JP2008270643A - Quaternary ammonium salt electrolyte, and electrolyte solution and electrochemical device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte solution capable of improving characteristic change of an electrochemical device over time. <P>SOLUTION: An electrolyte (B) containing a compound (A) expressed by general formula (1), an electrolyte solution containing the electrolyte (B), and an electrochemical device using the electrolyte solution are provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a quaternary ammonium salt electrolyte. More specifically, the present invention relates to an electrolyte suitable for an electrolytic solution for electrochemical devices.

An electrochemical element stores electrochemical energy inside the element. Specifically, the electrochemical element stores a battery for taking out chemical energy stored inside the element as electric energy, and a static electricity stored inside the element. A capacitor for taking out electric energy as electric energy to the outside, a dye-sensitized solar cell, and the like.
Conventionally, the electrolyte of the capacitor BF ₄ salt of tetraethyl ammonium, BF ₄ salt of triethyl methyl ammonium or 1-ethyl-3-BF ₄ salt of methyl imidazolium have been used as an electrolyte. Especially in new application fields such as hybrid electric vehicles that are used under harsh conditions and with large currents, electrolytes with excellent long-term reliability, high withstand voltage (wide potential window), and high electrical conductivity Development has become an urgent need.
Under such circumstances, a nonaqueous electrolytic solution for an electrochemical capacitor using a spiro-type ammonium electrolyte whose performance deterioration with time is improved is known. (For example, patent document 1). Even if the non-aqueous electrolyte described in Patent Document 1 is used, the withstand voltage may not be sufficient yet, and therefore electrochemical capacitors using these electrolytes may deteriorate over time.
JP 2005-175239 A

That is, an object of the present invention is to provide an electrolytic solution that can further improve performance deterioration with time of an electrochemical device.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention provides an electrolyte (B) containing the compound (A) represented by the general formula (1), an electrolytic solution containing the electrolyte (B), and an electrochemical element using the electrolytic solution. The gist.

［Ｒ^１はハロゲン原子、水酸基、ニトロ基、シアノ基及びエーテル結合を有する基からなる群より選ばれる少なくとも１種の基を有していてもよい炭素数１〜１０の１価炭化水素基である。なお、矢印で示された置換基Ｒ^１は紙面より上方に位置することを示している。Ｒ²〜Ｒ^４はハロゲン原子、ニトロ基、シアノ基及びエーテル結合を有する基からなる群より選ばれる少なくとも１種の基を有していてもよい炭素数１〜１０の１価炭化水素基、水素原子、又はハロゲン原子であり、同じでも異なっていてもよい。Ｒ^５〜Ｒ^７は、炭素数１〜５のアルキレン基又は炭素数１〜５のフルオロアルキレン基であり、同じでも異なっていてもよい。Ｘ⁻は対イオンを表す。］

[R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have at least one group selected from the group consisting of a halogen atom, a hydroxyl group, a nitro group, a cyano group and a group having an ether bond. is there. Incidentally, the substituents R ¹ indicated by arrows indicate that located above the plane of the paper. R ^{2 to} R ⁴ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have at least one group selected from the group consisting of a halogen atom, a nitro group, a cyano group and a group having an ether bond, A hydrogen atom or a halogen atom, which may be the same or different. R ^{5 to} R ⁷ are an alkylene group having 1 to 5 carbon atoms or a fluoroalkylene group having 1 to 5 carbon atoms, and may be the same or different. X ⁻ represents a counter ion. ]

Since the quaternary ammonium salt electrolyte of the present invention has a very high withstand voltage, an electrolytic solution using the quaternary ammonium salt electrolyte can produce an electrochemical device with little performance deterioration over time. Therefore, by using the electrolyte of the present invention, an electrochemical element having a large energy density and excellent charge / discharge cycle characteristics can be obtained.

The present invention is described in detail below.
The compound (A) represented by the general formula (1) has a feature that the cation-centered nitrogen is sterically protected by an alkyl group, and LUMO is used in molecular orbital calculation as compared with a conventional electrolyte. The value is large and it is difficult to be oxidized and reduced. As a result, the difference between the oxidation potential and the reduction potential is large, electrochemically stable, and the withstand voltage of the electrolyte is very high.

In the cationic species (a) of the compound (A) represented by the general formula (1), R ¹ is a halogen atom, a hydroxyl group, a nitro group, a cyano group, and a group having an ether bond (hereinafter referred to as a functional group Y). A monovalent hydrocarbon group having 1 to 10 carbon atoms which may have at least one group selected from the group consisting of a linear aliphatic hydrocarbon group and a branched aliphatic hydrocarbon. Groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups and the like. Specific examples of R ¹ are given below.

When the hydrocarbon group is a linear aliphatic hydrocarbon group: a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-decyl group, and a functional group Y Examples of the group include hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group, nitromethyl group, nitroethyl group, cyanomethyl group, cyanoethyl group, methoxymethyl group, fluoroalkyl group, and methoxyethyl group.

