JP2006107771A - Electrolyte composition, photoelectric conversion element and dye-sensitized solar cell using this - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte composition as well as a photoelectric conversion element and a dye-sensitized solar cell using this with output voltage and photoelectric conversion efficiency improved without damaging features of nonvolatile ionic liquid having high charge transport power. <P>SOLUTION: A first electrolyte composition, mainly composed of ionic liquid, has a copper complex dissolved in the ionic liquid as a probe material, and contains the ionic liquid in which an absorbing maximum wavelength is observed at a wavelength side longer than the absorbing maximum wavelength of HMIm-I, when visible light spectrum is measured with a wavelength range at 550 nm or more and 800 nm or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrolyte composition used for a photoelectric conversion element such as a dye-sensitized solar cell, a photoelectric conversion element using the same, and a dye-sensitized solar cell.

Dye-sensitized solar cells have been developed by Gretzel et al. In Switzerland, have advantages such as high conversion efficiency and low manufacturing costs, and are attracting attention as new types of solar cells (for example, patent documents) 1, Patent Document 2, Non-Patent Document 1).
The schematic structure of a dye-sensitized solar cell is that it has a porous film that is composed of oxide semiconductor fine particles (nanoparticles) such as titanium dioxide on a transparent conductive electrode substrate and carries a photosensitizing dye. An electrode and a counter electrode provided opposite to the working electrode are provided, and an electrolyte containing a redox pair is filled between the working electrode and the counter electrode. In this type of dye-sensitized solar cell, the oxide semiconductor fine particles are sensitized by a photosensitizing dye that absorbs incident light such as sunlight, and an electromotive force is generated between the working electrode and the counter electrode. It functions as a photoelectric conversion element that converts power into electric power.
As an electrolyte, it is common to use an electrolytic solution in which a redox pair (also referred to as a redox pair) such as I ⁻ / I ₃ ^— is dissolved in an organic solvent such as acetonitrile. In addition, a configuration using a non-volatile ionic liquid, a configuration in which a liquid electrolyte is gelled with an appropriate gelling agent to form a pseudo-solid, a configuration using a solid semiconductor such as a p-type semiconductor, and the like are known. Yes.

The ionic liquid is also called a room temperature melting salt, and exists as a stable liquid in a wide temperature range including around room temperature, and is a salt composed of a cation and an anion. An ionic liquid has a very low vapor pressure and does not substantially evaporate at room temperature, so there is no concern about volatilization or ignition like a general organic solvent. It has been proposed (see, for example, Non-Patent Document 2).
Further, when an electrolytic solution (liquid) is used as the electrolyte, there is a risk that the electrolytic solution is exposed and leaks out (liquid leakage) when the manufacturing process or the cell is broken. Addition of an appropriate gelling agent has also been attempted as a countermeasure against liquid leakage (see, for example, Patent Document 3).

  As described above, in the technical field of dye-sensitized solar cells, cell characteristics may be deteriorated due to volatilization / scattering of volatile components in the electrolyte during long-term use, for example, outdoors. Development of a technique for suppressing the volatilization of the components in the electrolyte solution is required. Among these, the ionic liquid mentioned above is non-volatile and has a high charge transporting ability, and thus attempts to apply it to an electrolytic solution have attracted attention.

  However, the dye-sensitized solar cell is required to improve the photoelectric conversion efficiency. However, when an ionic liquid is used as the electrolyte of the dye-sensitized solar cell, the output voltage, the output current, etc. The improvement is desired because it is lower than the battery.

  Although an example in which 1-ethyl-3-methylimidazolium-bistrifluoromethanesulfonylimide or the like is applied as an ionic liquid has been reported, an output voltage is not obtained with a composition in which an iodine redox pair is simply dissolved. Low and satisfactory characteristics cannot be obtained (for example, see Non-Patent Document 3). In order to increase the conversion efficiency, for example, it is necessary to develop and select an ionic liquid that gives a higher output voltage.

