CN104584162A - Electrode substrate and dye-sensitized solar cell - Google Patents

Electrode substrate and dye-sensitized solar cell Download PDF

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Publication number
CN104584162A
CN104584162A CN201380043843.3A CN201380043843A CN104584162A CN 104584162 A CN104584162 A CN 104584162A CN 201380043843 A CN201380043843 A CN 201380043843A CN 104584162 A CN104584162 A CN 104584162A
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Prior art keywords
perforated membrane
electrode base
base board
electrode
alkoxyl
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时田大辅
安西纯一郎
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Sekisui Chemical Co Ltd
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Sekisui Chemical 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
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • 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
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

An electrode substrate is provided with a conductive substrate, a porous film that is formed on the conductive substrate, and a catalyst layer that is applied to the porous film.

Description

Electrode base board and dye-sensitized solar cell
Technical field
The present invention relates to and a kind ofly can be used as the electrode base board of the opposite electrode of dye-sensitized solar cell and employ the dye-sensitized solar cell of this electrode base board.
No. 2012-273719, the Japanese Patent Application that the application filed an application in Japan based on December 14th, 2012 and CLAIM OF PRIORITY, and quote its content at this.
Background technology
As dye-sensitized solar cell, there will be a known the system (non-patent literature 1) of so-called Graetzel type.If irradiate light to the sensitization pigment being adsorbed in the oxide semiconductor porous layer forming optoelectronic pole, then produce electronics.This electronics successively to pigment, oxide semiconductor porous layer, nesa coating, external circuit flowing, thus is derived in the form of electric current.On the other hand, the pigment discharging electronics is reduced by the redox couple in electrolyte, and oxidized redox couple is regenerated as Reduction Body by forming the catalyst layer of opposite electrode.
As the catalyst layer of the opposite electrode of existing formation dye-sensitized solar cell, widely use the platinum electrode (platinum film) be formed on substrate.As the formation method of platinum electrode, knownly on substrate, be coated with platinum acid chloride solution and carry out the methods such as heating treatment method, vacuum evaporation, sputtering.But, because platinum is expensive noble metal, therefore, use platinum electrode to there is the problem of the manufacturing cost increasing dye-sensitized solar cell.Also there are the following problems in addition: platinum is to I in the presence of moisture -the durability of ion (iodide ion) is insufficient.
In order to solve this problem, have studied the material of the raw catelyst layer replacing platinum electrode, such as, disclose the example (non-patent literature 2, patent documentation 1 ~ 2) opposite electrode using the electroconductive polymers such as polythiophene, polyaniline, polypyrrole as catalyst layer being applied to dye-sensitized solar cell.
But, use generating efficiency when having the catalyst layer of these electroconductive polymers and use significantly lower compared with the generating efficiency during catalyst layer that platinum electrode is formed.Its reason is, the conductivity of electroconductive polymer and the reducing power (I as catalyst 3 -→ I -reducing power) than the conductivity of platinum and reducing power low.
The reducing power of catalyst layer is determined according to " catalyst activity " × " specific area of catalyst layer ", and the catalyst activity of electroconductive polymer is lower than platinum.Therefore, when the catalyst layer be made up of electroconductive polymer has the specific area with platinum electrode same degree, compared with platinum electrode, the reducing power of the catalyst layer be made up of electroconductive polymer is poor.Therefore, also disclose and a kind ofly in by the catalyst layer that electroconductive polymer is formed, mix the material with carbon element such as carbon nano-tube or carbon particle to improve specific area and the conductivity of catalyst layer, thus improve the method (patent documentation 3 ~ 4) of the reducing power of catalyst layer.Such as, the formation of existing catalyst layer as shown in the schematic of Figure 1.The catalyst layer of Fig. 1 has the structure of the film of the electroconductive polymer 23 being formed with embedding material with carbon element 22 on conductive board 21.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-313317 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-317814 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2006-147411 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2011-14411 publication
Non-patent literature
Non-patent literature 1:Nature, the 353rd volume, the 737th page, 1991
Non-patent literature 2:Electrochemistry71, No.11 (2003) 944-946
Summary of the invention
Invent technical problem to be solved
But, even if when using the catalyst layer manufactured with the method for patent documentation 3 ~ 4, because the specific area of catalyst layer is insufficient, therefore, the reducing power of catalyst layer do not reach platinum electrode equal more than.In addition, in the catalyst layer of patent documentation 3 ~ 4, electroconductive polymer and described material with carbon element mix with mixed and disorderly state, therefore, structure (vesicularity) controlling of catalyst layer is low, therefore, worries that the reducing power of the catalyst layer of every batch is uneven or film-strength is uneven.In addition, in described catalyst layer, material with carbon element does not directly contact each other and via electroconductive polymer bonding, also there is the region that multiple material with carbon element does not directly contact with conductive board, and therefore, resistance increases, about conductivity, also not as good as platinum electrode.Therefore, the performance seeking to employ the electrode base board of the catalyst layer with electroconductive polymer improves and uses described electrode base board as the raising of the generating efficiency of the dye-sensitized solar cell of opposite electrode.
The present invention completes in view of the foregoing, and its problem is, provides a kind of and realizes the existing electrode base board and the dye-sensitized solar cell that are used as the equal above generating efficiency of the platinum electrode of the opposite electrode of dye-sensitized solar cell.
For solving the technical scheme of problem
(1) electrode base board, it has conductive board, the perforated membrane of film forming on described conductive board, the catalyst layer coated on described perforated membrane.
(2) electrode base board according to above-mentioned (1), wherein, the three-dimensional structure along described perforated membrane is coated with described catalyst layer.
(3) electrode base board according to above-mentioned (1) or (2), wherein, containing company's pore structure that multiple separate openings links in the perforated membrane being coated with described catalyst layer.
(4) electrode base board according to above-mentioned (3), wherein, in the perforated membrane being coated with described catalyst layer, the described number connecting pore structure is greater than the number of described separate openings.
(5) electrode base board according to any one of above-mentioned (1) ~ (4), wherein, described perforated membrane is made up of metal or metallic compound.
(6) electrode base board according to any one of above-mentioned (1) ~ (4), wherein, described perforated membrane is made up of material with carbon element.
(7) electrode base board according to any one of above-mentioned (1) ~ (6), wherein, described catalyst layer is made up of electroconductive polymer.
(8) electrode base board according to above-mentioned (7), wherein, described electroconductive polymer is the polymer of the thiophene compound shown in following general formula (1).
[chemical formula 1]
[in formula, R 1and R 2separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl, work as R 1and R 2during for described alkyl or alkoxyl, the terminal carbon of described alkyl or alkoxyl can bond together and form ring.]
(9) electrode base board according to above-mentioned (7), wherein, described electroconductive polymer is the polymer of the azole compounds shown in following general formula (2).
[chemical formula 2]
[in formula, R 3and R 4separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl.R 3and R 4during for described alkyl or alkoxyl, the carbon atom of described alkyl or alkoxyl end each other can bonding and form ring.]
(10) electrode base board according to above-mentioned (7), wherein, described electroconductive polymer is the polymer of the aniline compound shown in following general formula (3).
[chemical formula 3]
[in formula, R 5~ R 8separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl.R 5and R 6or R 7and R 8during for described alkyl or alkoxyl, the carbon atom of described alkyl or alkoxyl end each other can bonding and form ring.]
