WO2012165483A1 - Gel-like ion conductor - Google Patents
Gel-like ion conductor Download PDFInfo
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- WO2012165483A1 WO2012165483A1 PCT/JP2012/063937 JP2012063937W WO2012165483A1 WO 2012165483 A1 WO2012165483 A1 WO 2012165483A1 JP 2012063937 W JP2012063937 W JP 2012063937W WO 2012165483 A1 WO2012165483 A1 WO 2012165483A1
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- FOEYMRPOKBCNCR-UHFFFAOYSA-N C(C1)C11CCCCC1 Chemical compound C(C1)C11CCCCC1 FOEYMRPOKBCNCR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
Definitions
- the present invention relates to a gel ion conductor composed of an ionic organic compound and an ionic liquid.
- An ionic liquid is formed from a cation and an anion and is a liquid at room temperature, and is also called a room temperature molten salt.
- Such an ionic liquid has high ion conductivity, and is expected to be applied as an electrolyte for various electrochemical devices such as lithium secondary batteries, solar batteries, electric double layer capacitors, and electronic devices.
- a method of gelling an ionic liquid a method using a polymer gelling agent, a method of confining in a crosslinked polymer gel, a method of mixing solid fine particles, a method of mixing a metal salt, a method of using a low molecular gelling agent, etc. are known.
- Non-patent Document 1 Poly (vinylidene fluoride) -hexafluoropropylene copolymer (Non-patent Document 1) and polymers of acrylic acid or methacrylic acid derivatives having polyfluoroalkyl groups at both ends (Patent Document 1) are dissolved and gelled.
- the method of confining in a crosslinked polymer by carrying out a polymerization reaction in an ionic liquid (Patent Document 2 and Non-Patent Document 2) requires an addition amount of the polymer of 10-20 wt% or more and does not contain a gelling agent. Compared to the electrolyte, the decrease in electrical conductivity when gelled is large.
- a method of kneading solid fine particles such as silica (Non-patent Document 2) and conductive particles (Patent Document 3) or a method of gelling by dissolving a metal salt (Patent Document 4) is prepared by preparing an electric device, etc.
- the operability in actual use is not good.
- the method using a low molecular gelling agent (Patent Documents 5 and 6 and Non-Patent Document 3) requires only a small amount of gelling agent and has little decrease in conductivity. Has low mechanical strength.
- Patent Document 7 a novel ionic organic compound that can be used as a hydrogelator or methanol gelator and can be produced by a relatively simple process. It has not been studied at all about the use of water-soluble organic compounds as a gelling agent for non-aqueous ionic liquids.
- the present invention provides a gel-like ionic conductor comprising an ionic organic compound and an ionic liquid that can be applied to a wide range of uses as a pseudo-solid electrolyte by gelling an ionic liquid without impairing electrical conductivity. Objective.
- the present inventor has gelled an ionic liquid in which a part of the ionic organic compound has a specific anion portion. It was found that it is effective as an agent and does not substantially impair the conductivity of the ionic liquid.
- the present invention is based on such knowledge and has the following characteristics.
- (i) It consists of an ionic organic compound represented by the following general formula (1) and an ionic liquid, the concentration of the ionic organic compound is 0.9 g / L or more, and the anion portion of the ionic liquid is bis (trifluoro) Gel-like ionic conductor which is methanesulfonyl) amide (TFSA) or bis (fluorosulfonyl) amide (FSA).
- TFSA methanesulfonyl
- FSA fluorosulfonyl
- A is a quaternized nitrogen atom selected from N, N, N ′, N′-tetramethylalkanediamine optionally having a substituent having 1 to 10 carbon atoms between nitrogen atoms
- X represents a monovalent anion
- n is a positive integer
- its average value is in the range of 1 to 800.
- It consists of an ionic organic compound represented by the following general formula (1) and an ionic liquid, the concentration of the ionic organic compound is 10 g / L or more, and the anionic part of the ionic liquid is tetrafluoroborate
- X represents a monovalent anion
- n is a positive integer
- its average value weight average polymerization degree
- It consists of an ionic organic compound represented by the following general formula (1) and an ionic liquid, the concentration of the ionic organic compound is 5 g / L or more, and the anion portion of the ionic liquid is trifluoromethanesulfonate ion A gel-like ionic conductor having (Tf) and a cation moiety of 1-butyl-3-methylimidazolium (BMI).
- the ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-methyl-1-propylpyrrolidi Ni-bis (trifluoromethanesulfonyl) amide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) amide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammoni
- the ionic organic compound as a gelling agent hardly impairs the conductivity of the ionic liquid.
- the gel-like ionic conductor of the present invention can control the gel phase transition temperature and the mechanical strength of the gel by adjusting the concentration of the ionic organic compound.
- the gel ion conductor of the present invention can be applied to a wide range of applications such as lithium secondary batteries, solar cells, electric double layer capacitors, and various electrochemical devices such as electronics elements as a quasi-solid electrolyte in which an ionic liquid is gelled. Is possible.
- Example 2 is a photograph of a gel ion conductor of Example 1.
- Example 26 it is a figure which shows the gelatinizer density
- Example 26 it is a figure which shows the temperature dependence of the electrical conductivity of the mixture of the ionic organic compound of Formula (2), and ionic liquid (EMI, TFSA).
- Example 27 it is a figure which shows the cyclic voltammogram of the ionic organic compound of Formula (2).
- Example 28 it is a figure which shows the frequency dependence of the dynamic viscoelasticity of the gel [Formula (2), EMI, TFSA] similar to Example 1.
- Example 28 it is a figure which shows the strain dependence of the dynamic viscoelasticity of the gel [Formula (2), EMI, TFSA] similar to Example 1.
- FIG. 29 it is a figure which shows the relationship between the gel-sol phase transition temperature and ionic organic compound density
- FIG. 29 it is a figure which shows the relationship between the gel-sol phase transition temperature of the gel [Formula (5), Py13, FSA] similar to Example 16, and an ionic organic compound density
- the ionic organic compound represented by the formula (1) of the present invention can be synthesized by a known method (Patent Document 7).
- a in the formula (1) is an N, N, N ′, N′-tetramethylalkanediamine which may have a substituent having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms between nitrogen atoms.
- a cationic functional group in which a nitrogen atom selected from is quaternized, and examples of the substituent include alkyl groups having about 1 to 6 carbon atoms such as methyl, ethyl and propyl groups, methoxy, ethoxy and propoxy groups. And an alkoxy group having about 1 to 6 carbon atoms.
- cationic functional group of A examples include, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N '-Tetramethylpropane-1,3-diamine, N, N, N', N'-tetramethylbutane-1,4-diamine, N, N, N ', N'-tetramethylhexane-1,6- Examples thereof include diamine, N, N, N ′, N′-tetramethyl-2-butene-1,4-diamine and the like.
- the cation portion is not limited.
- the anion portion is tetrafluoroborate (TFB) or trifluoromethanesulfonate ion (Tf)
- the cation portion is 1-butyl-3-methylimidazolium (BMI).
- ionic liquids in which the anion moiety is bis (trifluoromethanesulfonyl) amide include 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-butyl-3-methylimidazolium bis (trifluoro) Romethanesulfonyl) amide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) amide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) amide, N, N-diethyl-N-methyl -N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) amide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) amide, 1-ethyl-3-methylpyridinium bis (Trifluoromethanes
- ionic liquids in which the anion moiety is bis (fluorosulfonyl) amide include 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) amide, 1-butyl-3-methylimidazolium bis (fluorosulfonyl) Examples include, but are not limited to, amide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) amide, and the like.
- TFB tetrafluoroborate
- 1-butyl-3-methylimidazolium tetrafluoroborate is used as the ionic liquid.
- Tf trifluoromethanesulfonate ion
- Tf trifluoromethanesulfonate ion
- the gelling of the ionic liquid is accomplished by an operation in which the ionic organic compound is dissolved in the ionic liquid by heating at room temperature and below at the decomposition temperature of the ionic liquid represented by the formula (1).
- the mixed solution does not gel immediately, but can be handled as a liquid immediately after preparation, so that injection and filling operations into an electric device or the like are easy. Moreover, it is possible to return from a gel state to a liquid state by heating.
- the minimum concentration of the ionic organic compound necessary for gelation varies depending on the combination of the ionic organic compound and the ionic liquid. Generally, ionic organic compounds are used in the range of 0.9 g / L to 300 g / L.
- phase transition temperature of the gel and the mechanical strength of the gel can be controlled by adjusting the concentration of the ionic organic compound. Increasing the concentration raises the phase transition temperature of the gel and increases the mechanical strength of the gel.
- the gel-like ionic conductor composed of the ionic organic compound represented by the formula (1) and the ionic liquid has a small decrease in ionic conductivity because the ionic organic compound represented by the formula (1) itself is an ionic polymer, Excellent mechanical strength than low molecular gelling agents.
- the gel-like ionic conductor composed of the ionic organic compound and the ionic liquid is useful as a material that can be applied to a wide range of uses as a quasi-solid electrolyte.
- the gel ion conductor of the present invention can be used as it is as a quasi-solid electrolyte of various electrochemical devices or as a main component of the quasi-solid electrolyte.
- the quasi-solid electrolyte includes a small amount of component (for example, 20 wt% or less, preferably 10 wt% or less), for example, an ionic liquid other than the ionic liquid (preferably a non-aqueous ionic liquid), other organic or inorganic ionic conductors, and the like in a range where the gel state of the gel-like ionic conductor is maintained. Can be contained.
- the molecular weights of the ionic organic compounds of the formulas (2) and (3) used in the examples and comparative examples were measured by size exclusion chromatography of TFSA derivatives (using poly (methyl methacrylate) as a standard substance).
- the number average molecular weight (M n ) of the cation main chain portion is 1.20 ⁇ 10 4
- the weight average molecular weight (M w ) is 4.36 ⁇ 10 4
- M w / M n The degree of dispersion of molecular weight distribution (M w / M n ) is 3. It was estimated to be .6.
