JP4177172B2 - Dye-sensitized solar cell - Google Patents

Dye-sensitized solar cell Download PDF

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JP4177172B2
JP4177172B2 JP2003149253A JP2003149253A JP4177172B2 JP 4177172 B2 JP4177172 B2 JP 4177172B2 JP 2003149253 A JP2003149253 A JP 2003149253A JP 2003149253 A JP2003149253 A JP 2003149253A JP 4177172 B2 JP4177172 B2 JP 4177172B2
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Prior art keywords
dye
saccharin
sensitized solar
solar cell
electrolyte
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JP2004055536A (en
Inventor
淳二 中島
友美 元廣
亨 志賀
憲典 武市
竜生 豊田
智之 遠山
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アイシン精機株式会社
株式会社豊田中央研究所
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/54Material technologies
    • Y02E10/542Dye sensitized solar cells

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dye-sensitized solar cell.
[0002]
[Prior art]
In recent years, various developments of solar cells such as silicon pn junction solar cells and dye-sensitized solar cells have been promoted along with increasing interest in global warming and energy problems. Among the solar cells, since dye-sensitized solar cells have been proposed by Gretzel et al. (See, for example, Patent Document 1), the materials used are inexpensive and can be manufactured by a relatively simple process. Its practical application is expected.
[0003]
As described in Patent Document 1, in a conventional dye-sensitized solar cell, lithium iodide is used as a supporting electrolyte for the purpose of increasing photocurrent in addition to a redox couple such as I 3 / I −. It was added in the electrolyte.
[0004]
Lithium cations generated from lithium iodide in the electrolytic solution act to lower the Fermi level on the surface of the semiconductor electrode by its positive charge when attracted to the surface of the negatively charged semiconductor electrode (photoelectrode) (more positive It is thought that there is a function of shifting to the electric potential side of). As a result, the potential difference between the Fermi level on the surface of the semiconductor electrode and the excitation level of the sensitizing dye is widened. As a result, the electron transfer from the dye to the oxide semiconductor proceeds rapidly, and the photocurrent increases. It is considered to be.
[0005]
[Patent Document 1]
Japanese Patent No. 2664194 [0006]
[Problems to be solved by the invention]
However, when lithium iodide is used as the supporting electrolyte as in the conventional dye-sensitized solar cell including the battery described in Patent Document 1, the open circuit voltage (maximum output voltage) is reduced. . When the open circuit voltage decreases, the output voltage obtained during power generation also decreases, and sufficient photoelectric conversion efficiency cannot be obtained. The open-circuit voltage of a dye-sensitized solar cell is determined by the difference between the Fermi level of the semiconductor electrode and the redox potential of the redox couple in the electrolyte, but when lithium iodide is used as the supporting electrolyte, It is considered that one of the major causes of the above problem is that the Fermi level on the surface of the semiconductor electrode is shifted (shifted to the side where the open circuit voltage decreases) by the action of the cation.
[0007]
When the Fermi level on the surface of the semiconductor electrode shifts as described above, so-called reverse electron transfer (dark current) in which electrons move from the semiconductor electrode surface or photoexcited sensitizing dye into the electrolyte as the open circuit voltage decreases. There has also been a problem that it is likely to occur. When this dark current is generated, the output voltage and photocurrent density obtained during power generation are reduced.
[0008]
Therefore, an additive such as 4-tert-butylpyridine may be added to the electrolyte for the purpose of suppressing the reduction of the open circuit voltage and the generation of dark current associated therewith. This additive is believed to have a function of coordinating on the surface of the semiconductor electrode and suppressing generation of dark current from the surface of the semiconductor electrode into the electrolyte. However, the present inventors are still inadequate because a sufficient amount of dark current still flows and sufficient photoelectric conversion efficiency cannot be obtained only by adding the additive conventionally used for the above purpose. I found.
[0009]
The present invention has been made in view of the above-described problems of the prior art, and provides a dye-sensitized solar cell that can sufficiently prevent a decrease in open-circuit voltage and generation of dark current and can obtain high photoelectric conversion efficiency. The purpose is to provide.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have added at least one additive selected from the group consisting of saccharin and saccharin derivatives to the electrolyte, thereby reducing the open circuit voltage and reducing darkness. It has been found that the photocurrent density from the sensitizing dye to the surface of the semiconductor electrode (photoelectrode) can be increased while sufficiently suppressing the generation of current, and the present invention has been achieved.
[0011]
That is, the present invention has a photoelectrode having a semiconductor electrode having a light receiving surface, a transparent electrode disposed adjacent to the light receiving surface of the semiconductor electrode, and a counter electrode,
A dye-sensitized solar cell in which a semiconductor electrode and a counter electrode are arranged to face each other via an electrolyte containing at least a sensitizing dye,
The electrolyte contains at least one additive selected from the group consisting of saccharin, saccharin salt, saccharin derivative, and saccharin derivative salt;
A dye-sensitized solar cell is provided.