In addition, in order to improve the voltage characteristics, a device for adding an additive such as 4-t-butylpyridine (TBP) has been devised (for example, see Non-Patent Document 4), but a large amount of such a volatile additive is added. This impairs the characteristics of the ionic liquid as the non-volatile electrolyte and is not necessarily desirable.
Japanese Patent No. 2664194 JP 2001-160427 A JP 2002-184478 A M. Graetzel et al., Nature (UK), 1991, No. 737, p. 353 N. Papageorgiou et al., J. Electrochem. Soc., (USA), 1996, 143 (10), p. 3099 H. Matsui, K. Okada, N. Tanabe, R. Kawano and M. Watanabe: Trans. Mater. Res. Soc. Jpn., 29 (3), 1017, 2004 SYHuang, et.al .: J. Phys. Chem. B, 101 (14), 2576, 1997

  The present invention has been made in view of the above circumstances, and is an electrolyte composition capable of improving output voltage and photoelectric conversion efficiency without impairing the characteristics of an ionic liquid that is nonvolatile and has a high charge transport ability. An object of the present invention is to provide a photoelectric conversion element and a dye-sensitized solar cell using the same.

  An electrolyte composition according to claim 1 of the present invention (hereinafter also referred to as a first electrolyte composition) is an electrolyte composition in which an ionic liquid constitutes a main component, and copper is contained in the ionic liquid. Contains an ionic liquid in which the absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I when the complex is dissolved as a probe substance and the visible absorption spectrum is measured with a wavelength range of 550 nm to 800 nm. It is characterized by having.

  An electrolyte composition according to claim 2 of the present invention (hereinafter also referred to as a second electrolyte composition) is an electrolyte composition comprising an ionic liquid, and as an at least one component of the ionic liquid. When a visible light absorption spectrum is measured with a copper complex dissolved in an ionic liquid as a probe substance and a wavelength range of 550 nm to 800 nm, the absorption maximum wavelength is observed on the longer wavelength side of the HMIm-I absorption maximum wavelength. It is characterized by containing an ionic liquid.

  The electrolyte composition according to claim 3 of the present invention is the electrolyte composition according to claim 1 or 2, and is in a form of a gel.

  A photoelectric conversion element according to claim 4 of the present invention (hereinafter also referred to as a first photoelectric conversion element) includes the electrolyte composition according to any one of claims 1 to 3 as an electrolyte. .

  A photoelectric conversion element according to claim 5 of the present invention (hereinafter also referred to as a second photoelectric conversion element) is opposed to a working electrode having a dye-supported oxide semiconductor porous film on an electrode substrate. The electrolyte layer which consists of the electrolyte composition of any one of Claims 1 thru | or 3 was provided between the said working electrode and a counter electrode.

  A dye-sensitized solar cell according to claim 6 of the present invention includes a working electrode having a dye-supported oxide semiconductor porous film on an electrode substrate, and a counter electrode disposed to face the working electrode. An electrolyte layer made of the electrolyte composition according to any one of claims 1 to 3 is provided between the working electrode and the counter electrode.

The first electrolyte composition according to the present invention is an electrolyte composition comprising an ionic liquid as a main component, and a copper complex is dissolved in the ionic liquid as a probe substance, and the wavelength range is 550 nm or more. When the visible absorption spectrum is measured at 800 nm or less, it contains an ionic liquid whose absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I. By applying it to a sensitized solar cell, the output voltage is increased, and consequently the photoelectric conversion efficiency is improved.
The ionic liquid in the first electrolyte composition is a main component in the composition, and other ionic liquids may be mixed within the range. Here, the main component is not only the most abundant component (the content is the first component), but when it is contained in an approximately equivalent ratio, the second and subsequent components (for example, the first component) Second component).
In other words, if the ionic liquid is composed of main components and the ionic liquid is an ionic liquid whose absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I, The effect is brought about.