- the weight average degree of polymerization corresponds to 83.7.
- the ionic organic compound of formula (3) contains one molecule of water per repeating unit.
- an ionic liquid solution in which the concentration of the ionic organic compound was changed was created, and the lowest concentration of the ionic organic compound that formed the gel was defined as the lowest gelation concentration.
- Example 1 Concentrations of the ionic organic compound of formula (2) are 3 g / L, 5 g / L, 10 g / L, 20 g / L, 30 g / L, 40 g / L, 50 g / L, 100 g / L, 300 g / L
- 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide was placed in a 4 mL sample bottle and dissolved by heating to form a transparent solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. As can be seen in the photograph of FIG. 1, the gel did not drop the contents even when the sample bottle was inverted. When the same operation was performed so that the concentration of the ionic organic compound was 2 g / L or less, no gel was formed.
- Example 2 The ionic organic compound of the formula (2) is mixed with 1-butyl-3-methylimidazolium bis so that the concentration becomes 3 g / L, 5 g / L, 10 g / L, 50 g / L, 100 g / L, 300 g / L. Both (trifluoromethanesulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 2 g / L or less, no gel was formed.
- Example 3 The ionic organic compound of the formula (2) is used together with 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) amide so that the concentration is 10 g / L, 20 g / L, 50 g / L, 100 g / L.
- a transparent solution was obtained.
- gels were obtained at all the above concentrations.
- the concentration of the ionic organic compound was 9 g / L or less, no gel was formed.
- Example 4 The ionic organic compound of formula (2) is mixed with 1-methyl-1-sodium at a concentration of 4 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L, 300 g / L. Both propylpiperidinium bis (trifluoromethanesulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 3 g / L or less, no gel was formed.
- Example 5 The ionic organic compound of the formula (2) is mixed with N, N-diethyl-N-methyl-N- (2-methoxyethyl) so that the concentration is 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both ammonium bis (trifluoromethanesulfonyl) amide was placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 9 g / L or less, no gel was formed.
- Example 6 The ionic organic compound of formula (2) is mixed with 1-propyl-2,3,5-sodium so that the concentration is 6 g / L, 7 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both trimethylpyrazolium bis (trifluoromethanesulfonyl) amide was placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 5 g / L or less, no gel was formed.
- Example 7 The ionic organic compound of formula (2) is converted to 1-ethyl-3-methylpyridinium bis (trifluoromethanesulfonyl) such that the concentration is 4 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both amides were placed in a 4 mL sample bottle and dissolved by heating to a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 3 g / L or less, no gel was formed.
- Example 8 The ionic organic compound of the formula (3) is mixed with 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide so that the concentration is 10 g / L, 20 g / L, 50 g / L, 100 g / L. When placed in a 4 mL sample bottle and dissolved by heating, a clear solution was obtained. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 9 g / L or less, no gel was formed.
- Example 9 An ionic organic compound of the formula (2) is mixed with 1-butyl-3-methylimidazolium tetrafluoroborate so as to have a concentration of 20 g / L, 30 g / L, 50 g / L, 100 g / L, and an internal volume of 4 mL.
- a concentration of 20 g / L, 30 g / L, 50 g / L, 100 g / L, and an internal volume of 4 mL When the sample was placed in a sample bottle and dissolved by heating, a clear solution was obtained. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 10 g / L or less, no gel was formed.
- Example 10 The ionic organic compound of formula (2) is mixed with 1-butyl-3-methylimidazolium trifluoromethanesulfonate so that the concentration is 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L.
- a transparent solution was obtained.
- gels were obtained at all the above concentrations.
- the concentration of the ionic organic compound was 4 g / L or less, no gel was formed.
- Example 11 The ionic organic compound (295 mg) represented by the formula (3) used in Example 8 was dissolved in water (33 mL) at 100 ° C., and tetraethylammonium tetrafluoroborate (1.08 g) was dissolved in water (11 mL). The solution was added, stirred for 10 minutes and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (4) in a yield of 286 mg (yield 84%). This yield takes into account the structural water of the polymer and is the same in the following examples. Calcd (C 32 H 48 B 2 F 8 N 4 O 2 ⁇ (H 2 O) 0.5) C, 54.64; H, 7.02; N, 7.97% Measurements C, 54.38; H, 6.88; N, 7.96%
- Example 12 An ionic organic compound of the formula (4) is mixed with 4 mL content of 1-butyl-3-methylimidazolium tetrafluoroborate so that the concentration is 10 g / L, 20 g / L, 50 g / L, 100 g / L.
- a clear solution was obtained.
- a gel was obtained at all the above concentrations.
- the concentration of the ionic organic compound was 9 g / L or less, no gel was formed.
- Example 13 The ionic organic compound (295 mg) represented by the formula (3) used in Example 8 was dissolved in water (33 mL) at 100 ° C., and potassium bis (fluorosulfonyl) amide (1.10 g) was dissolved in water (7 mL). The dissolved solution was added, stirred for 10 minutes and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (5) in a yield of 417 mg (yield 97%). Calcd (C 32 H 48 F 4 N 6 O 10 S 4 ⁇ (H 2 O) 0.5) C, 43.18; H, 5.55; N, 9.44% Measured value C, 43.19; H, 5.29; N, 9.43%
- Example 14 The concentration of the ionic organic compound of formula (5) is 0.9 g / L, 1 g / L, 2 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L.
- Both 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) amide was placed in a 4 mL sample bottle and dissolved by heating to form a transparent solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 0.8 g / L or less, no gel was formed.
- Example 15 The ionic organic compound of the formula (5) is mixed with 1-butyl-3-methylimidazolium bis so that the concentration is 2 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both (fluorosulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 1 g / L or less, no gel was formed.
- Example 16 The ionic organic compound of formula (5) is mixed with 1-methyl-1-propylpyrrolidinium so that the concentration is 2 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both bis (fluorosulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 1 g / L or less, no gel was formed.
- Example 17 N, N ′-(trans-cyclohexane-1,4-diyl) bis [(4-chloromethyl) benzamide] (419 mg, 1.0 mmol) and N, N, N ′, N′-tetramethyl-1,4 Diaminobutane (144 mg, 1.0 mmol) was heated and stirred at 80 ° C. for 48 hours in N, N′-dimethylformamide (40 mL). The precipitate produced by the progress of the quaternization reaction was filtered off and washed with N, N′-dimethylformamide and acetone. After drying, an ionic organic compound represented by the following formula (6) was obtained in a yield of 448 mg (yield 77%). Calcd (C 30 H 44 Cl 2 N 4 O 2 ⁇ H 2 O) C, 61.95; H, 7.97; N, 9.63% Measured value C, 61.85; H, 7.82; N, 9.60%
- Example 18 The ionic organic compound (282 mg) represented by the formula (6) obtained in Example 17 was dissolved in water (33 mL) at 100 ° C., and lithium bis (trifluoromethanesulfonyl) amide (718 mg) was dissolved in water (7 mL). The dissolved solution was added, stirred for 10 minutes and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (7) in a yield of 496 mg (yield 97%). Calcd (C 34 H 44 F 12 N 6 O 10 S 4) C, 38.78; H, 4.21; N, 7.98% Measurements C, 38.94; H, 4.06; N, 8.16%
- Example 19 The ionic organic compound of the formula (7) is mixed with 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) so that the concentration is 6 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. ) Both amides were placed in a 4 mL sample bottle and dissolved by heating to a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 5 g / L or less, no gel was formed.
- Example 20 N, N ′-(trans-cyclohexane-1,4-diyl) bis [(4-chloromethyl) benzamide] (838 mg, 2.0 mmol) and N, N, N ′, N′-tetramerethylenediamine (232 mg, 2.0 mmol) was stirred in N, N′-dimethylformamide (80 mL) at 80 ° C. for 48 hours. The precipitate produced by the progress of the quaternization reaction was filtered off and washed with N, N′-dimethylformamide and acetone. After drying, an ionic organic compound represented by the following formula (8) was obtained in a yield of 851 mg (yield 78%). Elemental analysis: calculated value (C 28 H 40 Cl 2 N 4 O 2. (H 2 O) 0.5 ) C, 61.76; H, 7.59; N, 10.31% Measured value C, 61.49; H, 7.79; N, 10.35%
- Example 21 The ionic organic compound (429 mg) represented by the formula (8) obtained in Example 20 was dissolved in water (50 mL) at 100 ° C., and lithium bis (trifluoromethanesulfonyl) amide (2.30 g) was dissolved in water (14 mL). The solution dissolved in) was added and stirred for 10 minutes, and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (9) in a yield of 721 mg (yield 89%). Calcd (C 32 H 40 F 12 N 6 O 10 S 4) C, 37.50; H, 3.93; N, 8.20% Measured value C, 37.78; H, 3.80; N, 8.38%
- Example 22 An ionic organic compound of the formula (9) is mixed with 1 mL of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide so as to have a concentration of 20 g / L, 50 g / L, and 100 g / L. When it was put into a sample bottle and dissolved by heating, it became a transparent solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 10 g / L or less, no gel was formed.
- Example 23 N, N ′-(trans-cyclohexane-1,4-diyl) bis [(4-chloromethyl) benzamide] (1.68 g, 4.0 mmol) and N, N, N ′, N′-tetramethyl-1 , 4-Diaminodecane (914 mg, 4.0 mmol) was stirred in N, N′-dimethylformamide (160 mL) at 80 ° C. for 48 hours. The precipitate produced by the progress of the quaternization reaction was filtered off and washed with N, N′-dimethylformamide and acetone. After drying, an ionic organic compound represented by the following formula (10) was obtained in a yield of 448 mg (yield 92%). Elemental analysis: calculated value (C 36 H 56 Cl 2 N 4 O 2 ⁇ H 2 O) C, 64.94; H, 8.78; N, 8.42% Measured value C, 65.12; H, 8.75; N, 8.57%
- Example 24 The ionic organic compound (973 mg) represented by the formula (10) obtained in Example 23 was dissolved in water (85 mL) at 100 ° C., and lithium bis (trifluoromethanesulfonyl) amide (4.31 g) was dissolved in water (25 mL). The solution dissolved in) was added and stirred for 10 minutes, and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (11) in a yield of 1.55 g (yield 93%). Calcd (C 40 H 56 F 12 N 6 O 10 S 4) C, 42.25; H, 4.96; N, 7.39% Measured value C, 42.13; H, 4.78; N, 7.37%
- Example 25 The ionic organic compound of the formula (11) is mixed with 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) so that the concentration is 4 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. ) Both amides were placed in a 4 mL sample bottle and dissolved by heating to a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 3 g / L or less, no gel was formed.
