyte of a solar cell, which is operated under exposure to a severe external environment, from volatilizing from a sealing part, thereby extending a durable life, and providing a seal having resistance to external impact or damage and high strength, thereby extending the life of the dye-sensitized solar cell and improving the durability thereof.
Description
Technical field
The present invention relates to a kind of method for preparing DSSC; Particularly relate to the following method for preparing DSSC; It is laser sintered to reduce the damage to heat-labile device that thereby said method use low-melting glass feed composition and Photocurable resin composition make it possible to carry out low temperature; Thereby and carry out pre-sealedly improving frit-sealed validity and handling validity with light-cured resin; Prevent thus to volatilize from sealing at the electrolyte that is exposed to the solar cell that moves under the situation of abominable external environment condition; Thereby prolong endurance life, and tolerance and the high-intensity sealing that has external impact or damage is provided, thereby prolong the life-span of DSSC and improve its durability.
Background technology
Since Swiss Federal Institute of Technology Lausanne (Swiss Federal Institute of Technology (Lausanne); EPFL) Michael Gratzel etc. developed dye-sensitized nano particulate oxidation titanium solar battery in 1991, carried out relevant for this many researchs.It because comparing with existing silicon solar cell, DSSC has significantly lower production cost, so can substitute existing amorphous si solar cells.And, thereby DSSC is mainly by absorbing the Optical Electro-Chemistry solar cell that dye molecule that visible light produces electron-hole pair and the transition metal oxide that is used to transmit the electronics that is produced are formed.
Usually, the element cell of DSSC by transparent substrates up and down, be respectively formed at conductive clear electrode on these transparent substrates, be formed on the absorbing dye on the said conductive clear electrode that is equivalent to first electrode the transition metal oxide porous layer, be formed on the catalyst film electrode on the said conductive clear electrode that is equivalent to second electrode and be filled in said transition metal oxide (TiO for example
2) electrolyte between porous electrode and the said catalyst film electrode.
Therefore; In order stably to keep being filled in the electrolyte between first electrode and second electrode; Thermoplastic polymer film is placed between first electrode and second electrode and carries out hot pressing so that they are connected, can inject the electrolyte into and be stored in the space between first electrode and second electrode thereby form.
But; Because thermoplastic polymer film does not have structure closely, thus its easy Yin Gaowen, strong daylight, thermal cycle etc. and deterioration, and electrolyte volatilizees owing to the thermal cycle in day/night or winter/summer etc.; Thereby reduce the efficient of solar cell, finally finish its life-span.And thermoplastic polymer film is damaged by external impact owing to its limited mechanical strength easily, and this has shortened the life-span of solar cell, causes the problem of durability aspect thus.
Summary of the invention
In order to overcome above-mentioned prior art problems; An object of the present invention is to provide a kind of method for preparing DSSC; It is laser sintered to reduce the damage to heat-labile device that thereby said method use low-melting glass feed composition and Photocurable resin composition make it possible to carry out low temperature; Thereby and carry out pre-sealedly improving frit-sealed validity and handling validity with light-cured resin; Prevent thus to volatilize from sealing at the electrolyte that is exposed to the solar cell that moves under the situation of abominable external environment condition; Thereby prolong endurance life, and tolerance and the high-intensity sealing that has external impact or damage is provided, thereby prolong the life-span of DSSC and improve its durability.
In order to realize the object of the invention, the invention provides a kind of method for preparing DSSC, this method comprises last substrate and said method comprising the steps of with to wait to bond to the said bonding substrate of going up substrate mutually bonding:
Potted line along said DSSC is applied to frit on the bonding plane of said upward substrate or said bonding substrate;
In the periphery of said potted line, separate with said potted line, Photocurable resin composition is applied on the bonding plane of said upward substrate or said bonding substrate;
With said substrate and the said bonding substrate binding gone up, thereby form assembly;
The illumination that will be used to solidify said Photocurable resin composition is mapped on the said assembly so that its curing; With
Along the frit irradiating laser of said assembly with its sintering.
The present invention also provides the DSSC that is made by said method.