(11) electrode base board according to any one of above-mentioned (1) ~ (10), wherein, the surface of described conductive board connects with described perforated membrane.
(12) electrode base board according to any one of above-mentioned (7) ~ (11), wherein, described electroconductive polymer coats described perforated membrane by using described perforated membrane as the electrolysis polymerization method of work electrode.
(13) dye-sensitized solar cell, it possesses opposite electrode that the electrode base board according to any one of above-mentioned (1) ~ (12) forms, the optoelectronic pole of adsorpting pigment and electrolyte.
Invention effect
Electrode base board of the present invention is coated with the catalyst layers such as electroconductive polymer on the perforated membrane with larger specific area, therefore, has the larger specific area having given play to catalyst action.In addition, electrode base board of the present invention have following structure namely along have be coated with the structure of the catalyst layers such as electroconductive polymer compared with the three-dimensional structure of the perforated membrane of bigger serface time, there is the larger specific area having given play to catalyst action.Its result, can improve the reducing power of the catalyst determined according to " catalyst activity " × " specific area of catalyst layer ", and can improve the generating efficiency of the dye-sensitized solar cell using electrode base board of the present invention.
In addition, electrode base board of the present invention due to respectively evenly and reliably define the electrical contact portion of conductive board and perforated membrane and the electrical contact portion of the catalyst layer such as perforated membrane and electroconductive polymer coating, therefore, excellent electric conductivity.Its result, can improve the generating efficiency of the dye-sensitized solar cell using electrode base board of the present invention.
In addition, for electrode base board of the present invention, the three-dimensional structure of the perforated membrane of film forming on conductive board plays the effect of the support unit of the catalyst layer coatings such as electroconductive polymer, therefore, (compared with the film only formed by electroconductive polymer (catalyst layer)) compared with the past, structural strength improves.Its result, fabrication yield when using electrode base board of the present invention manufacture dye-sensitized solar cell can be improved, even and if be the environment of external force is applied to opposite electrode in the environment for use of described dye-sensitized solar cell, also can give excellent durability to described dye-sensitized solar cell.
Dye-sensitized solar cell of the present invention is owing to using electrode base board of the present invention, and therefore, generating efficiency is excellent, even and if also play excellent durability under the environment for use applying external force to opposite electrode.
Accompanying drawing explanation
Fig. 1 is the generalized section of existing opposite electrode.
Fig. 2 is the generalized section of the electrode base board (opposite electrode) of the first execution mode.
Fig. 3 is the generalized section of the dye-sensitized solar cell of the second execution mode.
Fig. 4 A is the SEM image on the surface of the opposite electrode observing embodiment 9.
Fig. 4 B is the SEM image on the surface of the perforated membrane observed before the surface of the opposite electrode of embodiment 9 coating PEDOT.
Fig. 4 C is the SEM image of the section of the opposite electrode observing embodiment 9.
Fig. 4 D is the enlarged image of the section of Fig. 4 C.
Fig. 5 A is the SEM image on the surface of the opposite electrode observing embodiment 10.
Fig. 5 B is the SEM image on the surface of the perforated membrane observed before the surface of the opposite electrode of embodiment 10 coating PEDOT.
Fig. 6 A is the SEM image on the surface of the opposite electrode observing embodiment 7.
Fig. 6 B is the SEM image on the surface of the perforated membrane observed before the surface of the opposite electrode of embodiment 7 coating PEDOT.
Fig. 7 A is the SEM image on the surface of the opposite electrode observing embodiment 8.
Fig. 7 B is the SEM image on the surface of the perforated membrane observed before the surface of the opposite electrode of embodiment 8 coating PEDOT.
Fig. 8 is the SEM image on the surface of the opposite electrode of observation and comparison example 6.
Fig. 9 is the SEM image on the surface of the opposite electrode of observation and comparison example 7.
Figure 10 is the SEM image on the surface of the opposite electrode of observation and comparison example 11.
Embodiment
Below, based on preferred embodiment, with reference to accompanying drawing, the present invention will be described, but the present invention is not limited to this execution mode.
" electrode base board "
The electrode base board of the first execution mode of the present invention as shown in Figure 2, possesses conductive board and the perforated membrane 2 of film forming on conductive board 1.Perforated membrane 2 has hole, and this hole is not only present in the surface towards outside, and is communicated in outside from film interior three-dimensional.Perforated membrane 2 is preferably containing company's pore structure that multiple single independently hole (separate openings) links.In perforated membrane 2, the number (there is ratio) preferably connecting pore structure is greater than the number (there is ratio) of separate openings.
For having the perforated membrane 2 connecting pore structure, redox couple contained in electrolyte fully can infiltrate into inside from surface, therefore preferably.In addition, have in the perforated membrane 2 connecting pore structure, the surface of perforated membrane and the area (surface area of electrochemical reaction occurs) of electrolyte contacts become many, thus, there is the advantage that reduction reaction is efficiently carried out.
At catalyst layers 3 such as the surface of perforated membrane 2 coating (being coated to) conductive macromolecules.At this, also comprise the surface with the inner porosity of ft connection on the surface of perforated membrane 2.In addition, preferably along the above-mentioned three-dimensional porous membrane structure painting catalyst layer 3 connecting pore structure and formed by perforated membrane 2.By surface (internal face) the coating catalytic oxidant layer 3 in three-dimensional porous matter structure described above, compared with the past, the specific area contributing to improving catalyst layer 3 catalyst activity significantly becomes large.
In the electrode base board of the first execution mode, perforated membrane 2 adopts the structure of three-dimensional communication, therefore, can reduce the resistance of perforated membrane inside, excellent electric conductivity.In addition, the lower surface due to perforated membrane 2 is overall directly to connect with the conductive film 1a forming conductive board 1, therefore, and can evenly and reliably form the electrical contact portion of conductive board 1 and perforated membrane 2.In addition, in the overwhelming majority in the region that perforated membrane 2 does not connect with conductive board 1, because the coating of perforated membrane 2 with electroconductive polymer 3 (catalyst layer 3) connects, therefore, the electrical contact portion of perforated membrane 2 and electroconductive polymer 3 (catalyst layer 3) can evenly and reliably be formed.As mentioned above, due to can evenly and reliably form electrical contact portion, therefore, the excellent electric conductivity of the electrode base board of the first execution mode.
(conductive board)
Conductive board 1 is made up of the conductive film 1a and substrate 1b giving conductivity.
The kind of above-mentioned conductive film is not particularly limited, such as, can apply nesa coating or metal film.
The kind of above-mentioned nesa coating is not particularly limited, and can apply the nesa coating used in existing known dye-sensitized solar cell, such as, can enumerate the film be made up of metal oxide.
As above-mentioned metal oxide, can enumerate: tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), indium doping zinc oxide (IZO), Ga-doped zinc oxide (GZO), aluminium-doped zinc oxide (AZO), zinc oxide, tin oxide etc.Wherein, the particularly preferably little and FTO of the ITO that conductance is high and thermal endurance and weatherability excellence of resistivity.
As above-mentioned metal film, can enumerate: gold (Au), platinum (Pt), silver (Ag), copper (Cu), chromium (Cr), tungsten (W), aluminium (Al), magnesium (Mg), titanium (Ti), nickel (Ni), manganese (Mn), zinc (Zn), iron (Fe) and alloy thereof etc., particularly preferably Au, Pt, Cr, Ti, Ni of conductance, weatherability excellence.
