CN101087011A - Photoelectric conversion device - Google Patents

Photoelectric conversion device Download PDF

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Publication number
CN101087011A
CN101087011A CNA2007101102214A CN200710110221A CN101087011A CN 101087011 A CN101087011 A CN 101087011A CN A2007101102214 A CNA2007101102214 A CN A2007101102214A CN 200710110221 A CN200710110221 A CN 200710110221A CN 101087011 A CN101087011 A CN 101087011A
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electrode
photo
conversion element
electric conversion
addition
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齐藤恭辉
菊田学
河野通之
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DKS Co Ltd
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Dai Ichi Kogyo Seiyaku Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2018—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte characterised by the ionic charge transport species, e.g. redox shuttles
    • 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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  • Photovoltaic Devices (AREA)

Abstract

Provided is an inexpensive and high-performance photoelectric conversion device of high practicability. The device comprises a semiconductor electrode, a counter electrode and an electrolyte layer held between the two electrodes, in which the electrolyte layer contains a compound of the following general formula (1) as an oxidation-reduction pair therein: (wherein M<+> represents an organic or inorganic cation; A represents an aromatic, non-aromatic, heteroaromatic or hetero-non-aromatic cyclic compound).

Description

Photo-electric conversion element
Technical field
The present invention relates to a kind of photo-electric conversion element that is suitable for as uses such as DSSC.
Background technology
In recent years, as being the photo-electric conversion element of electric energy, various solar cells were proposed with transform light energy.Wherein, people such as Graetzel by the Lausanne university of Switzerland were at " Nature " 1991 in 1991,353, the DSSC of delivering among the p737-740 etc. is because therefore used material, technology cheapness expect its practicability as the low-cost solar battery.
DSSC in general by: the semi-conducting electrode that has the photoelectric conversion layer that constitutes by the semiconductor that has adsorbed dyestuff on the conductive substrate, and this semi-conducting electrode practise physiognomy over the ground be provided with the counter electrode of catalyst layer on the conductive substrate that is provided with, the dielectric substrate that remains between these semi-conducting electrodes and the counter electrode constitutes.
The electrolyte of DSSC generally uses the material that has dissolved iodine class redox couple in organic solvent.Iodine class redox couple has following good performance, that is, the ionic conductance height, in addition that the speed of the reducing dyes of the state of oxidation is fast, on the other hand, on the conductive glass surface of the effect utmost point or titania surface reactive low etc.
But, because the sublimability height of iodine, therefore be difficult to potted component, become the reason that the element durability reduces under hot conditions, in addition, because iodine has highly corrosive to a lot of metals, therefore operable metal is restricted on device substrate, thereby the problems such as substrate that must use high prices such as conductive glass are arranged.In addition, particularly under the situation of large tracts of land element, in order to realize high performance, metal current collection line is set on the substrate of being everlasting, under this situation,, need prevent electrolyte and processing such as contacting of current collection line in order to prevent the corrosion of metal current collection line, it is complicated that flow chart becomes, problems such as effective area reduction that in addition can producing component.
In addition, iodine class redox couple has very strong absorption in the visible region, under the situation of the solvent that has used high viscositys such as ionic liquid, in order to work fully as solar cell device, need to improve iodine class redox couple concentration, will hinder the light absorption of dyestuff thus, become the reason that causes performance to reduce, in addition, emphasize under the situation of colorful property of solar cell using various dyestuffs, particularly under the situation of blue element, the color relation of iodine can counteract, and can not say so to match on element design.
Said, though iodine class redox couple also has shortcoming as the performance height of redox couple, therefore wish to have the redox couple of alternative iodine class, carried out some research (for example non-patent literature 1～5).
Proposed cobalt complex is used for the scheme of redox centering in the non-patent literature 1～3.Though under the faint light condition, can demonstrate and the equal performance of iodine class redox couple, because molecular dimension is big, so the translational speed of redox couple is slow, and under the simulated solar irradiation illuminate condition, performance reduces about half.In addition, with respect to iodine, cobalt complex price height, the practicality of can not saying so.
In non-patent literature 4～5, proposed (SCN) 2/ SCN -, (SeCN) 2/ SeCN -The scheme that is used for redox centering.Though (SCN) 2/ SCN -Can be used as redox couple work, yet compare, have only half following performance with iodine class redox couple.(SeCN) 2/ SeCN -Though demonstrate higher performance by comparison, yet aspect fail safe problem is arranged, not talkative practicality is very high.
In addition, the redox centering that except iodine, can be used for photo-electric conversion element, can also enumerate Br 2/ Br -, Fe (CN) 6 4-/Fe (CN) 6 3-, Fe 2+/ Fe 3+, S 2-/ S n 2-, Se 2-/ Se n 2-, V 2+/ V 3+, quinone/quinhydrones etc., yet at aspects such as performance, stability, fail safes problem is arranged, can't obtain the performance that is equal to iodine.
[non-patent literature 1] J.Phys.Chem.B, 105,10461-10464 (2001)
[non-patent literature 2] Chem.Eur.J.9,3756-3763 (2003)
[non-patent literature 3] J.Am.Chem.Soc., 124,11215-11222 (2002)
[non-patent literature 4] J.Phys.Chem.B, 105,6867-6873 (2001)
[non-patent literature 5] J.Am.Chem.Soc., 126,7164-7165 (2004)
Summary of the invention
The present invention finishes in view of above problem, and its purpose is, a kind of high photo-electric conversion element of practicality that has used non-aggressive than the iodine class redox couple with enough performances, durability, redox couple that the transparency is also high is provided.
The inventor etc. further investigate in order to solve described problem, found that, has high performance and stability with the redox couple of general formula (1) expression as the redox couple of photo-electric conversion element, and then by using the electroconductive polymer catalyst as counter electrode, can make the photo-electric conversion element that demonstrates very high element photoelectric conversion efficiency, thereby finish the present invention.
Promptly, photo-electric conversion element of the present invention is the photo-electric conversion element that has semi-conducting electrode, counter electrode, remains in the dielectric substrate between described the two poles of the earth, it is characterized in that described dielectric substrate contains the compound of representing with following general formula (1) as redox couple.
[changing 1]
(in the formula (1), M +Be the organic or inorganic cation, A is the ring type compound of aromatic series, non-aromatic, heteroaromatic or assorted non-aromatic.)
In the photo-electric conversion element of the present invention, described ring type compound is preferably selected from least a of thiadiazole compound, pyridine compounds and their and phenylene compounds.
In the photo-electric conversion element of the present invention, described counter electrode preferably contains the electroconductive polymer catalyst that has catalytic activity for described redox couple.
In the photo-electric conversion element of the present invention, described electroconductive polymer catalyst more preferably comprises 3, the polymer of 4-second dioxy support thiophene or derivatives thereof.