According to the method for preparing DSSC of the present invention; It is laser sintered to reduce the damage to heat-labile device that thereby use low-melting glass feed composition and Photocurable resin composition make it possible to carry out low temperature; Thereby and carry out pre-sealedly improving frit-sealed validity and handling validity with light-cured resin; Prevent thus to volatilize from sealing at the electrolyte that is exposed to the solar cell that moves under the situation of abominable external environment condition; Thereby prolong endurance life, and tolerance and the high-intensity sealing that has external impact or damage is provided, thereby prolong the life-span of DSSC and improve its durability.
Description of drawings
Fig. 1 schematically illustrates the preparation method according to the DSSC of an embodiment of the invention.
Embodiment
To set forth the present invention in detail with reference to accompanying drawing at present.
The present invention relates to a kind of method for preparing DSSC; This method comprises last substrate and said method comprising the steps of with to wait to bond to the said bonding substrate of going up substrate mutually bonding: along the potted line of said DSSC frit is applied on the said bonding plane of going up substrate or said bonding substrate; In the periphery of said potted line, separate with said potted line, Photocurable resin composition is applied on the bonding plane of said upward substrate or said bonding substrate; With said substrate and the said bonding substrate binding gone up, thereby form assembly; The illumination that will be used to solidify said Photocurable resin composition is mapped on the said assembly so that its curing; With along the frit irradiating laser of said assembly with its sintering.
Usually; DSSC is made up of first electrode (being equivalent to the following substrate among Fig. 1---bonding substrate), second electrode (being equivalent to the top electrode among Fig. 1) and the electrolyte that is filled between these electrodes; Said first electrode is made up of the substrate with the perforated membrane that contains dyestuff, and it is relative with said first electrode (bottom electrode) that said second electrode is set to.In the present invention,, first electrode and second electrode are spaced from each other, and frit-sealed through sintering used in the space between them, and will fill with electrolyte through sealed space in order to store the electrolyte between first electrode and second electrode steadily in the long term.As perforated membrane, can use the various known perforated membrane of absorbing dye, for example, with the for example TiO that is of a size of 10nm～15nm
2Thereby obtain perforated membrane Deng transition metal oxide coating and sintering.The transparent substrates that is formed with perforated membrane on it need not be confined to planar substrate; It can comprise curved substrate; Can use the various transparent substrates that are usually used in solar cell, comprise the substrate of processing by the material (for example glass) of visible light that can see through specific wavelength or ripple.For electrode, preferred conduction property substrate.The instantiation of transparent substrates comprises known clear glass, transparent resin, PET (PET), ITO (indium tin oxide) or FTO (fluorine doped tin oxide) etc.And, in order to give conductivity, except above-mentioned material, between perforated membrane and substrate, can further comprise conducting film or coating (ITO, FTO or electric conductive polymer).As being set to second electrode relative (going up substrate) with first electrode, can use any substrate of second electrode that is usually used in solar cell, it need not be confined to planar substrate, can comprise curved substrate.Preferably, said second electrode is by processing through the visible light of specific wavelength or the material (for example glass) of ripple, and to this, it can be processed by known clear glass, PET glass, ito glass or FTO glass etc.Preferably, in order to give conductivity, can further comprise conducting film or coating (ITO, FTO or electric conductive polymer).And, in order to improve day efficiency of light absorption and priming reaction, can further comprise catalyst metal layer in the outermost of first electrode.
The last substrate of DSSC can be processed by glass; And following substrate or bonding substrate can be processed by glass in case of necessity; As shown in Figure 1, also can process and (, then descend substrate to be equivalent to bonding substrate if DSSC only has substrate up and down by other materials; Surpass 2 layers sandwich construction if it has, then bonding substrate binding is to the bottom of last substrate, and can bonding one or more other substrates under bonding substrate).
As shown in Figure 1, can on a substrate, make the unit (in Fig. 1,2 * 2 matrixes) of a plurality of DSSCs, also can on a substrate, only make a unit.Because each unit should keep sealing on its bonding plane, so along potted line (sealing the outside of said unit with the mode of ring-type curve) coated glass feed composition, as shown in Figure 1.According to the shape of device, potted line can be different shape.As shown in Figure 1, the potted line coated glass material on the bonding plane.Bonding plane can be the bottom of last substrate or the top of following substrate (perhaps bonding to the bonding substrate of substrate), and this has kept the sealing of adhesive portion.Frit can be used the whole bag of tricks coating well known in the art, for example, can be glass paste with frit preparation, through silk screen print method printing and dry.