As long as the kind of substrate 1b can form above-mentioned conductive film on surface or metal film is just not particularly limited.Such as can enumerate: glass substrate, metal substrate, resin substrate etc.
For the conductive board 1 of the first execution mode, as long as its substrate surface has conductivity, therefore, necessarily do not possess above-mentioned conductive film.As conductive board 1, such as, can enumerate: the substrate that metal substrate, electroconductive resin are made.In addition, the conductive board 1 forming the electrode base board of the first execution mode comprises the conductive film or conductive sheet with flexibility.When conductive film or conductive sheet are used as conductive board 1, conductive board 1 can be renamed as conductive substrate.
(perforated membrane)
The perforated membrane 2 of the first execution mode is for having the film (layer) of three-dimensional porous matter structure, and its structure can be enumerated: the structure that particulate 2a engages, the single structure utilizing phase separation structure to be formed and the structure etc. be laminated by nano net lattice.
As long as the material forming particulate 2a has conductivity or characteristic of semiconductor, be not particularly limited, from the viewpoint of obtaining the much higher pore membrane of structural strength, the material with carbon elements etc. such as the metallic compound such as the metals such as preferred titanium or platinum, gold, silver, copper, aluminium, cobalt, iron, magnesium, nickel, zinc, titanium oxide or tin oxide, zinc oxide, gallium oxide, indium oxide, aluminium oxide, chromium oxide, cobalt oxide, cupric oxide, iron oxide, titanium carbide, vanadium carbide, tungsten carbide, titanium nitride, vanadium nitride, carbon black or carbon nano-tube, carbon fiber, active carbon, graphite.
Wherein, consider from low cost and mass-produced viewpoint, preferably use the particulate be made up of the metallic compound containing metal oxide or material with carbon element.As the material forming above-mentioned particulate, particularly preferably titanium oxide, tin oxide, zinc oxide, carbon black.
The shape of particulate 2a is not particularly limited, and can enumerate: the particulate of spherical, needle-like, threadiness, bag-shaped, sea urchin shape.
The preferable range of the primary particle size of spheroidal particle is sometimes according to different by the difference of above-mentioned particulate method of film forming on conductive board 1, usually preferred 1nm ~ 500 μm, more preferably 1nm ~ 250 μm, preferred 5nm ~ 100 μm further, particularly preferably 10nm ~ 10 μm, most preferably 10nm ~ 1 μm.In addition, as the method for primary particle size obtaining above-mentioned particulate, such as, can enumerate: the method that the form of the peak value of the distribution of the volume mean diameter obtained according to the mensuration by laser diffraction formula particle size distribution device is determined or observed by SEM and measure the major diameter of multiple particulate and the method be averaged.The primary particle size of above-mentioned particulate is observed preferably by above-mentioned SEM and is measured.
The preferable range of the primary particle size of needle-like, threadiness, bag-shaped particulate is sometimes according to different by the difference of above-mentioned particle method of film forming on conductive board 1, usually on long axis direction, preferred 1nm ~ 500 μm, more preferably 1nm ~ 250 μm, preferred 5nm ~ 100 μm further, particularly preferably 10nm ~ 10 μm, most preferably 10nm ~ 5 μm.On short-axis direction, preferred 1nm ~ 500 μm, more preferably 1nm ~ 250 μm, further preferred 5nm ~ 100 μm, particularly preferably 10nm ~ 10 μm, most preferably 10nm ~ 1 μm.
The particulate forming perforated membrane 2 can be used alone a kind, also may be combined with and uses two or more.
The thickness of perforated membrane 2 is not particularly limited, such as, can consider structural strength suitable adjustment simultaneously in the scope of 0.1 μm ~ 100 μm.Although also have relation with microparticle material, from the viewpoint of raising conductivity, the thickness of perforated membrane 2 preferably 0.1 μm ~ 10 μm.
In order to increasing specific surface area, the void content (voidage) of perforated membrane 2 is more large more preferred, if void content is excessive, then the structural strength of perforated membrane 2 likely dies down.Consider this situation, the void content of perforated membrane 2 preferably 50 ~ 80%.Above-mentioned void content (voidage) measures by known method such as such as gas adsorption method or mercury penetration method etc.
At this, when being coated with the specific area of perforated membrane 2 of the state of catalyst layer 3 by gas adsorption method mensuration, be preferably 0.1m 2/ more than g, is more preferably 1m 2/ more than g, more preferably 3m 2/ more than g.If be 3m 2/ more than g, be then coated with catalyst layer 3 and electrolytical contacting efficiency improve, and can go back original electrolyte efficiently.That is, can further improve catalytic efficiency.In addition, the higher limit of above-mentioned specific area is not particularly limited, such as can by 300m 2/ g is set to the standard of higher limit.
As long as the method for perforated membrane 2 film forming on conductive board 1 forming electrode base board in the first execution mode can be formed the method for the perforated membrane with suitable voidage, be not particularly limited, existing known film build method can be adopted.Such as the slurry containing the particulate 2a and known adhesive resin with conductivity or characteristic of semiconductor can be coated on conductive board 1 and also carry out further burning till film forming.At this, as particulate 2a, such as, can enumerate: electrically conductive microparticle or metal oxide microparticle.
In addition, by utilizing conveying gas, the particulate 2a with conductivity or characteristic of semiconductor is jetted on conductive board 1, particulate 2a and the conductive board 1 with conductivity or characteristic of semiconductor engage, the perforated membrane that the particulate 2a obtaining having conductivity or characteristic of semiconductor is engaged with each other.As winding-up, there is the particulate 2a of conductivity or characteristic of semiconductor and form the method for perforated membrane 2, such as, can enumerate: aerosol deposition method (AD method).
(catalyst layer)
In the electrode base board of the first execution mode, as the material forming the catalyst layer 3 be coated with along the three-dimensional structure of perforated membrane 2, as long as be by the conductive material of electrolytical for known formation redox couple reduction, can be not particularly limited.Specifically, such as, except electroconductive polymer described later, can enumerate: platinum; Conductive carbon material; The titanium compounds such as titanium carbide TiC, titanium nitride TiN; Vanadium oxide V 2o 3, the vfanadium compound etc. such as vanadium nitride VN.
The material forming catalyst layer 3 can only use a kind, also can use two or more.
As long as the method by platinum etc. with the metal formation catalyst layer 3 of catalyst activity can form the layer of platinum method along the surface of the three-dimensional structure of perforated membrane 2 be not particularly limited.As concrete example, can enumerate: utilize the electrolysis plating of the conductivity of perforated membrane 2 and conductive board 1, electroless plating method etc.
The lower limit of the thickness of the catalyst layer 3 that perforated membrane 2 is coated with can change according to the material of catalyst layer 3, is usually preferably more than 0.01nm, is more preferably more than 0.1nm, more preferably more than 1nm.By being more than 0.01nm, catalyst activity can be obtained fully.The higher limit of the thickness of catalyst layer 3 is not particularly limited, and preferably lower than the thickness of the degree of being filled up completely by the porous structure of perforated membrane 2, specifically, is more preferably below 1000nm.
