JP4421262B2 - Onium salt - Google Patents

Description

  The present invention relates to an electrochemical device such as a primary or secondary lithium battery, a dye-sensitized solar cell, an electric double layer capacitor, a display element, an electrodeposition bath, and an onium salt that can be used as a chemical synthesis medium.

  Lithium primary batteries, lithium secondary batteries, electrolytic capacitors, electric double layer capacitors, electrochromic display elements that have been widely used in recent years, or dye-sensitized types that have been studied for various practical applications in the future As a non-aqueous electrolyte solution in an electrochemical device such as a solar battery, an electrolyte was dissolved in an organic solvent such as ethylene carbonate, propylene carbonate, dimethoxyethane, γ-butyrolactone, N, N-dimethylformamide, tetrahydrofuran, or acetonitrile. Solutions have been used. However, since the organic solvent used in these electrolyte solutions is volatile and is a dangerous substance itself, there are problems in long-term reliability, durability, and safety.

  Therefore, various proposals have been made to apply an onium salt that is liquid at room temperature as an electrolyte without using an organic solvent as the electrolyte. For example, an onium salt composed of a 1-methyl-3-ethylimidazolium cation and a bistrifluoromethanesulfonic acid amide anion is liquid at ambient temperature and has been shown to exhibit high ionic conductivity (for example, Patent Documents). 1).

  In particular, it has been estimated that a dye-sensitized solar cell that has attracted attention in recent years can be manufactured at a manufacturing cost of 1/5 or less of a silicon solar cell. The photoelectric conversion efficiency in dye-sensitized solar cells is greatly influenced by the conductivity of triiodide ions and iodide ions in the electrolyte, and high ionic conductivity is required to obtain high photoelectric conversion efficiency. To do. In order to obtain such high ionic conductivity, it is important to make the viscosity of the electrolyte as low as possible. Iodide used as an electrolyte for dye-sensitized solar cells is a solid or extremely high-viscosity liquid. Conventionally, a low-viscosity electrolyte is prepared by mixing with a low-viscosity solvent. Was adopted.

  As an iodide used for such a purpose, 1-methyl-3-alkylimidazolium iodide is known (for example, Non-Patent Document 1).

JP-A-8-259543 Matsumoto Hajime, Matsuda Toshihiko, Kajiyama Hiroyuki, “Correlation between Physical Properties of Iodide Room Temperature Molten Salt and Dye-Sensitized Solar Cell Properties”, Polymer Preprints Japan, Polymer Society of Japan, 2001, Vol. 50, No. 13, p. 3464-3465

  However, a solar cell is usually installed in a place where sunlight is irradiated. However, when the solar battery is heated by this sunlight irradiation, for example, when installed on a roof, the temperature may rise to 100 ° C. or higher. And since the low-viscosity solvents as described above are usually highly volatile, they will volatilize over time when used at high temperatures. Therefore, when a solvent having high ion conductivity and low viscosity is used, the boiling point is lowered and the life is shortened. On the other hand, when a solvent having a high boiling point is used, the viscosity is increased and the photoelectric conversion efficiency is lowered. When a conventionally known electrolytic solution (charge transfer layer) is used, the photoelectric conversion efficiency and the durability at high temperature are There is a problem that it is difficult to achieve both.

  In order to solve this problem, in order to prevent volatilization, the electrolytic solution is made into a pseudo-solidified body, and more airtight sealing technology has been studied. However, these methods still provide sufficient durability. The current situation is not.

  Therefore, in order to increase the durability while obtaining high photoelectric conversion efficiency, a low-viscosity iodide is found that can adjust an electrolyte that exhibits high ionic conductivity without using a low-viscosity solvent. This was one of the major issues.

  In order to solve the above-mentioned problems, the present inventors diligently studied the correlation between the structure of the cation constituting the onium salt and its characteristics. As a result, the new finding that the iodide salt of the fluorinated pyridinium cation in which all five hydrogen atoms bonded to the heteroaromatic ring are replaced by fluorine atoms is lower than the viscosity of the corresponding pyridinium cation iodide salt that is not fluoride. Got. As a result of further studies, it was found that other iodide salts can be used as electrolytes for non-aqueous electrolytes when the number of substitution of fluorine atoms is 4 or more, and the present invention has been completed.