A second electrolyte composition according to the present invention is an electrolyte composition comprising an ionic liquid, wherein at least one component of the ionic liquid includes a copper complex as a probe substance in the ionic liquid. This is a composition containing an ionic liquid in which an absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I when a visible absorption spectrum is measured with a wavelength range of 550 nm to 800 nm. When applied to a dye-sensitized solar cell, the electrolyte composition consisting of increases the output voltage, and consequently improves the photoelectric conversion efficiency.
It means that the ionic liquid in the second electrolyte composition does not need to be a main component in the composition, and may be positioned as an additive. That is, the second electrolyte composition may contain, for example, a volatile component in addition to the ionic liquid.
In other words, even if the ionic liquid does not constitute a main component, if it contains at least an ionic liquid whose absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I, its inclusion Regardless of the amount, the above actions and effects are brought about.

  Moreover, by using the electrolyte composition having the above structure as an electrolyte or an electrolyte layer of a photoelectric conversion element, there is provided a photoelectric conversion element or a dye-sensitized solar cell that can stably achieve high output characteristics and photoelectric conversion characteristics. can get.

  Below, one Embodiment of the electrolyte composition which concerns on this invention is described based on drawing.

  First, an electrolyte composition comprising an ionic liquid as a main component, in which a copper complex is dissolved as a probe substance in the ionic liquid, and a visible light absorption spectrum is measured with a wavelength range of 550 nm to 800 nm. Next, a mode (first electrolyte composition) containing an ionic liquid in which the absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I will be described.

FIG. 1 is a graph showing the results of measuring a visible absorption spectrum by dissolving a probe substance for various ionic liquids according to the present invention. The graph of FIG. 1 shows [Cu (acac) (tmen)] BPh ₄ as shown in FIG. 2 in four kinds of ionic liquids (HMIm-I, BP-TFSI, BP-DCA, EMIm-TA). As a probe substance, a visible light absorption spectrum was measured with a wavelength range of 550 nm to 800 nm. Here, “acac” means “acetylacetone” and “tmen” means “N, N, N ′, N′-tetramethylenediamine”. The absorption maximum wavelength observed in the range of 550 nm to 800 nm is referred to as λmax.

Also, the formal names of the four types of ionic liquids taken up here are as follows.
HMIm-I (English name: 1-Hexyl-3-methylimidazolium iodide / Japanese name: 1-hexyl-3-methylimidazolium iodide)
BP-TFSI (English name: N-butylpyridinium bis (trifluoromethanesulfonyl) imide / Japanese name: N-butylpyridinium bistrifluoromethanesulfonylimide)
BP-DCA (English name: N-butylpyridinium dicyanamide / Japanese name: N-butylpyridinium dicyanoamide)
EMIm-TA (English name: 1-ethyl-3-methylimidazolium trifluoroacetate / Japanese name: 1-ethyl-3-methylimidazolium trifluoroacetic acid)
The notation of the ionic liquid used here indicates that the portion described before with a hyphen (-sign) represents a cation, and the portion described behind represents an anion, and their structures. Is shown in FIGS. 4 (a) and 4 (b). In FIG. 4, cations and anions constituting other ionic liquids described later are also shown.

  From FIG. 1, it was found that the ionic liquid composed of HMIm-I (curve indicated by a dotted line) has an absorption maximum wavelength (referred to as λa) in the vicinity of the wavelength of 610 nm. On the other hand, in the ionic liquid (curve shown by the solid line) made of BP-TFSI, no absorption maximum was observed in the above wavelength range. Further, an ionic liquid composed of BP-DCA (curve indicated by a one-dot chain line) and an ionic liquid composed of EMIm-TA (curve indicated by a two-dot chain line) each have a wavelength of 630 to 640 nm located on the longer wavelength side than λa. It was confirmed that the region has absorption maximum wavelengths (λb and λc).

  FIG. 3 is a graph showing the relationship between the open electromotive force and the equilibrium potential of the iodine redox couple, in which a dye-sensitized solar cell using a large number of ionic liquids including the above four types as an electrolyte is prepared. The horizontal axis is listed in the order of the magnitude of λmax obtained by the above-described measurement of the visible light absorption spectrum, and the ionic liquid located on the right side has a larger λmax.