The thickness being formed at the catalyst layer 3 that perforated membrane 2 is formed in the face of outside surface (outer surface) (that is, from surface seen during top view perforated membrane 2) is referred at the thickness of this illustrative catalyst layer 3.As the method for the thickness of the catalyst layer 3 that this outer surface of measurement is formed, be preferably formed with the method for the section of the perforated membrane 2 of catalyst layer 3 with microscopic examination.
Below, the situation using electroconductive polymer as the material forming catalyst layer 3 is described.
(electroconductive polymer)
In the electrode base board of the first execution mode, by being coated on perforated membrane 2 with electroconductive polymer 3 (catalyst layer 3) and forming catalyst layer.By above-mentioned coating, form the layer of electroconductive polymer 3 on the surface of perforated membrane 2.
The kind of above-mentioned electroconductive polymer is not particularly limited, and can apply existing known electroconductive polymer, such as, can enumerate: the electroconductive polymer that the thiophene compound shown in following general formula (1) is polymerized.
[chemical formula 4]
[in formula, R 1and R 2separately represent any one in the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl.R 1and R 2during for described alkyl or alkoxyl, the carbon atom of described alkyl or alkoxyl end each other can bonding and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, is more preferably straight-chain alkyl.
The carbon number of abovementioned alkyl preferably 1 ~ 8, more preferably 1 ~ 5, further preferably 1 ~ 3.
As above-mentioned alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group, butoxy, more preferably methoxy or ethoxy.
As above-mentioned aryl, can enumerate: phenyl, benzyl, tolyl, naphthyl etc.
As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine etc. can be enumerated.
At R 1and R 2during for abovementioned alkyl or alkoxyl, can except 1 hydrogen atom of carbon atom being bonded to abovementioned alkyl or alkoxyl end, the carbon atom of abovementioned alkyl or alkoxyl end bonds together and forms ring.
As the concrete example of the thiophene compound shown in above-mentioned general formula (1), the compound shown in following formula (1-1) ~ (1-4) can be enumerated.
[chemical formula 5]
In addition, as above-mentioned electroconductive polymer, such as, can enumerate: the electroconductive polymer that the azole compounds shown in following general formula (2) is polymerized.
[chemical formula 6]
[in formula, R 3~ R 4separately represent any one in the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl.R 3and R 4during for described alkyl or alkoxyl, the carbon atom of described alkyl or alkoxyl end each other can bonding and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, is more preferably straight-chain alkyl.
The carbon number of abovementioned alkyl preferably 1 ~ 8, more preferably 1 ~ 5, further preferably 1 ~ 3.
As above-mentioned alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group, butoxy, more preferably methoxy or ethoxy.
As above-mentioned aryl, can enumerate: phenyl, benzyl, tolyl, naphthyl etc.
As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine etc. can be enumerated.
At R 3and R 4during for abovementioned alkyl or alkoxyl, can except 1 hydrogen atom being bonded to the carbon atom of abovementioned alkyl or alkoxyl end, the carbon atom of abovementioned alkyl or alkoxyl end bonds together and forms ring.
As the concrete example of the azole compounds shown in above-mentioned general formula (2), the compound shown in following formula (2-1) ~ (2-4) can be enumerated.
[chemical formula 7]
In addition, as above-mentioned electroconductive polymer, such as, can enumerate: the electroconductive polymer that the aniline compound shown in following general formula (3) is polymerized.
[chemical formula 8]
[in formula, R 5~ R 8separately represent any one in the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl.R 5and R 6or R 7and R 8during for described alkyl or alkoxyl, the carbon atom of described alkyl or alkoxyl end each other also can bonding and form ring.]
Abovementioned alkyl is preferably straight-chain or branched-chain alkyl, is more preferably straight-chain alkyl.
The carbon number of abovementioned alkyl preferably 1 ~ 8, more preferably 1 ~ 5, further preferably 1 ~ 3.
As above-mentioned alkoxyl, preferred methoxyl group, ethyoxyl, propoxyl group, butoxy, more preferably methoxy or ethoxy.
As above-mentioned aryl, can enumerate: phenyl, benzyl, tolyl, naphthyl etc.
As above-mentioned halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine etc. can be enumerated.
At R 5~ R 8during for abovementioned alkyl or alkoxyl, can except 1 hydrogen atom of carbon atom being bonded to abovementioned alkyl or alkoxyl end, the carbon atom of abovementioned alkyl or alkoxyl end bonds together and forms ring.
As the concrete example of the aniline compound shown in above-mentioned general formula (3), the compound shown in following formula (3-1) ~ (3-4) can be enumerated.
[chemical formula 9]
On the perforated membrane 2 of the electrode base board of formation first execution mode, the high molecular method of applying conductive is not particularly limited, such as, can enumerate the method for following (a) ~ (d).
A perforated membrane impregnated in the solution containing the unconverted monomer forming electroconductive polymer by (), using above-mentioned perforated membrane as work electrode, carry out the electrolysis polymerization of above-mentioned monomer, on above-mentioned perforated membrane, compositing conducting macromolecule, is coated with thus.
B () makes solvent evaporates by containing the solution coat of electroconductive polymer of being polymerized in advance in perforated membrane, be coated with thus.
C mixture containing the electroconductive polymer be polymerized in advance and other known adhesive resin is coated perforated membrane and said mixture is solidified by (), be coated with thus.
D perforated membrane impregnated in the solution containing the unconverted monomer forming electroconductive polymer by (), known oxidant (such as iron chloride etc.) is added in above-mentioned solution, compositing conducting macromolecule on perforated membrane, is coated with thus thus.
In the method for above-mentioned (a) ~ (c), the preferably method of (a) or (b), the more preferably method of (a).C the method for () can remain on perforated membrane due to adhesive resin, therefore, the electrical contact of electroconductive polymer and perforated membrane likely dies down.D electroconductive polymer is likely excessively polymerized by the method for (), its result, likely the emptying aperture of the inside of landfill perforated membrane.On the other hand, the method for (a) and (b) directly connects due to perforated membrane and electroconductive polymer, therefore, fully can obtain both electrical contacts.In addition, according to the method for (a), the emptying aperture (porous structure) in the inside of perforated membrane (namely, the inside of the three-dimensional structure of perforated membrane) in also polymerization reaction take place, therefore, for forming the internal face of emptying aperture, also can applying conductive macromolecule fully.Therefore, the method for more preferably (a).
From the viewpoint of the reducing power improved as catalyst, the molar concentration preferably 0.00001 ~ 1mol/cm of the electroconductive polymer of applying porous film 2 3, more preferably 0.0001 ~ 0.1mol/cm 3, preferred 0.001 ~ 0.01mol/cm further 3.
In the electrode base board of the first execution mode, the specific area playing the region (catalyst layer) of the effect of catalyst increases, conductivity and structural strength improve, therefore, when above-mentioned electrode base board is used as the opposite electrode of dye-sensitized solar cell, the raising of generating efficiency can be gone far towards.
Below, the dye-sensitized solar cell of the electrode of the first execution mode is had to be described to use.
" dye-sensitized solar cell "
The dye-sensitized solar cell of the second execution mode of the present invention possesses the electrode base board of the first execution mode as opposite electrode (opposite electrode substrate), also possesses the optoelectronic pole (optoelectronic pole substrate) and electrolyte that are adsorbed with pigment.As the example of such dye-sensitized solar cell, can enumerate: the dye-sensitized solar cell 10 shown in Fig. 3.