  That is, the present invention has the following general formula:

(In the formula, R ₁ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are a fluorine atom, a cyano group, or a total carbon number of 1; a to 4 substituted or unsubstituted alkyl group, and _{R 2, R 3, R 4} , R 5, 4 or more of the _{R 6} is a fluorine atom.)
It is an onium salt shown by.

  The onium salt of the present invention is a novel compound, and can be used as a liquid ionic compound having a low viscosity at room temperature, as an electrolyte for a non-aqueous electrolyte or as a solvent in chemical synthesis. In general, iodide salts are solid or liquid, and have high viscosity and low ionic conductivity. However, the cation in the onium salt of the present invention has at least four hydrogen atoms bonded to carbon atoms constituting the pyridinium ring. By substituting with a fluorine atom, even with iodide, the viscosity is low and high ionic conductivity is exhibited. The reason for this is not clear, but it is presumed that substitution with a fluorine atom disperses the positive charge and weakens the interaction between the iodide ion (anion) and the pyridinium cation.

  The onium salt of the present invention has the following general formula

(In the formula, R ₁ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are a fluorine atom, a cyano group, or a total carbon number of 1; a to 4 substituted or unsubstituted alkyl group, and _{R 2, R 3, R 4} , R 5, 4 or more of the _{R 6} is a fluorine atom.)
It is a compound shown by these.

  Such a pyridinium fluorinated cation has not been synthesized so far, but can have a significantly lower viscosity than other iodide salts.

In the onium salt, R ₁ is a substituted or unsubstituted alkyl group having 1 to 6 total carbons. The alkyl group may have a substituent. In that case, the alkyl group needs to have 6 or less carbon atoms including the carbon of the substituent.

  The alkyl group is not particularly limited except for the limitation of the number of carbon atoms, and may be linear, branched or cyclic. Specific examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups. In addition, when these alkyl groups have a substituent, the substituent is not particularly limited, but when the viscosity is lowered and it is used as an electrolytic solution in various electrochemical devices, undesirable electrochemical A halogen atom is preferable and a fluorine atom is more preferable because it is difficult to cause a chemical reaction. Specific examples of the alkyl group having such a substituent include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 3,3,3, -trifluoropropyl group, and the like.

  Among these, since the viscosity of the onium salt tends to be lower as the number of carbon atoms is smaller, an unsubstituted alkyl group having 1 to 4 carbon atoms or an alkyl group substituted with a fluorine atom is particularly preferable.

In the above formula, R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are a fluorine atom, a cyano group, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ₂ , R ₃ , R ₄ , 4 or more of R ₅ and R ₆ are fluorine atoms. When the number of fluorine atoms bonded to the pyridinium ring is 3 or less, the viscosity is not sufficiently low.

When R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is a substituted or unsubstituted alkyl group, the alkyl group is not particularly limited as long as the total carbon number is in the range of 1 to 4. In addition, when it has a substituent, the carbon number including the carbon which a substituent has needs to be 4 or less. Specifically, it is the same as the group having 1 to 4 carbon atoms among the groups exemplified as R ₁ and, for the same reason, is substituted by an unsubstituted alkyl group having 1 to 4 carbon atoms or a fluorine atom. Particularly preferred are alkyl groups.

When R ₂ , R ₃ , R ₄ , R ₅ or R ₆ is a cyano group or a substituted or unsubstituted alkyl group, the bonding position is not particularly limited, but the availability of raw materials and synthesis In consideration of the yield and the like, R ₄ is preferably the group.

  Although the manufacturing method of the onium salt of this invention is not specifically limited, It can manufacture suitably with the following methods. That is, the following formula corresponding to the target compound

(Wherein R _{2 to} R ₆ are the same as above)
Is a method in which an alkyl iodide (R ₁ -I) is reacted. The ratio of the fluorinated pyridine compound and the alkyl iodide to be used is not particularly limited, but the molar ratio of the fluorinated pyridine compound to the alkyl iodide is preferably 0.5 to 2: 1 from the viewpoint of reaction efficiency.

  The reaction conditions are not particularly limited, and can be performed under heating, cooling, pressurization, reduced pressure, and normal pressure, but it is preferably performed under heating in order to increase the yield. Although the reaction temperature is not particularly limited, it is difficult to react at room temperature, so that the reaction temperature is higher than 50 ° C., preferably 70 ° C., more preferably 85 ° C. or higher. On the other hand, if the temperature is too high, decomposition or volatilization of the raw material may occur.