The following points became clear from FIG.
(1a) In an ionic liquid in which the magnitude of λmax is equal to or less than HMIm-I, the open electromotive voltage (Voc) can only be a value below 650 [mV].
(1b) On the other hand, in an ionic liquid in which the magnitude of λmax exceeds HMIm-I, the open electromotive force (Voc) is a numerical value exceeding 650 [mV].
(1c) On the other hand, the equilibrium potential (Eeq) does not depend on ionic liquids having different sizes of λmax and is scattered in the range of −175 to −250 [mV vs. Fc / Fc ⁺ ].

  From the results of the above (1a) to (1c), an ionic liquid is an electrolyte composition comprising a main component, and a copper complex is dissolved as a probe substance in the ionic liquid, and the wavelength range is 550 nm or more. An electrolyte composition containing an ionic liquid whose absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I when a visible absorption spectrum is measured at 800 nm or less is a dye-sensitized solar cell. Application has been found to increase the output voltage.

  5 and 6 are graphs showing IV curves (horizontal axis: voltage, vertical axis: photocurrent density) of a dye-sensitized solar cell using each of the ionic liquids described above as an electrolyte. In FIG. 5, ionic liquids having a λmax exceeding HMIm-I are referred to as group A, and these are collectively shown. On the other hand, in FIG. 6, ionic liquids having a λmax exceeding HMIm-I are called group B, and these are collectively shown.

Each line type in FIG. 5 represents the type of ionic liquid, a thick solid line is EMIm-TFSI (abbreviated as EMImTFSI), a thin solid line is EMIm-BF ₄ (abbreviated as EMImBF ₄ ), and a one-dot chain line is BMImPF ₆ (BMImPF _6). And a two-dot chain line is BP-TFSI (abbreviated as BPTFSI), and a dotted line is HMIm-I (abbreviated as HMImI).
Similarly, each line type in FIG. 6 also represents the type of ionic liquid. A thick solid line represents EMIm-DCA (abbreviated as EMImDCA), a thin solid line represents EMIm-TA (abbreviated as EMImTA), and a one-dot chain line represents EMIm-SCN ( (Abbreviated as EMImSCN), the two-dot chain line is BP-DCA (abbreviated as BPCCA).

  The point where each IV curve of group A intersects the horizontal axis (open circuit voltage Voc) is in the range of about 525 to 600 [mV] (FIG. 5), whereas Voc according to each IV curve of group B is 670 to 700. It is in the range of [mV] (FIG. 6). From this result, the open circuit voltage Voc is higher in the group B (ionic liquid in which the magnitude of λmax exceeds HMIm-I) than in the group A (ionic liquid in which the magnitude of λmax is less than or equal to HMIm-I). It was confirmed that

Table 1 shows the photocurrent density (Jsc [mA / cm ² ]) and open-circuit voltage (Voc [Voc [) of the dye-sensitized solar cell using each ionic liquid calculated from the graphs of FIGS. mV]), fill factor (FF), and photoelectric conversion efficiency (η [%]).

  From FIG. 5, FIG. 6 and Table 1, the electrolyte composition containing the ionic liquid described in the latter part of Table 1, that is, the electrolyte composition comprising the ionic liquid as the main component, An ionic liquid in which an absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I when a copper complex is dissolved as a probe substance and a visible absorption spectrum is measured with a wavelength range of 550 nm to 800 nm. It has been found that the electrolyte composition containing the first electrolyte composition (first electrolyte composition) increases the output voltage and improves the photoelectric conversion efficiency η when applied to a dye-sensitized solar cell.

  Next, an electrolyte composition comprising an ionic liquid, wherein at least one component of the ionic liquid, a copper complex is dissolved in the ionic liquid as a probe substance, and the wavelength range is 550 nm to 800 nm. In the following, a form (second electrolyte composition) containing an ionic liquid in which an absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I when a visible absorption spectrum is measured will be described. .