- Example 26 The conductivity was measured by AC impedance method using Solartron 1260 impedance analyzer and Radiometer Analytical conductivity cell (CDC-749) while keeping the temperature constant in a thermostatic bath.
- the conductivity was calculated from the Cole-Cole plot using the standard potassium chloride solution for conductivity as the standard. In the case of only an ionic liquid and a gelling agent concentration of 3 g / L and above 35 ° C., it is in a liquid state and the others are in a gel state. 2 and 3 show the measurement results of conductivity.
- Example 27 The oxidation-reduction potential of the ionic organic compound of the formula (2) used in Examples 1 to 7, 9, and 10 was measured.
- the measurement conditions are as follows. The measurement results are shown in FIG.
- Working electrode: Glassy carbon disk electrode (diameter 1 mm)
- Counter electrode platinum Reference electrode: Ag / Ag + (0.1 mol dm ⁇ 3 Ag [TFSA] in PC) Scanning speed: 50 mV / s Temperature: 25 ° C
- the measurement was performed in an Ar gas substitution glove box.
- Example 28 The dynamic viscoelasticity measurement was performed using ARES-RFS of TA Instruments Japan Co., Ltd.
- FIG. 5 is a graph in which the vertical axis represents the storage elastic modulus (G ′) and loss elastic modulus (G ′′) at a strain of 1%, and the horizontal axis represents the frequency. From the viewpoint of rheology, it was proved that the gel exhibited quasi-solidity.
- FIG. 5 is a graph in which the vertical axis represents the storage elastic modulus (G ′) and loss elastic modulus (G ′′) at a strain of 1%, and the horizontal axis represents the frequency. From the viewpoint of rheology, it was proved that the gel exhibited quasi-solidity.
- FIG. 5 is a graph in
- FIG. 6 is a graph in which the vertical axis represents storage elastic modulus (G ′) and loss elastic modulus (G ′′) at a frequency of 1 Hz, and the horizontal axis represents strain.
- G ′ storage elastic modulus
- G ′′ loss elastic modulus
- Example 29 The sample bottle containing the gel was placed sideways in a water bath or oil bath and heated at 1 ° C./min to measure the gel-sol phase transition temperature.
- Gel-sol phase transition temperature The gel-sol phase transition temperature was set to a temperature at which the gel started to melt.
- FIG. 7 is a graph in which the vertical axis represents the gel-sol phase transition temperature and the horizontal axis represents the concentration of the ionic organic compound of formula (2).
- FIG. 8 is a graph in which the vertical axis represents the gel-sol phase transition temperature and the horizontal axis represents the concentration of the ionic organic compound of formula (5).
- Comparative Example 1 An ionic organic compound of the formula (2) is mixed with 4 mL content of 1-ethyl-3-methylimidazolium tetrafluoroborate so that the concentration is 5 g / L, 10 g / L, 100 g / L, 300 g / L. When the sample was placed in a sample bottle and dissolved by heating, a clear solution was obtained. When these were allowed to stand at room temperature, precipitation occurred at all the above concentrations.
- Comparative Example 2 The ionic organic compound of formula (4) is placed in a 4 mL internal volume sample bottle together with 1-ethyl-3-methylimidazolium tetrafluoroborate so as to have a concentration of 10 g / L, 20 g / L, and 200 g / L. When it was added and dissolved by heating, it became a clear solution. When these were allowed to stand at room temperature, precipitation occurred at all the above concentrations.
- Comparative Example 3 The ionic organic compound of the formula (2) is placed in a sample bottle having a content of 4 mL together with 1-butyl-3-methylimidazolium acetate so that the concentration is 5 g / L, 10 g / L, and 100 g / L. When heated and dissolved at 160 ° C., a transparent solution was obtained. When these were allowed to stand at room temperature, they remained viscous liquids at all the above concentrations.
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Abstract
Description
本発明は、イオン性有機化合物とイオン液体とからなるゲル状イオン導電体に関する。 The present invention relates to a gel ion conductor composed of an ionic organic compound and an ionic liquid.
イオン液体とは、カチオンとアニオンとから形成されており、室温において液体であるものをいい、常温溶融塩とも呼ばれている。このようなイオン液体は、イオン伝導性が高く、リチウム二次電池、太陽電池、電気二重層キャパシタ、エレクトロニクス素子用など各種電気化学デバイスの電解質としての応用が期待されている。 An ionic liquid is formed from a cation and an anion and is a liquid at room temperature, and is also called a room temperature molten salt. Such an ionic liquid has high ion conductivity, and is expected to be applied as an electrolyte for various electrochemical devices such as lithium secondary batteries, solar batteries, electric double layer capacitors, and electronic devices.
さらに、液体状態の電解質では、電池などからの電解質の漏洩の問題が存在することから、イオン性液体を含む固体(擬固体)電解質を形成するため、イオン液体をゲル化することが提案されている。 Furthermore, in the electrolyte in a liquid state, there is a problem of leakage of the electrolyte from a battery or the like. Therefore, in order to form a solid (pseudo-solid) electrolyte containing an ionic liquid, it is proposed to gel the ionic liquid. Yes.
イオン液体をゲル化する方法としては高分子ゲル化剤を用いる方法、架橋高分子ゲルに閉じ込める方法、固体微粒子を混入する方法、金属塩を混入する方法、低分子ゲル化剤を用いる方法などが知られている。 As a method of gelling an ionic liquid, a method using a polymer gelling agent, a method of confining in a crosslinked polymer gel, a method of mixing solid fine particles, a method of mixing a metal salt, a method of using a low molecular gelling agent, etc. Are known.
ポリ(ビニリデンフルオリド)－ヘキサフルオロプロピレン共重合体(非特許文献１)や両末端にポリフルオロアルキル基を有するアクリル酸またはメタクリル酸誘導体の高分子(特許文献１)を溶解してゲル化する方法、イオン液体中で重合反応を行い架橋高分子に閉じ込める方法(特許文献２、非特許文献２)は高分子の添加量が１０－２０ｗｔ％あるいはそれ以上必要で、ゲル化剤を含まない元の電解質に比べてゲルにしたときの電導度の低下が大きい。シリカ(非特許文献２)や導電性粒子(特許文献３)など固体微粒子を混練する方法あるいは金属塩を溶解してゲル化する方法(特許文献４)はゲル化を調製した後、電気デバイス等に注入・充填する必要があり実際に使用する場合の操作性がよくない。低分子ゲル化剤を用いる方法(特許文献５，６、非特許文献３)はゲル化剤の添加量が少なくて済み、導電性の低下も少ないが、一般的に低分子ゲル化剤によるゲルは機械的強度が小さい。
Poly (vinylidene fluoride) -hexafluoropropylene copolymer (Non-patent Document 1) and polymers of acrylic acid or methacrylic acid derivatives having polyfluoroalkyl groups at both ends (Patent Document 1) are dissolved and gelled. The method of confining in a crosslinked polymer by carrying out a polymerization reaction in an ionic liquid (
一方、本発明者は、ハイドロゲル化剤やメタノールゲル化剤として使用でき、比較的簡単な工程で製造できる新規なイオン性有機化合物を発明したが(特許文献７)、その時点では、該イオン性有機化合物を非水系イオン液体のゲル化剤として用いることについて全く検討されなかった。 On the other hand, the present inventor has invented a novel ionic organic compound that can be used as a hydrogelator or methanol gelator and can be produced by a relatively simple process (Patent Document 7). It has not been studied at all about the use of water-soluble organic compounds as a gelling agent for non-aqueous ionic liquids.
本発明は、導電性を損なうことなくイオン液体をゲル化することにより擬固体電解質としての幅広い用途に応用が可能なイオン性有機化合物とイオン液体とからなるゲル状イオン導電体を提供することを目的とする。 The present invention provides a gel-like ionic conductor comprising an ionic organic compound and an ionic liquid that can be applied to a wide range of uses as a pseudo-solid electrolyte by gelling an ionic liquid without impairing electrical conductivity. Objective.
