CN101540233A - Dye sensitization solar cell and producing method thereof - Google Patents

Dye sensitization solar cell and producing method thereof Download PDF

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Publication number
CN101540233A
CN101540233A CN200910128656A CN200910128656A CN101540233A CN 101540233 A CN101540233 A CN 101540233A CN 200910128656 A CN200910128656 A CN 200910128656A CN 200910128656 A CN200910128656 A CN 200910128656A CN 101540233 A CN101540233 A CN 101540233A
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electrode
frit
sintering
dssc
perforated membrane
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CN101540233B (en
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孙祯炫
李祥圭
朱汉福
朴钟大
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Dongjin Semichem Co Ltd
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Dongjin Semichem Co Ltd
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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
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • 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
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • 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
    • 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
    • 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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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
  • Filling, Topping-Up Batteries (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention relates to a dye sensitization solar cell and producing method thereof, particularly relates to the following dye sensitization solar cell and producing method thereof, wherein the dye sensitization solar cell is capable of preventing electrolyte in a solar cell that is exposed to adverse external environment and operates in the environment from volatilization from a sealing part, so as to extend the durable life and provide excellent sealing effect to water and gas, good tolerance to external impact or damage and good sealing, also the solar cell can be easily machininged under low temperature, thereby service life of the solar cell can be extended and durability can be improved.

Description

DSSC and preparation method thereof
Technical field
The present invention relates to DSSC and preparation method thereof, particularly, relate to following DSSC and preparation method thereof, described DSSC can prevent to be exposed to abominable external environment condition and the electrolyte of the solar cell that moves under this environment volatilizees from sealing, thereby prolong endurance life, and provide for moisture and gas and have excellent sealing effectiveness, can easily process at low temperatures and have, thereby prolong the life-span of solar cell and improve its durability at the tolerance of external impact or damage and the sealing of excellent in strength.
Background technology
Since Swiss Federal Institute of Technology Lausanne (Swiss Federal Institute of Technology (Lausanne), EPFL) Michael Gratzel etc. have carried out the many researchs relevant for this since developing dye-sensitized nano particulate oxidation titanium solar battery in 1991.It because comparing with existing silicon solar cell, DSSC has significantly lower production cost, so can substitute existing amorphous si solar cells.And DSSC is mainly by can absorbing visible light, thereby produces the dye molecule of electron-hole pair and be used to transmit the Optical Electro-Chemistry solar cell that the transition metal oxide of the electronics that is produced is 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 transition metal oxide porous layer that is absorbed with dyestuff on the described conductive clear electrode that is equivalent to first electrode, be formed on the catalyst film electrode on the described conductive clear electrode that is equivalent to second electrode and be filled in described transition metal oxide (TiO for example 2) electrolyte between porous electrode and the described catalyst film electrode forms.
Therefore, in order stably to keep being filled in the electrolyte between first electrode and second electrode, be placed on thermoplastic polymer film between first electrode and second electrode and carry out hot pressing so that they are connected, thereby form the space that can inject the electrolyte into and be stored between first electrode and second electrode.
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 easily owing to its limited mechanical strength, and this has shortened the life-span of solar cell, causes the problem of durability aspect thus.
Summary of the invention
In order to solve above-mentioned prior art problems, an object of the present invention is to provide following DSSC, described DSSC can prevent to be exposed to abominable external environment condition and the electrolyte of the solar cell that moves under this environment volatilizees from sealing, thereby prolong endurance life, and provide for moisture and gas and have excellent sealing effectiveness, can easily process at low temperatures and have, thereby prolong the life-span of solar cell and improve its durability at the tolerance of external impact or damage and the sealing of excellent in strength.
In order to realize this purpose of the present invention, the invention provides a kind of DSSC, described DSSC comprises first electrode, be set to second electrode relative and the electrolyte between described first electrode and described second electrode with described first electrode, described first electrode is made up of the transparent substrates that has the perforated membrane that comprises dyestuff on its surface, wherein, described electrolyte is filled in the space that is formed by the frit through sintering, described frit through sintering separates with rule at interval with described first electrode and the sealing of second electrode and with them, described frit through sintering forms by the coated glass material and with its sintering, and described 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%.