When the hydrocarbon group is a branched aliphatic hydrocarbon group: iso-propyl group, 2-methylpropyl group, 2-butyl group, 2-pentyl group, 2-methylbutyl group, 3-methylbutyl group, 3-pentyl group, 2 -Methylbutyl group, 2-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 3-heptyl group, 2-ethylbutyl group, 3-methylpentyl group, 3-hexyl group, 2- Examples of the group having an ethylhexyl group, 3-methyl-2-pentyl group, 4-methyl-2-pentyl group, 2,3-dimethylbutyl group, fluoroalkyl group and 2-ethyloctyl group, and functional group Y are 2- Hydroxy-iso-propyl group, 1-hydroxy-2-methylpropyl group, 2-amino-iso-propyl group, 2-nitro-iso-propyl group, 1- Toro 2-methylpropyl group, 2-cyano -iso- propyl group, 1-cyano-2-methylpropyl group, 2-methoxy -iso- propyl, and 1-methoxy-2-methylpropyl group and the like.

When the hydrocarbon group is an alicyclic hydrocarbon group: a cyclohexyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, and a group having a functional group Y are 1 -Hydroxycyclohexyl group, 2-hydroxycyclohexyl group, 3-hydroxycyclohexyl group and 4-hydroxycyclohexyl group, 1-methoxycyclohexyl group, 2-methoxycyclohexyl group, 3-methoxycyclohexyl group and 4-methoxycyclohexyl group .

When the hydrocarbon group is an aromatic hydrocarbon group: a phenyl group, a toluyl group, a benzyl group, and the like can be given.

The fluoroalkyl group is a group represented by C _n F _{2n + 1} (n is an integer of 10 or less), and examples thereof include a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group.

Of these R ^1, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a group having an ether bond, and a fluoroalkyl group are preferable. More preferred are a methyl group, an ethyl group, a methoxyethyl group, a trifluoromethyl group and a pentafluoroethyl group. Particularly preferred are a methyl group, an ethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

In General Formula (1), R ^{2 to} R ⁴ may have at least one group selected from the group consisting of a halogen atom, a nitro group, a cyano group, and a group having an ether bond. A monovalent hydrocarbon group, a hydrogen atom, or a halogen atom, and the same functional group as R ¹ , a hydrogen atom, a halogen atom, and the like.

Of these R ^{2 to} R ^4, a hydrogen atom, a halogen atom, a linear or branched aliphatic hydrocarbon group and a fluoroalkyl group are preferable. More preferred are a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a methoxyethyl group, a trifluoromethyl group and a pentafluoroethyl group. Particularly preferred are a hydrogen atom, a fluorine atom, a methyl group, an ethyl group and a trifluoromethyl group. Most preferably, they are a hydrogen atom and a fluorine atom.

In general formula (1), R ^{5 to} R ⁷ are an alkylene group having 1 to 5 carbon atoms or a fluoroalkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms or 1 to 1 carbon atoms. 3 fluoroalkylene groups, which may be the same or different.

Examples of R ^{5 to} R ⁷ include the following.
[1] Linear alkylene group Methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group and the like.
[2] Branched alkylene group Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, butane-1,1-diyl group, butane-1,2-diyl group , Butane-1,3-diyl group, pentane-1,2-diyl and the like.
[3] Fluoroalkylene group Difluoromethylene group, tetrafluoroethylene group, hexafluoropropylene group, octafluorobutylene group and the like.

Of these, preferred are methylene group, ethylene group, trimethylene group, tetramethylene group, propane-1,2-diyl group, butane-1,2-diyl group, difluoromethylene group, tetrafluoroethylene group, hexafluoro group. Propylene group. More preferably, they are an ethylene group and a tetrafluoroethylene group.

  Tables 1 to 3 show preferable examples of the cation species (a) of the compound (A) represented by the general formula (1). Two or more compounds (A) can be used in combination.

The anion component of the compound (A) represented by the general formula (1) will be described.
X ⁻ represents I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , F ⁻ , Cl ⁻ , PCl ₆ ⁻ , BCl ₄ ⁻ , AsCl ₆ ⁻ , SbCl ₆ ⁻ , TaCl ₆ ⁻ , NbCl ₆ ⁻ , PBr ₆ ⁻ , BBr ₄ ⁻ , AsBr ₆ ⁻ , AlBr ₄ ⁻ , TaBr ₆ ⁻ , NbBr ₆ ⁻ , SbF ₆ ⁻ , AlF ₄ ⁻ , ClO ₄ ⁻ , AlCl ₄ ⁻ , TaF ₆ ⁻ , NbF ₆ ⁻ , CN ⁻ , F (HF) _n ⁻ (wherein n represents a numerical value of 1 or more and 4 or less), N (RfSO ₃ ) ₂ ⁻ , C (RfSO ₃ ) ₃ ⁻ , RfSO ₃ ⁻ , RfCO ₂ ^{— and the} like.

^{_{N (RfSO 3) 2 -,}} C (RfSO 3) 3 -, RfSO 3 - or RfCO ₂ ^- Rf contained in the anions represented by represents a fluoroalkyl group having 1 to 12 carbon atoms, trifluoromethyl, Examples include pentafluoroethyl, heptafluoropropyl, and nonafluorobutyl. Of these, trifluoromethyl, pentafluoroethyl and heptafluoropropyl are preferable, trifluoromethyl and pentafluoroethyl are more preferable, and trifluoromethyl is particularly preferable. Moreover, a carboxylate anion, More preferably, an aromatic carboxylate anion, More preferably, a phthalate anion etc. are mentioned.
Of the above anions, from the viewpoint of electrochemical stability, preferably, a counter anion represented by I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ or N (RfSO ₃ ) ₂ ^— , more preferably I ⁻ , PF ₆ ^- or BF ₄ ^- represented by counter anion in, particularly preferably BF ₄ ^- is a counter anion represented by.