上述のような従来技術を背景とし、上記イオン性有機化合物の可能性について研究を進める過程で、本発明者は、上記イオン性有機化合物の一部が特定のアニオン部を有するイオン液体のゲル化剤として有効であり、しかも、イオン液体の導電性をほとんど損なわないことを知見した。
本発明は、このような知見に基づくものであり、次のような特徴を有するものである。
(i)下記一般式(１)で表されるイオン性有機化合物とイオン液体とからなり、イオン性有機化合物の濃度は０.９ｇ／Ｌ以上を有し、イオン液体のアニオン部はビス(トリフルオロメタンスルホニル)アミド(ＴＦＳＡ)またはビス(フルオロスルホニル)アミド(ＦＳＡ)であるゲル状イオン導電体。
(ii)下記一般式(１)で表されるイオン性有機化合物とイオン液体とからなり、イオン性有機化合物の濃度は１０ｇ／Ｌ以上を有し、イオン液体のアニオン部はテトラフルオロボラート(ＴＦＢ)であり、カチオン部は１－ブチル－３－メチルイミダゾリウム(ＢＭＩ)であるゲル状イオン導電体。
(iii)下記一般式(１)で表されるイオン性有機化合物とイオン液体とからなり、イオン性有機化合物の濃度は５ｇ／Ｌ以上を有し、イオン液体のアニオン部はトリフルオロメタンスルホン酸イオン(Ｔｆ)であり、カチオン部は１－ブチル－３－メチルイミダゾリウム(ＢＭＩ)であるゲル状イオン導電体。
(iv)イオン液体が、１－エチル－３－メチルイミダゾリウムビス(トリフルオロメタンスルホニル)アミド、１－ブチル－３－メチルイミダゾリウムビス(トリフルオロメタンスルホニル)アミド、１－メチル－１－プロピルピロリジニウムビス(トリフルオロメタンスルホニル)アミド、１－メチル－１－プロピルピペリジニウムビス(トリフルオロメタンスルホニル)アミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－(２－メトキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)アミド、１－プロピル－２，３，５－トリメチルピラゾリウムビス(トリフルオロメタンスルホニル)アミド、１－エチル－３－メチルピリジニウムビス(トリフルオロメタンスルホニル)アミド、１－エチル－３－メチルイミダゾリウムビス(フルオロスルホニル)アミド、１－ブチル－３－メチルイミダゾリウムビス(フルオロスルホニル)アミド、１－メチル－１－プロピルピロリジニウムビス(フルオロスルホニル)アミドから選択されるものである上記(i)に記載のゲル状イオン導電体。
(v)上記(i)～(iv)のいずれか１項に記載のゲル状イオン導電体を主要部として含む電気化学デバイス用非水系擬固体電解質。
In the process of researching the possibility of the ionic organic compound against the background of the above-described conventional technology, the present inventor has gelled an ionic liquid in which a part of the ionic organic compound has a specific anion portion. It was found that it is effective as an agent and does not substantially impair the conductivity of the ionic liquid.
The present invention is based on such knowledge and has the following characteristics.
(i) It consists of an ionic organic compound represented by the following general formula (1) and an ionic liquid, the concentration of the ionic organic compound is 0.9 g / L or more, and the anion portion of the ionic liquid is bis (trifluoro) Gel-like ionic conductor which is methanesulfonyl) amide (TFSA) or bis (fluorosulfonyl) amide (FSA).
(ii) It consists of an ionic organic compound represented by the following general formula (1) and an ionic liquid, the concentration of the ionic organic compound is 10 g / L or more, and the anionic part of the ionic liquid is tetrafluoroborate ( A gel-like ionic conductor having a cation portion of 1-butyl-3-methylimidazolium (BMI).
(iii) It consists of an ionic organic compound represented by the following general formula (1) and an ionic liquid, the concentration of the ionic organic compound is 5 g / L or more, and the anion portion of the ionic liquid is trifluoromethanesulfonate ion A gel-like ionic conductor having (Tf) and a cation moiety of 1-butyl-3-methylimidazolium (BMI).
(iv) the ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-methyl-1-propylpyrrolidi Ni-bis (trifluoromethanesulfonyl) amide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) amide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethane Sulfonyl) amide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) amide, 1-ethyl-3-methylpyridinium bis (trifluoromethanesulfonyl) amide, 1-ethyl-3-methylimidazo Lilium bis (fluorosulfonyl) amide 1-butyl-3-methylimidazolium bis (fluorosulfonyl) amide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) amide conductor.
(v) A non-aqueous quasi-solid electrolyte for an electrochemical device comprising the gelled ionic conductor according to any one of (i) to (iv) as a main part.
本発明のイオン性有機化合物とイオン液体とからなるゲル状イオン導電体は、ゲル化剤としてのイオン性有機化合物がイオン液体の導電性をほとんど損なうことがない。
本発明のゲル状イオン導電体は、イオン性有機化合物の濃度を調整することによりゲルの相転移温度、ゲルの機械的強度を制御することができる。
本発明のゲル状イオン導電体は、イオン液体がゲル化された擬固体電解質として、リチウム二次電池、太陽電池、電気二重層キャパシタ、エレクトロニクス素子用など各種電気化学デバイス等の幅広い用途に応用が可能である。
In the gel-like ionic conductor comprising the ionic organic compound and the ionic liquid of the present invention, the ionic organic compound as a gelling agent hardly impairs the conductivity of the ionic liquid.
The gel-like ionic conductor of the present invention can control the gel phase transition temperature and the mechanical strength of the gel by adjusting the concentration of the ionic organic compound.
The gel ion conductor of the present invention can be applied to a wide range of applications such as lithium secondary batteries, solar cells, electric double layer capacitors, and various electrochemical devices such as electronics elements as a quasi-solid electrolyte in which an ionic liquid is gelled. Is possible.
本発明の式(１)で示されるイオン性有機化合物は、既知の方法で合成することができる(特許文献７)。
式(１)におけるＡは、窒素原子間の炭素数が１～１０、好ましくは炭素数が２～６の置換基を有してもよいＮ，Ｎ，Ｎ’，Ｎ’－テトラメチルアルカンジアミンから選択された窒素原子が四級化されたカチオン性官能基であり、該置換基としては、メチル、エチル、プロピル基等の炭素数１～６程度のアルキル基や、メトキシ、エトキシ、プロポキシ基等の炭素数１～６程度のアルコキシ基が挙げられる。
Ａのカチオン性官能基の具体例としては、例えばＮ，Ｎ，Ｎ’，Ｎ’－テトラメチルジアミノメタン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルプロパン－１，３－ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルブタン－１，４－ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルヘキサン－１，６－ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチル－２－ブテン－１，４－ジアミン等が挙げられる。
The ionic organic compound represented by the formula (1) of the present invention can be synthesized by a known method (Patent Document 7).
A in the formula (1) is an N, N, N ′, N′-tetramethylalkanediamine which may have a substituent having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms between nitrogen atoms. A cationic functional group in which a nitrogen atom selected from is quaternized, and examples of the substituent include alkyl groups having about 1 to 6 carbon atoms such as methyl, ethyl and propyl groups, methoxy, ethoxy and propoxy groups. And an alkoxy group having about 1 to 6 carbon atoms.
Specific examples of the cationic functional group of A include, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N '-Tetramethylpropane-1,3-diamine, N, N, N', N'-tetramethylbutane-1,4-diamine, N, N, N ', N'-tetramethylhexane-1,6- Examples thereof include diamine, N, N, N ′, N′-tetramethyl-2-butene-1,4-diamine and the like.
式(１)におけるアニオンＸは、限定するものではないが、例えば、ハロゲン化物イオン(Ｆ-，Ｃｌ-，Ｂｒ-，Ｉ-)、ビス(トリフルオロメタンスルホニル)アミドイオン、ビス(フルオロスルホニル)アミドイオン、テトラフルオロホウ酸イオン(ＢＦ4 ‐)、ヘキサフルオロリン酸イオン(ＰＦ6 ‐)、チオシアン酸イオン(ＳＣＮ‐)、硝酸イオン(ＮＯ3 ‐)、メト硫酸イオン(ＣＨ3ＯＳＯ3 ‐)、炭酸水素イオン(ＨＣＯ3 ‐)、次亜リン酸イオン(Ｈ2ＰＯ2 ‐)、各ハロゲンのオキソ酸イオン(ＸＯ4 ‐，ＸＯ3 ‐，ＸＯ2 ‐，ＸＯ‐：Ｘ＝Ｃｌ，Ｂｒ，Ｉ)、トリス(トリフルオロメタンスルホニル)炭素酸イオン、トリフルオロメタンスルホン酸イオン、ジシアナミドイオン、酢酸イオン(ＣＨ3ＣＯＯ‐)、ハロゲン化酢酸イオン((ＣＸnＨ3-n)ＣＯＯ-，Ｘ＝Ｆ，Ｃｌ，Ｂｒ，Ｉ；ｎ＝１，２，３)、テトラフェニルホウ酸イオン(ＢＰｈ4 -)およびその誘導体(Ｂ(Ａｒｙｌ)4 -：Ａｒｙｌ＝置換フェニル基)が挙げられる。好適には、イオン液体と同じアニオン(ＴＦＳＡ、ＴＦＢ、ＦＳＡ)とすることができる。 The anion X in the formula (1) is not limited, for example, halide ion (F − , Cl − , Br − , I − ), bis (trifluoromethanesulfonyl) amide ion, bis (fluorosulfonyl) amide Ion, tetrafluoroborate ion (BF 4 − ), hexafluorophosphate ion (PF 6 − ), thiocyanate ion (SCN − ), nitrate ion (NO 3 − ), methosulphate ion (CH 3 OSO 3 − ) , Bicarbonate ion (HCO 3 − ), hypophosphite ion (H 2 PO 2 − ), oxo acid ion of each halogen (XO 4 − , XO 3 − , XO 2 − , XO − : X = Cl, Br , I), tris (trifluoromethanesulfonyl) carbonic acid ion, trifluoromethanesulfonic acid ion, dicyanamide ion, acetate ion (CH 3 COO − ), halogenated acetate ion ((CX n H 3-n ) COO − , X═F, Cl, Br, I; n = 1,2,3), tetraphenylborate ion (BPh 4 − ) and its derivative (B (Aryl) 4 − : Aryl = substitution Phenyl group). Preferably, the same anion (TFSA, TFB, FSA) as the ionic liquid can be used.