By redox couple of the present invention being used for photo-electric conversion elements such as DSSC element, just can have with in the past use photoelectric conversion efficiency and stability that the element of iodine class redox couple is equal to, and can solve as the corrosivity of the weakness of in the past iodine class, the problem of the transparency.Specifically, because electrolyte of the present invention does not corrode a lot of metals, it is medium therefore metallic plate can be used for substrate, and the degree of freedom of element material improves.In addition, owing to do not have strong absorption in the visible region, therefore circuit elements design raising, this is external to have used under the situation of electrolyte of high concentration, owing to not causing that dielectric substrate absorbs the phenomenon that visible light hinders the light absorption of dyestuff, therefore can provide practicality high photo-electric conversion element.
Description of drawings
Fig. 1 is the schematic cross sectional view of essential structure of the photo-electric conversion element of expression execution mode.
Fig. 2 is visible absorption spectrum figure.
Wherein, 1 ... transparent base
2 ... nesa coating
3 ... porous metal oxide semiconductor (layer)
4 ... sensitizing dyestuff
5 ... dielectric substrate
6 ... catalyst layer
7 ... electrode base material
8 ... electrode matrix
9 ... counter electrode
10 ... photo-electric conversion element
Embodiment
Below with reference to accompanying drawings the mode that is used to implement the best of the present invention is elaborated.
Fig. 1 is the schematic cross sectional view of an example of expression photo-electric conversion element 10 of the present invention.
Among Fig. 1, symbol 1 expression transparent base, symbol 2 expression nesa coatings, symbol 3 expression porous metal oxide semiconductor layers, symbol 4 expression sensitizing dyestufves, symbol 5 expression dielectric substrates, symbol 6 expression catalyst layers, symbol 7 expressions support the electrode base material of symbol 6, symbol 8 expression electrode matrixs, symbol 9 expression counter electrodes.
As shown in the figure, the surface at the electrode matrix 8 that is made of transparent base 1 and nesa coating 2 formed thereon is formed with porous metal oxide semiconductor layer 3, in addition on the surface of this porous metal oxide semiconductor 3, is adsorbed with sensitizing dyestuff 4.In addition, folder disposes the counter electrode 9 that has formed catalyst layer 6 on the surface of electrode base material 7 every dielectric substrate 5 of the present invention, forms photo-electric conversion element 10.
Below, will preferred mode be described to each constituent material of photo-electric conversion element 10 of the present invention.
[transparent base]
The transparent base 1 of formation electrode matrix 8 can use the material through visible light, can use transparent glass suitably.In addition, also can use and glass surface is processed and made the material of incident light scattering.In addition, be not limited to glass,, also can use plastic plate or plastic film etc. so long as see through the material of light.
The thickness of transparent base 1 is because according to the shape of photo-electric conversion element 10 or service condition and difference, therefore be not particularly limited, yet for example under the situation of having used glass or plastics etc., durability when considering practical application, about preferred 1mm～1cm, at needs flexibility (flexibility), used under the situation of plastic film etc., about preferred 1 μ m～1mm.
[nesa coating]
As nesa coating 2, can use through visible light and material with conductivity.As this kind material, can enumerate for example metal oxide.Be not particularly limited, (following brief note is for " FTO " can preferably to use the tin oxide of the fluorine that for example mixed.), (following brief note is " ITO " for the mixture of indium oxide, tin oxide and indium oxide.), tin oxide of the antimony that mixed, zinc oxide etc.
In addition, if utilize processing such as making it dispersion to see through visible light, then also can use opaque conductive material.As this kind material, can enumerate material with carbon element or metal.As material with carbon element, be not particularly limited, can enumerate for example graphite (Graphite), carbon black, vitreous carbon, carbon nano-tube or fullerene etc.In addition,, be not particularly limited, can enumerate for example platinum, gold, silver, ruthenium, copper, aluminium, nickel, cobalt, chromium, iron, molybdenum, titanium, tantalum and their alloy etc. as metal.
So,, can will comprise that at least a above electric conducting material setting in the described conductive material is formed at the surface of transparent base 1 as electrode matrix 8.Perhaps also can be by among the material with described conductive material adding formation transparent base 1, with transparent base 1 and the nesa coating 2 integrated electrode matrixs 8 that are used as.
As the method that on transparent base 1, forms nesa coating 2, under the situation of using metal oxide, vapor phase methods such as liquid phase method, sputter or CVD such as sol-gal process are arranged, disperse the coating of pastel etc.In addition, using under the situation of opaque conductive material, can enumerate powder etc. with fixing methods such as transparent adhesives.
In addition, for transparent base 1 and nesa coating 2 is integrated, there is when the moulding of transparent base 1 filler as conductivity mix the method etc. of described conducting membrane material.
For the thickness of nesa coating 2, because conductivity is different because of used material, therefore be not particularly limited, but in the general used glass that has the FTO tunicle, be 0.01 μ m～5 μ m, preferred 0.1 μ m～1 μ m.In addition, necessary conductivity is different because of the area of used electrode, requires then low resistance of large-area electrode, in general is 100 Ω/below the, preferred 10 Ω/below the, more preferably 5 Ω/below the.
For electrode matrix 8 that constitutes by transparent base 1 and nesa coating 2 or transparent base 1 and nesa coating 2 is the integrated and thickness electrode matrix 8 that forms, because as mentioned above, shape or service condition difference because of photo-electric conversion element 10, therefore be not particularly limited, but in general be about 1 μ m～1cm.
[porous metal oxide semiconductor]
As porous metal oxide semiconductor 3, be not particularly limited, can enumerate titanium oxide, zinc oxide, tin oxide etc., preferred especially titanium dioxide, further preferred anatase titanium dioxide.
In addition, in order to reduce resistance value, wish that the crystal boundary of metal oxide is few.In addition, in order to adsorb sensitizing dyestuff more, the material that the preferred specific area of this semiconductor layer is big.Specifically, preferred 10～200m 2/ g.In addition, in order to increase the absorbing amount of sensitizing dyestuff, the particle diameter that preferably makes used oxide has the dispersion of distribution and with light scattering, or is that big oxide semiconductor particle about 300～400nm is as the reflector in that particle diameter is set on the porous layer.
This kind porous metal oxide semiconductor layer 3 is not particularly limited, and can utilize known method to be located on the nesa coating 2.The method that coating and the electrolysis or the electro-deposition of sol-gal process, dispersion pastel are for example arranged.
Therefore the thickness of this kind semiconductor layer 3 be not particularly limited because optimum value is different because of used oxide, can be 0.1 μ m～50 μ m, preferred 3～30 μ m.
[sensitizing dyestuff]
As sensitizing dyestuff 4, the material that injects electronics so long as can be excited by sunlight in described metal-oxide semiconductor (MOS) 3 gets final product, can use the dyestuff that generally is used in the photo-electric conversion element, in order to improve conversion efficiency, preferred its absorbs spectrogram and overlap the light resistance height with the sunlight spectrogram in very wide wavelength region may.