As frit, can use any frit well known in the art, preferably, use to comprise P
2O
50～30mol%; V
2O
50～50mol%; ZnO 0～20mol%; BaO 0～15mol%; As
2O
30～20mol%; Sb
2O
30～20mol%; In
2O
30～5mol%; Fe
2O
30～10mol%; Al
2O
30～5mol%; B
2O
30～20mol%; Bi
2O
30～10mol%; And TiO
2The frit of 0～10mol%.
Preferably, coating comprises the frit paste of frit along the edge, and said frit paste composite can comprise: a) said frit; B) organic bond; And c) organic solvent.Preferably, said frit paste composite comprises: a) the said frit of 60 weight portions～90 weight portions; B) organic bond of 0.1 weight portion～5 weight portions; And c) organic solvent of 5 weight portions～35 weight portions.
Preferably, said frit comprises: P
2O
510～25mol%; V
2O
540～50mol%; ZnO 10～20mol%; BaO 1～15mol%; Sb
2O
31～10mol%; Fe
2O
31～10mol%; Al
2O
30.1～5mol%; B
2O
30.1～5mol%; Bi
2O
31～10mol%; And TiO
20.1～5mol% more preferably comprises: P
2O
515～20mol%; V
2O
540～50mol%; ZnO 10～20mol%; BaO 5～10mol%; Sb
2O
33～7mol%; Fe
2O
35～10mol%; Al
2O
30.1～5mol%; B
2O
30.1～5mol%; Bi
2O
31～5mol%; And TiO
20.1～5mol%.
If the content of frit composition exceeds above-mentioned scope, then vitrifying possibly can't realize that water proofing property possibly significantly descend, perhaps laser sintered possibly can't the realization.
Preferably, the glass transition temperature (T of said frit
g) be 300 ℃～400 ℃, softening temperature (T
Dsp) be 300 ℃～400 ℃.In these scopes, the low-temperature sintering excellent in stability.
And said frit preferably has the particle diameter of 0.1 μ m～20 μ m.In this scope, be applicable to sealing to heat-labile device thereby make it possible to carry out low temperature process, thereby and make it possible to carry out the sealing validity that laser processing improves electric device.
In said frit paste composite, said a) frit as stated, and as said b) organic bond, organic bond that can commodity in useization.The instantiation of organic bond comprises ethyl cellulose class or acrylic copolymer.And; As said c) organic solvent; Can use the organic bond compatible any organic solvent used with frit paste composite of the present invention; For ethyl cellulose class organic bond, the instantiation of organic solvent comprises acetate of butyl carbitol (BCA), terpineol (TPN), dibutyl phthalate (DBP) or their mixture.Preferably; Organic solvent and the mixed carrier that gets of organic bond with 30 weight portions in the organic solvent of 100 weight portions to be used～70 weight portions; Make the frit paste composite thereby then frit and remaining organic solvent are mixed with prepared carrier, this can further improve the dispersiveness of frit paste composite.More preferably; In the preparation of carrier; The organic solvent of said 30 weight portions～70 weight portions is made up of the BCA of 20 weight portions～55 weight portions, the TPN of 3 weight portions～10 weight portions and the DBP of 1 weight portion～5 weight portions, and when mixing with frit, uses BCA as said solvent.
In order to control thermal coefficient of expansion, said frit paste composite can further comprise filler.The instantiation amount of comprising of filler is preferably the 0.1 μ m～20 μ m cordierites of 0.1 weight portion～30 weight portions.
And the viscosity of said frit paste composite is preferably 500cp～50000cp, more preferably 2000cp～35000cp.In this scope, make it possible to be coated with, thereby further improve machinability through silk screen print method.