Particularly preferred examples of the compound (A) (cation component + anionic component), BF ₄ salt of a cationic species (a-1), BF ₄ salt, the cationic species of a cationic species (a-2) of (a-3) BF ₄ salt, BF ₄ cationic species (a-5) BF ₄ salt of the cationic species (a-6) BF ₄ salt, BF ₄ salt of a cationic species (a-7), cationic species (a-12) salt, PF ₆ salt of the cationic species (a-1) PF ₆ salt of the cationic species (a-2) PF ₆ salt, PF ₆ salt of the cationic species (a-3), cationic species (a-5), PF ₆ salt of the cationic species (a-6), cationic species (a-7) PF ₆ salt of the cationic species (a-12) PF ₆ salt, I salt of the cationic species (a-1), cationic species ( I salt of a-2), I salt of cationic species (a-3), I salt of cationic species (a-5), I of cationic species (a-6) A I salt of I salts and cationic species of a cationic species (a-7) (a-12).

The following are mentioned as a manufacturing method of the tertiary amine which is a raw material of a compound (A).
For example, (2aα, 4aα, 6aα) -octahydro-1H-6b-aza-cyclopenta [cd] pentalene is produced by hydrogenating 2,5-pyrrolidinedipropanoic acid with methyl acrylate added to pyrrole. It is obtained by heating to cause cyclization reaction and reduction with lithium aluminum hydride or the like (Tetrahedron Letters, 1996, 37, 1, 131-134).

[3aα, 6aα, 9aα] Dodecahydropyrido [2,1,6-de] quinolidine is produced by reacting 1,5,9-cyclododecatriene with borane-dimethylsulfuric acid to obtain organoborane. A method for obtaining dodecahydropyrido [2,1,6-de] quinolidine by oxidation with RuO2 or the like to form 1,5,9-cyclododecantrione and reacting with ammonia has been reported (J. Org). Chem. 1984, 49, 2217-2231).

Compound (A) is obtained, for example, by quaternizing the tertiary amine compound with a carbonate such as dialkyl carbonate, and subjecting the resulting carbonate salt to a counter anion (X ⁻ ) (for example, Japanese Patent No. 3145049). No.). It can also be obtained by a method in which a tertiary amine is quaternized with an alkyl halide and the resulting halide salt is subjected to anion exchange.

The electrolyte (B) containing the compound (A) represented by the general formula (1) will be described.
The electrolyte (B) may contain other organic salt compounds in addition to the compound (A). Other organic salt compounds include alkylammonium salts and imidazolium salts. Specifically, for example, BF ₄ salt and PF ₆ salt of an alkyl ammonium, a BF ₄ salt and PF ₆ salts of imidazolium. For example, tetraethylammonium BF ₄ salt, triethylmethylammonium BF ₄ salt, 1,2,3-trimethylimidazolium BF ₄ salt and 1-ethyl-2,3-dimethylimidazolium BF ₄ salt, 1, 2, 3, 4 - tetramethyl imidazolium BF ₄ salts. The content of the compound (A) is preferably 50 to 100% by weight with respect to the weight of the electrolyte (B).

Moreover, you may contain various additives. As additives, LiBF ₄ , LiPF ₆ , phosphoric acids and derivatives thereof (phosphoric acid, phosphorous acid, phosphoric acid esters, phosphonic acids, etc.), boric acids and derivatives thereof (boric acid, boric acid oxide, boric acid esters) , Complexes of boron with compounds having a hydroxyl group and / or carboxyl group, etc.), nitrates (lithium nitrate, etc.), nitro compounds (nitrobenzoic acid, nitrophenol, nitrophenetole, nitroacetophenone, aromatic nitro compounds, etc.), etc. Can be given. From the viewpoint of electrochemical stability and conductivity, the amount of the additive is preferably 50% by weight or less, more preferably 20% by weight or less, based on the weight of the electrolyte (B).

The chemical structure of the compound (A) can be specified by an ordinary organic chemical method. For example, 1H-NMR (for example, instrument: AVANCE 300 (manufactured by Nippon Bruker Co., Ltd.), solvent: deuterated dimethyl sulfoxide, frequency: 300 MHz), 19 F-NMR and 13 C-NMR (for example, instrument: AL-300 (manufactured by JEOL Ltd.), solvent: deuterated dimethyl sulfoxide, frequency: 300 MHz) and the like. The purity of the compound (A) can be measured by 1H-NMR.

The electrolytic solution of the present invention contains an electrolyte (B), and preferably contains an electrolyte (B) and a non-aqueous solvent (C). The content (% by weight) of the electrolyte (B) in the electrolytic solution is preferably 5 to 100, more preferably based on the weight of the electrolytic solution, from the viewpoint of the electrical conductivity of the electrolytic solution and the internal resistance of the electrochemical capacitor. It is 10-80, Most preferably, it is 15-50, Most preferably, it is 20-40.