The present invention also provides a kind of method for preparing DSSC, described DSSC comprises first electrode, is set to second electrode relative with described first electrode and the electrolyte bath between described first electrode and described second electrode, described first electrode is made up of the transparent substrates that has the perforated membrane that comprises dyestuff on its surface, said method comprising the steps of: coated glass material on the bonding plane between described first electrode and second electrode, described frit comprises: P 2O 50～30mol%; V 2O 50～50mol%; ZnO 0～20mol%; BaO0～15mol%; 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%; With with described frit-sintered, thereby separate at interval with rule with the sealing of described first electrode and second electrode and with them.
According to the present invention; owing to can prevent the loss of electrolyte and can guarantee mechanical strength by using frit through sintering to seal; so the electrolyte of the solar cell that can prevent to be exposed to abominable external environment condition and move volatilizees from sealing, thereby prolong endurance life under this environment.And, can provide for moisture and gas to have excellent sealing effectiveness, can easily process at low temperatures and have, thereby prolong the life-span of solar cell and improve its durability at the tolerance of external impact or damage and the sealing of excellent in strength.
Description of drawings
Fig. 1 is the sectional view of the DSSC of first execution mode of the present invention,
Fig. 2 is the sectional view of the DSSC of second execution mode of the present invention,
Fig. 3 is the sectional view of the DSSC of the 3rd execution mode of the present invention,
Fig. 4 is the sectional view of the DSSC of the 4th execution mode of the present invention,
Fig. 5 is the sectional view of the DSSC of the 5th execution mode of the present invention,
Fig. 6 is the sectional view of the DSSC of the 6th execution mode of the present invention,
Fig. 7 is the sectional view of the DSSC of the 7th execution mode of the present invention,
Fig. 8 be show electrolyte entrance sealing DSSC of the present invention sectional view and
Fig. 9 is the sectional view that shows the DSSC of the present invention of connecting line.
* description of reference numerals *
10: the first electrodes
11: transparent substrates
The 12:(transparent substrates) edge
13:(comprises dyestuff) perforated membrane
On 15:(first electrode) conducting film
16: shot layer (bulk layer)
20: the second electrodes
21: support substrate
22:(supports substrate) edge
23: catalyst metal layer
25:(electrolyte) inlet
On 26:(second electrode) conductive film
30: electrolyte
40:(is between electrode) through the frit of sintering
50:(inlet) through the frit of sintering
60: connecting line
The 70:(connecting line) through the frit of sintering
Embodiment
Now elaborate the present invention with reference to the accompanying drawings.
The present invention relates to a kind of DSSC, described DSSC comprises first electrode 10, be set to and relative second electrode 20 and the electrolyte 30 between described first electrode and second electrode of described first electrode 10, described first electrode 10 is made up of the transparent substrates 11 that has the perforated membrane 13 that comprises dyestuff on its surface, wherein, described electrolyte 30 is filled in the space that is formed by the frit 40 through sintering, described frit 40 through sintering separates with rule at interval with described first electrode 10 and 20 sealings of described second electrode and with them, described frit through sintering forms by the coated glass material and with its sintering, and described 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%.
Usually, DSSC comprises first electrode 10, be set to and relative second electrode 20 and the electrolyte 30 between described first electrode and second electrode of described first electrode 10, and described first electrode 10 is made up of the transparent substrates 11 that has the perforated membrane 13 that comprises dyestuff on its surface.In the present invention, in order electrolyte stably to be remained between first electrode and second electrode for a long time, first electrode and second electrode are spaced from each other layout, and the space between them used frit (can and form airtight sealing in low-temperature sintering) sealing through sintering, institute's sealed space is filled with electrolyte.Instantiation is shown in Fig. 1～9, and its explanation will be described below.
As perforated membrane, can use the various known perforated membrane of absorbing dye, for example, will be of a size of for example TiO 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 making by the material (for example glass) of visible light that can see through specific wavelength or ripple.For electrode, preferred conductivity substrate.The instantiation of transparent substrates comprises known clear glass, transparent resin, PET (polyethylene terephthalate), 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 conductive film or coating (ITO, FTO or electric conductive polymer).As being set to second electrode relative 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, described second electrode is by making through the visible light of specific wavelength or the material of ripple, and to this, it can be made by known clear glass, transparent resin, PET, ITO or FTO etc.Preferably, in order to give conductivity, can further comprise conductive 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 such as catalyst metal layers such as Pt in the outermost of first electrode.