Dye-sensitized solar cell 10 has the optoelectronic pole 11, opposite electrode 12 and the electrolyte 5 that are made up of the nesa coating 7 be stacked on transparency carrier 6 and oxide semiconductor porous layer 8.Electrolyte 5 is sealed between optoelectronic pole 11 and opposite electrode 12 by encapsulant 4.
(optoelectronic pole)
Optoelectronic pole 11 is formed by as the glass substrate of transparency carrier 6, nesa coating 7 and oxide semiconductor porous layer 8.The surface (also comprising the surface of the inside of perforated membrane (porous plastid)) of the oxide semiconductor porous layer 8 of electrolyte 5 contact is adsorbed with known sensitizing coloring matter.
The substrate (base material) forming optoelectronic pole 11 is not limited to glass system, as long as the substrate with the permeability of visible ray is just not particularly limited.Such as except glass substrate, can also enumerate: the substrate that transparent resin is made or film or sheet material.
As above-mentioned glass, preferably there is the glass of the permeability of visible ray, can enumerate: soda-lime glass, quartz glass, pyrex, Vycor glass (vycor glass, vycor glass), alkali-free glass, backboard glass, blank glass etc.
As above-mentioned resin (plastics), preferably there is the resin of visible light permeability, such as, can enumerate: polyacrylic, Merlon, polyester, polyimides, polystyrene, polyvinyl chloride, polyamide etc.Wherein, polyester, particularly PETG (PET) or PEN (PEN) are produced in large quantities as transparency and heat-proof film and are used.From the viewpoint of manufacturing thin and light flexible dye-sensitized solar cell, above-mentioned base material is preferably plastic transparent base, is more preferably PET or pen film.
As the oxide semiconductor forming oxide semiconductor porous layer 8, existing known material can be adopted, as long as be the material of adsorbable sensitization pigment.Such as can enumerate: titanium oxide, zinc oxide, strontium titanates etc.
When oxide semiconductor porous layer 8 (porous layer) is made up of the particulate of oxide semiconductor, above-mentioned porous layer can burn till for passing through the porous layer formed containing the known thickener of above-mentioned particulate on aforesaid substrate.In addition, also adopt following porous layer: by carrying gas by the winding-up of above-mentioned particulate on aforesaid substrate, combine with the same aforesaid substrate of above-mentioned particulate and the morphogenetic porous layer of shape that is bonded to each other of above-mentioned particulate.Form the method for porous layer as winding-up particulate, such as, can enumerate: aerosol deposition method (AD method).
The preferable range of the primary particle size of above-mentioned particulate is sometimes according to different by the method for above-mentioned particulate film forming on aforesaid substrate difference, usually preferred 1nm ~ 500 μm, more preferably 1nm ~ 250 μm, further preferred 5nm ~ 100 μm, particularly preferably 10nm ~ 10 μm.In addition, as the method for primary particle size obtaining above-mentioned particulate, such as can enumerate: adopt laser diffraction formula particle size distribution device to measure, obtain the peak value of the distribution of volume mean diameter, determine the method for primary particle size thus or observed by SEM and measure the major diameter of multiple particulate and the method be averaged.The primary particle size of above-mentioned particulate is observed preferably by above-mentioned SEM and is measured.
[electrolyte]
Electrolyte 5 can apply the electrolyte used in existing known dye-sensitized solar cell.
Redox couple (electrolyte) is dissolved with in electrolyte 5.Redox couple can adopt existing known redox couple.In addition, without departing from the spirit and scope of the invention, other additive such as filler or tackifier can also be contained in electrolyte 5.
As above-mentioned redox couple, such as, can enumerate: the combination of the combination of iodine molecule and iodide or molecular bromine and bromine compounds.
As above-mentioned iodide, such as, can enumerate: the salt compounded of iodine such as the metal iodides such as sodium iodide (NaI), KI (KI) or tetraalkylammonium iodides, Propidium iodide, iodate imidazoles, these are preferred iodide.
As above-mentioned bromine compounds, such as, can enumerate: the bromine salt such as metal bromide or tetraalkyl ammonium bromide, pyridinium bromide, limidazolium such as sodium bromide (NaBr), KBr (KBr), these are preferred bromides.
The concentration of the above-mentioned redox couple in electrolyte 5 is not particularly limited, and is preferably 0.1 ~ 10 mole/L, is more preferably 0.2 ~ 2 mole/L.In addition, preferred iodine concentration when adding iodine in the solvent of electrolyte 5 is 0.01 ~ 1 mole/L.
Dielectric substrate (solid electrolyte layer) can be adopted to replace electrolyte 5.Above-mentioned dielectric substrate has the function same with electrolyte 5, is any state of gel or solid shape.As above-mentioned dielectric substrate, such as, can adopt following dielectric substrate: in electrolyte 5, add gelating agent or tackifier, as required except desolventizing, make electrolyte 5 gelation or solidification thus and obtain dielectric substrate.When using the dielectric substrate of gel or solid shape, electrolyte can not spill from dye-sensitized solar cell 10.
Existing known electroconductive polymer can also be contained in electrolyte 5 or above-mentioned dielectric substrate.
As above-mentioned encapsulant, preferably electrolyte can be held in the parts of cell internal.As such encapsulant, such as, can apply the synthetic resin such as existing known thermoplastic resin, thermosetting resin.
(opposite electrode)
Opposite electrode 12 in the dye-sensitized solar cell of the second execution mode is the electrode base board of the first execution mode.
(manufacture method of dye-sensitized solar cell)
The dye-sensitized solar cell of the second execution mode except the electrode base board (opposite electrode 12) of use first execution mode, also by common method manufacture.
Because electroconductive polymer (catalyst layer) coating of the electrode base board of the first execution mode as opposite electrode 12 is supported by perforated membrane, therefore, there is higher structural strength.Therefore, during manufacture when above-mentioned coatings of contact such as fixtures, the impaired danger of above-mentioned coating can also be reduced.Therefore, by the electrode base board of the first execution mode is used as opposite electrode, the fabrication yield of the dye-sensitized solar cell of the second execution mode can be improved.
Embodiment
Then, by embodiment, the present invention is described in further detail, but the present invention does not limit by these examples.
[embodiment 1]
(forming oxide semiconductor porous layer)
Use the slurry be made up of Titanium particles (particle diameter Φ 19nm) 19 quality %, ethyl cellulose 9 quality %, terpineol 72 quality %, form oxide semiconductor porous layer (thickness 8 μm).As transparent conductive substrate, use the glass substrate being furnished with the sheet resistance 10 ohm (Ω) of FTO film, with the area of 4mm × 4mm, above-mentioned slurry is coated on FTO film by silk screen print method, then, burn till 30 minutes with 500 DEG C in air atmosphere, nesa coating is formed oxide semiconductor porous layer (hyaline layer).
(pigment absorption)
In the pigment solution obtained sensitization pigment N719 to be dissolved in the 1:1 mixed liquor of acetonitrile and the tert-butyl alcohol with the concentration of 0.3mM, 20 hours are flooded to the substrate being formed with above-mentioned oxide semiconductor porous layer, makes sensitization pigment be adsorbed in the oxide semiconductor porous layer of optoelectronic pole thus.