本発明におけるイオン液体は、アニオン部がＴＦＳＡまたはＦＳＡである場合、カチオン部は限定されないが、アニオン部がテトラフルオロボラート(ＴＦＢ)またはトリフルオロメタンスルホン酸イオン(Ｔｆ)である場合、カチオン部は、１－ブチル－３－メチルイミダゾリウム(ＢＭＩ)である必要がある。
アニオン部がビス(トリフルオロメタンスルホニル)アミド(ＴＦＳＡ)であるイオン液体の例としては１－エチル－３－メチルイミダゾリウムビス(トリフルオロメタンスルホニル)アミド、１－ブチル－３－メチルイミダゾリウムビス(トリフルオロメタンスルホニル)アミド、１－メチル－１－プロピルピロリジニウムビス(トリフルオロメタンスルホニル)アミド、１－メチル－１－プロピルピペリジニウムビス(トリフルオロメタンスルホニル)アミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－(２－メトキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)アミド、１－プロピル－２，３，５－トリメチルピラゾリウムビス(トリフルオロメタンスルホニル)アミド、１－エチル－３－メチルピリジニウムビス(トリフルオロメタンスルホニル)アミドなどが挙げられるがこれらに限定されるものではない。
アニオン部がビス(フルオロスルホニル)アミド(ＦＳＡ)であるイオン液体の例としては１－エチル－３－メチルイミダゾリウムビス(フルオロスルホニル)アミド、１－ブチル－３－メチルイミダゾリウムビス(フルオロスルホニル)アミド、１－メチル－１－プロピルピロリジニウムビス(フルオロスルホニル)アミドなどが挙げられるがこれらに限定されるものではない。
アニオン部がテトラフルオロボラート(ＴＦＢ)である場合、イオン液体としては１－ブチル－３－メチルイミダゾリウムテトラフルオロボラートを用いる。
アニオン部がトリフルオロメタンスルホン酸イオン(Ｔｆ)である場合、イオン液体としては１－ブチル－３－メチルイミダゾリウムトリフルオロメタンスルホナートを用いる。
In the ionic liquid in the present invention, when the anion portion is TFSA or FSA, the cation portion is not limited. However, when the anion portion is tetrafluoroborate (TFB) or trifluoromethanesulfonate ion (Tf), the cation portion is 1-butyl-3-methylimidazolium (BMI).
Examples of ionic liquids in which the anion moiety is bis (trifluoromethanesulfonyl) amide (TFSA) include 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide, 1-butyl-3-methylimidazolium bis (trifluoro) Romethanesulfonyl) amide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) amide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) amide, N, N-diethyl-N-methyl -N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) amide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) amide, 1-ethyl-3-methylpyridinium bis ( (Trifluoromethanesulfonyl) Although such bromide and the like are not limited thereto.
Examples of ionic liquids in which the anion moiety is bis (fluorosulfonyl) amide (FSA) include 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) amide, 1-butyl-3-methylimidazolium bis (fluorosulfonyl) Examples include, but are not limited to, amide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) amide, and the like.
When the anion portion is tetrafluoroborate (TFB), 1-butyl-3-methylimidazolium tetrafluoroborate is used as the ionic liquid.
When the anion portion is trifluoromethanesulfonate ion (Tf), 1-butyl-3-methylimidazolium trifluoromethanesulfonate is used as the ionic liquid.
イオン液体をゲル化するには式(１)で示されるイオン液体の分解温度以下でイオン性有機化合物をイオン液体に加熱溶解し室温で放置する操作で達成される。混合液は直ちにゲル化するわけではなく、調製直後は液体として扱うことができるので、電気デバイス等への注入・充填操作も容易である。また加熱することによりゲル状態から液体状態に戻すことが可能である。ゲル化に必要なイオン性有機化合物の最少濃度は、イオン性有機化合物とイオン液体の組み合わせによって異なる。一般的にはイオン性有機化合物は０.９ｇ／Ｌから３００ｇ／Ｌの範囲で用いられる。望ましくは３ｇ／Ｌから２００ｇ／Ｌの範囲、より望ましくは１０ｇ／Ｌから１００ｇ／Ｌの範囲でもちいられる。イオン性有機化合物の濃度を調整することによりゲルの相転移温度、ゲルの機械的強度を制御することができる。濃度を大きくすればゲルの相転移温度は上昇し、ゲルの機械的強度は大きくなる。式(１)で示されるイオン性有機化合物とイオン液体からなるゲル状イオン導電体は、式(１)で示されるイオン性有機化合物自体がイオン性の高分子なのでイオン導電率の低下が小さく、低分子ゲル化剤より機械的強度に優れる。 The gelling of the ionic liquid is accomplished by an operation in which the ionic organic compound is dissolved in the ionic liquid by heating at room temperature and below at the decomposition temperature of the ionic liquid represented by the formula (1). The mixed solution does not gel immediately, but can be handled as a liquid immediately after preparation, so that injection and filling operations into an electric device or the like are easy. Moreover, it is possible to return from a gel state to a liquid state by heating. The minimum concentration of the ionic organic compound necessary for gelation varies depending on the combination of the ionic organic compound and the ionic liquid. Generally, ionic organic compounds are used in the range of 0.9 g / L to 300 g / L. Desirably, it is in the range of 3 g / L to 200 g / L, more desirably in the range of 10 g / L to 100 g / L. The phase transition temperature of the gel and the mechanical strength of the gel can be controlled by adjusting the concentration of the ionic organic compound. Increasing the concentration raises the phase transition temperature of the gel and increases the mechanical strength of the gel. The gel-like ionic conductor composed of the ionic organic compound represented by the formula (1) and the ionic liquid has a small decrease in ionic conductivity because the ionic organic compound represented by the formula (1) itself is an ionic polymer, Excellent mechanical strength than low molecular gelling agents.
上記イオン性有機化合物とイオン液体とからなるゲル状イオン導電体は、擬固体電解質としての幅広い用途に応用が可能な材料として有用なものである。
本発明のゲル状イオン導電体は、各種電気化学デバイスの擬固体電解質としてそのまま、又は、該擬固体電解質の主要成分として用いることができる。該擬固体電解質は、主要成分のゲル状イオン導電体を構成するイオン性有機化合物と、アニオン部がＴＦＳＡやＦＳＡ等であるイオン液体との外に、少量成分(例えば、２０ｗｔ％以下、好ましくは１０ｗｔ％以下)として、例えば、前記イオン液体以外のイオン性液体(好ましくは非水系イオン性液体)、他の有機又は無機イオン導電体などをゲル状イオン導電体のゲル状態が維持される範囲で含有することができる。
The gel-like ionic conductor composed of the ionic organic compound and the ionic liquid is useful as a material that can be applied to a wide range of uses as a quasi-solid electrolyte.
The gel ion conductor of the present invention can be used as it is as a quasi-solid electrolyte of various electrochemical devices or as a main component of the quasi-solid electrolyte. In addition to the ionic organic compound constituting the main component gel-like ionic conductor and the ionic liquid whose anion portion is TFSA, FSA or the like, the quasi-solid electrolyte includes a small amount of component (for example, 20 wt% or less, preferably 10 wt% or less), for example, an ionic liquid other than the ionic liquid (preferably a non-aqueous ionic liquid), other organic or inorganic ionic conductors, and the like in a range where the gel state of the gel-like ionic conductor is maintained. Can be contained.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれらの実施例により限定されるものではない。実施例・比較例で使用した式(２)および式(３)のイオン性有機化合物の分子量は、ＴＦＳＡ誘導体のサイズ排除クロマトグラフィーによる測定(標準物質として、ポリ(メチルメタクリラート)を使用)から、カチオン主鎖部分の数平均分子量(Ｍn)が１.２０×１０4、重量平均分子量(Ｍw)が４.３６×１０4、分子量分布の分散度(Ｍw/Ｍn)が３.６と見積もられた。重量平均重合度は８３.７に相当する。なお、元素分析より式(３)のイオン性有機化合物は繰り返し単位当たり１分子の水を含んでいる。ゲル化試験においてイオン性有機化合物の濃度を変えたイオン液体溶液を作成し、ゲルを形成したイオン性有機化合物の最低濃度を、最低ゲル化濃度とした。また、ゲルを形成してから１０日間放置しても、相分離や沈殿などを生じない場合はゲルが安定であると評価した。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The molecular weights of the ionic organic compounds of the formulas (2) and (3) used in the examples and comparative examples were measured by size exclusion chromatography of TFSA derivatives (using poly (methyl methacrylate) as a standard substance). The number average molecular weight (M n ) of the cation main chain portion is 1.20 × 10 4 , the weight average molecular weight (M w ) is 4.36 × 10 4 , and the degree of dispersion of molecular weight distribution (M w / M n ) is 3. It was estimated to be .6. The weight average degree of polymerization corresponds to 83.7. From the elemental analysis, the ionic organic compound of formula (3) contains one molecule of water per repeating unit. In the gelation test, an ionic liquid solution in which the concentration of the ionic organic compound was changed was created, and the lowest concentration of the ionic organic compound that formed the gel was defined as the lowest gelation concentration. Moreover, even if it left to stand for 10 days after forming a gel, when a phase separation, precipitation, etc. were not produced, it evaluated that a gel was stable.
実施例１
実施例２
式(２)のイオン性有機化合物を、濃度が３ｇ／Ｌ、５ｇ／Ｌ、１０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌ、３００ｇ／Ｌになるように１－ブチル－３－メチルイミダゾリウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が２ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 2
The ionic organic compound of the formula (2) is mixed with 1-butyl-3-methylimidazolium bis so that the concentration becomes 3 g / L, 5 g / L, 10 g / L, 50 g / L, 100 g / L, 300 g / L. Both (trifluoromethanesulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 2 g / L or less, no gel was formed.
実施例３
式(２)のイオン性有機化合物を、濃度が１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－メチル－１－プロピルピロリジニウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が９ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 3
The ionic organic compound of the formula (2) is used together with 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) amide so that the concentration is 10 g / L, 20 g / L, 50 g / L, 100 g / L. When the solution was placed in a 4 mL sample bottle and dissolved by heating, a transparent solution was obtained. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 9 g / L or less, no gel was formed.
実施例４
式(２)のイオン性有機化合物を、濃度が４ｇ／Ｌ、５ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌ、３００ｇ／Ｌになるように１－メチル－１－プロピルピペリジニウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が３ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 4
The ionic organic compound of formula (2) is mixed with 1-methyl-1-sodium at a concentration of 4 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L, 300 g / L. Both propylpiperidinium bis (trifluoromethanesulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 3 g / L or less, no gel was formed.