Described frit through sintering obtains by following manner: be coated with between these substrates along the edge of substrate that the frit that comprises frit is stuck with paste and with its sintering, thereby form fine and close sealing body (seal-making solid), described 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%.
Preferably, described frit paste composite comprises: a) frit; B) organic bond; And c) organic solvent preferably 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.
Preferably, described 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 may significantly descend, perhaps laser sintered possibly can't the realization.
Particularly, if the content of ZnO surpasses 20mol%, then crystalline phase is separated out, thereby causes being difficult to sealing, and if the content of BaO surpasses 15mol%, glass instability then, thus produce devitrification.
And, if Al 2O 3Content surpass 5mol%, if glass instability then is and B 2O 3Content surpass 20mol%, then softening temperature surpasses 500 ℃, thereby causes being difficult to low temperature seal.
And, if Bi 2O 3Content surpass 10mol%, then thermal coefficient of expansion increases, thereby causes being difficult to sealing, and if TiO 2Content surpass 10mol%, then thermal coefficient of expansion increases, thereby causes being difficult to low temperature seal.
Preferably, the glass transition temperature (T of described frit g) be 300 ℃～400 ℃, softening temperature (T Dsp) be 300 ℃～400 ℃.In these scopes, the low-temperature sintering excellent in stability.
And described frit preferably has the particle diameter of 0.1 μ m～20 μ m.In this scope, be applicable to airtight sealing 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 heat-labile device.
In described frit paste composite, described a) frit as mentioned above, and as described b) organic bond, can the commodity in use organic bond.The instantiation of organic bond comprises ethyl cellulose class or acrylic copolymer.And, as described 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 described 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 described solvent.
In order to control thermal coefficient of expansion, described 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 described 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 by silk screen print method.
Preferred implementation according to DSSC of the present invention, described first electrode 10 is made up of transparent substrates 11, perforated membrane 13 and dyestuff, described transparent substrates 11 is made by transparent material, described perforated membrane 13 is formed on the described transparent substrates 11 and separates with the edge 12 of rule interval with described transparent substrates to the inside, and described dyestuff absorbs on the described perforated membrane 13; Described second electrode 20 is by supporting substrate 21 and catalyst metal layer 23 to form, described catalyst metal layer 23 is formed on the whole described support substrate 21, perhaps by being formed on the described support substrate with the mode that the edge 22 of described support substrate separates at interval with rule to the inside; Described first electrode 10 and second electrode 20 are provided so that described perforated membrane 13 and described catalyst metal layer 23 face mutually, and described frit 40 through sintering is formed between the edge that is not formed with described catalyst metal layer 22 of the catalyst metal layer 23 of the edge that is not formed with described perforated membrane 12 of described transparent substrates and described support substrate 21 or described support substrate, thereby with the space sealing between described first electrode 10 and described second electrode 20.
As transparent substrates 11, can use various known transparent substrates, for example, it can perhaps can be provided with ITO or FTO coating or transparent conductivity polymer coating etc. by making such as conductive clear materials such as ITO or FTO shown in Fig. 1,2 or 7 on glass substrate (perhaps as transparent polymer substrates such as PET).Shown in Fig. 3,4 and 6, conductive film can be with frit-sealed through sintering that bonds on it, perhaps as shown in Figure 5, can be with conductive film according to separating at interval with the edge of glass substrate with the same rule of perforated membrane, and can directly be bonded to glass substrate through the frit of sintering.In the later case, should the outside that lead to conductive film with connecting line will be electrically connected.
And dyestuff is absorbed on the perforated membrane that is formed on the transparent substrates, thereby constitutes a side of transparent substrates.Perforated membrane 13 is preferably formed on the transparent substrates 11 and separates with the edge 12 of rule interval with transparent substrates to the inside, thereby prevents that electrolyte from leaking through perforated membrane.