[0012]
Here, in the present invention, “saccharin” refers to saccharin (saccharin free type). The “saccharin salt” refers to a compound having a structure in which a hydrogen atom in an atomic group corresponding to an imino group (—NH— group) constituting a saccharin molecule is substituted with a metal atom. Furthermore, the “saccharin derivative” refers to an atom of an element other than a hydrogen atom in which at least one of four hydrogen atoms of an atomic group corresponding to an o-phenylene group (—C 6 H 4 — group) constituting a saccharin molecule or The compound which has the structure substituted by the other atomic group (functional group) is shown. The “saccharin derivative salt” refers to a compound having a structure in which a hydrogen atom in an atomic group corresponding to an imino group (—NH— group) constituting the “saccharin derivative” molecule is substituted with a metal atom.
[0013]
In the present specification, “at least one additive selected from the group consisting of saccharin, saccharin salt, saccharin derivative, and saccharin derivative salt” is collectively referred to as “saccharin compound” as necessary. Express.
[0014]
In the present invention, by adding the above-described saccharin compound to the electrolyte, it is possible to increase the photocurrent density from the sensitizing dye to the semiconductor electrode surface while sufficiently suppressing the reduction of the open circuit voltage and the generation of dark current. Although the detailed mechanism of becoming like this is not clearly clarified, the present inventors consider as follows.
[0015]
That is, when the above-described saccharin compound is added to the electrolyte, the atomic group corresponding to the imino group (—NH— group) described above or H of the —NH— group is substituted with another metal atom. The portion of the atomic group having the above structure is ionized to generate an anion having a bulky bicyclic structure and a cation (hydrogen ion or metal ion). This cation can be coordinated at a high density to the non-adsorbed portion of the sensitizing dye on the surface of the semiconductor electrode (photoelectrode), so that the Fermi level on the surface of the semiconductor electrode is lowered (shifted to a more positive potential side). ), It is considered that the photoelectron transfer from the sensitizing dye to the surface of the semiconductor electrode proceeds more rapidly. On the other hand, the bulky anion strongly inhibits reverse electron transfer from the semiconductor electrode surface or photoexcited sensitizing dye to the electrolyte (for example, reverse electron transfer to the oxidant of the redox pair in the electrolyte). It is thought that it has the function to do.
[0016]
The anion and cation having the above functions coexist in the same electrolyte, thereby preventing the back electron transfer from the semiconductor electrode surface to the electrolyte and the photoelectron transfer from the sensitizing dye to the semiconductor electrode surface. The present inventors consider that it is possible to proceed selectively and rapidly, and that the photoelectric conversion efficiency of the battery is improved.
[0017]
In the present invention, when the above-described saccharin compound is added to the electrolyte, it is excellent even in a high temperature (60 to 85 ° C.) operating environment or in a high temperature (60 to 85 ° C.) storage state. The present inventors have found that the photoelectric conversion performance can be maintained over a long period of time.
[0018]
Although the detailed mechanism about the above effect being obtained by the addition of the saccharin compound is not clearly clarified, the present inventors consider as follows. That is, as one of the factors that lower the photoelectric conversion performance at high temperatures, decomposition of the sensitizing dye that occurs due to reverse electron transfer from the sensitizing dye to the electrolytic solution can be considered. As a result of adding to the inside, the reverse electron transfer is strongly inhibited due to the above-mentioned reasons, so that the decomposition of the sensitizing dye is greatly suppressed, and the high temperature holding property is improved.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the photoelectrode and the dye-sensitized solar cell of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.
[0020]
[First Embodiment]
FIG. 1 is a schematic cross-sectional view showing the basic configuration of the first embodiment of the dye-sensitized solar cell of the present invention.
[0021]
A dye-sensitized solar cell 20 shown in FIG. 1 mainly includes a photoelectrode 10, a counter electrode CE, and an electrolyte E filled in a gap formed between the photoelectrode 10 and the counter electrode CE by a spacer S. Has been. 1 mainly includes a semiconductor electrode 2 having a light receiving surface F2 and a transparent electrode 1 disposed adjacently on the light receiving surface F2 of the semiconductor electrode 2. And the semiconductor electrode 2 is contacting the electrolyte E in the back surface F22 on the opposite side to the light-receiving surface F2.
[0022]
In the dye-sensitized solar cell 20, the sensitizing dye adsorbed in the semiconductor electrode 2 is excited by the light L <b> 10 that passes through the transparent electrode 1 and is applied to the semiconductor electrode 2. Electrons are injected into the electrode 2. The electrons injected in the semiconductor electrode 2 are collected by the transparent electrode 1 and taken out to the outside.