As sensitizing dyestuff 4, be not particularly limited preferred ruthenium complex, preferred especially ruthenium polypyridine class complex compound, the more preferably ruthenium complex of representing with Ru (L) 2 (X) 2.Here, L is 4,4 '-dicarboxyl-2, and 2 '-bipyridine or its quaternary ammonium salt and imported the polypyridine class part of carboxyl, in addition, X is SCN, Cl, CN.For example can enumerate two (4,4 '-dicarboxyl-2,2 '-bipyridine) diisothio-cyanate ruthenium complexs etc.
As other dyestuff, can enumerate ruthenium metal complex dyes in addition, for example iron complex, copper complex etc.In addition, can also enumerate organic dyestuff such as cyanogen class dyestuff, porphyrin class dyestuff, polyenoid class dyestuff, Coumarins dyestuff, the peaceful class dyestuff of match, squaric acid (squaric acid) class dyestuff, styrene base class dyestuff, eosin (eosine) class dyestuff, dihydroindole class dyestuff.
In these dyestuffs,, preferably has the base that combines with this metal-oxide semiconductor (MOS) 3 in order to improve the efficient of in metal-oxide semiconductor (MOS) 3, injecting electronics.In conjunction with base, be not particularly limited preferred carboxyl, sulfonic group, hydroxyl etc. as this.
In addition, dyestuff by will absorbing red area or near infrared region and visible transparent electrolyte of the present invention combination can be made the photo-electric conversion element of blueness or Transparent color, can obtain to require the purposes of colorful property etc., increase the use of element.
As the example of the solvent that uses in order to dissolve described dyestuff, can enumerate alcohols such as ethanol; Nitrogen compounds such as acetonitrile; Ketones such as acetone; Ethers such as Anaesthetie Ether; Halogenated aliphatic hydrocarbon such as chloroform; Aliphatic hydrocarbons such as hexane; Aromatic hydrocarbons such as benzene; Ester classes such as ethyl acetate etc.Dye strength in the solution can be according to used dye well solvent types and suitably adjust, in order to make it to be adsorbed on fully on the semiconductor surface, and high concentration to a certain degree preferably.For example, preferred 4 * 10 -5The concentration that mol/L is above.
The method that sensitizing dyestuff 4 adsorbs on porous metal oxide semiconductor 3 is not particularly limited, as its example, can enumerate at ambient temperature, under atmospheric pressure, dipping has formed the method for the electrode matrix 8 of described porous metal oxide semiconductor 3 in being dissolved with the solution of dyestuff.Dip time is preferably suitably regulated according to the concentration of used semiconductor, dyestuff, solvent types, dyestuff, so that be formed uniformly the monomolecular film of sensitizing dyestuff 4 on semiconductor layer 3.And, in order to adsorb effectively, flood under the preferred heating.
[dielectric substrate]
For dielectric substrate 5, in the present invention, dielectric substrate 5 contains the compound of representing with following general formula (1) as redox couple.
[changing 2]
(in the formula (1), M +Be the organic or inorganic cation, A is the ring type compound of aromatic series, non-aromatic, heteroaromatic or assorted non-aromatic.)
As the concrete example of A, can enumerate and have C 6～C 12Aryl, C 1～C 12Heteroaryl, C 1～C 12Heterocyclic radical, C 6～C 30The compound of alkylaryl.
Described aryl is meant aromatic series monocycle or polycyclic compound, for example can preferably use phenyl, naphthyl etc.
Described heteroaryl is meant, has at least one N, O, heteroatomic aromatic series monocycle or the polycyclic compound of S etc. and so on can preferably use for example furyl, thienyl, pyridine radicals, quinolyl, isoquinolyl, indyl, isoindolyl, triazolyl, pyrrole radicals, tetrazole radical, imidazole radicals, pyrazolyl, _ azoles base, thiazolyl, thiadiazolyl group, benzofuranyl, benzothienyl, carbazyl, benzo _ azoles base, pyrimidine radicals, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthridinyl, different _ the azoles base, isothiazolyl, purine radicals, quinazolyl etc.
Described heterocyclic radical is meant the heteroatomic non-aromatic ring type compound with at least one N, O, S etc. and so on, can preferably use the saturated derivatives or the undersaturated derivative of part of the heteroaryl shown in for example above-mentioned.As object lesson, can enumerate pyrrolidinyl, tetrahydrofuran base, morpholinyl, thio-morpholinyl, piperidyl, piperazinyl, thiazolyl, isothiazolyl, imidazole radicals.
In addition, these compounds also can have 0～3 substituting group.As substituting group, can enumerate H, OH, F, Cl, Br, I, CF 3, CN, NO 2, SO 3H, C 1～C 30Straight chain type, branched chain type or part halo type alkyl, C 3～C 12Cycloalkyl, C 1～C 12Heterocyclic radical, C 2～C 8Alkenyl, C 6～C 12Aryl, C 6～C 30Alkylaryl, C 1～C 12Heteroaryl, C 6～C 30Miscellaneous alkyl aryl, C 6～C 30Alkyl heterocyclic, C 1～C 48Alkyl, C 1～C 6Alkoxyl, C 1～C 6Hydroxy alkyl, Ph 2P (O)-, Ph 2P-, Me 2P (O)-, Me 2P-, Ph 2P (S)-, Me 2P (S)-, Ph 3P=N-, Me 3P=N-, C 6H 5C nH 2n-, C nH 2n+1C 6H 4-, C mH 2m+1C 6H 4C nH 2n-, CH 2=CHC nH 2n-, CH 2=CHC 6H 5-, CH 2=CHC 6H 4C nH 2n+1-, CH 2=CHC nH 2nC 6H 4-, CF 3-, C nF 2n+1-, HC nF 2n+1-, CF 3O-, C nF 2n+1O-, HC nF 2n+1O-, CF 3S-, HCF 3S-, HC nF 2n+1S-, ClC nF 2n+1-, ClC nF 2n+1O-, ClC nF 2n+1S-, BrC nF 2n+1-, BrC nF 2n+1O-, BrC nF 2n+1S-, IC nF 2n+1-, IC nF 2n+1O-, IC nF 2n+1S-, CH 2=CHC nF 2n+1-, CH 2=CHC nF 2n+1O-, CH 2=CHC nF 2n+1S-, CH 3OC nF 2n+1-, CH 3OC nF 2n+1O-, CH 3OC nF 2n+1S-, C 2H 5OC nF 2n+1-, C 2H 5OC nF 2n+1O-, C 2H 5OC nF 2n+1S-, CF 3CH 2-, CF 3CH 2O-, (CF 3) 2CH-, (CF 3) 2CHO-, CHF 2-, CHF 2O-, CHF 2S-, CClF 2-, CClF 2O-, CClF 2S-, CCl 2FO-, CCl 2FS-, CCl 3-, CCl 3O-, C 6Cl 5-, C 6Cl 5O-, FSO 2CF 2-, ClSO 2(CF 2) n-,-SO 3(CF 2) n-,-CO 2(CF 2) n-, FSO 2N (-)SO 2(CF 2) n-, CF 3SO 2N (-)SO 2(CF 2) n-, C nF 2n+1SO 2N (-)SO 2(CF 2) n-, FSO 2(CF 2) n-, ClSO 2(CF 2) n-, C nF 2n+1SO 2N (-)(CF 2) n-etc.(Ph represents phenyl, and Me represents methyl, and m, n represent 1 to 48 integer respectively.Below identical).