  In the case of a dye-sensitized solar cell using an electrolyte containing an iodine redox couple, the output voltage of the dye-sensitized solar cell can also be increased by using a solvent or additive whose Lewis basicity is higher than that of iodide ions. Can be increased.

FIG. 7 is a graph showing an IV curve (horizontal axis: voltage, vertical axis: photocurrent density) of a dye-sensitized solar cell using an electrolyte composition containing BPDCA or TBP as an additive as an electrolyte. As the main solvent or a component of the mixed solvent, methylAN (English name: methoxyacetonitrile / Japanese name: methoxyacetonitrile) was used for the electrolytic solution here.
Each line type in FIG. 7 represents the type of solvent and additive, and the contents thereof are as follows.
A thick solid line represents a comparative example, and represents a composition not containing BP-DCA (abbreviated as DCA; English name: N-butylpyridinium dicyanamide / Japanese name: N-butylpyridinium dicyanoamide) and TBP (solvent: methylAN). .
Represents.
The alternate long and short dash line represents a mixture of methylAN and DCA at a ratio of 9 to 1 (DCA is 0.55M).
A chain double-dashed line represents a mixture of METANAN and DCA in a 1: 1 ratio (DCA is 2.75M).
A dotted line represents a comparative example, and represents a solution obtained by adding 0.55M of TBP to the METANAN.

Table 2 shows the photocurrent density (Jsc [mA / cm ² ]), open-circuit voltage (Voc [mV]), fill factor (F) of the dye-sensitized solar cell using each electrolyte calculated from the graph of FIG. F.) and photoelectric conversion efficiency (η [%]) are collectively shown.

From FIG. 7 and Table 2, the following points became clear.
(2a) When no additive was used [solvent: methoxyAN (thick solid line)], the open circuit voltage was low.
(2b) In the case where DCA is added as an additive (one-dot chain line), the photocurrent density (Jsc) is reduced as compared with the case of methoxyAN alone (thick solid line), but the open circuit voltage (Voc) is 628 [mV]. As a result, the fill factor (FF) slightly increased to 0.62. As a result, the photoelectric conversion efficiency (η) was further improved to 4.4 [%].
(2c) In the case where the addition amount of DCA is further increased (two-dot chain line), the photocurrent density (Jsc) is reduced as compared with the case of methoxyAN alone (thick solid line), but the open circuit voltage (Voc) is further 665. It increased to [mV] and the fill factor (FF) could be improved to 0.63.
(2d) The one containing TBP as an additive (dotted line) has a photocurrent density (Jsc) of 11.0 [mA / cm ² ], an open circuit voltage (Voc) of 681 [mV], a fill factor (F. F.) has a performance of 0.58 and a photoelectric conversion efficiency (η) of 4.3 [%]. However, since TBP forming this additive is volatile, it is not always preferable for maintaining the effect as an additive for a long period of time.

  From the results of (2a) to (2d) above, an electrolyte composition comprising an ionic liquid, wherein at least one component of the ionic liquid has a copper complex as a probe substance in the ionic liquid. An electrolyte composition comprising an ionic liquid that is dissolved and has an absorption maximum wavelength observed on a longer wavelength side than the absorption maximum wavelength of HMIm-I when a visible light absorption spectrum is measured at a wavelength range of 550 nm to 800 nm. It has been found that (second electrolyte composition) increases the output voltage and thus improves the photoelectric conversion efficiency η when applied to a dye-sensitized solar cell.

  That is, in the case of a dye-sensitized solar cell using an electrolytic solution containing an iodine redox couple, the output voltage increases when the Lewis basicity of the solvent or additive is higher than that of the iodide ion (conversely, the low In some cases, the Lewis basicity of iodide ions dominates). At present, the present inventors have inferred that such a Lewis basic component is adsorbed on the surface of the semiconductor porous film and appears to affect the Fermi level.