Specific examples of the non-aqueous solvent (C) include the following. Two or more of these can be used in combination.
Ethers: chain ether [carbon number 2-6 (diethyl ether, methyl isopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc.); carbon number 7-12 (diethylene glycol diethyl ether, triethylene glycol dimethyl ether, etc.)], cyclic ether [C2-C4 (tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, etc.); C5-C18 (4-butyldioxolane, crown ether, etc.)].
Amides: N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, hexamethylphosphorylamide, N-methylpyrrolidone and the like.
Carboxylic acid esters: methyl acetate, methyl propionate, etc.
Lactones: γ-butyrolactone, α-acetyl-γ-butyrolactone, β-butyrolactone, γ-valerolactone, δ-valerolactone, and the like.
Nitriles: acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, acrylonitrile, benzonitrile and the like.
Carbonates: ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and the like.
Sulfoxides: dimethyl sulfoxide, sulfolane, 3-methyl sulfolane, 2,4-dimethyl sulfolane, etc.
・ Nitro compounds: Nitromethane, nitroethane, etc.
Benzenes: toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene and the like.
-Heterocyclic solvent: N-methyl-2-oxazolidinone, 3,5-dimethyl-2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidinone and the like.
Ketones: acetone, 2,5 hexanedione, cyclohexane, etc.
-Phosphate esters: trimethyl phosphoric acid, triethyl phosphoric acid, tripropyl phosphoric acid and the like.

Of these, nitriles, lactones, carbonates, sulfoxides and benzenes are preferable, and propylene carbonate, ethylene carbonate, butylene carbonate, sulfolane, methyl sulfolane, acetonitrile, γ-butyrolactone, dimethyl carbonate, Ethyl methyl carbonate, diethyl carbonate, xylene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene and 1,4-dichlorobenzene.

The water content in the electrolytic solution of the present invention is preferably 300 ppm or less, more preferably 100 ppm or less, particularly preferably 50 ppm or less based on the weight of the electrolytic solution from the viewpoint of electrochemical stability. Within this range, it is possible to suppress the deterioration in performance of the electrochemical capacitor over time.
The water content in the electrolytic solution can be measured by the Karl Fischer method (JIS K0113-1997, coulometric titration method).
Examples of the method for setting the water content in the electrolytic solution in the above range include a method using a sufficiently dried electrolyte (B) and a non-aqueous solvent sufficiently dehydrated in advance.
Examples of the drying method include heating and drying under reduced pressure (for example, heating at 150 ° C. under reduced pressure of 20 Torr), evaporating and removing a trace amount of water contained therein, recrystallization, and the like.
As the dehydration method, heat dehydration under reduced pressure (for example, heating at 100 Torr) to evaporate and remove a trace amount of water, molecular sieve (manufactured by Nacalai Tesque, 3A 1/16, etc.), activated alumina powder And a method using a dehydrating agent.
In addition to these, the electrolytic solution is heated and dehydrated under reduced pressure (for example, heated at 100 ° C. under reduced pressure of 100 Torr) to evaporate and remove a trace amount of water, molecular sieve, activated alumina powder, etc. And a method of using a dehydrating agent. These methods may be performed alone or in combination. Of these, the method of highly purifying the electrolyte (B) by recrystallization and further heating and drying (B) under reduced pressure, and the method of adding molecular sieve to the non-aqueous solvent (C) or the electrolytic solution are preferable.

An electrolytic solution using the electrolyte of the present invention can be used for an electrochemical element. An electrochemical element shows an electrochemical capacitor, a secondary battery, a dye-sensitized solar cell, etc. An electrochemical capacitor includes an electrode, a current collector, and a separator as basic components, and optionally includes a case, a gasket, and the like that are usually used for the capacitor. The electrolytic solution is impregnated into the electrode and the separator, for example, in a glove box in an argon gas atmosphere (dew point −50 ° C.). The electrolytic solution of the present invention is suitable for an electric double layer capacitor (one using a polarizable electrode such as activated carbon) as an electrochemical capacitor.

As a basic structure of the electric double layer capacitor, a separator is sandwiched between two polarizable electrodes and impregnated with an electrolytic solution. The main component of the polarizable electrode is preferably a carbonaceous material such as activated carbon, graphite, or polyacene organic semiconductor because it is electrochemically inert to the electrolyte and has an appropriate electrical conductivity. Thus, at least one of the positive electrode and the negative electrode is a carbonaceous material. A porous carbon material (for example, activated carbon) having a specific surface area of 10 m ² / g or more determined by the BET method by the nitrogen adsorption method is more preferable because of the large electrode interface where charges are accumulated. The specific surface area of the porous carbon material is selected in consideration of the target capacitance per unit area (F / m ² ) and the decrease in bulk density associated with the increase in the specific surface area. preferably it has a specific surface area determined is 30~2,500m ² / g by the BET method, since the electrostatic capacity per volume is large, the specific surface area is particularly preferably activated carbon 300~2,300m ² / g.

The electrolytic solution for electrochemical capacitors of the present invention can also be used for aluminum electrolytic capacitors. The basic structure of an aluminum electrolytic capacitor is that an oxide film is formed by electrochemical treatment on the surface of the aluminum foil to be an electrode, which is used as a dielectric, and an electrolytic solution is impregnated between the aluminum foil to be the other electrode Electrolytic paper is sandwiched between them.

Examples of the electrochemical capacitor of the present invention include a coin type, a wound type, and a rectangular type. The electrolytic solution for electrochemical capacitors of the present invention can be applied to any electric double layer capacitor or any aluminum electrolytic capacitor.