In these compounds, also can contain-O-in addition, ,=N-,-S-,=P-,=(P=O)-,-SO-,-SO 2-wait assorted base.
In addition, preferred above-mentioned especially central thiadiazole compound, pyridine compounds and their, phenylene compounds of described A.
These compounds also can have 1～3 substituting group, for example can enumerate OH, F, Cl, Br, I, CF 3, CN, NO 2, SO 3H, SO 3-, C 1～C 6Alkoxyl, C 1～C 6Hydroxy alkyl, C 1～C 12Straight chain type or branch chain type alkyl, C 6～C 12Aryl, C nF 2n+1-, Ph 2P (O)-, Ph 2P-, Me 2P (O)-, Me 2P-, Ph 2P (S)-, Me 2P (S)-, Ph 3P=N-, Me 3P=N-, C 6H 5C nH 2n-, C nH 2n+1C 6H 4-, C mH 2m+1C 6H 4C nH 2n-, CH 2=CHC nH 2n-, CH 2=CHC 6H 5-, CH 2=CHC 6H 4C nH 2n+1-, CH 2=CHC nH 2nC 6H 4-etc., wherein, especially preferably have substituent compound with following any one expression of general formula.
[changing 3]
Figure A20071011022100121
As the concrete example of the M in the described general formula (1), can enumerate C with positive charge 1～C 12Heteroaryl, C 1～C 12Heterocyclyl compounds.
These compounds also can have 1～3 substituting group, can enumerate for example OH, F, Cl, Br, I, CF 3, CN, NO 2, SO 3H, SO 3-, C 1～C 6Alkoxyl, C 1～C 6Hydroxy alkyl, C 1～C 12Straight chain type or branch chain type alkyl, C 6～C 12Aryl, C nF 2n+1-, Ph 2P (O)-, Ph 2P-, Me 2P (O)-, Me 2P-, Ph 2P (S)-, Me 2P (S)-, Ph 3P=N-, Me 3P=N-, C 6H 5C nH 2n-, C nH 2n+1C 6H 4-, C mH 2m+1C 6H 4C nH 2n-, CH 2=CHC nH 2n-, CH 2=CHC 6H 5-, CH 2=CHC 6H 4C nH 2n+1-, CH 2=CHC nH 2nC 6H 4-etc.
In addition, as the concrete example of the M in the described general formula (1), can enumerate H +, Li +, K +, Na +Deng inorganic cation, with the organic cation of any one expression of following general formula.
[changing 4]
Figure A20071011022100122
R 1～R 15Represent C respectively 1～C 20Straight chain type or branch chain type alkyl, C 3～C 12Cycloalkyl, C 1～C 12Heterocyclic radical, C 2～C 20Alkenyl, C 2～C 20Alkynyl, C 6～C 12Aryl, C 6～C 20Alkylaryl, C 1～C 12Heteroaryl, R 1～R 4, R 5～R 8, R 9～R 11, R 12～R 15Respectively can be identical, also can be different.
In addition, R 1～R 15Also can have 1～3 substituting group respectively, can enumerate for example OH, F, Cl, Br, I, CF 3, CN, NO 2, SO 3H, SO 3-, C 1～C 6Alkoxyl, C 1～C 6Hydroxy alkyl, C 1～C 12Straight chain type or branch chain type alkyl, C 6～C 12Aryl, C nF 2n+1-, C 6H 5C nH 2n-, C nH 2n+1C 6H 4-, C mH 2m+1C 6H 4C nH 2n-, CH 2=CHC nH 2n-, CH 2=CHC 6H 5-, CH 2=CHC 6H 4C nH 2n+1-, CH 2=CHC nH 2nC 6H 4-etc.
In addition, M +Having in the N position in the middle of preferred especially use is above-mentioned linked C 1～C 12The imidazoles of the level Four nitrogen-atoms of straight chain type or branch chain type alkyl _ compound cation, has separately independently C 1～C 12The tetraalkyl ammonium compound cation of straight chain type or branch chain type alkyl.
As the solvent of the described redox couple of dissolving, so long as can dissolved oxygen the right compound of reduction, just be not particularly limited, can from non-aqueous organic solvent, normal temperature fuse salt, water or protic organic solvent etc., at random select.
For example, can enumerate nitrile compounds such as acetonitrile, methoxyacetonitrile, valeronitrile, 3-methoxypropionitrile as organic solvent; Lactone compounds such as γ-butyl caprolactone or valerolactone; Carbonate products such as ethylene carbonate or propylene carbonate; Ethers such as two _ alkane or Anaesthetie Ether, ethylene glycol bisthioglycolate alkyl ether; Alcohols such as methyl alcohol, ethanol; And dimethyl formamide or imidazoles etc., wherein can preferably use acetonitrile, valeronitrile, 3-methoxypropionitrile, propylene carbonate etc.
In addition, as described solvent, also can use ionic liquid, i.e. fuse salt.As ionic liquid, so long as at " Inorg.Chem " 1996,35, p1168-1178, " Electrochemistry " 2002,2, p130-136, the flat 9-507334 communique of special table, spy open in the flat 8-259543 communique etc. in disclosed known battery or the photo-electric conversion element etc., general operable liquid, just be not particularly limited the preferred salt that uses with the fusing point that is lower than room temperature (25 ℃); Though or have a fusing point that is higher than room temperature, yet by other fuse salt or the additive beyond the fuse salt and the salt of aqueousization at room temperature of dissolving.And they can distinguish use separately, also can mix two or more uses.
Specifically, cation as fuse salt, preferred ammonium, imidazoles _, _ azoles _, thiazole _, _ diazole _, triazole _, pyrrolidines _, pyridine _, piperidines _, pyrazoles _, pyrimidine _, pyrazine _, triazine _, _, sulfonium, carbazole _, indoles _ and their derivative, preferred especially ammonium, imidazoles _, pyridine _, piperidines _, pyrazoles _, sulfonium.
In addition, as the anion of fuse salt, can enumerate AlCl 4 -, Al 2Cl 7 -Deng metal chloride, PF 6 -, BF 4 -, CF 3SO 3 -, N (FSO 2) 2 -, N (CF 3SO 2) 2 -, N (C 2F 5SO 2) 2 -, F (HF) n -, CF 3COO -Etc. fluorine-containing thing, NO 3 -, CH 3COO -, C 6H 11COO -, CH 3OSO 3 -, CH 3OS 2 -, CH 3SO 3 -, CH 3SO 2 -, (CH 3O) 2PO 2 -, SCN -Deng the nonfluorinated compound, halide such as iodine, bromine etc.