<Evaluation of Lewis basicity>
In the present invention, the copper complex {[Cu (acac) (tmen)] BPh ₄ , acac; acetylacetone, tmen; N, N, N ′, N′-tetramethylenediamine} shown in FIG. 2 was dissolved as a probe substance. The absorption maximum wavelength (λmax) of the solution is used as an indicator of Lewis basicity. The absorption maximum shifts to the longer wavelength side as the Lewis basicity of the coexisting sample, that is, the donor property is higher.

  When evaluating the Lewis basicity of an ionic liquid (liquid salt), a technique is used in which a visible absorption spectrum is measured by directly dissolving the probe substance in a target ionic liquid. When evaluating a solid salt, a salt having an anion similar to the target salt (for example, tetrabutylammonium salt) is used, and this and the probe substance are placed in a solvent having a sufficiently low Lewis basicity. It is recommended to use a method of dissolving and measuring the visible absorption spectrum [reference: RW Soukup et al., Bull. Chem. Soc. Jpn., 60, 2286 (1987)].

<Ionic liquid containing iodide ion>
When 1-hexyl-3-methylimidazolium iodide (HMImI) is used as an ionic liquid containing iodide ions according to the present invention, its λmax is observed in the vicinity of 610 [nm].

  Further, as a solid salt containing iodide ions, for example, when tetrabutylammonium iodide is dissolved in 1,2-dichloroethane together with a probe substance, λmax obtained by the above-described method can be used as an index. it can.

<Ionic liquid>
As an ionic liquid that gives an absorption maximum on the longer wavelength side than λmax (near 610 [nm]), for example, a dicyanoamide ion, a thiocyanate ion, a trifluoroacetate ion, an acetate ion, a bromide ion, Chloride ion, methyl sulfate [English name: methyl sulfate] ion, 1,2,4-triazole [English name: 1,2,4-triazole] ion, 1,2,3,4-tetrazole [English name: 1,2, 3,4-tetrazole] ion, 4,5-dicyano-1,2,3-triazole [English name: 4,5-dicyano-1,2,3-triazole] ion, tricyanomethanide; (C ( CN) ₃ ⁻ )] ion, trifluoromethanesulfonic acid ion and the like.
Further, the cation is not particularly limited. For example, quaternized imidazolium ions (such as 1,2-dialkylimidazolium ions), pyrididium ions (such as butylpyridium ions), and pyrrolidinium ions. Examples thereof include ions (such as butylmethylpyrrolidinium ion), tetraalkylammonium ions, and derivatives thereof.

<Solid salt>
As a solid salt that gives an absorption maximum on the longer wavelength side than λmax (near 610 [nm]), for example, a dicyanoamide ion, a thiocyanate ion, a trifluoroacetate ion, an acetate ion, a bromide ion, Chloride ion, methyl sulfate [English name: methyl sulfate] ion, 1,2,4-triazole [English name: 1,2,4-triazole] ion, 1,2,3,4-tetrazole [English name: 1,2, 3,4-tetrazole] ion, 4,5-dicyano-1,2,3-triazole [English name: 4,5-dicyano-1,2,3-triazole] ion, tricyanomethanide; (C ( CN) ₃ ⁻ )] ion, trifluoromethanesulfonic acid ion and the like.
Further, the cation is not particularly limited, and examples thereof include alkali metal ions, alkaline earth metal ions, quaternized imidazolium ions (1,2-dialkylimidazolium ions, etc.), pyrididium ions ( Butylpyridinium ions, etc.), pyrrolidinium ions (such as butylmethylpyrrolidinium ions), tetraalkylammonium ions, and derivatives thereof.

In addition to the ionic liquid, the electrolyte composition may contain a solvent component or other ionic liquid. In the case of an ionic liquid, in addition to those having the above characteristics, those having, for example, bistrifluoromethanesulfonylimide ion, PF ₆ ⁻ , BF ₄ ⁻ , I ^{− and the} like can be used. Examples of counter cations at this time include quaternized imidazolium ions (1,2-dialkylimidazolium ions, etc.), pyrididium ions (butylpyridium ions, etc.), and pyrrolidinium ions (butylmethylpyrrolidini ion). And the like, tetraalkylammonium ions, and those having derivatives thereof. Examples of the molecular solvent include acetonitrile, methoxyacetonityryl, propionitrile, propylene carbonate, diethyl carbonate, and γ-butyrolactone. Moreover, it is not limited to the above.