EXAMPLES Next, specific examples of the present invention will be described, but the present invention is not limited thereto. Hereinafter, “parts” means “parts by weight” unless otherwise specified.
In the following examples, 1H-NMR, 19F-NMR and 13C-NMR were measured by the following methods.
Measurement conditions for 1H-NMR Instrument: AVANCE 300 (manufactured by Nippon Bruker Co., Ltd.), solvent: deuterated dimethyl sulfoxide, frequency: 300 MHz.
Measurement conditions for 19F-NMR Instrument: AL-300 (manufactured by JEOL Ltd.), solvent: deuterated dimethyl sulfoxide, frequency: 300 MHz
Measurement conditions for 13C-NMR Instrument: AL-300 (manufactured by JEOL Ltd.), solvent: deuterated dimethyl sulfoxide, frequency: 300 MHz

<Production Example 1>
Preparation of (2aα, 4aα, 6aα) -octahydro-1H-6b-aza-cyclopenta [cd] pentalene 67 parts of pyrrole, 86 parts of methyl acrylate and 14 parts of zinc chloride were added to 5280 parts of dichloromethane at room temperature and stirred for 4 hours. . The reaction product was dissolved in 4000 parts of water, and extracted by adding 5280 parts of dichloromethane three times. The organic phases were mixed, dehydrated with sodium sulfate, and then desolvated under reduced pressure at room temperature. The residue was separated on a silica gel column (petroleum ether / ethyl acetate) to obtain 102 parts of a yellow liquid.
3 parts of 5% rhodium-supported alumina was added to 120 parts of the yellow liquid, and the mixed solution was shaken under a hydrogen atmosphere of 2.8 kgf / cm ² . The solvent was removed under reduced pressure and 1056 parts of dichloromethane and 800 parts of saturated potassium carbonate solution were added. The organic phase and the aqueous phase were separated, and the aqueous phase was washed twice with 1056 parts of dichloromethane. The mixed dichloromethane was washed with 800 parts of a saturated aqueous calcium carbonate solution. Thereafter, 90 parts of magnesium sulfate was added for dehydration. Impurities were removed using a column (4: 1 ether / methanol) to give 105 parts of a yellow oily liquid.

244 parts of the above oily liquid was added to 1654 parts of toluene and refluxed in a nitrogen atmosphere for 10 days. Thereafter, the solvent was removed at 80 ° C. under reduced pressure, and the residue was separated using a column (30: 1 → 10: 1 ether / methanol) to obtain 178 parts of a colorless oily liquid.
211 parts of the liquid and 700 parts of soda lime powder were flame pyrolyzed in a distillation apparatus in an argon atmosphere. Heat until liquid is gone and the residue turns gray. The distillate was dissolved in a mixed solution of 500 parts of water and 660 parts of dichloromethane and separated, and the aqueous phase was washed twice with 660 parts of dichloromethane. 54 parts of magnesium sulfate was added to dichloromethane for dehydration. Desolvation under reduced pressure at room temperature gave 116 parts of a brown oily liquid. The oily liquid was distilled at 1 Torr to obtain 74 parts of a yellow oily liquid as a distillate.
135 parts of the above yellow oily liquid was dissolved in 270 parts in dichloromethane and added to 6343 parts of 1.0 M hydrochloric acid. Volatile components were removed by reducing the pressure to 1 Torr, and the resulting brown solid was separated with a column (CH ₂ Cl ₂ → CH ₂ Cl ₂ / methanol (4/1)) to obtain 83 parts of a beige solid. It was.

151 parts of lithium aluminum hydride was added to the suspension of 154 parts of the solid dissolved in 20000 parts of THF. When the gas generation stopped, 203 parts of lithium aluminum hydride was further added and refluxed for 62 hours. The mixture was cooled to 0 ° C., 113 parts of water was added carefully, followed by 2252 parts of 2M aqueous sodium hydroxide. The slurry was stirred at room temperature for 30 minutes and 4504 parts of potassium carbonate was added. The mixture was further stirred at room temperature for 1 hour and filtered through a layer of celite and potassium carbonate. The obtained solid was washed with 4505 parts of a dichloromethane-methanol (20: 1) solution. To the filtrate was added 6757 parts of a 0.5 M aqueous hydrochloric acid solution, and volatile components were removed at room temperature under a reduced pressure of 1 Torr to obtain a pale yellow oily liquid. Chromatography (CH ₂ Cl ₂ → CH ₂ Cl ₂ / methanol (4/1)) gave 121 parts of a hygroscopic beige solid.
173 parts of the beige solid was added to a mixture of 7142 parts of ether and 1000 parts of 2M KOH aqueous solution. After vigorous stirring for 2 minutes, the mixture was separated, and 7142 parts of ether was added to the aqueous phase for extraction. To the mixed ether phase, 429 parts of magnesium sulfate was added and dried, and the solvent was removed under reduced pressure at room temperature. As a result, 120 parts of a white solid was obtained.
As a result of analyzing the white solid by 1H-NMR, it was found that the raw material disappeared and (2aα, 4aα, 6aα) -octahydro-1H-6b-aza-cyclopenta [cd] pentalene was produced.