(making opposite electrode)
The paste be made up of Titanium particles (particle diameter Φ 19nm) 19 quality %, ethyl cellulose 9 quality %, terpineol 72 quality % is used to form porous oxide.As transparent conductive substrate, use is equipped with FTO film and the glass substrate of sheet resistance 10 ohm (Ω), above-mentioned slurry is coated on after on FTO film with the area of 4mm × 4mm by silk screen print method, burn till 30 minutes with 500 DEG C in air atmosphere, nesa coating is formed the perforated membrane (thickness 1.5 μm) of titanium oxide.Because the Titanium particles forming the perforated membrane as above formed directly contacts with FTO film, therefore, the excellent electric conductivity between perforated membrane and FTO film.
Then, by electrolysis polymerization method, electroconductive polymer is coated perforated membrane.Use above-mentioned perforated membrane and FTO film as work electrode, use platinum line as to electrode, use Ag/Ag +electrode, as reference electrode, carries out the electrolysis polymerization of electroconductive polymer.In electrolysis polymerization, containing 10 -2the EDOT (3,4-ethyldioxythiophene: the compound shown in above-mentioned formula (1-1)), 10 of M -1above-mentioned work electrode is flooded, to electrode, reference electrode in the acetonitrile solution of the LiTFSI (two trifluoromethanesulfonimide lithium) of M, use potentiostat (IVIUM Inc.) to apply 40 seconds 1.2V voltage, porous film surface is formed electroconductive polymer (PEDOT:TFSI).That is, the catalyst layer 3 (above-mentioned electroconductive polymer layer) along perforated membrane three-dimensional structure as shown in Figure 2 schematically can be formed.
(evaluation of film-strength)
The opposite electrode of making be impregnated in ethanol, after giving stimulation in 5 minutes with ultrasonic wave (frequency of oscillation 42kHz), observe the surface of the perforated membrane with electroconductive polymer coating of above-mentioned opposite electrode, evaluated for film intensity thus.Evaluate and carry out with a following amounts stage.Its result is remembered in the lump in table 1.
Well (A): almost do not see and peeling off or damage.
Bad (B): stripping or the damage of seeing very important degree.
(assembling of battery and power generation performance evaluation)
The opposite electrode make said method and optoelectronic pole are superimposed together across the resinousness pad (barrier film) of thickness 30 μm and clamp with fixture, inject electrolyte, assemble dye-sensitized solar cell (battery) thus between two electrodes.As electrolyte, to use in acetonitrile iodine 0.03M, iodate 1,3-dimethyl-2-propyl imidazole 0.6M, lithium iodide 0.10M, tert .-butylpyridine 0.5M be dissolved in as solvent and the electrolyte obtained.
As the power generation performance of made battery, solar simulator (AM1.5) is utilized to evaluate photoelectric conversion efficiency η, short circuit current Isc, open circuit voltage Voc, Fill factor FF.The results are shown in table 1.
[embodiment 2]
The particulate forming opposite electrode is changed to zinc oxide particles (particle diameter Φ 23nm), in addition, makes dye-sensitized solar cell similarly to Example 1, carry out the evaluation of power generation performance.The results are shown in table 1.
[embodiment 3]
The particulate forming opposite electrode is changed to carbon black (particle diameter Φ 23nm), in addition, makes dye-sensitized solar cell similarly to Example 1, carry out the evaluation of power generation performance.The results are shown in table 1.
[comparative example 1]
The platinum electrode substrate that use forms platinum film on the glass substrate by sputtering method and obtains, as opposite electrode, in addition, makes dye-sensitized solar cell similarly to Example 1, carries out the evaluation of power generation performance.The results are shown in table 1.
[comparative example 2]
Using is equipped with the glass substrate of the FTO film identical with embodiment 1 as work electrode, carries out electrolysis polymerization similarly to Example 1, FTO film forms electroconductive polymer, makes opposite electrode.
Except opposite electrode, make dye-sensitized solar cell similarly to Example 1, carry out the evaluation of power generation performance.The results are shown in table 1.
[comparative example 3]
Applying conductive macromolecule on the perforated membrane forming opposite electrode, in addition, does not make dye-sensitized solar cell similarly to Example 1, carries out the evaluation of power generation performance.The results are shown in table 1.
[comparative example 4]
Applying conductive macromolecule on the perforated membrane forming opposite electrode, in addition, does not make dye-sensitized solar cell similarly to Example 2, carries out the evaluation of power generation performance.The results are shown in table 1.
[comparative example 5]
Applying conductive macromolecule on the perforated membrane forming opposite electrode, in addition, does not make dye-sensitized solar cell similarly to Example 3, carries out the evaluation of power generation performance.The results are shown in table 1.
Can be clear and definite by the result of table 1, photoelectric conversion efficiency (generating efficiency) η of embodiments of the invention 1 ~ 3 has or its above performance equal with comparative example 1 ~ 5.
[embodiment 4]
In the making of optoelectronic pole, in the reflector (thickness 4 μm) that the oxide semiconductor porous layer (hyaline layer) formed similarly to Example 1 (thickness 8 μm) superimposed layer is made up of the Titanium particles of particle diameter 400nm, then, pigment is made to be adsorbed in above-mentioned hyaline layer and reflector, in addition, battery (dye-sensitized solar cell) is made similarly to Example 1.
Above-mentioned reflector is by operating formation as follows: in the same manner as forming the situation of above-mentioned hyaline layer, the paste be made up of titanium oxide (particle diameter Φ 400nm) 19 quality %, ethyl cellulose 9 quality % and terpineol 72 quality % is printed on above-mentioned hyaline layer, then burns till at 500 DEG C.
At this, above-mentioned hyaline layer is different with the particle diameter of titanium oxide contained in above-mentioned reflector.Above-mentioned hyaline layer can be renamed as ground floor, above-mentioned reflector is renamed as the second layer.
In addition, pigment be adsorbed on to above-mentioned ground floor and the second layer stacked, burn till after, carry out similarly to Example 1.
[embodiment 5]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to the Titanium particles of particle diameter 30nm, in addition, make electrode similarly to Example 4.
[embodiment 6]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to the Titanium particles of particle diameter 200nm, in addition, make electrode similarly to Example 4.
[embodiment 7]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to ATO (antimony-doped tin oxide) particle of particle diameter 10 ~ 30nm, in addition, make electrode similarly to Example 4.
[embodiment 8]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to the ATO acicular particles of major axis particle diameter 200 ~ 2000nm, minor axis particle diameter 10 ~ 20nm, in addition, make electrode similarly to Example 4.
[embodiment 9]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to the Titanium particles of the ATO being coated with particle diameter 200 ~ 500nm, in addition, make electrode similarly to Example 4.
[embodiment 10]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to the carbon black particle of particle diameter 23nm, in addition, make electrode similarly to Example 4.
[embodiment 11]
In the making of opposite electrode, the perforated membrane that the Titanium particles by particle diameter 19nm is formed is changed to the nickel screen lattice of 8 μm, mesh, wire diameter 8 μm, thickness 3 μm, in addition, make electrode similarly to Example 4.
[embodiment 12]
In the making of opposite electrode, as the coating material of catalyst layer, by the polypyrrole that the pyrroles that the PEDOT that the EDOT of above-mentioned formula (1-1) is polymerized changes to above-mentioned formula (2-2) is polymerized, in addition, make battery similarly to Example 10.