[0023]
The structure of the transparent electrode 1 is not specifically limited, The transparent electrode mounted in a normal dye-sensitized solar cell can be used. For example, the transparent electrode 1 shown in FIG. 1 has a configuration in which a so-called transparent conductive film 3 is coated on the semiconductor electrode 2 side of a transparent substrate 4 such as a glass substrate. As the transparent conductive film 3, a transparent electrode used for a liquid crystal panel or the like may be used.
[0024]
Examples thereof include fluorine-doped SnO 2 coated glass, ITO coated glass, ZnO: Al coated glass, and antimony-doped tin oxide (SnO 2 —Sb). In addition, a transparent electrode obtained by doping cations or anions with different valences into tin oxide or indium oxide, or a metal electrode having a structure capable of transmitting light, such as a mesh shape or a stripe shape, provided on a substrate such as a glass substrate Good.
[0025]
As the transparent substrate 4, a transparent substrate used for a liquid crystal panel or the like may be used. Specific examples of the transparent substrate material include transparent glass substrates, materials that prevent the reflection of light by appropriately roughening the surface of the glass substrate, and materials that transmit light, such as a ground glass-like translucent glass substrate. Note that the material may not be glass as long as it transmits light, and may be a transparent plastic plate, a transparent plastic film, an inorganic transparent crystal, or the like.
[0026]
A semiconductor electrode 2 shown in FIG. 1 is composed of an oxide semiconductor layer containing oxide semiconductor particles as a constituent material. The oxide semiconductor particles contained in the semiconductor electrode 2 are not particularly limited, and a known oxide semiconductor or the like can be used. As the oxide semiconductor, for example, TiO 2 , ZnO, SnO 2 , Nb 2 O 5 , In 2 O 3 , WO 3 , ZrO 2 , La 2 O 3 , Ta 2 O 5 , SrTiO 3 , BaTiO 3 or the like is used. be able to. Among these oxide semiconductors, anatase TiO 2 is preferable.
[0027]
The sensitizing dye contained in the semiconductor electrode 2 is not particularly limited as long as it is a dye having absorption in the visible light region and / or the infrared light region. More preferably, any material that emits electrons when excited by light having a wavelength of at least 200 nm to 10 μm may be used. As such a sensitizing dye, a metal complex, an organic dye, or the like can be used. Examples of metal complexes include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll or derivatives thereof, hemin, ruthenium, osmium, iron and zinc complexes (for example, cis-dicyanate-N, N′-bis (2,2′-bipyridyl). -4,4'-dicarboxylate) ruthenium (II)) and the like. As the organic dye, metal-free phthalocyanine, cyanine dye, merocyanine dye, xanthene dye, triphenylmethane dye, and the like can be used.
[0028]
The counter electrode CE is not particularly limited as long as the counter electrode CE is made of a material capable of passing electrons to an oxidation-reduction pair (for example, I 3 / I etc.) in the electrolyte with high efficiency. For example, you may use the same thing as the counter electrode normally used for a silicon solar cell, a liquid crystal panel, etc. For example, it may have the same structure as the transparent electrode 1 described above, a metal thin film electrode such as Pt is formed on the transparent conductive film 3 similar to the transparent electrode 1, and the metal thin film electrode is placed on the electrolyte E side. It may be arranged to face. Alternatively, a small amount of platinum may be attached to the transparent conductive film 3 of the transparent electrode 1, or a metal thin film such as platinum, a conductive film such as carbon, or the like may be used.
[0029]
Further, the electrolyte E is not particularly limited as long as it contains the saccharin compound described above and contains a redox species for reducing the dye after photoexcitation and electron injection into the semiconductor. For example, it may be a liquid electrolyte, or may be a gel electrolyte obtained by adding a known gelling agent (polymer or low molecular gelling agent) thereto.
[0030]
For example, the solvent for the liquid electrolyte used for the electrolyte E is not particularly limited as long as it is a compound that can dissolve the solute component, but is electrochemically inert, has a high relative dielectric constant, and has a low viscosity (and These are preferably dissolved in a mixed solvent) such as nitrile compounds such as methoxypropionitrile and acetonitrile, lactone compounds such as γ-butyrolactone and valerolactone, carbonate compounds such as ethylene carbonate and propylene carbonate, and carbonic acid. And propylene.