Then, at last substrate or wait to bond on the bonding plane of bonding substrate of substrate,, separate with potted line in the periphery of potted line, the coating Photocurable resin composition, this can further improve frit-sealed validity.As shown in Figure 1, can Photocurable resin composition be applied on the last substrate that is coated with frit, also can it be applied to down the top of substrate.Preferably Photocurable resin composition is being applied on the same substrate that is coated with frit aspect the layout.Particularly; As shown in Figure 1; The following substrate (or bonding substrate) that is equivalent to first electrode is furnished with electrode and the perforated membrane that comprises dyestuff (in case of necessity; Can also comprise the line that is used for the linkage unit battery), be equivalent to second electrode on the substrate, coated glass material and Photocurable resin composition as shown.Preferably, during being coated with, whole potted line is not implemented the sealing of frit and resin combination, but the part of potted line is unlimited to electrolyte entrance, so that after this can electrolyte be filled in the space between the bonding plane of assembly.
Said Photocurable resin composition can for example, can use silk screen print method or intaglio printing etc. through the whole bag of tricks coating well known in the art.
As said Photocurable resin composition, can use Photocurable resin composition commonly used, preferably, it comprises: a) 100 parts by weight of epoxy resin; B) Photoepolymerizationinitiater initiater of 0.01 weight portion～20 weight portions; C) coupling agent of 0.01 weight portion～10 weight portions; D) inorganic filler of 0.01 weight portion～100 weight portions; And e) photo-acid agent of 0.05 weight portion～10 weight portions.
The viscosity of said Photocurable resin composition is 5,000cp～150, and 000cp is preferably 10,000cp～100,000cp (25 ℃) handle to shorten the processing time and reduces cost thereby make it possible to carry out silk screen printing thus.
The preferred component of said Photocurable resin composition is following.
As said a) epoxy resin, can use copolymer or their mixture of prepolymer, polyether modified epoxy epoxy resins, silicone modified epoxy, said epoxy resin and other polymer of bisphenol-A based epoxy resin, Bisphenol F based epoxy resin, bisphenol-A D based epoxy resin, naphthalene based epoxy resin, biphenyl based epoxy resin, glycidyl amine epoxy resin, naphthols novolac (novolac) based epoxy resin, dicyclopentadiene based epoxy resin, phenol novolac based epoxy resin, cycloaliphatic epoxy resin, above-mentioned epoxy resin.
As said b) Photoepolymerizationinitiater initiater, can use diazol, aromatic series sulfonium salt, aromatic series iodine aluminium salt, aromatic matte aluminium salt, Metallocenic compound, iron arene compound and their mixture.
Particularly, optimization aromatic sulfonium salt with regard to photo-curable, optimization aromatic sulfonium hexafluorophosphate, aromatic matte hexafluoro antimonite or their mixture with regard to curable and adhesiveness.
Based on 100 parts by weight of epoxy resin, the consumption of said Photoepolymerizationinitiater initiater is preferably 0.01 weight portion～20 weight portions, and more preferably 0.1 weight portion～10 weight portions most preferably are 1 weight portion～6 weight portions.If said Photoepolymerizationinitiater initiater surpasses 20 weight portions, then it can not participate in reaction, and residual components possibly make the character deterioration of Photocurable resin composition.
Said c) coupling agent is used to improve adhesiveness (adhesion), can use such as silane coupler, titanium coupling agent (titan coupling agent), silicone compounds or their mixtures such as trimethoxysilyl benzoic acid or γ-glycidyl ether oxygen propyl trimethoxy silicanes.
Based on 100 parts by weight of epoxy resin, the consumption of said coupling agent is preferably 0.01 weight portion～10 weight portions, and more preferably 0.1 weight portion～5 weight portions most preferably are 0.1 weight portion～2 weight portions.If said coupling agent surpasses 10 weight portions, then it can not participate in reaction, and residual components possibly make the character deterioration of Photocurable resin composition.
As said d) inorganic filler, can use plate shape or inorganic spherical filler, like silicon dioxide, talcum, MgO, mica, montmorillonite, aluminium oxide, graphite, beryllium oxide, aluminium nitride, carborundum, mullite, silicon etc.
As said inorganic filler, special preferably talc because it has excellent barrier and light transmission, and can prevent the photocuring after-contraction.