実施例５
式(２)のイオン性有機化合物を、濃度が１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／ＬになるようにＮ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－(２－メトキシエチル)アンモニウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が９ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 5
The ionic organic compound of the formula (2) is mixed with N, N-diethyl-N-methyl-N- (2-methoxyethyl) so that the concentration is 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both ammonium bis (trifluoromethanesulfonyl) amide was placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 9 g / L or less, no gel was formed.
実施例６
式(２)のイオン性有機化合物を、濃度が６ｇ／Ｌ、７ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－プロピル－２，３，５－トリメチルピラゾリウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が５ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 6
The ionic organic compound of formula (2) is mixed with 1-propyl-2,3,5-sodium so that the concentration is 6 g / L, 7 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both trimethylpyrazolium bis (trifluoromethanesulfonyl) amide was placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 5 g / L or less, no gel was formed.
実施例７
式(２)のイオン性有機化合物を、濃度が４ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－エチル－３－メチルピリジニウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が３ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 7
The ionic organic compound of formula (2) is converted to 1-ethyl-3-methylpyridinium bis (trifluoromethanesulfonyl) such that the concentration is 4 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both amides were placed in a 4 mL sample bottle and dissolved by heating to a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 3 g / L or less, no gel was formed.
実施例８
実施例９
式(２)のイオン性有機化合物を、濃度が２０ｇ／Ｌ、３０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－ブチル－３－メチルイミダゾリウムテトラフルオロボラートとともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が１０ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 9
An ionic organic compound of the formula (2) is mixed with 1-butyl-3-methylimidazolium tetrafluoroborate so as to have a concentration of 20 g / L, 30 g / L, 50 g / L, 100 g / L, and an internal volume of 4 mL. When the sample was placed in a sample bottle and dissolved by heating, a clear solution was obtained. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 10 g / L or less, no gel was formed.
実施例１０
式(２)のイオン性有機化合物を、濃度が５ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－ブチル－３－メチルイミダゾリウムトリフルオロメタンスルホナートともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が４ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 10
The ionic organic compound of formula (2) is mixed with 1-butyl-3-methylimidazolium trifluoromethanesulfonate so that the concentration is 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. When the solution was placed in a 4 mL sample bottle and dissolved by heating, a transparent solution was obtained. When these were allowed to stand at room temperature, gels were obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 4 g / L or less, no gel was formed.
実施例１１
実施例８で用いた式(３)で表されるイオン性有機化合物(２９５ｍｇ)を１００℃で水(３３ｍＬ)に溶かし、テトラエチルアンモニウムテトラフルオロボラート(１.０８ｇ)を水(１１ｍＬ)に溶かした溶液を加え、１０分間撹拌後室温まで冷却した。沈殿物をろ別し、水で洗浄した。風乾後、五酸化りんデシケータで乾燥し、下記の式(４)で表される化合物を収量２８６ｍｇ(収率８４％)で得た。この収率はポリマーが有する構造水を考慮したものであり、以下の実施例でも同様である。
元素分析：計算値(C32H48B2 F8N4O2・(H2O)0.5) C，54.64；H，7.02；N，7.97%
測定値 C，54.38；H，6.88；N，7.96%
The ionic organic compound (295 mg) represented by the formula (3) used in Example 8 was dissolved in water (33 mL) at 100 ° C., and tetraethylammonium tetrafluoroborate (1.08 g) was dissolved in water (11 mL). The solution was added, stirred for 10 minutes and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (4) in a yield of 286 mg (yield 84%). This yield takes into account the structural water of the polymer and is the same in the following examples.
Calcd (C 32 H 48 B 2 F 8 N 4
Measurements C, 54.38; H, 6.88; N, 7.96%
実施例１２
式(４)のイオン性有機化合物を、濃度が１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－ブチル－３－メチルイミダゾリウムテトラフルオロボラートともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が９ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 12
An ionic organic compound of the formula (4) is mixed with 4 mL content of 1-butyl-3-methylimidazolium tetrafluoroborate so that the concentration is 10 g / L, 20 g / L, 50 g / L, 100 g / L. When the sample was placed in a sample bottle and dissolved by heating, a clear solution was obtained. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 9 g / L or less, no gel was formed.
実施例１３
実施例８で用いた式(３)で表されるイオン性有機化合物(２９５ｍｇ)を１００℃で水(３３ｍＬ)に溶かし、カリウムビス(フルオロスルホニル)アミド(１.１０ｇ)を水(７ｍＬ)に溶かした溶液を加え、１０分間撹拌後室温まで冷却した。沈殿物をろ別し、水で洗浄した。風乾後、五酸化りんデシケータで乾燥し、下記の式(５)で表される化合物を収量４１７ｍｇ(収率９７％)で得た。
元素分析：計算値(C32H48F4N6O10S4・(H2O)0.5) C，43.18；H，5.55；N，9.44%
測定値 C，43.19；H，5.29；N，9.43%
The ionic organic compound (295 mg) represented by the formula (3) used in Example 8 was dissolved in water (33 mL) at 100 ° C., and potassium bis (fluorosulfonyl) amide (1.10 g) was dissolved in water (7 mL). The dissolved solution was added, stirred for 10 minutes and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (5) in a yield of 417 mg (yield 97%).
Calcd (C 32 H 48 F 4 N 6 O 10
Measured value C, 43.19; H, 5.29; N, 9.43%
実施例１４
式(５)のイオン性有機化合物を、濃度が０.９ｇ／Ｌ、１ｇ／Ｌ、２ｇ／Ｌ、５ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－エチル－３－メチルイミダゾリウムビス(フルオロスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が０.８ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 14
The concentration of the ionic organic compound of formula (5) is 0.9 g / L, 1 g / L, 2 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) amide was placed in a 4 mL sample bottle and dissolved by heating to form a transparent solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 0.8 g / L or less, no gel was formed.
実施例１５
式(５)のイオン性有機化合物を、濃度が２ｇ／Ｌ、５ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－ブチル－３－メチルイミダゾリウムビス(フルオロスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が１ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 15
The ionic organic compound of the formula (5) is mixed with 1-butyl-3-methylimidazolium bis so that the concentration is 2 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both (fluorosulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 1 g / L or less, no gel was formed.
実施例１６
式(５)のイオン性有機化合物を、濃度が２ｇ／Ｌ、５ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－メチル－１－プロピルピロリジニウムビス(フルオロスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が１ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 16
The ionic organic compound of formula (5) is mixed with 1-methyl-1-propylpyrrolidinium so that the concentration is 2 g / L, 5 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. Both bis (fluorosulfonyl) amide were placed in a 4 mL sample bottle and dissolved by heating to give a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 1 g / L or less, no gel was formed.
実施例１７
Ｎ，Ｎ’－(trans－シクロヘキサン－１，４－ジイル)ビス［(４－クロロメチル)ベンズアミド］(４１９ｍｇ、１.０ｍｍｏｌ)とＮ，Ｎ，Ｎ’，Ｎ’－テトラメチル―１，４―ジアミノブタン(１４４ｍｇ、１.０ｍｍｏｌ)をＮ，Ｎ’－ジメチルホルムアミド(４０ｍL)中、８０℃で４８時間加熱攪拌した。四級化反応が進行することにより生じた沈殿をろ別し、Ｎ，Ｎ’－ジメチルホルムアミド及びアセトンで洗浄した。乾燥後、下記の式(６)で表されるイオン性有機化合物を収量４４８ｍｇ(収率７７％)で得た。
元素分析：計算値(C30H44Cl2N4O2・H2O) C，61.95；H,7.97；N，9.63%
測定値 C，61.85；H，7.82；N，9.60%
N, N ′-(trans-cyclohexane-1,4-diyl) bis [(4-chloromethyl) benzamide] (419 mg, 1.0 mmol) and N, N, N ′, N′-tetramethyl-1,4 Diaminobutane (144 mg, 1.0 mmol) was heated and stirred at 80 ° C. for 48 hours in N, N′-dimethylformamide (40 mL). The precipitate produced by the progress of the quaternization reaction was filtered off and washed with N, N′-dimethylformamide and acetone. After drying, an ionic organic compound represented by the following formula (6) was obtained in a yield of 448 mg (yield 77%).
Calcd (C 30 H 44 Cl 2 N 4
Measured value C, 61.85; H, 7.82; N, 9.60%
実施例１８
実施例１７で得られた式(６)で表されるイオン性有機化合物(２８２ｍｇ)を１００℃で水(３３ｍＬ)に溶かし、リチウムビス(トリフルオロメタンスルホニル)アミド(７１８ｍｇ)を水(７ｍＬ)に溶かした溶液を加え、１０分間撹拌後室温まで冷却した。沈殿物をろ別し、水で洗浄した。風乾後、五酸化りんデシケータで乾燥し、下記の式(７)で表される化合物を収量４９６ｍｇ(収率９７％)で得た。
元素分析：計算値(C34H44F12N6O10S4) C，38.78；H，4.21；N，7.98%
測定値 C，38.94；H，4.06；N，8.16%
The ionic organic compound (282 mg) represented by the formula (6) obtained in Example 17 was dissolved in water (33 mL) at 100 ° C., and lithium bis (trifluoromethanesulfonyl) amide (718 mg) was dissolved in water (7 mL). The dissolved solution was added, stirred for 10 minutes and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (7) in a yield of 496 mg (yield 97%).
Calcd (C 34 H 44 F 12 N 6 O 10 S 4) C, 38.78; H, 4.21; N, 7.98%
Measurements C, 38.94; H, 4.06; N, 8.16%
実施例１９
式(７)のイオン性有機化合物を、濃度が６ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－エチル－３－メチルイミダゾリウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が５ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 19
The ionic organic compound of the formula (7) is mixed with 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) so that the concentration is 6 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. ) Both amides were placed in a 4 mL sample bottle and dissolved by heating to a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 5 g / L or less, no gel was formed.