  In the reaction, a solvent may or may not be used, but separation is facilitated after completion of the reaction by selecting an appropriate solvent that dissolves the raw material for production and does not dissolve the onium salt produced. Such a solvent is usually a nonpolar solvent, and specific examples include aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

  When such a solvent is used, since the produced target product and the organic solvent are phase-separated, the organic solvent layer is separated and removed after completion of the reaction, and the remaining solvent is removed by vacuum or heating. By removing, the target onium salt can be isolated.

Identification of the obtained onium salt is usually possible by NMR and mass spectrometry. That is, the spectrum of the hydrogen atom of R ₁ and R ₂ bonded to the nitrogen atom can be found by 1H-NMR. Moreover, it can be found that it is a fluorinated pyridinium ring from the mass number found by mass spectrometry.

  The onium salt of the present invention thus obtained has a low melting point and high ionic conductivity. Therefore, primary and secondary Li batteries, dye-sensitized (wet) solar cells, capacitors, and electrochromic displays alone. It can be suitably used as an electrochemical device such as an element, an electrolytic solution for plating, or as an electrolyte in these electrolytic solutions by adding another solvent, or as a solvent in a synthesis reaction or the like. Since the onium salt of the present invention has low viscosity, it has superior ionic conductivity at low temperatures compared to other conventionally known electrolytes. When used in the above applications, an electrochemical device having good low-temperature characteristics can be obtained. It can also be constructed.

  When used in such an electrochemical device, the onium salt of the present invention may be used alone as an electrolytic solution, and if necessary, for example, in order to further reduce the viscosity of the electrolytic solution, You may mix and use a well-known solvent as a solvent in electrolyte solution (In this case, the onium salt of this invention acts as an electrolyte in electrolyte solution). Examples of such solvents include carbonates of ethylene carbonate and propylene carbonate, nitriles such as acetonitrile, methoxyacetonitrile, propionitrile, and methoxypropionitrile, and mixtures thereof. When these solvents are used, it is preferable to use a solvent having a boiling point of 100 ° C. or higher at normal pressure in order to take advantage of the feature that the onium salt of the present invention is nonvolatile.

Further, when used in combination with such a solvent, a matrix having a polymerizable group such as an acryloyl group or a methacryloyl group, for example, acrylonitrile or methacrylonitrile, is added to the matrix, and the matrix is added to the matrix. It can also be used in the form of retaining the onium salt of the invention and the above solvent.
Moreover, when using for these electrochemical devices, you may add another well-known electrolyte as needed. For example, in the case of a dye-sensitized solar cell, a metal iodide such as lithium iodide, sodium iodide, or potassium iodide, an alkyl ammonium iodide, a quaternary pyridinium iodide, or a quaternary imidazolium iodide. An electrolyte used in conventional dye-sensitized solar cells can be further added. In addition, additives such as tert-butylpyridine and N-methylbenzimidazole can be added and used.
When such other components are blended and used in an electrochemical device, the concentration of the onium salt of the present invention is not particularly limited, and may be appropriately set as necessary. Preferably, for example, when used as a charge transfer layer (electrolyte) of a dye-sensitized solar cell, a small amount may decrease the amount of short-circuit current and cause a decrease in photocurrent conversion efficiency. It is preferable to set it to mol / l or more.
In either case, the onium salt of the present invention may be used alone or in combination of a plurality of types.
Hereinafter, the synthesis method of the compound used in the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

1. NMR measurement 10 to 20 mg of a sample was dissolved in about 1 ml of dimethyl sulfoxide-d6 (containing 1,4-bistrifluoromethylbenzene as a standard substance), and ¹ H nucleus was measured by JEOL nuclear magnetic resonance apparatus JNM-LA500. .

2. Method for Measuring Photoelectric Conversion Efficiency A dye-sensitized solar cell was prepared by the following method using each onium salt, and the photoelectric conversion efficiency was measured using the dye-sensitized solar cell. Photochemical cells can be produced by the method described in paragraphs 44 to 53 of “The latest technology of dye-sensitized solar cells” (CMC Corporation, 2001) and on the homepage of the Institute for Multidisciplinary Research for Advanced Materials on the Internet. Based on the published method (kuroppe.icrs.tohoku.ac.jp/~masaki/wet_cell/main-j.htm), etc. The conversion efficiency was measured as shown in (4) below.