<Additives>
In the electrolyte composition according to the present invention, lithium iodide, TBP, benzimidazole, lithium thiocyanate, or the like can be added without particular limitation, if necessary.

<Gel (Pseudo-solidification)>
The electrolyte composition according to the present invention may be quasi-solidified using a physical gelling agent, a chemical gelling agent, nanoparticles, or the like [reference document: for example, Japanese Patent Application No. 2003-347193]. The category of such a gel electrolyte includes a wide range of substances excluding self-fluidity found in liquid electrolytes, from agar-like appearances to pastes.

In the case of a physical gel, for example, a polyvinylidene fluoride-hexafluoropropylene copolymer or a sorbitol-based low molecular gelling agent is used. It can be obtained by adding a gelling agent capable of constructing the structure. Furthermore, a quasi-solid electrolyte in which various nanoparticles such as titanium oxide, silica, and carbon nanotubes are added to the electrolytic solution and gelled (pasted) can also be used.
The type of gelling agent is not particularly limited in any case.

<Dye-sensitized solar cell element>
The dye-sensitized solar cell element according to the present invention includes the above-described electrolyte composition as an electrolyte or an electrolyte layer, and includes, for example, one having a schematic cross-sectional view shown in FIG.
A dye-sensitized solar cell (photoelectric conversion element) 1 shown in FIG. 8 includes a working electrode (hereinafter also referred to as a window electrode) 6 having a dye-supported oxide semiconductor porous film 5 on an electrode substrate 2, and this function. A counter electrode 8 disposed opposite to the electrode 6 is provided, and an electrolyte layer 7 made of the above-described electrolyte composition according to the present invention is provided between the working electrode 6 and the counter electrode 8.

Below, each other element which comprises this dye-sensitized solar cell element is explained in full detail.
As the electrode substrate (hereinafter also referred to as electrode material) 2 constituting the window electrode 6, for example, a glass or transparent resin (PET, PEN, PC, PES, etc.) sheet or plate on which a transparent conductive film is formed is used. Can do. As the transparent conductive film, for example, ITO, SnO ₂ , fluorine-doped SnO ₂ (FTO) or the like can be used alone or in combination, but it is not particularly limited, and is in terms of light transmittance and conductivity. Choose one that fits your purpose of use. Further, in order to provide a conductive assist (collecting current) effect, a metal wiring or the like may be added within a range that does not significantly impair the light transmittance.

There are no particular limitations on the material and formation method of the oxide semiconductor porous film 5, but for example, TiO ₂ , SnO ₂ , WO ₃ , ZnO, Nb ₂ O _5, etc. are used alone or in combination. And can be obtained from commercially available fine particles or a colloidal solution obtained by a sol-gel method. As a method for forming a porous (material) film, various coating methods such as screen printing, ink jet printing, roll coating, doctor blade, spin coating, spray coating, for example, colloidal solution or dispersion (including additives as necessary) are used. In addition to coating using a fine particle, electrophoretic electrodeposition of fine particles, combined use of a foaming agent, or the like may be used.

  As sensitizing dyes, there can be used metal dyes such as ruthenium complexes, polyphylline, phthalocyanine, and other organic dyes such as eosin, rhodamine, merocyanine, etc. Depending on the semiconductor porous membrane to be used, an appropriate one can be selected (without being particularly limited).

  There are no particular limitations on the redox species in the electrolyte, but iodine / iodide ions, bromine / bromide ions, etc. can be selected. For example, in the former case, iodide salts (lithium salts, quaternized imidazoliums) can be selected. Salt, tetrabutylammonium salt or the like can be used alone or in combination) and iodine can be added alone or in combination.