And certainly in being under the situation of liquid under the room temperature state, also mixed solvent ground does not use at redox couple.
The oxysome of described redox couple is not particularly limited with the mixing ratio of going back substance, preferably represents oxysome/go back substance=0.001～10 with mol ratio, and more preferably 0.01～1.In addition, the concentration of the redox couple in the dielectric substrate is generally 0.05～10mol/L, more preferably 0.1～5mol/L.
In described dielectric substrate 5, can also add lithium salts or imidazoles _ salt, quaternary ammonium salt etc., as thiocyanic acid salts such as alkali such as the tert .-butylpyridine of additive, positive methylimidazole or guanidine thiocyanates as supporting electrolyte.These additives can add with the degree of the characteristic of not damaging dielectric substrate.In addition, by adding suitable gelating agent, also can be physically or chemically gelation.
[counter electrode]
Counter electrode 9 adopts the structure that is formed with catalyst layer 6 on the surface of electrode base material 7.Therefore this electrode base material 7 preferably has conductivity at surface portion owing to be used as the supporting mass of catalyst layer 6 collector body of holding concurrently.
As this kind material, can preferably use the metal or metal oxide, material with carbon element or the electroconductive polymer etc. that for example have conductivity.As metal, can enumerate for example platinum, gold, silver, ruthenium, copper, aluminium, nickel, cobalt, chromium, iron, molybdenum, titanium, tantalum and their alloy etc.As material with carbon element, be not particularly limited, can enumerate for example graphite (Graphite), carbon black, vitreous carbon, carbon nano-tube, fullerene etc.In addition, under the situation of having used metal oxides such as FTO, ITO, indium oxide, zinc oxide, antimony oxide,, therefore can increase the incident light quantity in sensitizing dyestuff layer 4 owing to be transparent or semitransparent.
In addition, electrolyte of the present invention is owing to compare with iodine class electrolyte in the past, low to corrosion of metal, therefore metal substrate is being used under the situation of electrode base material 7, dielectric substrate 5 was contacted with electrode base material 7, also it can not corroded basically, the long-term reliability of element compared with the past improves, and, be preferred therefore by using the high metal of conductivity, the particularly performance in the large tracts of land element to improve.
And, if to the surface treatment of this electrode base material 7 of major general for having conductivity, then also can use for example insulator such as glass or plastics.As making this kind insulator keep the processing method of conductivity, can enumerate and utilize described conductive material the part of this insulating properties material surface or the method that covers comprehensively; For example using under the situation of metal, can enumerate vapor phase methods such as solwution method such as plating or electrolysis and sputter, vacuum evaporation, under the situation of using metal oxide, can use sol-gal process etc.In addition, can also enumerate the method for one or more and the insulating properties material mixing etc. of the powder that uses described conductive material etc.
In addition, used at base material 7 under the situation of insulating properties material as counter electrode 9, by the high catalyst layer of conductivity 6 is set on this base material 7, this catalyst layer 6 just can play the effect of collector body and catalyst two aspects separately, can be used as counter electrode 9 and uses.
In addition because therefore the shape of electrode base material 7 can be not particularly limited according to the change of shape of the photo-electric conversion element 10 that uses as catalyst electrode, no matter be made as tabular, still can with the shape of film like bending.In addition, electrode base material 7 no matter be transparent or opaque can, yet in order to increase the incident light quantity in sensitizing dyestuff layer 4, in addition can be according to circumstances different and improve design so preferably clear or translucent.
As electrode base material 7, in general use glass, the PET that has the ITO film that has the FTO tunicle, the PEN film that has the ITO film, yet because conductivity is different because of used material, therefore the thickness for conductive layer is not particularly limited.For example, if having the glass of FTO tunicle, then be 0.01 μ m～5 μ m, preferred 0.1 μ m～1 μ m.
In addition, required conductivity is different because of the area of used electrode, requires large-area electrode, and in general low resistance then is 100 Ω/below the, preferred 10 Ω/below the, more preferably 5 Ω/below the.
The thickness of electrode base material 7 because of the shape or the service condition of photo-electric conversion element 10 are different, therefore is not particularly limited because as mentioned above, in general is about 1 μ m～1cm.
As catalyst layer 6, so long as have the electrode characteristic that can carry out the oxysome of the redox couple in the electrolyte is reduced to the reduction reaction of substance apace, do not have particular determination, can use be coated with chlorination platinic acid and heat treatment material; Evaporation the platinum catalyst electrode of platinum; The material with carbon element of activated carbon, vitreous carbon, carbon nano-tube and so on; Inorganic sulfide compounds such as cobalt sulfide; The electroconductive polymers of polythiophene, polypyrrole, polyaniline etc. etc. wherein, preferably use the electroconductive polymer catalyst.
As the preferred concrete example of the monomer that constitutes the electroconductive polymer catalyst, can enumerate thiophene compound with following general formula (2) expression.
[changing 5]
Figure A20071011022100161
(in the formula (2), R 16, R 17Represent independently respectively hydrogen atom, carbon number be 1～8 alkyl or alkoxyl, carbon number be 6～12 aryl, cyano group, thiocyanogen, halogen radical, nitro, amino, carboxyl, sulfo group or _ base, R 16With R 17Also can link and form ring.)
Wherein, can preferably use thiophene, four decylthiophene, isothianaphthene, 3-phenyl thiophene, 3,4-second dioxy support thiophene and derivative thereof etc., can preferably use 3 especially, 4-second dioxy support thiophene, hydroxymethyl-3,4-second dioxy support thiophene, amino methyl-3,4-second dioxy support thiophene etc.And, also can use the thiophene compound more than a kind or 2 kinds to form electroconductive polymer catalyst layer 6.
The monomer that uses in order to form electroconductive polymer catalyst layer 6 be preferably formed polymerization the conductivity of film 10 -9The material that S/cm is above.
In addition, in electroconductive polymer catalyst layer 6,, preferably add dopant in order to improve conductivity.As this dopant, can use material known.
As the concrete example of dopant, can enumerate halide anions such as iodine, bromine, chlorine; Halide anions such as phosphorus hexafluoride, arsenic hexafluoride, antimony hexafluoride, tetrafluoride boron, perchloric acid; Alkyl such as methanesulfonic acid, dodecyl sodium sulfonate replaces ring-type sulfonic acid anions such as organic sulfonic acid anion, camphorsulfonic acid; Alkyl such as benzene sulfonic acid, p-methyl benzenesulfonic acid, DBSA, benzenedisulfonic acid replace or do not have the benzene list or the disulfonic acid anion of replacement; 2-naphthalene sulfonic acids, 1,7-naphthalenedisulfonic acid etc. have replaced the alkyl replacement of 1～3 sulfonic naphthalene sulfonic acids or have not had the anion of replacement; The alkyl of rylnthracene sulfonin, anthraquinone sulfonic acid, alkyl biphenyl base sulfonic acid, xenyl disulfonic acid etc. replaces or does not have the xenyl azochlorosulfonate acid ion of replacement; The macromolecule sulfonic acid anion of polystyrolsulfon acid, naphthalene sulfonic acids formalin condensation product etc.; Replace or do not have aromatic sulphonic acid anion, salicyl salicylate (salsalate) boron (born bis-salicylate), two catechu phenolic acid boron boron compound anion such as (boron bis-catecholate) of replacement; Perhaps heteropolyacid anions such as molybdophosphate, tungstophosphoric acid, tungsten phosphoric acid, acid imide acid etc.Dopant can use a kind of, also can be used in combination two or more.