[embodiment 13]
In the making of opposite electrode, as the coating material of catalyst layer, the PEDOT that the EDOT of above-mentioned formula (1-1) is polymerized is changed to the polyaniline of the aniline polymerization of above-mentioned formula (3-1), in addition, make battery similarly to Example 10.
[embodiment 14]
In the making of opposite electrode, by perforated membrane being impregnated in the 2-propanol solution of the chloroplatinic acid of 10mM, then, burn till at 450 DEG C, the catalyst layer that the catalyst layer be made up of platinum replaces being formed by electrolysis polymerization method PEDOT is formed thus on the surface of perforated membrane, in addition, battery is made similarly to Example 4.
[embodiment 15]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to ATO (antimony-doped tin oxide) particle of particle diameter 10 ~ 30nm, in addition, make electrode similarly to Example 14.
[embodiment 16]
In the making of opposite electrode, the Titanium particles of particle diameter 19nm is changed to the carbon black particle of particle diameter 23nm, in addition, make electrode similarly to Example 14.
[comparative example 6]
In the making of optoelectronic pole, behind the reflector (thickness 4 μm) that oxide semiconductor porous layer (hyaline layer) (the thickness 8 μm) superimposed layer similarly formed with comparative example 1 is made up of the Titanium particles of particle diameter 400nm, pigment is made to be adsorbed in above-mentioned hyaline layer and reflector, in addition, battery is made in the same manner as comparative example 1.Above-mentioned reflector is formed by the method identical with embodiment 4.
[comparative example 7]
In the making of optoelectronic pole, behind the reflector (thickness 4 μm) that oxide semiconductor porous layer (hyaline layer) (the thickness 8 μm) superimposed layer similarly formed with comparative example 2 is made up of the Titanium particles of particle diameter 400nm, pigment is made to be adsorbed in above-mentioned hyaline layer and reflector, in addition, battery is made in the same manner as comparative example 2.Above-mentioned reflector is formed by the method identical with embodiment 4.
[comparative example 8]
In the making of opposite electrode, as the coating material of catalyst layer, by the polypyrrole that the pyrroles that the PEDOT that the EDOT of above-mentioned formula (1-1) is polymerized changes to above-mentioned formula (2-2) is polymerized, in addition, battery is made in the same manner as comparative example 7.
[comparative example 9]
In the making of opposite electrode, as the coating material of catalyst layer, the PEDOT that the EDOT of above-mentioned formula (1-1) is polymerized is changed to the polyaniline of the aniline polymerization of above-mentioned formula (3-1), in addition, make battery in the same manner as comparative example 7.
[comparative example 10]
In the making of opposite electrode, the glass substrate being equipped with FTO film on surface is coated with the dispersion liquid that weight ratio 2:1:16 mixes by making PEDOT, carbon black particle (particle diameter 23nm) and ethanol, drying 60 minutes at 120 DEG C, the catalyst layer be made up of PEDOT and carbon black is formed thus on the surface of conductive glass substrate, the catalyst layer being formed PEDOT by electrolysis polymerization method is replaced with this, in addition, battery is made similarly to Example 4.
[comparative example 11]
In the making of opposite electrode, use the coating Titanium particles (particle diameter 200 ~ 500nm) of ATO to replace carbon black particle, in addition, make electrode in the same manner as comparative example 10.
[comparative example 12]
In the making of opposite electrode, coating conducting macromolecule on perforated membrane, in addition, does not make battery similarly to Example 4.
[comparative example 13]
In the making of opposite electrode, coating conducting macromolecule on perforated membrane, in addition, does not make battery similarly to Example 7.
[comparative example 14]
In the making of opposite electrode, coating conducting macromolecule on perforated membrane, in addition, does not make battery similarly to Example 10.
Similarly to Example 1 each battery made in above embodiment 4 ~ 16 and comparative example 6 ~ 14 is evaluated.The results are shown in table 2.
As can be known from the above results, no matter be coated with the kind of electrode base board catalyst layer, the kind of perforated membrane of the embodiment of catalyst layer on perforated membrane, excellent generating efficiency all can be obtained.
In addition, the generating efficiency of the known electrode base board that specific area is larger in embodiment 4 ~ 6 improves.
Although the electrode base board of comparative example 10 ~ 11 is coated with electroconductive polymer on the surface of conductive glass, coated face is not porous structure, and therefore, generating efficiency is poorer than embodiment 4.
The SEM image that the opposite electrode surface observing embodiment 9 obtains is shown in Fig. 4 A.In addition, the SEM image that the porous film surface before having illustrated the surface coating PEDOT of the opposite electrode in embodiment 9 in Fig. 4 B is observed and obtained.Comparison diagram 4A and Fig. 4 B, the surface of the known perforated membrane at Fig. 4 A is coated with the situation of PEDOT along three-dimensional porous matter structure.
The section of the opposite electrode of embodiment 9 will be observed and the SEM image that obtains is shown in Fig. 4 C.In addition, the enlarged image of this section is shown in Fig. 4 D.In Fig. 4 C and Fig. 4 D, the known company's pore structure that there is separate openings and link in perforated membrane.In addition, in the enlarged image of Fig. 4 D, the Range Representation shown in black dotted line is coated with the surface (border) of the titanium oxide of ATO, the surface (border) of the catalyst layer that the Range Representation shown in white dotted line is made up of PEDOT.The distance of black dotted line and white dotted line represents the thickness of catalyst layer.
The surface of the opposite electrode of embodiment 10 will be observed and the SEM image that obtains is shown in Fig. 5 A.In addition, Fig. 5 B illustrates and observes the surface of perforated membrane before the opposite electrode surface coating PEDOT of embodiment 10 and the SEM image that obtains.Comparison diagram 5A and Fig. 5 B, the surface of the known perforated membrane at Fig. 5 A is coated with the situation of PEDOT along three-dimensional porous matter structure.
The opposite electrode surface of embodiment 7 will be observed and the SEM image that obtains is shown in Fig. 6 A.In addition, Fig. 6 B shows the SEM image obtained observing at the surperficial porous film surface be coated with before PEDOT of the opposite electrode of embodiment 7.Comparison diagram 6A and Fig. 6 B, the surface of the known perforated membrane at Fig. 6 A, is coated with the situation of PEDOT along three-dimensional porous matter structure.
The opposite electrode surface of embodiment 8 will be observed and the SEM image that obtains is shown in Fig. 7 A.In addition, Fig. 7 B shows and observes the carrying out of porous film surface before the opposite electrode surface coating PEDOT of embodiment 8 and the SEM image that obtains.Comparison diagram 7A and Fig. 7 B, the surface of the known perforated membrane at Fig. 7 A, along the situation of three-dimensional porous matter structure coating PEDOT.
The SEM image that the opposite electrode of observation and comparison example 6 surface obtains is shown in Fig. 8.The known state being formed flatly the film be made up of platinum.In addition, the SEM image obtained on the opposite electrode of observation and comparison example 7 surface is shown in Fig. 9.The known state being formed flatly the film comprising PEDOT.In addition, the SEM image obtained on the opposite electrode of observation and comparison example 11 surface is shown in Figure 10.The roughness of film of PEDOT is being comprised, the situation of general planar ground film forming although known.Known in the opposite electrode of these arbitrary comparative examples, do not form the membrane structure with three dimensional depth.