And, for improve with Photocurable resin composition in the adhesiveness and the dispersiveness of epoxy resin, said inorganic filler can be substituted with substituting group.
Based on 100 parts by weight of epoxy resin, the consumption of said inorganic filler is preferably 0.01 weight portion～100 weight portions, more preferably 0.1 weight portion～80 weight portions.If said inorganic filler surpasses 100 weight portions, but the then reaction of its interfere resin combination, thus make its character deterioration.Said inorganic filler preferably has the average grain diameter of 0.1 μ m～30 μ m.
As said e) photo-acid agent, can produce lewis acid or Bronsted acid any compound thereby can unrestrictedly use through photogenerated acid through making public.For example, can use like organic sulfonate sulfonate such as (esters) or sulfonate compound, like compound or their mixtures such as salt.The instantiation of photo-acid agent comprises the phthalimido triflate; Dinitro benzene methyl tosylate; Positive decyl two sulfones; Naphthalene imino group triflate; The hexafluorophosphoric acid diphenyl iodnium; The hexafluoroarsenate diphenyl iodnium; The hexafluoro-antimonic acid diphenyl iodnium; TFMS diphenyl p-methoxyphenyl sulfonium salt; The TFMS diphenyl is to the isobutyl phenenyl sulfonium salt; Hexafluoroarsenate triphenyl sulfonium salt; Hexafluoro-antimonic acid triphenyl sulfonium salt; TFMS triphenyl sulfonium salt; TFMS dibutyl naphthyl sulfonium salt etc.
Based on 100 parts by weight of epoxy resin, the consumption of photo-acid agent is preferably 0.05 weight portion～10 weight portions.If it surpasses 10 weight portions, then photo-acid agent absorbs more far ultraviolet and produces a large amount of acid, thereby makes the character deterioration of Photocurable resin composition.
Said Photocurable resin composition can further comprise spacer (spacer).As spacer, can unrestrictedly use can constant maintenance plate thickness any spacer, preferably, use those spacers of the plate thickness that keeps 5 μ m～50 μ m, preferred 5 μ m～25 μ m.The shape of spacer can be sphere, round log shape etc., and the not concrete restriction of shape, as long as its constant maintenance plate thickness.Based on 100 parts by weight of epoxy resin, the consumption of spacer is preferably 0.01 weight portion～10 weight portions.
Above-mentioned Photocurable resin composition preferably has the cured resin epoxy conversion ratio more than 85%.
Then, with the last substrate that makes with wait to bond to the bonding substrate binding of substrate, thereby make assembly.In Fig. 1, following substrate is equivalent to bonding substrate.Form and innerly behind the assembly get into limitedly owing to will go up substrate and bonding substrate binding, the bonding of above substrate of institute and bonding substrate should must operation (comprising electrode formation, dyestuff absorption etc.) be carried out in all of completion structure battery afterwards, and be as shown in Figure 1.
And, when along potted line coated glass material and Photocurable resin composition, can they fully be coated with to keep sealing fully, in case of necessity, also can keep connecting line to be connected with the inner space.In DSSC of the present invention, because should filling electrolyte, so can keep electrolyte entrance.
In bonding assembly, frit and Photocurable resin composition also are not cured.Therefore, next step is exactly with being used to the illumination that Photocurable resin composition solidifies to be mapped on the assembly so that its curing.As shown in Figure 1, in the situation that Photocurable resin composition is solidified, irradiation UV makes its curing.Then, the frit of assembly is solidified.To this, along the frit irradiating laser that is coated with its sintering.As stated, can use the low-melting glass material, can use low power laser thus, thereby the fire damage of device is minimized.Wherein, during the sintering of frit, be cured and prevented that around the resin combination layer of frit gas from generating and contacting with oxygen, and supported this assembly.Therefore, frit-sealed validity can be improved through pre-sealed with processing validity.
The double containment that has kept DSSC thus through frit and resin combination.Then, as shown in Figure 1, can the cutting sealing line and the Photocurable resin composition coating part between the space, thereby the cured portion of Photocurable resin composition is left.In Fig. 1, on a substrate, make a plurality of batteries, thereby carry out cutting step to make a plurality of batteries.And, after the sintering of frit or cutting, can in above-mentioned electrolyte entrance, inject electrolyte, for example can use then that frit comes finally to seal, thus sealing fully.