In order to suppress the disengaging of dopant, to compare with inorganic anion, more preferably organic anion preferably is difficult to cause the material of thermal decomposition.In addition, compare with the dopant of macromolecular compound, if the dopant of low molecular compound, then because the conductivity raising behind the formation film is therefore preferred.Specifically, can enumerate p-methyl benzenesulfonic acid, DBSA, naphthalene sulfonic acids etc.
The use amount of the dopant in the electroconductive polymer catalyst layer because optimum value is different because of used dopant species, therefore is not particularly limited preferred 5～60 quality %, more preferably 10～45 quality %.
When forming the electroconductive polymer catalyst layer, can make the monomer coexistence of this kind dopant and electroconductive polymer.
Described electroconductive polymer catalyst layer 6 is formed on the electrode base material 7.The formation method is not particularly limited, and for example can enumerate by electroconductive polymer being become the method that molten condition or lysed solution come film forming.
In addition,, therefore can enumerate under solution that makes the monomer that contains electroconductive polymer and electrode base material 7 state of contact, with the monomer method of oxidation polymerization chemically or electrochemically owing to preferably have the porous state of bigger surface area.
In addition, can also be following method, that is, and with the electroconductive polymer powder-processed be pasty state or emulsion form or contain Polymer Solution and the mixture form of adhesive after, utilize silk screen printing, spraying, hairbrush coating etc. on this electrode base material 7, to form.
As the formation method of described electroconductive polymer catalyst layer 6, at above-mentioned central preferred electrolysis polymerization method or chemical polymerization, preferred especially chemical polymerization.Chemical polymerization is to use the method for oxidant with polymerization single polymerization monomer oxidation polymerization.On the other hand, the electrolysis polymerization method is the method that forms the film of electroconductive polymer by carry out electrolytic oxidation in containing the solution of polymerization single polymerization monomer on the electrode of metal etc.
As oxidant used in the chemical polymerization, halide such as iodine, bromine, bromine iodide, chlorine dioxide, acid iodide, periodic acid, hypochlorous acid are arranged; Metal halides such as antimony pentafluoride, phosphorus pentachloride, phosphorus pentafluoride, aluminium chloride, molybdenum chloride; Permanganate, bichromate, chromic anhybride, molysite, the contour valence slaine of mantoquita; Bronsted acids such as sulfuric acid, nitric acid, trifluoromethane sulfonic acid; Oxide such as sulfur trioxide, nitrogen dioxide; Peroxy acid or its salt such as hydrogen peroxide, ammonium persulfate, sodium perborate; Perhaps heteropoly acid such as molybdophosphate, tungstophosphoric acid, tungsten phosphoric acid or its salt etc. can use at least a of them.
Though described chemical polymerization is towards production in enormous quantities, yet when in the solution that contains the aromatic compound monomer, making it to do the time spent with oxidant, the macromolecule of gained will become particle shape or block form, is difficult to embody required porousness, is shaped to electrode shape.So, preferably in electrode base material 7 being impregnated in any the solution that contains aromatic compound monomer or oxidant, or after on them, being coated with this solution, next impregnated in the solution that has dissolved another kind of composition or with its coating etc., carry out polymerization on described electrode base material 7 surfaces, form electroconductive polymer.
Perhaps, can be at the additive that in the solution that has mixed monomer and polymerization initiator, add to reduce polymerization speed, at room temperature can not cause become membranization under the condition of polymerization after, make the porous, electrically conductive polymeric membrane by adding thermal response.Be not particularly limited for the method that becomes membranization, can enumerate spin coating method, casting, squeegee extrusion method (squeegeemethod), silk screen print method etc. as an example.
For the additive that polymerization speed is reduced, according to known document " SyntheticMetals " 66, (1994) 263, because at polymerization initiator is high valence slaine, for example under the situation of Fe (III) salt, therefore the oxidizing potential of Fe (III) salt can change with pH, by adding the alkali polymerization speed that just can slow down.As the example of alkali, can enumerate imidazoles or methyl-sulfoxide etc.
Described monomer and polymerization initiator, additive dissolving, the solvent that mixes are not dissolved the solvent of electrode base material 7 and polymer so long as dissolve used compound, just be not particularly limited, for example can enumerate alcohols such as methyl alcohol, ethanol, propyl alcohol, n-butanol.
The mixing ratio of described monomer and polymerization initiator, additive changes because of used compound, the purpose degree of polymerization, polymerization speed, represent with mol ratio, if monomer: polymerization initiator, then preferably from 1: 0.3 to 1: 10, if polymerization initiator: additive, then preferably from 1: 0.05 to 1: 4.
In addition, heating condition after being coated with described mixed solution under the situation of heated polymerizable is different because of the kind of used monomer, polymerization catalyst, additive and their mixing ratio, concentration, coating film thickness etc., as preferred condition, when in air, heating, between preferred 25 ℃ to 120 ℃ of the heating-up temperature, between preferred 1 minute to 12 hours of heating time.
In addition, also can adopt following method, promptly, at electroconductive polymer particle dispersion that uses making in addition or pastel etc., at electrode base material 7 or after having the electrode base material surface formation electroconductive polymer film of conducting film, carry out described chemical polymerization, the electroconductive polymer particle is grown up.
The preferred 5nm of thickness of the catalyst layer 6 in the counter electrode 9～5 μ m, preferred especially 50nm～2 μ m.
After having prepared as above each the inscape material shown in the explanation, utilize in the past that known method installs metal-oxide semiconductor (MOS) electrode and catalyst electrode, their folders are faced mutually every electrolyte, make photo-electric conversion element 10.
[embodiment]
Below, will be described in more detail the present invention based on embodiment, yet the present invention is not subjected to their any qualification.
＜embodiment 1 〉
[the semi-conductive making of porous metal oxide]
On the transparent base of making by glass 1, utilize vacuum evaporation to form SnO by the fluorine that mixed 2The nesa coating that constitutes on nesa coating 2, utilizes following method to form porous metal oxide semiconductor layer 3.