(1) Production of semiconductor electrode 125 ml of titanium isopropoxide purchased from Wako Pure Chemical Industries, Ltd. was slowly added dropwise to 750 ml of 0.1 M nitric acid aqueous solution while stirring. After stirring at 80 ° C. for 8 hours, the mixture was allowed to cool to room temperature and then hydrothermally treated at 225 ° C. for 12 hours using an autoclave so that the titanium oxide content was adjusted to 11% by weight. To 1 part by weight of the obtained colloid solution, 0.02 to 0.05 parts by weight of Triton-X manufactured by Wako Pure Chemical Industries, Ltd. was added to obtain a uniform dispersion. This dispersion was applied to a glass substrate with tin oxide transparent electrodes doped with fluorine by a blade method, dried at 100 ° C. for 1 hour, and then fired at 450 ° C. for 1 hour. Thereafter, a drop of 0.1M titanium tetrachloride aqueous solution was dropped and left overnight. Thereafter, it was washed with water, dried again at 100 ° C. for 1 hour, and then fired at 450 ° C. for 1 hour.

(2) Fixation of dye The fixation of dye is the above titania in an ethanol solution containing 0.3 mmol of ruthenium sensitizing dye (cis-dicyanate-bis-2, 2′-dipyridyl-4, 4′-dicarboxylate) ruthenium (II). The plate was immersed and fixed overnight.

(3) Assembly of cell The titania substrate produced in the above (1) was used as a photoelectric conversion element, and a glass substrate obtained by sputtering platinum as a counter electrode was used. The electrode was sandwiched between spacers, and the injection port was sealed with an epoxy adhesive, leaving two injection ports, and the electrolyte was injected. After the injection, the injection port was sealed with an epoxy adhesive. Thereafter, a lead wire was attached to the electrode to obtain a photochemical battery.

(4) Measurement of photoelectric conversion efficiency The power generation performance was measured by irradiating the photochemical cell which produced the pseudo-sunlight which passed the light of 500W xenon lamp through the AM1.5 filter and the UV cut filter. Moreover, the photoelectric conversion efficiency before and behind irradiation for 240 hours at 80 degreeC was measured as a life test. The open circuit voltage, short circuit voltage, and conversion efficiency of the photoelectrochemical cell obtained by these are summarized in Table 1. In addition, as a numerical value indicating the degree of deterioration, conversion efficiency reduction degree = conversion efficiency after 240 hours / initial conversion efficiency X 100
Was used as an indicator of how much it had declined.

Example 1
Synthesis of 1-butyl-2,3,4,5,6-pentafluoropyridinium iodide Iodine 2.0 g (0.012 mol) 2,3,4,5,6-pentafluoropyridine was added to a thermometer, a dropping funnel, And a 50 mL three-necked flask equipped with a nitrogen balloon, 4.5 g (0.024 mol) of butyl iodide was added, and the mixture was reacted at 90 ° C. for 8 hours. Thereafter, this solution was concentrated overnight at 80 ° C. under reduced pressure to obtain 0.6 g of a reddish brown liquid. ^{In 1} H-NMR, 0.98 (t), 1.89 (m), 2.12 (m), and 4.58 (t) ppm derived from a butyl group were confirmed. Furthermore, in MS-ESI measurement (solvent: methanol: water = 1: 1), a cation having a molecular weight of 226, which is considered to be 1-butyl-2,3,4,5,6-pentafluoropyridinium cation, was observed. The above measurements confirmed that the desired iodide salt was synthesized.

Example 2
Synthesis of 1-butyl-4-cyano-2,3,5,6- tetrafluoropyridinium -iodide Instead of 2.0 g of 2,3,4,5,6-pentafluoropyridine, 4-cyano-2, The same operation as in Example 1 was performed except that 2.0 g of 3,5,6-tetrafluoropyridine was used to obtain 0.7 g of a reddish brown liquid. In 1H-NMR, 0.99 (t), 1.91 (m), 2.14 (m), 4.54 (t), and ppm derived from a butyl group were confirmed. Furthermore, in MSESI measurement (solvent: methanol: water = 1: 1), a cation having a molecular weight of 233, which is considered to be 1-butyl-4-cyano-2,3,5,6-pentafluoropyridinium cation, was observed. The above measurements confirmed that the desired iodide salt was synthesized.