As dyestuff, can use the various dyestuffs that are usually used in DSSC, can it be absorbed on the perforated membrane by the whole bag of tricks well known in the art.
And as shown in Figure 7, described first electrode can further comprise the shot layer of transition metal oxide on perforated membrane.Particularly, can be by coating 400nm～500nm TiO 2And its sintering obtained the shot layer, this can improve a day efficiency of light absorption.
As the support substrate 21 of second electrode, can use various known support substrates, preferably use transparent substrates.For example, described support substrate can perhaps can be provided with ITO or FTO coating or transparent conductivity polymer coating etc. by making such as conductive clear materials such as ITO or FTO shown in Fig. 1,2 or 7 on glass substrate (perhaps as transparent polymer substrates such as PET).As shown in Figure 4, conductive film can be with frit-sealed through sintering that bonds on it, perhaps as shown in Figure 5, can be with conductive film according to separating at interval with the edge of glass substrate with the same rule of the perforated membrane of first electrode, and can directly be bonded to glass substrate or ITO/FTO substrate through the frit of sintering.In the later case, should the outside that lead to conductive film with connecting line will be electrically connected.
Except that supporting substrate 21, described second electrode also comprises catalyst metal layer 23.Described catalyst metal layer can: i) supporting to form (coating or lining) on the whole surface of substrate, as shown in figs. 1 and 3, perhaps ii) by to the inside with rule at interval and the mode of supporting substrate to separate be formed on and support on the substrate, shown in Fig. 2 and 4～7.
Thus, the catalyst metal layer (Fig. 1 and 3) of second electrode be can be bonded to, glass substrate (Fig. 5), ITO/FTO substrate (Fig. 2,6 and 7) or conductivity rete (Fig. 4) perhaps optionally are bonded to through the frit of sintering.
Described first electrode and second electrode are arranged so that perforated membrane and catalyst metal layer face mutually, and described frit 40 through sintering is formed on the edge that is not formed with described perforated membrane and the i of described transparent substrates) between the catalyst metal layer of described support substrate or the edge that is not formed with described catalyst metal layer of ii) described support substrate, thereby with the space sealing between described first electrode and second electrode.
In addition, DSSC of the present invention can comprise the inlet that is used to inject electrolyte 30.Preferably, described second electrode 20 comprises the inlet 25 that is used to inject described electrolyte, and this electrolyte entrance 25 is by frit 50 sealings through sintering, and its preferred implementation as shown in Figure 8, thereby prevent that electrolyte from leaking through this inlet, so guaranteed the durability of solar cell.
And, DSSC of the present invention can also comprise the connecting line 60 that leads to the outside of element cell from described first electrode 10 or described second electrode 20, preferably, described connecting line 60 optionally is embedded in described in the frit 70 of sintering and be connected to the side of described solar cell.Particularly, element cell refers to a unit shown in Fig. 1～9, and each element cell all has the current delivery that is used for that they are connected to external device (ED) or will therefrom the obtains connecting line to external device (ED).If connecting line is exposed to the outside, then may produce short circuit or discharge.Therefore, in order to prevent short circuit or discharge, the outside of described connecting line is coated with the insulator frit, and in order to prevent connecting line because external impact and impaired, preferably be connected to the side of solar cell.So, being led in the situation of side of solar cell at connecting line 60, coated glass material and sintering are to be embedded in connecting line in the frit 70 of sintering and to be connected to the side of solar cell.
The present invention also provides a kind of method for preparing DSSC, described DSSC comprises first electrode 10, be set to and relative second electrode 20 and the electrolyte 30 between described first electrode and second electrode of described first electrode 10, described first electrode is made up of the transparent substrates 11 that has the perforated membrane 13 that comprises dyestuff on its surface, said method comprising the steps of: coated glass material on the bonding plane between described first electrode 10 and second electrode 20, described 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%; With, with described frit-sintered, thereby separate at interval with rule with described first electrode 10 and described second electrode 20 sealing and with them.
So, in the present invention, the particular glass material is coated between first electrode and second electrode and sintering, so that form sealing between first electrode and second electrode by specific frit through sintering.