実施例２０
Ｎ，Ｎ’－(trans－シクロヘキサン－１，４－ジイル)ビス［(４－クロロメチル)ベンズアミド］(８３８ｍｇ、２.０ｍｍｏｌ)とＮ，Ｎ，Ｎ’，Ｎ’－テトラメルエチレンジアミン(２３２ｍｇ、２.０ｍｍｏｌ)をＮ，Ｎ’－ジメチルホルムアミド(８０ｍL)中、８０℃で４８時間加熱攪拌した。四級化反応が進行することにより生じた沈殿をろ別し、Ｎ，Ｎ’－ジメチルホルムアミド及びアセトンで洗浄した。乾燥後、下記の式(８)で表されるイオン性有機化合物を収量８５１ｍｇ(収率７８％)で得た。
元素分析：計算値(C28H40Cl2N4O2・(H2O)0.5) C，61.76；H,7.59；N，10.31%
測定値 C，61.49；H，7.79；N，10.35%
N, N ′-(trans-cyclohexane-1,4-diyl) bis [(4-chloromethyl) benzamide] (838 mg, 2.0 mmol) and N, N, N ′, N′-tetramerethylenediamine (232 mg, 2.0 mmol) was stirred in N, N′-dimethylformamide (80 mL) at 80 ° C. for 48 hours. The precipitate produced by the progress of the quaternization reaction was filtered off and washed with N, N′-dimethylformamide and acetone. After drying, an ionic organic compound represented by the following formula (8) was obtained in a yield of 851 mg (yield 78%).
Elemental analysis: calculated value (C 28 H 40 Cl 2 N 4 O 2. (H 2 O) 0.5 ) C, 61.76; H, 7.59; N, 10.31%
Measured value C, 61.49; H, 7.79; N, 10.35%
実施例２１
実施例２０で得られた式(８)で表されるイオン性有機化合物(４２９ｍｇ)を１００℃で水(５０ｍＬ)に溶かし、リチウムビス(トリフルオロメタンスルホニル)アミド(２.３０ｇ)を水(１４ｍＬ)に溶かした溶液を加え、１０分間撹拌後室温まで冷却した。沈殿物をろ別し、水で洗浄した。風乾後、五酸化りんデシケータで乾燥し、下記の式(９)で表される化合物を収量７２１ｍｇ(収率８９％)で得た。
元素分析：計算値(C32H40F12N6O10S4) C，37.50；H，3.93；N，8.20%
測定値 C，37.78；H，3.80；N，8.38%
The ionic organic compound (429 mg) represented by the formula (8) obtained in Example 20 was dissolved in water (50 mL) at 100 ° C., and lithium bis (trifluoromethanesulfonyl) amide (2.30 g) was dissolved in water (14 mL). The solution dissolved in) was added and stirred for 10 minutes, and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (9) in a yield of 721 mg (yield 89%).
Calcd (C 32 H 40 F 12 N 6 O 10 S 4) C, 37.50; H, 3.93; N, 8.20%
Measured value C, 37.78; H, 3.80; N, 8.38%
実施例２２
式(９)のイオン性有機化合物を、濃度が２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－エチル－３－メチルイミダゾリウムビス(トリフルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が１０ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 22
An ionic organic compound of the formula (9) is mixed with 1 mL of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) amide so as to have a concentration of 20 g / L, 50 g / L, and 100 g / L. When it was put into a sample bottle and dissolved by heating, it became a transparent solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 10 g / L or less, no gel was formed.
実施例２３
Ｎ，Ｎ’－(trans－シクロヘキサン－１，４－ジイル)ビス［(４－クロロメチル)ベンズアミド］(１.６８ｇ、４.０ｍｍｏｌ)とＮ，Ｎ，Ｎ’，Ｎ’－テトラメチル―１，４―ジアミノデカン(９１４ｍｇ、４.０ｍｍｏｌ)をＮ，Ｎ’－ジメチルホルムアミド(１６０ｍL)中、８０℃で４８時間加熱攪拌した。四級化反応が進行することにより生じた沈殿をろ別し、Ｎ，Ｎ’－ジメチルホルムアミド及びアセトンで洗浄した。乾燥後、下記の式(１０)で表されるイオン性有機化合物を収量４４８ｍｇ(収率９２％)で得た。
元素分析：計算値(C36H56Cl2N4O2・H2O) C，64.94；H,8.78；N，8.42%
測定値 C，65.12；H，8.75；N，8.57%
N, N ′-(trans-cyclohexane-1,4-diyl) bis [(4-chloromethyl) benzamide] (1.68 g, 4.0 mmol) and N, N, N ′, N′-tetramethyl-1 , 4-Diaminodecane (914 mg, 4.0 mmol) was stirred in N, N′-dimethylformamide (160 mL) at 80 ° C. for 48 hours. The precipitate produced by the progress of the quaternization reaction was filtered off and washed with N, N′-dimethylformamide and acetone. After drying, an ionic organic compound represented by the following formula (10) was obtained in a yield of 448 mg (yield 92%).
Elemental analysis: calculated value (C 36 H 56 Cl 2 N 4 O 2 · H 2 O) C, 64.94; H, 8.78; N, 8.42%
Measured value C, 65.12; H, 8.75; N, 8.57%
実施例２４
実施例２３で得られた式(１０)で表されるイオン性有機化合物(９７３ｍｇ)を１００℃で水(８５ｍＬ)に溶かし、リチウムビス(トリフルオロメタンスルホニル)アミド(４.３１ｇ)を水(２５ｍＬ)に溶かした溶液を加え、１０分間撹拌後室温まで冷却した。沈殿物をろ別し、水で洗浄した。風乾後、五酸化りんデシケータで乾燥し、下記の式(１１)で表される化合物を収量１.５５ｇ(収率９３％)で得た。
元素分析：計算値(C40H56F12N6O10S4) C，42.25；H，4.96；N，7.39%
測定値 C，42.13；H，4.78；N，7.37%
The ionic organic compound (973 mg) represented by the formula (10) obtained in Example 23 was dissolved in water (85 mL) at 100 ° C., and lithium bis (trifluoromethanesulfonyl) amide (4.31 g) was dissolved in water (25 mL). The solution dissolved in) was added and stirred for 10 minutes, and then cooled to room temperature. The precipitate was filtered off and washed with water. After air drying, it was dried with a phosphorus pentoxide desiccator to obtain a compound represented by the following formula (11) in a yield of 1.55 g (yield 93%).
Calcd (C 40 H 56 F 12 N 6 O 10 S 4) C, 42.25; H, 4.96; N, 7.39%
Measured value C, 42.13; H, 4.78; N, 7.37%
実施例２５
式(１１)のイオン性有機化合物を、濃度が４ｇ／Ｌ、１０ｇ／Ｌ、２０ｇ／Ｌ、５０ｇ／Ｌ、１００ｇ／Ｌになるように１－エチル－３－メチルイミダゾリウムビス(フルオロメタンスルホニル)アミドともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これを室温で放置させると、上記すべての濃度でゲルが得られた。イオン性有機化合物の濃度が３ｇ／Ｌ以下になるようにして同様な操作をした場合はゲルを形成しなかった。
Example 25
The ionic organic compound of the formula (11) is mixed with 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) so that the concentration is 4 g / L, 10 g / L, 20 g / L, 50 g / L, 100 g / L. ) Both amides were placed in a 4 mL sample bottle and dissolved by heating to a clear solution. When this was allowed to stand at room temperature, a gel was obtained at all the above concentrations. When the same operation was performed so that the concentration of the ionic organic compound was 3 g / L or less, no gel was formed.
実施例２６
電導度の測定は恒温槽で温度を一定に保ちながらSolartron社の1260型インピーダンスアナライザーとRadiometer Analytical社の伝導率セル(CDC-749)を用いて交流インピーダンス法により行った。実施例１と同様にして得たゲルについておよびイオン液体について、電導度用の塩化カリウム標準溶液を標準として、Cole-Coleプロットから電導度を算出した。イオン液体のみの場合とゲル化剤濃度３ｇ／Ｌの３５℃以上の場合は液体状態、他はゲル状態である。図２と図３に電導度の測定結果を示す。
Example 26
The conductivity was measured by AC impedance method using Solartron 1260 impedance analyzer and Radiometer Analytical conductivity cell (CDC-749) while keeping the temperature constant in a thermostatic bath. For the gel obtained in the same manner as in Example 1 and for the ionic liquid, the conductivity was calculated from the Cole-Cole plot using the standard potassium chloride solution for conductivity as the standard. In the case of only an ionic liquid and a gelling agent concentration of 3 g / L and above 35 ° C., it is in a liquid state and the others are in a gel state. 2 and 3 show the measurement results of conductivity.
実施例２７
実施例１～７、９、１０で用いた式(２)のイオン性有機化合物について酸化還元電位の測定を行った。測定条件は次の通り。測定結果を図４に示す。
ゲル化剤濃度：０.１ｍｏｌ ｄｍ-3(アニオンの濃度)
溶媒：プロピレンカルボナート(ＰＣ)
支持電解質：無し
作用電極：グラッシーカーボンディスク電極(直径=1mm)
対極：白金
参照電極：Ａｇ/Ａｇ+(０.１ｍｏｌ ｄｍ-3 Ａｇ［ＴＦＳＡ］ ｉｎ ＰＣ)
走査速度：５０ｍＶ/ｓ
温度：２５℃
Ａｒガス置換グローブボックス内にて測定した。BAS ALS405電気化学アナライザー使用。還元側、酸化側個別に測定。(試料液体中でのフェロセンの酸化還元電位を測定し内部標準とした。
Example 27
The oxidation-reduction potential of the ionic organic compound of the formula (2) used in Examples 1 to 7, 9, and 10 was measured. The measurement conditions are as follows. The measurement results are shown in FIG.
Gelling agent concentration: 0.1 mol dm -3 (concentration of anion)
Solvent: Propylene carbonate (PC)
Supporting electrolyte: None Working electrode: Glassy carbon disk electrode (diameter = 1 mm)
Counter electrode: platinum Reference electrode: Ag / Ag + (0.1 mol dm −3 Ag [TFSA] in PC)
Scanning speed: 50 mV / s
Temperature: 25 ° C
The measurement was performed in an Ar gas substitution glove box. Uses BAS ALS405 electrochemical analyzer. Measured separately on reducing side and oxidizing side. (The redox potential of ferrocene in the sample liquid was measured and used as an internal standard.