[embodiment 17]
Make battery similarly to Example 9.In the opposite electrode of this battery, the thickness of the perforated membrane be made up of the Titanium particles being coated with ATO is 2.2 μm.In addition, thickness is measured by the method measuring thickness difference with contact pin type surface shape measuring device.
[embodiment 18]
In the making of opposite electrode, by the number of times increasing silk screen printing, the thickness of formed perforated membrane is changed to 5.6 μm, in addition, make battery in the same manner as embodiment 17 (embodiment 9).
[embodiment 19]
In the making of opposite electrode, by the number of times increasing silk screen printing, the thickness of formed perforated membrane is changed to 10.1 μm, in addition, make battery in the same manner as embodiment 17 (embodiment 9).
[comparative example 15]
Battery is made in the same manner as comparative example 6.In the opposite electrode of this battery, the thickness of the platinum film (platinum electrode) formed by sputtering method is 20nm.In addition, thickness utilizes SEM observe the profile image of platinum electrode and estimate.
[comparative example 16]
The thickness of platinum film is changed to 50nm, in addition, makes battery in the same manner as comparative example 15 (comparative example 6).
[comparative example 17]
The thickness of platinum film is changed to 100nm, in addition, makes battery in the same manner as comparative example 15 (comparative example 6).
[comparative example 18]
Battery is made in the same manner as comparative example 7.In the opposite electrode of this battery, the thickness of the film be made up of PEDOT formed by electrolysis polymerization method is 20nm.In addition, thickness utilizes SEM observe the profile image of PEDOT electrode and estimate.
[comparative example 19]
In the making of opposite electrode, by the polymerization time extending electrolysis polymerization method, the thickness of the formed film be made up of PEDOT is changed to 40nm, in addition, make battery in the same manner as comparative example 18 (comparative example 7).
[comparative example 20]
In the making of opposite electrode, by the polymerization time extending electrolysis polymerization method, the thickness of the formed film be made up of PEDOT is changed to 100nm, in addition, make battery in the same manner as comparative example 18 (comparative example 7).
[comparative example 21]
In the making of opposite electrode, by the polymerization time extending electrolysis polymerization method, the thickness of the formed film be made up of PEDOT is changed to 200nm, in addition, make battery in the same manner as comparative example 18 (comparative example 7).
To the evaluation that each battery made in above embodiment 17 ~ 19 and comparative example 15 ~ 21 carries out similarly to Example 1.The results are shown in table 3.
From the result of the embodiment 17 ~ 19 of above-mentioned table, the thickness (thickness) of the catalyst layer of opposite electrode more increases, and the generating efficiency of battery improves.As this reason, think that the catalyst layer of embodiment is owing to having the structure linked along porous structure three-dimensional, therefore, along with the increase of thickness, catalyst reaction area increases.
On the other hand, when the battery using platinum film as the comparative example 15 ~ 17 of opposite electrode, even if increase the thickness of platinum electrode, generating efficiency also has almost no change.In this, the situation that the film be made up of PEDOT directly formed on the surface at conductive glass substrate is set to the battery of the comparative example 18 ~ 21 of opposite electrode is also identical.The unchanged reason of this generating efficiency is, even if increase the thickness of the opposite electrode of comparative example, catalyst reaction area does not also increase.In addition, make PEDOT be in the battery of comparative example 21 of the thickness of about 200nm, because film strength is not enough, film is being peeled off.
Each technical scheme in each execution mode described above and their combination etc. are examples of the present invention, can carry out without departing from the spirit and scope of the invention technical scheme additional, omit, displacement and other change.In addition, the present invention does not limit by each execution mode, only limits by claim (claim) book.
Industrial applicibility
Electrode base board of the present invention and use have the dye-sensitized solar cell of this electrode base board can be widely used in the field of solar cell.
Symbol description
1 ... conductive board, 1a ... conductive film, 1b ... substrate, 2 ... perforated membrane, 2a ... there is the particulate of conductivity or characteristic of semiconductor, 3 ... electroconductive polymer (catalyst layer), 4 ... encapsulant, 5 ... electrolyte, 6 ... transparency carrier, 7 ... nesa coating, 8 ... oxide semiconductor porous layer, 10 ... dye-sensitized solar cell, 11 ... optoelectronic pole (optoelectronic pole substrate), 12 ... opposite electrode (opposite electrode substrate), 21 ... conductive board, 21a ... nesa coating, 21b ... glass substrate, 22 ... material with carbon element, 23 ... electroconductive polymer

Claims (13)

1. an electrode base board, it has conductive board, the perforated membrane of film forming on described conductive board, the catalyst layer coated on described perforated membrane.
2. electrode base board as claimed in claim 1, wherein, the three-dimensional structure along described perforated membrane is coated with described catalyst layer.
3. electrode base board as claimed in claim 1 or 2, wherein, is coated with in the perforated membrane of described catalyst layer containing company's pore structure that multiple separate openings links.
4. electrode base board as claimed in claim 3, wherein, in the perforated membrane being coated with described catalyst layer, the described number connecting pore structure is greater than the number of described separate openings.
5. the electrode base board according to any one of Claims 1 to 4, wherein, described perforated membrane is made up of metal or metallic compound.
6. the electrode base board according to any one of Claims 1 to 4, wherein, described perforated membrane is made up of material with carbon element.
7. the electrode base board according to any one of claim 1 ~ 6, wherein, described catalyst layer is made up of electroconductive polymer.
8. electrode base board as claimed in claim 7, wherein, described electroconductive polymer is the polymer of the thiophene compound formation that following general formula (1) represents:
In formula, R 1and R 2separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl, work as R 1and R 2during for described alkyl or alkoxyl, the terminal carbon of described alkyl or alkoxyl can bond together and form ring.
9. electrode base board as claimed in claim 7, wherein, described electroconductive polymer is the polymer of the azole compounds formation that following general formula (2) represents:
In formula, R 3and R 4separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl, work as R 3and R 4during for described alkyl or alkoxyl, the terminal carbon of described alkyl or alkoxyl can bond together and form ring.
10. electrode base board as claimed in claim 7, wherein, described electroconductive polymer is the polymer of the aniline compound formation that following general formula (3) represents:
In formula, R 5~ R 8separately represent the aryl of the alkoxyl of the alkyl of hydrogen atom, carbon number 1 ~ 8, carbon number 1 ~ 4, carbon number 6 or 8, carboxyl, ester group, aldehyde radical, hydroxyl, halogen atom, cyano group, amino, nitro, azo group, sulfo group or sulfonyl, work as R 5and R 6, or R 7and R 8during for described alkyl or alkoxyl, the terminal carbon of described alkyl or alkoxyl can bond together and form ring.
11. electrode base boards according to any one of claim 1 ~ 10, wherein, the surface of described conductive board is connected with described perforated membrane.
12. electrode base boards according to any one of claim 7 ~ 11, wherein, described electroconductive polymer coats described perforated membrane by employing described perforated membrane as the electrolysis polymerization method of work electrode.
13. 1 kinds of dye-sensitized solar cells, it possesses counter electrode, the optoelectronic pole being adsorbed with pigment and electrolyte that the electrode base board according to any one of claim 1 ~ 12 is formed.
CN201380043843.3A 2012-12-14 2013-09-26 Electrode substrate and dye-sensitized solar cell Pending CN104584162A (en)

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