Frit can be by the whole bag of tricks coating well known in the art.Preferably, the paste that comprises described frit along the edge coating of first electrode and second electrode.Sintering can be undertaken by any method well known in the art, and perhaps the coating part that can only heat described frit with laser is with its sintering, and this thermal shock that remainder is subjected to minimizes.
Preferably, the method for preparing DSSC of the present invention may further comprise the steps: provide the transparent substrates of being made by transparent material to be used for first electrode; By at interval on described transparent substrates, forming perforated membrane with rule to the inside with the mode that the edge of described transparent substrates separates; Dyestuff is absorbed on the described perforated membrane; Provide support substrate to be used for second electrode; On the whole surface of described support substrate, form catalyst metal layer, perhaps by at interval on described support substrate, forming catalyst metal layer with rule to the inside with the mode that the edge of described support substrate separates; The described frit of coating between the edge that is not formed with described catalyst metal layer of the catalyst metal layer of the edge that is not formed with described perforated membrane of described transparent substrates and described support substrate or described support substrate; And, with described first electrode and described second electrode engagement so that described perforated membrane and described catalyst metal layer face mutually, thereby and the described frit-sintered that will be coated with described first electrode and the sealing of second electrode.
Described transparent substrates can be any transparent substrates well known in the art, and for example, it can be by having forming such as insulators such as glass or PET such as conductive films such as ITO, FTO.Described perforated membrane can be any perforated membrane well known in the art, and preferably, it can be of a size of the TiO of 10nm～15nm by coating 2And its sintering obtained.And, can dyestuff be absorbed on the described perforated membrane by any method well known in the art, preferably, the substrate that is formed with perforated membrane on it is flooded with the mixed solution that is dissolved with dyestuff, thereby absorb this dyestuff.The dyestuff absorption step is not to carry out in this stage, can after the shot layer that forms as shown in Figure 7, carry out, perhaps after with first electrode and second electrode engagement and filling electrolyte (through electrolyte entrance injection mixed solution) carry out before.Can carry out the dyestuff absorption step and can make dyestuff absorb described perforated membrane no matter it in proper order, needs only it.And, on described perforated membrane, can further comprise the shot layer.
Next step is by providing above-mentioned support substrate and forming second electrode through the catalyst metal layer that is covered such as plating, sputter thereon.
Described perforated membrane is preferably formed on the described transparent substrates and separates with the edge at interval with rule to the inside.Described catalyst metal layer can be formed on the described support substrate and separate with the edge at interval with rule to the inside, but also can be formed on the whole support substrate.
First electrode and second electrode sticking with paste and its sintering (comprising the LASER HEATING sintering) will so be made by the coated glass material seal, shown in Fig. 1～9.
In addition, the method for preparing DSSC of the present invention can also may further comprise the steps: the inlet that is formed for injecting electrolyte in described second electrode; In described inlet, inject electrolyte; With the described frit of coating on described inlet and with its sintering, thereby with described inlet seal.The step that forms electrolyte entrance can be carried out in any stage before injecting electrolyte.Therefore, this step can be carried out before or after described support substrate is provided, and perhaps carried out after forming described catalyst metal layer, perhaps carried out after engaging described first electrode and second electrode.
Then, the required electrolyte of preparation DSSC is injected through formed electrolyte entrance, and the coated glass material is stuck with paste and sintering on this inlet, thereby with this inlet seal, as shown in Figure 8.
In addition, for structure as shown in Figure 9, the method for preparing DSSC of the present invention can be further comprising the steps of: will merge from the connecting line that described first electrode or second electrode lead to the outside of element cell; With, optionally described connecting line is led to the side of described solar cell, be coated with described frit in the side periphery of described connecting line and described solar cell, and with its sintering so that described connecting line is connected to the side of described solar cell.Thereby the step that connecting line is merged can carry out making electronics removable so that connecting line can be drawn from first electrode and second electrode in the suitable stage, and this merging also can be undertaken by further processing.And, because solar cell commonly used needs connecting line, so can pass through the known technology outconnector.