The invention is not restricted to previous examples and appended accompanying drawing, those of ordinary skills can make various improvement or variation not deviating under the situation of liking scheme of the present invention described in the claim and scope enclosed.
Claims (12)
1. method for preparing DSSC, this method comprise last substrate and said method comprising the steps of with to wait to bond to the said bonding substrate of going up substrate mutually bonding:
Potted line along said DSSC is applied to frit on the bonding plane of said upward substrate or said bonding substrate;
In the periphery of said potted line, separate with said potted line, Photocurable resin composition is applied on the bonding plane of said upward substrate or said bonding substrate;
With said substrate and the said bonding substrate binding gone up, thereby form assembly;
The illumination that will be used to solidify said Photocurable resin composition is mapped on the said assembly so that its curing; With
Along the frit irradiating laser of said assembly with its sintering.
2. the method for claim 1, said method is further comprising the steps of: cut the space between said potted line and the said Photocurable resin composition coating part, thereby the cured portion of said light-cured resin is left.
3. the method for claim 1, wherein said frit comprises: P
2O
50～30mol%; V
2O
50～50mol%; ZnO 0～20mol%; BaO 0～15mol%; As
2O
30～20mol%; Sb
2O
30～20mol%; In
2O
30～5mol%; Fe
2O
30～10mol%; Al
2O
30～5mol%; B
2O
30～20mol%; Bi
2O
30～10mol%; And TiO
20～10mol%.
4. the step of the method for claim 1, wherein said coated glass material comprises coated glass material paste composite, and said frit paste composite comprises: a) frit; B) organic bond; And c) organic solvent.
5. method as claimed in claim 4, wherein, said frit paste composite comprises: a) frit of 60 weight portions～90 weight portions; B) organic bond of 0.1 weight portion～5 weight portions; And c) organic solvent of 5 weight portions～35 weight portions.
6. the method for claim 1, wherein said Photocurable resin composition comprises: a) 100 parts by weight of epoxy resin; B) Photoepolymerizationinitiater initiater of 0.01 weight portion～20 weight portions; C) coupling agent of 0.01 weight portion～10 weight portions; D) inorganic filler of 0.01 weight portion～100 weight portions; And e) photo-acid agent of 0.05 weight portion～10 weight portions.
7. method as claimed in claim 6; Wherein, said a) epoxy resin is selected from by the copolymer of prepolymer, polyether modified epoxy epoxy resins, silicone modified epoxy, said epoxy resin and other polymer of bisphenol-A based epoxy resin, Bisphenol F based epoxy resin, bisphenol-A D based epoxy resin, naphthalene based epoxy resin, biphenyl based epoxy resin, glycidyl amine epoxy resin, naphthols novolac based epoxy resin, dicyclopentadiene based epoxy resin, phenol novolac based epoxy resin, cycloaliphatic epoxy resin, said epoxy resin and the group that their mixture is formed.
8. method as claimed in claim 6, wherein, said b) Photoepolymerizationinitiater initiater is selected from the group of being made up of diazol, aromatic series sulfonium salt, aromatic series iodine aluminium salt, aromatic matte aluminium salt, Metallocenic compound, iron arene compound and their mixture.
9. method as claimed in claim 6, wherein, said c) coupling agent is selected from the group of being made up of silane coupler, titanium coupling agent, silicone compounds and their mixture.
10. method as claimed in claim 6, wherein, said d) inorganic filler is selected from the group of being made up of silicon dioxide, talcum, MgO, mica, montmorillonite, aluminium oxide, graphite, beryllium oxide, aluminium nitride, carborundum, mullite, silicon and their mixture.
11. method as claimed in claim 6, wherein, said e) photo-acid agent is selected from the group of being made up of sulfonate or sulfonate compound, compound and their mixture.