<Production Example 2>
Preparation of [3aα, 6aα, 9aα] -dodecahydropyrido- [2,1,6-de] quinolidine 84 parts cyclooctane in 56 parts dry THF and 163 parts 1,5,9-cyclododecatriene (Aldrich Japan) was added. To this solution, 76 parts of borane-dimethyl sulfide was added dropwise over 2.5 hours.
The solvent was removed under reduced pressure at 150 ° C., and the remaining mixture was heated in an oil bath at 220 ° C. for 15 hours.
When the reaction solution was distilled at 1.2 Torr, 165 parts of a viscous yellow liquid (organoborane) was obtained as a distillate at 85 to 95 ° C.
2282 parts of water, 1290 parts of acetone, 21 parts of sodium acetate, 648 parts of sodium periodate and 9 parts of ruthenium dioxide were added. Finally, 88 parts of the above organoborane was added. The mixed solution was vigorously mixed while cooling with ice water, and the temperature was maintained at 15 to 30 ° C. It was confirmed that the black ruthenium dioxide was dissolved and the reaction solution became a yellowish green color characteristic of ruthenium tetroxide. After confirming that the solution returned from yellowish green to black, it was filtered to remove the solid. When the filtrate was transferred to a separatory funnel and a sufficient amount of sodium periodate was added, the mixture returned to yellow-green again. 22 parts of activated carbon was added and mixed vigorously for 1 minute. Further, 52 parts of isopropanol was added and mixed. The mixture was filtered and extracted with 1139 parts of dichloromethane.

The dichloromethane phase was washed with 1087 parts of saturated sodium bicarbonate solution, after which 34 parts of magnesium sulfate were added to dehydrate the solution. After filtration, desolvation under reduced pressure yielded a yellowish green oily solid. 156 parts of ether were added and heated to 30 ° C. It left still at 5 degreeC and the crystal | crystallization was obtained. Filtration and drying under reduced pressure at room temperature gave 34 parts of crystals.
To 105 parts of the crystals, 11 parts of 10% palladium carbon, 813 parts of isopropanol, 1325 parts of 2.2 M ammonia in isopropanol and 31 parts of acetic acid were added. Hydrogen was blown into this solution at a pressure of 4.2 kgf / cm ² . After 16 hours, the mixed solution was filtered and desolvated at 50 ° C. under reduced pressure. Excess hydrochloric acid was added to the residue and 1057 parts of ether were added twice to extract the product from the aqueous phase. The aqueous phase was made alkaline with potassium hydroxide and extracted by adding 1941 parts of dichloromethane four times. Ether and dichloromethane were mixed, and magnesium sulfate was added for dehydration, followed by desolvation under reduced pressure at 0.5 Torr and 80 ° C. to obtain 84 parts of a colorless liquid.
As a result of analyzing the white solid by 1H-NMR, it was found that the raw material disappeared and [3aα, 6aα, 9aα] -dodecahydropyrido- [2,1,6-de] quinolidine was produced.

<Example 1>
137 parts of (2aα, 4aα, 6aα) -octahydro-1H-6b-aza-cyclopenta [cd] pentalene obtained in Production Example 1 and 339 parts of acetone were charged into a glass beaker and uniformly dissolved. While stirring the solution, 156 parts of methyl iodide was slowly added dropwise, and stirring was continued at 30 ° C. for 3 hours. The precipitated white solid was filtered and dried at 80 ° C. under reduced pressure to obtain 278 parts of an iodide salt of the cation species (a-1) in Table 1 above.
-Preparation of AgBF ₄ solution A solution obtained by mixing 116 parts of silver oxide and 209 parts of 42 wt% aqueous borofluoric acid solution at 100 ° C under reduced pressure was dissolved in 550 parts of methanol, and dissolved in AgBF ₄ methanol. A solution was obtained.
-Preparation of BF ₄ salt 745 parts of the above AgBF ₄ solution was slowly added dropwise to a mixed solution of 279 parts of the iodide salt of the cationic species (a-1) and 253 parts of methanol, and then filtered to collect the filtrate. did. An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 238 parts of white crystals. After adding 600 parts of methanol and dissolving at 30 ° C., the mixture was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried under reduced pressure at 80 ° C. to obtain 113 parts of electrolyte (A-1). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-1) was a BF ₄ salt of a cationic species (a-1). From the integral value of 1H-NMR, the purity was 99%.
-3 parts of molecular sieve was added to 100 parts of dehydrated propylene carbonate as an electrolyte solvent, and the mixture was allowed to stand at 25 ° C for 60 hours for drying. Then, the molecular sieve was filtered off to obtain dehydrated propylene carbonate.
-Preparation of electrolyte solution 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-1) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 16 ppm.

<Example 2>
-Add 3 parts of molecular sieves to 100 parts of dehydrated propylene carbonate and 100 parts of dimethyl carbonate as electrolyte solvents, and let stand at 25 ° C for 60 hours to dry. Then, the molecular sieves are separated by filtration, and dehydrated propylene carbonate and dehydrated dimethyls. Carbonate was obtained.
-Preparation of electrolyte solution 40 parts of propylene carbonate dehydrated by the above method, 40 parts of dimethyl carbonate and 20 parts of electrolyte (A-1) were uniformly mixed to obtain an electrolyte solution. The water content of the electrolytic solution was 20 ppm.

<Example 3>
-3 parts of molecular sieve was added to 100 parts of dehydrated sulfolane as the electrolyte solvent, and the mixture was allowed to stand at 40 ° C for 60 hours for drying. Then, the molecular sieve was filtered off to obtain dehydrated sulfolane.
-Preparation of electrolytic solution 80 parts of sulfolane dehydrated by the above method and 20 parts of electrolyte (A-1) were uniformly mixed and dissolved at 40 ° C to obtain an electrolytic solution. The water content of the electrolytic solution was 17 ppm.