Next step, the insulation of the connecting line of being drawn with being connected of side of solar cell not being and must after the preparation of finishing solar cell, carrying out, these steps can be carried out in any stage, as long as the side view of first electrode and second electrode engagement and solar cell no longer can be changed.The sintering of described frit can be undertaken by sintering method commonly used, its also can by with laser only heating glass material coating part carry out.
Set forth the present invention with reference to following embodiment, but, these embodiment only are used to describe the present invention, and scope of the present invention is not limited thereto.
The preparation of [embodiment 1] frit
Following table 1 described composition prepares the frit of embodiment 1～7.In table 1, each value is all based on mol%.
[table 1]
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
P 2O 5 20 20 18 18 26 25 18
V 2O 5 47 50 42 43 47 47 42
ZnO 15 15 14 14 0 15 11
BaO 0 8 10 9 0 6 9
As 2O 3 0 3 1 0 0 3 0
Sb 2O 3 7 0 4 4 18 0 4
In 2O 3 0 0.5 0 0 0 0.5 0
Fe 2O 3 7 0 6 7 7 0 10
Al 2O 3 0 0 1 1 1 0 1
B 2O 3 0 0 1 1 0 0 1
Bi 2O 3 3 2.5 2 2 0 2.5 3
TiO 2 1 1 1 1 1 1 1
The preparation and the sealing test of [embodiment 8] frit paste composite
Use the frit preparation frit paste composite of the embodiment 1～7 of above-mentioned preparation.Described frit paste composite prepares by following manner: it is BCA: TPN: DBP=75 that the ethyl cellulose class organic bond of 5 weight portions is dissolved in weight ratio: make carrier in 15: 5 the mixed solvent, and the frit as every kind of prepared embodiment 1～7 of the BCA of organic solvent and 71 weight portions of the prepared carrier of 17 weight portions, 12 weight portions is mixed equably.
Use prepared frit paste composite to carry out the sealing test of solar cell.Thereby the silk screen printing of frit paste composite, drying, presintering and the laser radiation of every kind embodiment 1～7 are formed sealing.As laser, use Ti: sapphire (810nm) laser, and, use transparent glass substrate (Samsung Coming Company as substrate; ProductName: Eagle 2000).During sealing, on glass plate, do not observe recognizable temperature and rise or break.
The frit paste composite of following evaluation embodiment 1～7, the result is summarised in the following table 2.
1. glass transition temperature (T g)
Measure glass transition temperature with DTA equipment (DTG-60H Shimatz) with 10 ℃/minute intensification.
2. softening temperature (T Dsp)
Measure softening temperature with DTA equipment (DTG-60H Shimatz) with 10 ℃/minute intensification.
3. (CTE (* 10 for thermal coefficient of expansion -7/ ℃))
Measure thermal coefficient of expansion with TMA equipment (TMA-Q400 TA instrument) with 5 ℃/minute intensification.
4. water proofing property
To be immersed in 80 ℃ of pure water and measure weight through the OLED sample of sealing, with Magnification less than 0.5% those be designated as O, be that more than 0.5% those are designated as X with Magnification.
5. package sealing with laser test
Thereby frit is stuck with paste silk screen printing, dry and sintering formation seal pattern, carry out sealing test with laser then.The integra-MP that uses Spectra-Physics irradiating laser under the 13mm/ condition of second and determines whether sealing carrying out sealing test.
Zero: excellent sealing *: poor sealing
[table 2]
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7
T g(℃) 336 332 332 328 323 340 332
T dsp(℃) 342 344 344 348 349 347 339
CTE(×10 -7/℃) 74 75 75 75 70 75 75
Water proofing property ○ ○ ○ ○ ○ ○ ○
Package sealing with laser ○ ○ ○ ○ ○ ○ ○
As above shown in the table 2, frit paste composite of the present invention provides good low temperature process and excellent water proofing property and package sealing with laser.
The invention is not restricted to previous examples and accompanying drawing, those of ordinary skills can make various improvement or variation under the situation that does not deviate from the solution of the present invention described in claims and scope.

Claims (13)

1. DSSC, described DSSC comprises first electrode, be set to second electrode relative and the electrolyte between described first electrode and described second electrode with described first electrode, described first electrode is made up of the transparent substrates that has the perforated membrane that comprises dyestuff on its surface, wherein, described electrolyte is filled in the space that is formed by the frit through sintering, described frit through sintering separates at regular intervals with described first electrode and the sealing of second electrode and with them, described frit through sintering forms by the coated glass material and with its sintering, and described 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%.