[0031]
Further, among the solutes added to the electrolyte E, other solutes of the saccharin compound described later include a redox pair (I 3 / I system) that can exchange electrons with the dye supported on the semiconductor electrode 2 and the counter electrode CE. electrolyte, Br 3 - / Br - based electrolyte, hydroquinone / redox electrolyte such as quinone-based electrolyte) and this compound having an effect of promoting the transfer of electrons (compounds other than saccharin compounds of the present invention), and the like These may be included singly or in combination. Thus, in the present invention, compounds other than saccharin compounds that have an action of promoting the delivery of electrons may coexist. Thereby, photoelectric conversion efficiency can be improved more reliably.
[0032]
More specifically, examples of the substance constituting the redox pair include halogens such as iodine, bromine, and chlorine, halides such as dimethylpropylimidazolium iodide, tetrapropylammonium iodide, and lithium iodide. Can be mentioned.
[0033]
In addition, examples of compounds for efficiently transferring electrons other than saccharin compounds include heterocyclic compounds such as 4-t-butylpyridine and N-methylbenzimidazole.
[0034]
The saccharin compound used for the electrolyte E is at least one compound selected from the group consisting of saccharin, saccharin salts, saccharin derivatives, and saccharin derivative salts, and each component included in the electrolyte exemplified above From the viewpoint of more reliably increasing the photocurrent density from the sensitizing dye to the surface of the semiconductor electrode (photoelectrode) while sufficiently suppressing the decrease in open-circuit voltage and the generation of dark current when combined, particularly among the above compounds It is preferable that it is a compound represented by following formula (1).
[Chemical 2]
[0035]
Here, in formula (1), X represents an alkali metal atom, R represents an alkyl group having 1 to 5 carbon atoms, an unsaturated chain hydrocarbon group having 2 to 5 carbon atoms, a halogen atom, silyl And at least one substituent selected from the group consisting of a group and an alkylsilyl group, m represents an integer of 0 to 4, provided that when m is 2 to 4, each R is the same. May be different.
[0036]
Furthermore, from the same viewpoint as the viewpoint described above, particularly preferable compounds among the compounds represented by the formula (1) include saccharin, lithium saccharin, sodium saccharin, and potassium saccharin. These may be used alone or in any combination.
[0037]
Moreover, it is preferable that the density | concentration of the saccharin compound in the electrolyte E is 0.01-1 mol / L. When the concentration of the saccharin compound is less than 0.01 mol / L, the tendency that the liquid electrolyte cannot be sufficiently gelled increases. On the other hand, when the concentration of the saccharin compound exceeds 1 mol / L, there is a greater tendency for the problem of a decrease in ion conductivity of the electrolyte E to occur.
[0038]
The constituent material of the spacer S is not particularly limited, and for example, silica beads or the like can be used.
[0039]
Moreover, as a sealing material used for integrating the photoelectrode 10, the counter electrode CE, and the spacer S for the purpose of sealing the electrolyte E, it can be sealed so that the components of the electrolyte E do not leak to the outside as much as possible. Although there is no particular limitation, for example, an epoxy resin, a silicone resin, an ethylene / methacrylic acid copolymer, a thermoplastic resin made of surface-treated polyethylene, or the like can be used.
[0040]
Next, an example of a method for manufacturing the dye-sensitized solar cell 20 shown in FIG. 1 will be described.
[0041]
When manufacturing the transparent electrodes 1, it can form a transparent conductive film 3 of fluorine-doped SnO 2 or the like as described above on a substrate 4 such as a glass substrate using known thin film manufacturing technique such as spray coating . For example, in addition to this, it can be formed using a known thin film manufacturing technique such as a vacuum deposition method, a sputtering method, a CVD method, and a sol-gel method.
[0042]
Examples of a method for forming the semiconductor electrode 2 on the transparent conductive film 3 of the transparent electrode 1 include the following methods. That is, first, a dispersion liquid in which oxide semiconductor particles having a predetermined size (for example, a particle diameter of about 10 to 30 nm) is dispersed is prepared. The solvent of this dispersion liquid is not particularly limited as long as it can disperse oxide semiconductor particles such as water, an organic solvent, or a mixed solvent of both. Moreover, you may add surfactant and a viscosity modifier to a dispersion liquid as needed.
[0043]
Next, the dispersion is applied onto the transparent conductive film 3 of the transparent electrode 1 and then dried. As a coating method at this time, a bar coater method, a printing method, or the like can be used. Then, after drying, the semiconductor electrode 2 (porous semiconductor film) is formed by heating and firing in air, inert gas or nitrogen.
[0044]
Next, a sensitizing dye is contained in the semiconductor electrode 2 by a known technique such as an adhesion method. The sensitizing dye is contained by adhering to the semiconductor electrode 2 (chemical adsorption, physical adsorption or deposition). As this adhesion method, for example, a method of immersing the semiconductor electrode 2 in a solution containing a dye can be used. At this time, adsorption and deposition of the sensitizing dye can be promoted by heating and refluxing the solution. At this time, a metal such as silver or a metal oxide such as alumina may be contained in the semiconductor electrode 2 in addition to the pigment, if necessary.