<Example 4>
· AgPF ₆ to 60 wt% of HPF ₆ solution 243 parts instead prepared in Example 1 of 42 wt% fluoroboric acid aqueous solution is mixed with silver oxide 116 parts After 100 ° C. vacuum dewatering, methanol 550 part was added dissolved, to obtain a methanol solution of AgPF _6.
-Preparation of PF ₆ salt 803 parts of the above AgPF ₆ solution was gradually mixed with a mixed solution of 279 parts of the iodide salt of the cationic species (a-1) and 255 parts of methanol, and then filtered to collect the filtrate. . An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 295 parts of white crystals. 600 parts of methanol was added to the obtained solid and dissolved at 30 ° C., then cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried under reduced pressure at 80 ° C. to obtain 242 parts of electrolyte (A-2). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-2) was a PF ₆ salt of the cation species (a-1). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution 80 parts of propylene carbonate dehydrated in the same manner as in Example 1 and 20 parts of electrolyte (A-2) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 34 ppm.

<Example 5>
· AgCF ₃ SO ₃ to 60 wt% of _CF 3 SO ₃ H solution 250 parts instead create Example 1 in a 42% by weight fluoroboric acid aqueous solution is mixed with silver oxide 116 parts, after dehydration under reduced pressure 550 parts of methanol was added and dissolved to obtain a methanol solution of AgCF ₃ SO ₃ .
-Preparation of CF ₃ SO ₃ salt After gradually mixing 807 parts of the above AgCF ₃ SO ₃ solution with 279 parts of iodide salt of cation species (a-1) and methanol, the mixture was filtered and the filtrate was filtered. It was collected. An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. Desolvation under reduced pressure at 80 ° C. was performed to obtain 299 parts of white crystals. After adding 600 parts of methanol to the obtained solid and dissolving at 30 ° C., it was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and desolvated at 80 ° C. under reduced pressure to obtain 239 parts of electrolyte (A-3). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-3) was a CF ₃ SO ₃ salt of the cation species (a-1). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution In the same manner as in Example 1, 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-3) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 37 ppm.

<Example 6>
Synthesis of iodide salt 137 parts of (2aα, 4aα, 6aα) -octahydro-1H-6b-aza-cyclopenta [cd] pentalene obtained in Production Example 1 and 339 parts of acetone were charged into a glass beaker and uniformly dissolved. . While the solution was stirred, 172 parts of ethyl iodide was gradually added dropwise, and stirring was continued at 30 ° C. for 3 hours. The precipitated white solid was filtered and dried at 80 ° C. under reduced pressure to obtain an iodide salt of the cation species (a-2) in Table 1 above.
-Preparation of AgBF ₄ solution A methanol solution of AgBF ₄ was obtained in the same manner as in Example 1.
-Preparation of BF ₄ salt The above AgBF ₄ solution 745 parts was slowly mixed with a mixed solution of 293 parts of the iodide salt of the cationic species (a-2) and 267 parts of methanol, and then filtered to collect the filtrate. . An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 251 parts of white crystals. After adding 600 parts of methanol to the crystal and dissolving at 30 ° C., it was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried at 80 ° C. under reduced pressure to obtain 205 parts of electrolyte (A-4). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-4) was a BF ₄ salt of a cationic species (a-2). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution In the same manner as in Example 1, 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-4) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 35 ppm.

<Example 7>
・ Synthesis of iodide salt 137 parts of (2aα, 4aα, 6aα) -octahydro-1H-6b-aza-cyclopenta [cd] pentalene obtained in Production Example 1 and 339 parts of acetone were charged uniformly into a stainless steel autoclave with a cooling condenser. Dissolved in. Next, the temperature was raised to 50 ° C., and 394 parts of a 50 wt% trifluoromethyl iodide acetone solution was added dropwise over 3 hours. Next, the reaction was carried out at 80 ° C., and after 30 hours, the solution was cooled to 30 ° C., and the solution was taken out and desolvated under reduced pressure at 80 ° C. It was.
-Preparation of AgBF ₄ solution A methanol solution of AgBF ₄ was obtained in the same manner as in Example 1.
-Preparation of BF ₄ salt 745 parts of the above AgBF ₄ solution was slowly mixed with a mixed solution of 333 parts of the iodide salt of the cationic species (a-3) and 307 parts of methanol, and then filtered to collect the filtrate. . An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 292 parts of white crystals. After adding 600 parts of methanol to the crystal and dissolving at 30 ° C., it was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried at 80 ° C. under reduced pressure to obtain 234 parts of electrolyte (A-5). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-5) was a BF ₄ salt of a cationic species (a-3). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution In the same manner as in Example 1, 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-5) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 28 ppm.