2. DSSC as claimed in claim 1, wherein, described frit through sintering forms by coated glass material paste composite and with its sintering, and described frit paste composite comprises: a) described frit; B) organic bond; And c) organic solvent.
3. DSSC as claimed in claim 1, wherein, described frit through sintering forms by coated glass material paste composite and with its sintering, and described frit paste composite comprises: a) the described 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.
4. DSSC as claimed in claim 1, wherein, described 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%.
5. DSSC as claimed in claim 3, wherein, described frit paste composite also comprises the filler of 0.1 weight portion～30 weight portions.
6. DSSC as claimed in claim 1, wherein, described first electrode comprises transparent substrates, perforated membrane and dyestuff, described transparent substrates is made by transparent material, described perforated membrane is formed on the described transparent substrates and separates with the edge of rule interval with described transparent substrates to the inside, and described dyestuff absorbs on the described perforated membrane; Described second electrode comprises supports substrate and catalyst metal layer, described catalyst metal layer to be formed on the whole described support substrate or by being formed on the described support substrate with the mode that the edge of described support substrate separates at interval with rule to the inside; Described first electrode and second electrode are provided so that described perforated membrane and described catalyst metal layer face mutually, and described frit through sintering is formed between the edge that is not formed with described catalyst metal layer of the catalyst metal layer of the edge that is not formed with described perforated membrane of described transparent substrates and described support substrate or described support substrate, thereby with described first electrode and the sealing of described second electrode.
7. DSSC as claimed in claim 1, wherein, described second electrode also comprises the inlet that is used to inject described electrolyte, and described inlet frit-sealed by through sintering.
8. DSSC as claimed in claim 1, wherein, described first electrode or described second electrode also comprise from the connecting line of the outside that wherein leads to element cell, and described connecting line optionally is embedded in described in the frit of sintering and be connected to the side of described solar cell.
9. method for preparing DSSC, described DSSC comprises first electrode, is set to second electrode relative with described first electrode and the electrolyte between described first electrode and described second electrode, described first electrode is made up of the transparent substrates that has the perforated membrane that comprises dyestuff on its surface, said method comprising the steps of:
Coated glass material on the bonding plane between described first electrode and second electrode, described 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%; With
With described frit-sintered, thereby separate at interval with rule with the sealing of described first electrode and second electrode and with them.
10. method as claimed in claim 9 wherein, said method comprising the steps of:
Provide the transparent substrates of making by transparent material to be used for first electrode;
By at interval on described transparent substrates, forming perforated membrane with rule to the inside with the mode that the edge of described transparent substrates separates;
Dyestuff is absorbed on the described perforated membrane;
Provide support substrate to be used for second electrode;
On the whole surface of described support substrate, form catalyst metal layer, perhaps by at interval on described support substrate, forming catalyst metal layer with rule to the inside with the mode that the edge of described support substrate separates;
The described frit of coating between the edge that is not formed with described catalyst metal layer of the catalyst metal layer of the edge that is not formed with described perforated membrane of described transparent substrates and described support substrate or described support substrate; With
With described first electrode and described second electrode engagement so that described perforated membrane and described catalyst metal layer face mutually, thereby and the described frit-sintered that will be coated with described first electrode and the sealing of second electrode.
11. method as claimed in claim 9, described method is further comprising the steps of:
In described second electrode, be formed for injecting the inlet of electrolyte;
In described inlet, inject electrolyte; With
Coating described frit and on described inlet with its sintering, thereby with described inlet seal.
12. method as claimed in claim 9, described method is further comprising the steps of:
To merge from the connecting line that described first electrode or second electrode lead to the outside of element cell; With
Optionally described connecting line is led to the side of described solar cell, is coated with described frit in the side periphery of described connecting line and described solar cell, and with its sintering so that described connecting line is connected to the side of described solar cell.
13. method as claimed in claim 9, wherein, by the coating part that only heats described frit with laser with described frit-sintered.
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