[0045]
The surface oxidation treatment for removing impurities that inhibit the photoelectric conversion reaction contained in the semiconductor electrode 2 may be appropriately performed by a known method every time each layer is formed or when all the layers are formed. .
[0046]
Other methods for forming the semiconductor electrode 2 on the transparent conductive film 3 of the transparent electrode 1 include the following methods. That is, a method of vapor-depositing a semiconductor such as TiO 2 on the transparent conductive film 3 of the transparent electrode 1 may be used. As a method for depositing a semiconductor on the transparent conductive film 3, a known thin film manufacturing technique can be used. For example, a physical vapor deposition method such as electron beam vapor deposition, resistance heating vapor deposition, sputter vapor deposition, or cluster ion beam vapor deposition may be used. Metal or the like is evaporated in a reactive gas such as oxygen, and the reaction product is converted into the transparent conductive film 3. A reactive vapor deposition method may be used. Furthermore, chemical vapor deposition such as CVD can be used by controlling the flow of the reaction gas.
[0047]
After the photoelectrode 10 is produced in this manner, for example, a counter electrode CE is produced by a known thin film manufacturing technique similar to the method used for producing the photoelectrode 10, and as shown in FIG. The counter electrode CE is assembled so as to be opposed to each other through the spacer S. At this time, the space formed between the photoelectrode 10 and the counter electrode CE by the spacer S is filled with the electrolyte E containing the saccharin compound, and the dye-sensitized solar cell 20 is completed.
[0048]
[Second Embodiment]
FIG. 2 is a schematic cross-sectional view showing a second embodiment of the dye-sensitized solar cell of the present invention. Hereinafter, the dye-sensitized solar cell 30 illustrated in FIG. 2 will be described. In addition, the same code | symbol is attached | subjected about the element same as the element demonstrated regarding the dye-sensitized solar cell 20 shown in the above-mentioned FIG. 1, and the overlapping description is abbreviate | omitted.
[0049]
A dye-sensitized solar cell 30 shown in FIG. 2 uses the photoelectrode 10 shown in FIG. 1 and a counter electrode CE similar to the counter electrode CE shown in FIG. In the dye-sensitized solar cell 20 shown in FIG. 1, the dye shown in FIG. 2 is compared with the case where the space formed between the photoelectrode 10 and the counter electrode CE is filled with the electrolyte E by the spacer S. In the sensitized solar cell 30, the porous body layer PS is disposed between the photoelectrode 10 and the counter electrode CE. And the transparent substrate 6 is arrange | positioned at the surface on the opposite side to the porous body layer PS of counter electrode CE.
[0050]
The porous layer PS has a structure having a large number of pores, and the saccharin similar to that used in the dye-sensitized solar cell 20 shown in FIG. Electrolyte E containing the compound is impregnated and held.
[0051]
The electrolyte E is also held in the counter electrode CE in the semiconductor electrode 2 or depending on the constituent material used (for example, a porous conductive film such as carbon). The electrolyte leaks from the side surfaces of the semiconductor electrode 2, the porous body layer PS, and the counter electrode CE to the outside of the semiconductor electrode 2, the porous body layer PS, and the counter electrode CE of the dye-sensitized solar cell 30 shown in FIG. In order to prevent this, it is covered with a sealing material 5.
[0052]
The porous body layer PS is not particularly limited as long as it is capable of holding the electrolyte E and does not have electron conductivity. For example, you may use the porous body formed with the rutile type titanium oxide particle. Examples of constituent materials other than rutile type titanium oxide include zirconia, alumina, and silica.
[0053]
Moreover, as the sealing material 5, for example, a thermoplastic resin film such as polyethylene or an epoxy adhesive can be used. As the transparent substrate 6 disposed on the counter electrode CE side, a substrate similar to the transparent substrate 4 used for the transparent electrode 1 of the photoelectrode 10 can be used.
[0054]
Next, an example of a method for manufacturing the dye-sensitized solar cell 30 shown in FIG. 2 will be described. First, the photoelectrode 10 is produced in the same manner as the dye-sensitized solar cell 20 shown in FIG. Next, the porous layer PS is formed on the surface F22 of the semiconductor electrode 2 of the photoelectrode 10 by the same procedure as that for producing the semiconductor electrode 2 of the photoelectrode 10. For example, a dispersion (slurry) containing a constituent material of the porous layer PS such as rutile type titanium oxide may be prepared, and this may be applied to the surface F22 of the semiconductor electrode 2 and dried.