実施例２８
動的粘弾性測定はティー・エイ・インスツルメント・ジャパン(株)のARES-RFSを用いて行った。実施例１と同様にして得た式(２)のイオン性有機化合物濃度が５ｇ／Ｌのゲルについて５０ｍｍのコーン型治具を装着してゲルの周波数依存性測定、歪依存性測定を行った。図５は、縦軸に歪１％における貯蔵弾性率(Ｇ′)と損失弾性率(Ｇ″)を、横軸に周波数をとった場合のグラフである。測定した全周波数範囲で、常にＧ′＞Ｇ″となり、このゲルが擬固体性を示すことがレオロジー的にも明らかになった。図６は縦軸に周波数１Ｈｚにおける貯蔵弾性率(Ｇ′)と損失弾性率(Ｇ″)を、横軸に歪をとった場合のグラフである。歪が３１.８％未満ではＧ′＞Ｇ″となり擬固体性を示し、歪が３１.８％を超えるとＧ′＜Ｇ″となり液体性を示すことが明らかとなった。
Example 28
The dynamic viscoelasticity measurement was performed using ARES-RFS of TA Instruments Japan Co., Ltd. A gel having a ionic organic compound concentration of formula (2) of 5 g / L obtained in the same manner as in Example 1 was fitted with a 50 mm cone-shaped jig, and the gel was subjected to frequency dependency measurement and strain dependency measurement. . FIG. 5 is a graph in which the vertical axis represents the storage elastic modulus (G ′) and loss elastic modulus (G ″) at a strain of 1%, and the horizontal axis represents the frequency. From the viewpoint of rheology, it was proved that the gel exhibited quasi-solidity. FIG. 6 is a graph in which the vertical axis represents storage elastic modulus (G ′) and loss elastic modulus (G ″) at a frequency of 1 Hz, and the horizontal axis represents strain. When the strain is less than 31.8%, G ′> It became clear that it became G ″ and showed pseudo-solidity, and when the strain exceeded 31.8%, G ′ <G ″ and liquid property.
実施例２９
ゲルの入っているサンプル瓶を横向きにして水浴または油浴中に置き１℃／ｍｉｎで昇温しゲル－ゾル相転移温度を測定した。ゲル－ゾル相転移温度目視によりゲルが溶け始める温度とした。実施例１と同様にして得たゲル〔式(２)、ＥＭＩ、ＴＦＳＡ〕についての測定結果を図７に示す。図７は、縦軸にゲル－ゾル相転移温度を、横軸に式(２)のイオン性有機化合物濃度をとった場合のグラフである。また、実施例１６と同様にして得たゲル〔式(５)、Ｐｙ１３、ＦＳＡ〕についての測定結果を図８に示す。図８は、縦軸にゲル－ゾル相転移温度を、横軸に式(５)のイオン性有機化合物濃度をとった場合のグラフである。
Example 29
The sample bottle containing the gel was placed sideways in a water bath or oil bath and heated at 1 ° C./min to measure the gel-sol phase transition temperature. Gel-sol phase transition temperature The gel-sol phase transition temperature was set to a temperature at which the gel started to melt. The measurement results for the gel [formula (2), EMI, TFSA] obtained in the same manner as in Example 1 are shown in FIG. FIG. 7 is a graph in which the vertical axis represents the gel-sol phase transition temperature and the horizontal axis represents the concentration of the ionic organic compound of formula (2). Moreover, the measurement result about the gel [Formula (5), Py13, FSA] obtained similarly to Example 16 is shown in FIG. FIG. 8 is a graph in which the vertical axis represents the gel-sol phase transition temperature and the horizontal axis represents the concentration of the ionic organic compound of formula (5).
比較例１
式(２)のイオン性有機化合物を、濃度が５ｇ／Ｌ、１０ｇ／Ｌ、１００ｇ／Ｌ、３００ｇ／Ｌになるように１－エチル－３－メチルイミダゾリウムテトラフルオロボラートともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度で沈殿を生じた。
Comparative Example 1
An ionic organic compound of the formula (2) is mixed with 4 mL content of 1-ethyl-3-methylimidazolium tetrafluoroborate so that the concentration is 5 g / L, 10 g / L, 100 g / L, 300 g / L. When the sample was placed in a sample bottle and dissolved by heating, a clear solution was obtained. When these were allowed to stand at room temperature, precipitation occurred at all the above concentrations.
比較例２
式(４)のイオン性有機化合物を、濃度が１０ｇ／Ｌ、２０ｇ／Ｌ、２００ｇ／Ｌになるように１－エチル－３－メチルイミダゾリウムテトラフルオロボラートともに、内容量４ｍＬのサンプル瓶に入れ、加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度で沈殿を生じた。
Comparative Example 2
The ionic organic compound of formula (4) is placed in a 4 mL internal volume sample bottle together with 1-ethyl-3-methylimidazolium tetrafluoroborate so as to have a concentration of 10 g / L, 20 g / L, and 200 g / L. When it was added and dissolved by heating, it became a clear solution. When these were allowed to stand at room temperature, precipitation occurred at all the above concentrations.
比較例３
式(２)のイオン性有機化合物を、濃度が５ｇ／Ｌ、１０ｇ／Ｌ、１００ｇ／Ｌになるように１－ブチル－３－メチルイミダゾリウムアセタートともに、内容量４ｍＬのサンプル瓶に入れ、１６０℃で加熱溶解させると透明な溶液になった。これらを室温で放置させると、上記すべての濃度で粘調な液体のままだった。
Comparative Example 3
The ionic organic compound of the formula (2) is placed in a sample bottle having a content of 4 mL together with 1-butyl-3-methylimidazolium acetate so that the concentration is 5 g / L, 10 g / L, and 100 g / L. When heated and dissolved at 160 ° C., a transparent solution was obtained. When these were allowed to stand at room temperature, they remained viscous liquids at all the above concentrations.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2013518125A JP5682936B2 (en) | 2011-05-30 | 2012-05-30 | Gel ion conductor |
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| JP2011120251 | 2011-05-30 | ||
| JP2011-120251 | 2011-05-30 | ||
| JP2011247455 | 2011-11-11 | ||
| JP2011-247455 | 2011-11-11 |
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| WO2012165483A1 true WO2012165483A1 (en) | 2012-12-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/JP2012/063937 Ceased WO2012165483A1 (en) | 2011-05-30 | 2012-05-30 | Gel-like ion conductor |
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| JP (1) | JP5682936B2 (en) |
| WO (1) | WO2012165483A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2016055908A1 (en) * | 2014-10-10 | 2017-04-27 | 株式会社半導体エネルギー研究所 | Power storage device |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006082768A1 (en) * | 2005-02-02 | 2006-08-10 | National Institute Of Advanced Industrial Science And Technology | Ionic organic compound |
| JP2008214529A (en) * | 2007-03-06 | 2008-09-18 | National Institute Of Advanced Industrial & Technology | Ionic organic compound and method for producing the same, and hydrogelator and hydrogel comprising the ionic organic compound |
| JP2008248224A (en) * | 2007-03-06 | 2008-10-16 | National Institute Of Advanced Industrial & Technology | Ionic organic compound and process for producing the same, and hydrogelator and hydrogel comprising the ionic organic compound |
| JP2009140641A (en) * | 2007-12-04 | 2009-06-25 | Nec Tokin Corp | Non-aqueous electrolyte, gel electrolyte and secondary battery using them |
| WO2010027067A1 (en) * | 2008-09-08 | 2010-03-11 | 独立行政法人産業技術総合研究所 | Ionic organic compound, production method thereof, hydrogelling agent composed of the ionic organic compound, hydrogel containing same, methanol gelling agent, methanol gel containing same, and carbon nanotube dispersant |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011124122A (en) * | 2009-12-11 | 2011-06-23 | Konica Minolta Holdings Inc | Electrochemical device |
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- 2012-05-30 JP JP2013518125A patent/JP5682936B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006082768A1 (en) * | 2005-02-02 | 2006-08-10 | National Institute Of Advanced Industrial Science And Technology | Ionic organic compound |
| JP2008214529A (en) * | 2007-03-06 | 2008-09-18 | National Institute Of Advanced Industrial & Technology | Ionic organic compound and method for producing the same, and hydrogelator and hydrogel comprising the ionic organic compound |
| JP2008248224A (en) * | 2007-03-06 | 2008-10-16 | National Institute Of Advanced Industrial & Technology | Ionic organic compound and process for producing the same, and hydrogelator and hydrogel comprising the ionic organic compound |
| JP2009140641A (en) * | 2007-12-04 | 2009-06-25 | Nec Tokin Corp | Non-aqueous electrolyte, gel electrolyte and secondary battery using them |
| WO2010027067A1 (en) * | 2008-09-08 | 2010-03-11 | 独立行政法人産業技術総合研究所 | Ionic organic compound, production method thereof, hydrogelling agent composed of the ionic organic compound, hydrogel containing same, methanol gelling agent, methanol gel containing same, and carbon nanotube dispersant |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2016055908A1 (en) * | 2014-10-10 | 2017-04-27 | 株式会社半導体エネルギー研究所 | Power storage device |
| JP2018060778A (en) * | 2014-10-10 | 2018-04-12 | 株式会社半導体エネルギー研究所 | Power storage device |
| US10497979B2 (en) | 2014-10-10 | 2019-12-03 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and electronic device |
| US11267707B2 (en) | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| US12187609B2 (en) | 2019-04-16 | 2025-01-07 | Honeywell International Inc. | Purification of bis(fluorosulfonyl) imide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2012165483A1 (en) | 2015-02-23 |
| JP5682936B2 (en) | 2015-03-11 |
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