12. the DSSC that makes according to each described method in the claim 1～11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2008-0025962 | 2008-03-20 | ||
| KR1020080025962 | 2008-03-20 | ||
| KR1020080025962A KR101518871B1 (en) | 2008-03-20 | 2008-03-20 | Method of preparing the dye-sensitized solar cell |
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| CN101540234A CN101540234A (en) | 2009-09-23 |
| CN101540234B true CN101540234B (en) | 2012-07-04 |
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|---|---|---|---|
| CN2009101286575A Expired - Fee Related CN101540234B (en) | 2008-03-20 | 2009-03-20 | Method for preparing dye-sensitized solar cell |
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| Country | Link |
|---|---|
| JP (1) | JP5492433B2 (en) |
| KR (1) | KR101518871B1 (en) |
| CN (1) | CN101540234B (en) |
| DE (1) | DE102009012545A1 (en) |
| TW (1) | TWI469381B (en) |
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| JP5507954B2 (en) * | 2009-10-19 | 2014-05-28 | 三星エスディアイ株式会社 | Glass paste composition, electrode substrate, production method thereof, and dye-sensitized solar cell |
| KR101097270B1 (en) * | 2010-03-25 | 2011-12-21 | 삼성에스디아이 주식회사 | Photoelectric conversion device |
| KR20120028494A (en) * | 2010-09-15 | 2012-03-23 | 주식회사 동진쎄미켐 | Dye sensitized solar cell with advanced power efficiency |
| CN101950690A (en) * | 2010-09-27 | 2011-01-19 | 彩虹集团公司 | Dye sensitized solar cell and sealing method thereof |
| KR101144038B1 (en) | 2010-11-11 | 2012-05-24 | 현대자동차주식회사 | Curved dye-sensitized solar cell and method for manufacturing the same |
| KR20120087657A (en) * | 2011-01-28 | 2012-08-07 | 엘지이노텍 주식회사 | Solar cell |
| CN102324308B (en) * | 2011-06-29 | 2012-10-17 | 西安建筑科技大学 | Method for improving interface caking property of dye sensitized solar cell substrate |
| KR101349344B1 (en) * | 2011-12-06 | 2014-01-17 | 한국전기연구원 | organic-inorganic sealant for internal and external protection of photovoltaic cell |
| CN102709062B (en) * | 2012-06-05 | 2016-07-13 | 南昌航空大学 | A kind of encapsulating method of dye-sensitized solar cells |
| KR101674449B1 (en) * | 2012-11-28 | 2016-11-09 | 주식회사 오리온 | Method for manufacturing dye-sensitized solar cell using the same |
| WO2015030193A1 (en) * | 2013-08-30 | 2015-03-05 | 積水化学工業株式会社 | Method for reactivating counter electrode active material for dye-sensitive solar cell, method for regenerating dye-sensitive solar cell in which said method is used, catalyst layer for dye-sensitive solar cell, counter electrode, electrolyte, and dye-sensitive solar cell |
| KR101570740B1 (en) * | 2014-05-21 | 2015-11-23 | 주식회사 오리온 | Glass materials for large scale dye-sensitized solar cell sealing |
| CN105693097B (en) * | 2015-03-26 | 2018-12-18 | 王双喜 | A kind of high thermal conductivity low meiting sealing frils |
| PL3182466T3 (en) * | 2015-12-14 | 2020-11-02 | Oxford Photovoltaics Limited | Photovoltaic module encapsulation |
| CN108885944B (en) * | 2016-03-30 | 2020-11-24 | 日本瑞翁株式会社 | Sealing agent composition for organic solar cell, sealing agent, electrode, and organic solar cell |
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- 2009-03-17 TW TW98108569A patent/TWI469381B/en not_active IP Right Cessation
- 2009-03-19 JP JP2009067240A patent/JP5492433B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5492433B2 (en) | 2014-05-14 |
| JP2009231285A (en) | 2009-10-08 |
| CN101540234A (en) | 2009-09-23 |
| KR20090100651A (en) | 2009-09-24 |
| KR101518871B1 (en) | 2015-05-21 |
| TW200950123A (en) | 2009-12-01 |
| TWI469381B (en) | 2015-01-11 |
| DE102009012545A1 (en) | 2009-10-22 |
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