[0055]
For the counter electrode CE, for example, when a porous conductive film such as carbon is used as the counter electrode CE, for example, a carbon paste is prepared, and this is applied to the surface of the porous body layer PS and dried. May be formed. Then, the transparent substrate 6 is formed on the surface opposite to the porous layer PS side of the counter electrode CE by a known thin film manufacturing technique, and the side surfaces of the semiconductor electrode 2, the porous layer PS and the counter electrode CE are sealed with the sealing material 5. To complete the dye-sensitized solar cell 30.
[0056]
The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.
[0057]
For example, the dye-sensitized solar cell of the present invention may have a module form in which a plurality of batteries are provided as in the dye-sensitized solar cell 40 shown in FIG. The dye-sensitized solar cell 40 shown in FIG. 4 shows an example in which a plurality of the dye-sensitized solar cells 30 shown in FIG. 2 are provided in series.
[0058]
Compared to the dye-sensitized solar cell 30 shown in FIG. 2, the dye-sensitized solar cell 40 shown in FIG. 3 is different from the seal material 5 provided between the photoelectrodes 10 of single cells of adjacent solar cells. A groove is formed between the photoelectrode 10 of a single cell (hereinafter referred to as a single cell A).
[0059]
This groove is formed by scraping the semiconductor electrode 2 of the single cell A by a technique such as laser scribing. The portion of the groove in the vicinity of the sealing material 5 reaches the depth at which the layer of the transparent conductive film 3 of the transparent electrode 1 appears by completely removing the semiconductor electrode 2 portion. Further, in the vicinity of the semiconductor electrode 2 of the single cell A in this groove, the semiconductor electrode 2 portion and the transparent conductive film 3 portion are completely removed to reveal the transparent substrate 4 layer of the transparent electrode 1. It has reached.
[0060]
Further, in the vicinity of the sealing material 5 in the groove, the transparent conductive film 3 of the adjacent photoelectrode 10 and the portions of the semiconductor electrode 2 on the transparent conductive film 3 are not electrically contacted with each other. The edge part formed in the shape of a bowl of the porous body layer PS of the single cell A is inserted between these parts so as to contact the transparent substrate 4 of the transparent electrode 1.
[0061]
Further, in the vicinity of the semiconductor electrode 2 of the single cell A in the groove, that is, in the portion between the porous layer PS of the single cell A and the sealing material 5, the counter electrode CE of the single cell A has a bowl shape. The formed edge portion is inserted so as to be in contact with the transparent conductive film 3 of the transparent electrode 1 of the other single cell.
[0062]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and it demonstrates in more detail about the dye-sensitized solar cell of this invention, this invention is not limited to these Examples at all.
[0063]
(Example 1)
A photoelectrode having the same configuration as that of the photoelectrode 10 shown in FIG. 1 is prepared by the following procedure, and the same as the dye-sensitized solar cell 20 shown in FIG. 1 except that this photoelectrode is used. A dye-sensitized solar cell having a configuration (area of light receiving surface: 0.7 cm 2 ) was produced.
[0064]
First, a solution was prepared by suspending commercially available TiO 2 particles (trade name: “P25”, manufactured by Nippon Aerosil Co., Ltd.) in butyl carbitol containing hydroxypropyl cellulose (3 mass%). Next, this liquid was apply | coated on the transparent conductive glass substrate, and the titanium oxide electrode was obtained by baking at 450 degreeC in air | atmosphere for 30 minutes. Next, the titanium oxide electrode was converted into a red dye, di (thiocyanate) -N- (2,2′-bipyridyl-4,4′-dicarboxylic acid) -N ′-{2,2′-bipyridyl-4, 4′-Dicarboxylic acid-bis (tetrabutylammonium)}-ruthenium (II) dye (manufactured by Solaronics, trade name: “N719”) in an acetonitrile solution containing 5 mmol / L under a temperature condition of 25 ° C. Left for 24 hours. As a result, a sensitizing dye was adsorbed at about 1.1 × 10 −7 mol / cm 2 inside the semiconductor electrode to obtain a semiconductor electrode. The thickness of the layer made of an oxide semiconductor of the semiconductor electrode was about 10 μm.
[0065]
Next, a counter electrode having the same shape and size as the above photoelectrode was produced. First, an isopropanol solution of chloroplatinic acid hexahydrate was dropped on a transparent conductive glass, dried in the air, and then baked at 450 ° C. for 30 minutes to obtain a platinum sintered counter electrode. The counter electrode was previously provided with an electrolyte injection hole (diameter 1 mm).