As the counter electrode 8, for example, various carbon-based materials, platinum, gold, or the like is formed on a conductive or non-conductive substrate by vapor deposition or sputtering, or a platinum film is formed by heat treatment after coating with chloroplatinate. However, it is not particularly limited.
Based on the above, a photoelectric conversion element is obtained with a basic structure in which a window-side electrode and a counter electrode according to the present invention are arranged to face each other, an electrolyte is filled therebetween, and each cell is sealed by an appropriate technique. Can do.

  According to the present invention, an electrolyte composition capable of improving output voltage and photoelectric conversion efficiency without impairing the characteristics of a non-volatile ionic liquid having a high charge transport capability, and photoelectric conversion using the same An element and a dye-sensitized solar cell can be provided.

  Therefore, the electrolyte composition according to the present invention is prepared in advance because it is non-volatile. For example, it can be stored and stored in a desired place, and can be moved and transported without being restricted by the time after the production. Alternatively, an electrolyte composition having a high degree of freedom in handling is provided.

  Furthermore, by using the electrolyte composition according to the present invention, it becomes possible to easily maintain the initial characteristics over a long period of time, so that the long-term reliability of the photoelectric conversion element and the dye-sensitized solar cell excellent in long-term reliability In addition to improving the performance, it is possible to provide a high degree of freedom in the production speed of the production line and the design of the production process in mass production.

It is a graph which shows the result of having measured the visible light absorption spectrum about the various electrolyte composition which concerns on this invention. It is a figure which shows the probe substance which consists of a copper complex based on this invention. It is a graph which shows the relationship between the open electromotive force of the dye-sensitized solar cell using the ionic liquid which concerns on this invention as electrolyte, and the equilibrium potential of an iodine redox couple. It is a figure which illustrates the cation (cation) and the anion (anion) which comprise the ionic liquid which concerns on this invention. It is a graph which shows an example of IV curve of the dye-sensitized solar cell which used each ionic liquid as an electrolyte, respectively. It is a graph which shows another example of IV curve of the dye-sensitized solar cell which used each ionic liquid as an electrolyte, respectively. It is a graph which shows the IV curve of the dye-sensitized solar cell which used the electrolyte composition containing BPDCA or TBP as an additive as electrolyte. It is sectional drawing which shows an example of the photoelectric conversion element which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Dye-sensitized solar cell (photoelectric conversion element), 2 Electrode substrate, 5 Oxide semiconductor porous film | membrane carry | supported dye, 6 Working electrode, 7 Electrolyte layer, 8 Counter electrode.

Claims (6)

An electrolyte composition comprising an ionic liquid as a main component,
When a copper complex is dissolved in an ionic liquid as a probe substance and a visible absorption spectrum is measured with a wavelength range of 550 nm to 800 nm, an absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I. An electrolyte composition comprising an ionic liquid. An electrolyte composition comprising an ionic liquid,
As at least one component of the ionic liquid,
When a copper complex is dissolved in an ionic liquid as a probe substance and a visible absorption spectrum is measured with a wavelength range of 550 nm to 800 nm, an absorption maximum wavelength is observed on the longer wavelength side than the absorption maximum wavelength of HMIm-I. An electrolyte composition comprising an ionic liquid.   The electrolyte composition according to claim 1, wherein the electrolyte composition is in a gel form.   A photoelectric conversion element comprising the electrolyte composition according to any one of claims 1 to 3 as an electrolyte.   A working electrode having a dye-carrying oxide semiconductor porous film on an electrode substrate, and a counter electrode disposed opposite to the working electrode, wherein the working electrode and the counter electrode are disposed between the working electrode and the counter electrode. A photoelectric conversion element comprising an electrolyte layer made of the electrolyte composition according to any one of the above. A working electrode having a dye-carrying oxide semiconductor porous film on an electrode substrate, and a counter electrode disposed opposite to the working electrode, wherein the working electrode and the counter electrode are disposed between the working electrode and the counter electrode. A dye-sensitized solar cell, comprising an electrolyte layer made of the electrolyte composition according to any one of the above.

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