As the electrode matrix 8 that on transparent base 1, has formed nesa coating 2, use FTO glass (Nippon Sheet Glass Co Ltd's system), thickness about its surface utilizes silk screen print method with 6 μ m, area about 5mm * 10mm is on the surface of nesa coating 2 sides, (catalyst changes into Co., Ltd.'s system to print commercially available titanium oxide pastel, trade name: TSP-18NR, particle size 20nm), then utilize silk screen print method with equal area thereon, (catalyst changes into Co., Ltd.'s system with the commercially available titanium oxide pastel of the coating of the thickness about 4 μ m, trade name: TSP-400C, particle size 400nm), under 500 ℃, sintering is 30 minutes in the atmosphere.Consequently, having obtained thickness is oxidation titanium film (porous metal oxide semiconductor film 3) about 10 μ m.
[absorption of sensitizing dyestuff]
As sensitizing dyestuff 4, two (4-carboxyl-4 '-tetrabutylammonium carboxyl-2,2 '-bipyridine) the diisothiocyanic acid salt ruthenium complexs (Solaronix corporate system) that are generally known as N719dye have been used.Described porous titanium oxide semi-conducting electrode be impregnated in the ethanol solution that dye strength is 0.4mmol/L, under the shading condition, left standstill an evening.Thereafter, air-dry by carrying out after cleaning unnecessary dyestuff with absolute ethyl alcohol, made the semi-conducting electrode of solar cell.
[modulation of electrolyte]
Then, modulated the electrolyte that constitutes dielectric substrate 5.As solvent, use the 3-methoxypropionitrile, by to two (5-methyl isophthalic acid, 3,4-thiadiazoles) the 2-disulphide that wherein dissolve 0.05mol/L, 5-methyl-2-sulfydryl-1,3 of 0.6mol/L, 4-thiadiazoles: tetrabutylammonium salt and making.What illustrated is, described compound has used commercially available material, or by commercially available material according to known method or following shown in synthesis example and synthetic material.
[making of counter electrode (to electrode)]
As counter electrode 9, used poly-(3,4-second dioxy support thiophene) (following note is made PEDOT) to electrode.Use glass (the Asahi Glass Co., Ltd's system that has the FTO tunicle as electrode base material 7,～10 Ω/), in organic solvent, carried out on the electrode base material 7 of ultrasonic waves for cleaning, utilize spin coating method to be coated with 3,4-second dioxy support thiophene, three-p-methyl benzenesulfonic acid iron (III), methyl-sulfoxide are dissolved in reaction solution in the n-butanol with 1: 8: 1 weight ratio.The rotating condition that rotation applies is to carry out with 30 seconds condition of rotation under 2000rpm, 3 in the solution, and the concentration of 4-second dioxy support thiophene is 0.48M.Next, the electrode base board that has been coated with solution is put into the thermostat that remains 110 ℃, after the polymerization,, making counter electrode 9 by cleaning with methyl alcohol by being heated 5 minutes.The thickness of the PEDOT film of made is about 0.3 μ m respectively.
[assembling of solar battery cell battery]
After the electricity consumption brill has been drilled with the electrolyte injecting hole of 2 1mm φ in position on the counter electrode of making as described above 9, between the electrode matrix 8 (the effect utmost point) and counter electrode 9 made as described above, (HIMILAN 1652 for the clamping sheet thermoplastic, the POLYCHEMICAL of Mitsui Du Pont corporate system, thickness 30 μ m), with two electrode engagement, described electrode matrix 8 has the oxidation peptide film on the transparent base 1 with nesa coating 2 by carrying out thermo-compressed.Then, after the electrolyte that utilizes capillarity to make as previously mentioned from electrolyte injecting hole is impregnated between two electrodes, on electrolyte injecting hole, place the thick glass plate of 1mm, coating UV sealant (the preproduction of ス リ one ボ Application De corporate system thereon, 31X-101), by using 100mW/cm 230 seconds UV light of intensity irradiation, implement sealing, made solar cell.
＜embodiment 2 〉
Except solvent as dielectric substrate 5, used beyond two (trifyl) acid imides of 1-methyl-3-ethyl imidazol(e) _ salt, made solar cell in the same manner with embodiment 1.
＜comparative example 1 〉
Except as dielectric substrate 5, use the 3-methoxypropionitrile as solvent, use beyond the solution of the 1-of the iodine that has wherein dissolved 0.05mol/L, 0.6mol/L methyl-3-propyl imidazole _ salt iodide, made solar cell in the same manner with embodiment 1.
＜comparative example 2 〉
Except as dielectric substrate 5; use 1-methyl-3-ethyl imidazol(e) _ two (trifyl) acid imide as solvent; use has been made solar cell in the same manner with embodiment 1 beyond the solution of the 1-of the iodine that has wherein dissolved 0.05mol/L, 0.6mol/L methyl-3-propyl imidazole _ salt iodide.
＜comparative example 3 〉
Except as counter electrode 9, used utilize sputtering method on the ITO conductive glass evaporation Pt Pt to electrode (Diomatech system) in addition, made solar cell in the same manner with comparative example 1, described ITO conductive glass obtains by sputtering method.
＜comparative example 4 〉
Except as counter electrode 9, used utilize sputtering method on the ITO conductive glass evaporation Pt Pt to electrode (Diomatech system) in addition, made solar cell in the same manner with embodiment 1, described ITO conductive glass obtains by sputtering method.
[photoelectric conversion efficiency of solar cell, durability evaluation]
Utilize following method to implement the evaluation of the solar cell of made.In performance evaluation, be the solar simulator XES-502S (Northwest science machinery Co., Ltd. system) that utilizes the xenon lamp possessed the AM filter, adjusted the spectrum of AM1.5G after, at 100mW/cm 2Illuminate condition under, estimated the load characteristic (I-V characteristic) of potentiostat (potentiostat).The evaluation of estimate of solar cell can be enumerated open circuit voltage Voc (V), short-circuit current density Jsc (mA/cm 2), form factor FF (-), efficiency eta (%), yet the whether good of final Solar cell performance is to estimate with the size of efficiency eta.Its result is shown in the table 1.
[table 1]
Voc [V] Jsc [mA/cm 2] FF η [％]
Embodiment 1 0.637 10.15 0.677 4.38
Embodiment 2 0.557 3.74 0.666 1.39
Comparative example 1 0.694 11.68 0.679 5.50
Comparative example 2 0.574 4.65 0.652 1.74
Comparative example 3 0.692 11.50 0.682 5.43
Comparative example 4 0.634 10.08 0.542 3.46
From table 1, can be clear that, no matter be under which kind of situation of organic solvent class or ionic liquid class, used the element of the redox couple of the present invention resulting opto-electronic conversion performance of element of iodine class redox couple that all under the simulated solar irradiation illuminate condition, demonstrated utilization use in the past.If the cobalt complex redox couple shown in the non-patent literature 1～3, then the element function under the simulated solar irradiation illuminate condition is about half of iodine class, and redox couple of the present invention is more good.In addition, described cobalt complex is owing to causing that easily the inversion electron from accept electronics as the FTO conductive glass surface of effect electrode substrate moves, therefore between FTO conductive glass and porous semiconductor layer, in order to prevent contacting of dielectric substrate and conductive glass surface, the semiconductor layer of the densification of titanium oxide etc. need be set, yet redox couple of the present invention is because reactive low on the FTO conductive glass, even therefore compacted zone is not set, also can demonstrate aforesaid high element function, the practicality height.