[0066]
Next, dimethylpropylimidazolium iodide, iodine, 4-tert-butylpyridine, and lithium saccharin are dissolved in γ-butyrolactone serving as a solvent to obtain a liquid electrolyte (concentration of dimethylpropylimidazolium iodide: 0). 0.6 mol / L, lithium iodide concentration: 0.1 mol / L 4-tert-butylpyridine concentration: 0.5 mol / L, lithium saccharin concentration: 0.1 mol / L). Next, 8% by mass of 1,3: 2,4-di-O- (p-methylbenzylidene) -D-sorbitol (gelling agent) is added to the liquid electrolyte and dissolved by heating to form a gel. An electrolyte was obtained.
[0067]
Saccharin lithium was synthesized as follows. 0.1 mol of saccharin was dissolved in 200 mL of ion-exchanged water, and 0.05 mol of lithium carbonate was gradually added thereto with stirring to replace “H” of the —NH— group constituting the saccharin molecule with “Li”. Stirring was continued until the reaction was completely converged. After the convergence, water was distilled off to obtain white crystals. Then, this crystal was recrystallized from ion-exchanged water to obtain lithium saccharin.
[0068]
Next, a spacer S (trade name: “HIMILAN”, ethylene / methacrylic acid random copolymer ionomer film) manufactured by Mitsui Dupont Polychemical Co., Ltd. having a shape matched to the size of the semiconductor electrode is prepared and shown in FIG. As described above, the photoelectrode and the counter electrode were opposed to each other through a spacer, and each was bonded by thermal welding to obtain a battery casing (no electrolyte filled).
[0069]
Next, the gel electrolyte is melted by heating and injected into the housing from the hole of the counter electrode, and then the hole is closed with a member made of the same material as the spacer, and this member is thermally welded to the hole of the counter electrode to seal the hole. The dye-sensitized solar cell was completed. The gel electrolyte is in a liquid state in a heated state (90 ° C. or higher), but is gelled inside the battery by cooling after being injected into the battery casing.
[0070]
(Example 2)
A dye-sensitized solar cell was produced in the same procedure and conditions as in Example 1 except that a gel electrolyte prepared using a liquid electrolyte containing saccharin at the same concentration instead of saccharin lithium was used.
[0071]
(Example 3)
A dye-sensitized solar cell was produced in the same procedure and conditions as in Example 1 except that a gel electrolyte prepared using a liquid electrolyte containing saccharin potassium at the same concentration instead of saccharin lithium was used.
[0072]
Example 4
A dye-sensitized solar cell was produced in the same procedure and conditions as in Example 1 except that the thickness of the layer made of an oxide semiconductor of the semiconductor electrode was changed from about 10 μm to about 8 μm.
[0073]
(Example 5)
As a sensitizing dye, di (thiocyanate) -N- (2,2′-bipyridyl-4,4′-dicarboxylic acid) -N ′-{2,2′-bipyridyl-4,4′-dicarboxylic acid-bis ( Tetrabutylammonium)}-ruthenium (II) dye (manufactured by Solaronics, trade name: “N719”) instead of black dye, tri (thiocyanate) -NN′-N ″-(2,2 ': 6''2''-terbipyridyl-4,4'4''-tricarboxylic acid-tri-tetrabutylammonium) -ruthenium (II) dye (manufactured by Solaronics) and in liquid electrolyte A dye-sensitized solar cell was produced in the same procedure and conditions as in Example 1 except that the concentration of saccharin was changed from 0.1 mol / L to 0.3 mol / L.
[0074]
(Comparative Example 1)
A dye-sensitized solar cell was produced in the same procedure and conditions as in Example 1 except that a gel electrolyte prepared using a liquid electrolyte containing no saccharin lithium was used.
[0075]
(Comparative Example 2)
Dye sensitization was performed in the same procedure and conditions as in Example 1 except that a gel electrolyte prepared using a liquid electrolyte containing lithium iodide at the same concentration (0.1 mol / L) instead of saccharin lithium was used. Type solar cells were produced.
[0076]
(Comparative Example 3)
Dye sensitization in the same procedure and conditions as in Example 4 except that a gel electrolyte prepared using a liquid electrolyte containing lithium iodide at the same concentration (0.1 mol / L) instead of lithium saccharin was used. Type solar cells were produced.
[0077]
(Comparative Example 4)
Dye sensitization was carried out under the same procedure and conditions as in Example 5 except that a gel electrolyte prepared using a liquid electrolyte containing lithium iodide at the same concentration (0.3 mol / L) instead of saccharin lithium was used. Type solar cells were produced.
[0078]
[Battery characteristics test]
A battery characteristic test was performed according to the following procedure, and the energy conversion efficiency η of the dye-sensitized solar cells of Examples 1 to 3, Comparative Example 1, and Comparative Example 2 was measured.
[0079]
The battery characteristic test was performed by using a solar simulator (trade name; “WXS-85-H type” manufactured by Wacom) and irradiating 100 mW / cm 2 of pseudo-sunlight from a xenon lamp light source through an AM filter (AM1.5). It was done by doing.