Example 3
Synthesis of 1-butyl-4-methyl-2,3,5,6- tetrafluoropyridinium iodide iodide In place of 2.0 g of 2,3,4,5,6-pentafluoropyridine, 4-methyl-2, Except using 2.0 g of 3,5,6-tetrafluoropyridine, the same operation as in Example 1 was performed to obtain 0.9 g of a reddish brown liquid. In 1H-NMR, 0.99 (t), 1.93 (m), 2.17 (m), 4.51 (t), and ppm derived from a butyl group were confirmed. Further, in MSESI measurement (solvent: methanol: water = 1: 1), a cation having a molecular weight of 222, which is considered to be 1-butyl-4-methyl-2,3,5,6-pentafluoropyridinium cation, was observed. The above measurements confirmed that the desired iodide salt was synthesized.

Example 4
To 1-butyl-2,3,4,5,6-pentafluoropyridinium iodide synthesized in Example 1, iodine was added to 0.05 M and N-methylbenzimidazole to 0.5 M, and an electrolyte solution A dye-sensitized solar cell was manufactured using this electrolytic solution. The photoelectric conversion efficiency at the initial stage and after 240 hours was measured. The results are shown in Table 1.

Example 5
Instead of 1-butyl-2,3,4,5,6-pentafluoropyridinium iodide, 1-butyl-4-cyano-2,3,5,6-tetrafluoropyridinium synthesized in Example 2 The photoelectric conversion efficiency at the initial stage and after 240 hours was measured in the same manner as in Example 4 except that iodide was used. The results are shown in Table 1.

Example 6
Instead of 1-butyl-2,3,4,5,6-pentafluoropyridinium iodide, 1-butyl-4-methyl-2,3,5,6-tetrafluoropyridinium synthesized in Example 3 was used. The photoelectric conversion efficiency at the initial stage and after 240 hours was measured in the same manner as in Example 4 except that iodide was used. The results are shown in Table 1.

Comparative Example 1
Example 1 was repeated except that 1-butyl-2,6-difluoropyridinium iodide was used instead of 1-butyl-2,3,4,5,6-pentafluoropyridinium iodide. The photoelectric conversion efficiency at the initial stage and after 240 hours was measured. The results are shown in Table 1.

Comparative Example 2
Example 4 was used except that 1-methyl-3-propyl-2-fluoroloyazolium iodide was used instead of 1-butyl-2,3,4,5,6-pentafluoropyridinium iodide. Similarly, the photoelectric conversion efficiency at the initial stage and after 240 hours was measured. The results are shown in Table 1.

Comparative Example 3
Instead of 1-butyl-2,3,4,5,6-pentafluoropyridinium iodide, 1-butyl-pyridinium iodide, which is a compound in which the pyridinium ring is not substituted by a fluorine atom, was used. In the same manner as in Example 4 , the photoelectric conversion efficiency at the initial stage and after 240 hours was measured. The results are shown in Table 1.

Comparative Example 4
Electrolyte added by adding 0.3M lithium iodide, 0.5M 1,2-dimethyl-3-propylimidazolium iodide, 0.05M iodine, 0.5M N-methylbenzimidazole to propionitrile Adjusted. A dye-sensitized solar cell was manufactured using this electrolytic solution. The photoelectric conversion efficiency at the initial stage and after 240 hours was measured. The results are shown in Table 1.

  As shown in Table 1, the dye-sensitized solar cell using the fluorinated pyridinium salt of the present invention had good photoelectric conversion efficiency and durability. On the other hand, although the pyridinium ring is substituted with fluorine, Comparative Example 1 is an example when the number of substitution of fluorine atoms is less than that defined in the present invention, and Comparative Example is an example when using a conventionally known compound Although 2 and 3 were excellent in durability, the photoelectric conversion efficiency was inferior to the said Example.

Moreover, in the comparative example 4 using a volatile solvent, although the initial photoelectric conversion efficiency was favorable, it was inferior to durability.

Claims (3)

The following general formula

(In the formula, R ₁ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are a fluorine atom, a cyano group, or a total carbon number of 1; a to 4 substituted or unsubstituted alkyl group, and _{R 2, R 3, R 4} , R 5, 4 or more of the _{R 6} is a fluorine atom.)
Onium salt indicated by A nonaqueous electrolytic solution comprising the onium salt according to claim 1. An electrochemical device using the electrolytic solution according to claim 2.