In addition, used the embodiment 1 of PEDOT electrode to compare with the comparative example 4 that has used the Pt electrode as counter electrode as counter electrode, element function is higher, and particularly the value of FF is good.This be because, for the catalytic activity of redox couple of the present invention, compare with Pt, the catalytic activity of PEDOT is higher, this also can be according to utilizing the resulting surface reaction Resistance Analysis of impedance measuring to confirm.Thus, with electroconductive polymer catalyst such as redox couple of the present invention and PEDOT, can make the photo-electric conversion element that demonstrates high-photoelectric transformation efficiency by also.In addition, the element of made was stable during 2 months under room temperature, opening-wide state.
[permeability evaluation]
Be produced on two (5-methyl isophthalic acid, 3,4-thiadiazolyl group) the 2-disulphide that dissolved 5mmol/L in the 3-methoxypropionitrile, 5-methyl-2-sulfydryl-1,3 of 60mmol/L, 4-thiadiazoles: the solution of tetrabutylammonium salt (embodiment 3); In the 3-methoxypropionitrile, dissolved the solution (comparative example 5) of the iodine of 5mmol/L, the 1-methyl of 60mmol/L-3-propyl imidazole drone iodide, utilize ultra-violet and visible spectrophotometer (UV-2100, (strain) Shimadzu Seisakusho Ltd. system) measures absorption spectrum, compare.Its result is shown among Fig. 2.
According to Fig. 2 as can be known, electrolyte of the present invention is compared with iodine class electrolyte in the past, and the visible absorption zone is few.Therefore in addition,,, be encased under the situation of solar cell, even (under 0.5～2mol/L), in electrolyte, also can't see paintedly, can be used as transparent dielectric substrate and use at the working concentration of practical application owing to compare for a short time with iodine for absorptivity.
[corrosivity evaluation]
Surface at commercially available glass substrate, utilize silk screen print method, with the thickness about 10 μ m, 1mm width printing silver coating pastel (capital of a country ェ レ ッ Network ス Co., Ltd. system, trade name: DD-1050), by heating 30 minutes down, on glass substrate, formed silver-colored line at 500 ℃.Be coated with employed electrolyte and iodine class electrolyte in embodiment 2, the comparative example 2 on the part on silver-colored line respectively, under 25 ℃, left standstill 8 hours.Thereafter, wipe electrolyte, compared the corrosion of silver-colored line and the resistance between silver-colored line end, its result is, employed iodine class electrolyte can be seen the corrosion of silver-colored line and the rising of resistance in the comparative example 2, yet employed electrolyte of the present invention is not seen outward appearance and changes in resistance among the embodiment 2.
As mentioned above, consider from the viewpoint of element function, corrosivity, the transparency, redox contrast of the present invention iodine class redox couple in the past is more good, redox couple of the application of the invention and organic conductive macromolecule be to electrode, can be provided in performance, durability, cost, the high photo-electric conversion element of practicality that the design aspect is good.
＜synthesis example of the present invention 〉
Below will provide the synthesis example of redox couple of the present invention, yet synthetic method is not limited by it, can use material known, synthetic method to make.
[redox couple: go back the synthetic of substance]
With 5-methyl-2-sulfydryl-1,3,4-thiadiazoles 1 molar equivalent and potash 0.5 molar equivalent are dissolved in the methyl alcohol, carry out the ultrasonic wave bath and handle (bathtreatment) when stirring, till the potash dissolving disappears (about 2.5 hours)., use filter paper remove solid content, utilize Rotary Evaporators that the solvent distillation is removed, after cleaning the white solid content that is generated, by carrying out vacuumize, synthesized 5-methyl-2-sulfydryl-1,3,4-thiadiazoles sylvite with carrene thereafter.Described reaction yield is 70%.
Next, the compound that the is synthesized (concentration: 1M) of dissolving 1 molar equivalent in acetone, in this solution, be blended in the solution (concentration: 1M), after having carried out ultrasonic wave bath processing in about 1 hour, in freezer, place an evening of the perchloric acid tetrabutylammonium that has dissolved 1 molar equivalent in the acetone., utilize remove by filter solid content, the solvent distillation is removed thereafter.By the white solid vacuumize that will be generated 12 hours, synthesized 5-methyl-2-sulfydryl-1,3 of going back the substance compound, 4-thiadiazoles: 4-butyl ammonium as redox couple.Reaction yield is 95%.
[redox couple: oxysome synthetic]
At the 5-methyl-2-sulfydryl-1,3 that will utilize described method to make, after 4-thiadiazoles sylvite 1 molar equivalent is dissolved in the water, add iodine 0.5 molar equivalent, agitating solution dissolves until iodine., utilize filter collect the white precipitate that generated, after water cleans,, obtained two (5-methyl isophthalic acid, 3,4-thiadiazolyl group) 2-disulphide as the oxysome compound of redox couple by carrying out vacuumize in 24 hours thereafter.Reaction yield is 30%.What illustrated is that each material shown in described each synthesis example uses commercially available material.
Photo-electric conversion element of the present invention is suitable as and can uses at the photo-electric conversion element that indoor and outdoor is used, and in addition, by utilizing electrolytical characteristic of the present invention, can be used for particularly requiring the civilian machine of design etc.In addition, not only can be used as the photo-electric conversion element utilization, can also be as utilizations such as optical sensors.

Claims (4)

1. a photo-electric conversion element is the photo-electric conversion element that possesses semi-conducting electrode, counter electrode, remains in the dielectric substrate between described the two poles of the earth, it is characterized in that, described dielectric substrate contains the compound of representing with following general formula (1) as redox couple,
Figure A2007101102210002C1
In the formula (1), M +Be the organic or inorganic cation, A is the ring type compound of aromatic series, non-aromatic, heteroaromatic or assorted non-aromatic.
2. photo-electric conversion element according to claim 1 is characterized in that, described ring type compound is be selected from thiadiazole compound, pyridine compounds and their and phenylene compounds at least a.
3. photo-electric conversion element according to claim 1 and 2 is characterized in that, described counter electrode contains the electroconductive polymer catalyst that has catalytic activity for described redox couple.
4. photo-electric conversion element according to claim 3 is characterized in that, described electroconductive polymer catalyst comprises 3, the polymer of 4-second dioxy support thiophene or derivatives thereof.
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CN101991610B (en) * 2009-08-13 2012-05-23 中国农业大学 Method for structuring hepatitis E infection model
CN103415505A (en) * 2011-03-10 2013-11-27 国立大学法人岐阜大学 Compound having heptamethine structure, sensitizing dye and photoelectric conversion element
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CN105304339A (en) * 2010-07-27 2016-02-03 岛根县 Dye-sensitized solar cell
CN105304339B (en) * 2010-07-27 2018-08-31 岛根县 Dye-sensitized solar cell
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