[0080]
For each dye-sensitized solar cell, the current-voltage characteristics were measured at room temperature using an IV tester, and the open circuit voltage (Voc / V), short circuit current (Isc / mA · cm −2 ), fill factor ( FF) and the initial energy conversion efficiency η [%] (energy conversion efficiency after 1 minute has elapsed from the start of light irradiation). The results are shown in Table 1.
[0081]
[Table 1]
[0082]
As is clear from the results shown in Table 1, it was confirmed that the addition of the saccharin compound to the electrolytic solution is very effective in improving the photoelectric conversion efficiency of the dye-sensitized solar cell.
[0083]
Moreover, each dye-sensitized solar cell of Example 4, Example 5, and Comparative Example 3 and Comparative Example 4 is put in a thermostat kept at 60 ° C., and is stored in a light-shielded state and in a circuit-open state. It took out from the thermostat whenever time passed, measured the current-voltage characteristic similar to the above at room temperature, and calculated | required energy conversion efficiency (eta) after progress for a predetermined time. And the evaluation about the time-dependent change was obtained. The results are shown in FIGS.
[0084]
As is clear from the results regarding the dye-sensitized solar cells of Examples 4 and 5 and Comparative Examples 3 and 4 shown in FIGS. 4 and 5, Examples 4 and 5 according to the present invention are used. This dye-sensitized solar cell was confirmed to be able to maintain excellent photoelectric conversion performance even after being stored for a long time in an environment of 60 ° C. On the other hand, it was confirmed that the photoelectric conversion performance of the dye-sensitized solar cells of Comparative Example 1 and Comparative Example 2 was lowered with the passage of storage time.
[0085]
【The invention's effect】
As described above, according to the dye-sensitized solar cell of the present invention, it is possible to sufficiently prevent the reduction of the open circuit voltage and the generation of dark current, and the photocurrent density can be effectively increased. High photoelectric conversion efficiency can be obtained. Moreover, according to the dye-sensitized solar cell of the present invention, excellent photoelectric conversion performance even under a high temperature (60 to 85 ° C.) operating environment or under a high temperature (60 to 85 ° C.) storage condition. Can be maintained for a long time.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing the basic configuration of a first embodiment of a dye-sensitized solar cell of the present invention.
FIG. 2 is a schematic cross-sectional view showing a basic configuration of a second embodiment of the dye-sensitized solar cell of the present invention.
3 is a schematic cross-sectional view showing an example when a plurality of dye-sensitized solar cells shown in FIG. 2 are provided.
4 is a graph showing the change with time of η obtained for the dye-sensitized solar cells of Example 4 and Comparative Example 3. FIG.
5 is a graph showing the change with time of η obtained for the dye-sensitized solar cells of Example 5 and Comparative Example 4. FIG.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Transparent electrode, 2 ... Semiconductor electrode, 3 ... Transparent electrically conductive film, 4 ... Transparent substrate, 5 ... Sealing material, 6 ... Transparent substrate, 10 ... Photoelectrode, 20 ... Dye-sensitized solar cell, 30, 40 DESCRIPTION OF SYMBOLS ... Dye-sensitized solar cell, CE ... Counter electrode, E ... Electrolyte, F1, F2, F3 ... Light-receiving surface, F22 ... Back surface of semiconductor electrode 2, L10 ... Incident light, S ... Spacer, PS ... Porous body layer.

Claims (4)

  1. A photoelectrode having a semiconductor electrode having a light receiving surface and a transparent electrode disposed adjacent to the light receiving surface of the semiconductor electrode, and a counter electrode,
    A dye-sensitized solar cell in which the semiconductor electrode and the counter electrode are arranged to face each other via an electrolyte containing at least a sensitizing dye,
    The electrolyte contains at least one additive selected from the group consisting of saccharin, saccharin salt, saccharin derivative, and saccharin derivative salt;
    A dye-sensitized solar cell characterized by
  2. The dye-sensitized solar cell according to claim 1, wherein the saccharin derivative is represented by the following formula (1).
    [In the formula (1), X represents an alkali metal atom,
    R is at least one selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, an unsaturated chain hydrocarbon group having 2 to 5 carbon atoms, a halogen atom, a silyl group, and an alkylsilyl group. Indicates a substituent,
    m represents an integer of 0 to 4,
    However, when m is 2 to 4, each R may be the same or different. ]
  3. The compound represented by the formula (1) is saccharin, lithium saccharin, sodium saccharin or potassium saccharin,
    The dye-sensitized solar cell according to claim 2.
  4. The concentration of the additive in the electrolyte is 0.01 to 1 mol / L,
    The dye-sensitized solar cell according to any one of claims 1 to 3.
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