<Example 8>
[3aα, 6aα, 9aα] -dodecahydropyrido- [2,1,6-de] quinolidine obtained in Production Example 2 and 339 parts of acetone were charged into a glass beaker and uniformly dissolved. While stirring the solution, 156 parts of methyl iodide was slowly added dropwise, and stirring was continued at 30 ° C. for 3 hours. The precipitated white solid was filtered and dried at 80 ° C. under reduced pressure to obtain 320 parts of an iodide salt of the cation species (a-5) in Table 1 above.
-Preparation of AgBF ₄ solution A solution obtained by mixing 116 parts of silver oxide and 209 parts of 42 wt% aqueous borofluoric acid solution at 100 ° C under reduced pressure was dissolved in 550 parts of methanol, and dissolved in AgBF ₄ methanol. A solution was obtained.
-Preparation of BF ₄ salt 745 parts of the above AgBF ₄ solution was slowly added dropwise to a mixed solution of 321 parts of the iodide salt of the cationic species (a-5) and 253 parts of methanol, and then filtered to collect the filtrate. did. An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 280 parts of white crystals. After adding 600 parts of methanol and dissolving at 30 ° C., the mixture was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried at 80 ° C. under reduced pressure to obtain 225 parts of electrolyte (A-6). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-6) was a BF ₄ salt of a cationic species (a-5). From the integral value of 1H-NMR, the purity was 99%.
-3 parts of molecular sieve was added to 100 parts of dehydrated propylene carbonate as an electrolyte solvent, and the mixture was allowed to stand at 25 ° C for 60 hours for drying. Then, the molecular sieve was filtered off to obtain dehydrated propylene carbonate.
-Preparation of electrolytic solution 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-6) were uniformly mixed and dissolved at 25 ° C to obtain an electrolytic solution. The water content of the electrolytic solution was 16 ppm.

<Example 9>
-Add 3 parts of molecular sieves to 100 parts of dehydrated propylene carbonate and 100 parts of dimethyl carbonate as electrolyte solvents, and let stand at 25 ° C for 60 hours to dry. Then, the molecular sieves are separated by filtration, and dehydrated propylene carbonate and dehydrated dimethyls. Carbonate was obtained.
-Preparation of electrolyte solution 40 parts of propylene carbonate dehydrated by the above method, 40 parts of dimethyl carbonate and 20 parts of electrolyte (A-6) were uniformly mixed to obtain an electrolyte solution. The water content of the electrolytic solution was 20 ppm.

<Example 10>
-3 parts of molecular sieve was added to 100 parts of dehydrated sulfolane as the electrolyte solvent, and the mixture was allowed to stand at 40 ° C for 60 hours for drying. Then, the molecular sieve was filtered off to obtain dehydrated sulfolane.
-Preparation of electrolyte solution 80 parts of sulfolane dehydrated by the above method and 20 parts of electrolyte (A-6) were uniformly mixed and dissolved at 40 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 17 ppm.

<Example 11>
· AgPF ₆ to 60 wt% of HPF ₆ solution 243 parts instead prepared in Example 1 of 42 wt% fluoroboric acid aqueous solution is mixed with silver oxide 116 parts After 100 ° C. vacuum dewatering, methanol 550 part was added dissolved, to obtain a methanol solution of AgPF _6.
-Preparation of PF ₆ salt 803 parts of the above AgPF ₆ solution was gradually mixed with a mixed solution of 321 parts of the iodide salt of the cationic species (a-5) and 255 parts of methanol, and then filtered to collect the filtrate. . An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 339 parts of white crystals. After adding 600 parts of methanol to the obtained solid and dissolving at 30 ° C., it was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried under reduced pressure at 80 ° C. to obtain 275 parts of electrolyte (A-7). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-7) was a PF ₆ salt of a cationic species (a-5). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution 80 parts of propylene carbonate dehydrated in the same manner as in Example 1 and 20 parts of electrolyte (A-7) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 34 ppm.

<Example 12>
· AgCF ₃ SO ₃ 60% by weight of _CF 3 SO ₃ H aqueous solution 250 parts instead create Example 1 in a 42 wt% fluoroboric acid aqueous solution is mixed with silver oxide 116 parts, after dehydration under reduced pressure 550 parts of methanol was added and dissolved to obtain a methanol solution of AgCF ₃ SO ₃ .
Preparation of CF ₃ SO ₃ salt After gradually mixing 807 parts of the above AgCF ₃ SO ₃ solution with a mixed solution of iodide salt of cation species (a-5) and methanol, the filtrate was filtered and the filtrate was filtered. It was collected. An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. Desolvation under reduced pressure was performed at 80 ° C. to obtain 341 parts of white crystals. After adding 600 parts of methanol to the obtained solid and dissolving at 30 ° C., it was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and desolvated under reduced pressure at 80 ° C. to obtain 280 parts of electrolyte (A-8). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-8) was a CF ₃ SO ₃ salt of a cation species (a-5). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution In the same manner as in Example 1, 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-8) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 37 ppm.

<Example 13>
・ Synthesis of iodide salt [3aα, 6aα, 9aα] -dodecahydropyrido- [2,1,6-de] quinolidine obtained in Production Example 2 and 339 parts of acetone were charged into a glass beaker and uniformly dissolved. I let you. While the solution was stirred, 172 parts of ethyl iodide was gradually added dropwise, and stirring was continued at 30 ° C. for 3 hours. The precipitated white solid was filtered and dried at 80 ° C. under reduced pressure to obtain an iodide salt of the cation species (a-6) in Table 1 above.
-Preparation of AgBF ₄ solution A methanol solution of AgBF ₄ was obtained in the same manner as in Example 1.
-Preparation of BF ₄ salt 745 parts of the above AgBF ₄ solution was slowly mixed with a mixed solution of 335 parts of the iodide salt of (a-6) and 267 parts of methanol, and then filtered to collect the filtrate. An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 293 parts of white crystals. After adding 600 parts of methanol to the crystal and dissolving at 30 ° C., it was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried at 80 ° C. under reduced pressure to obtain 237 parts of electrolyte (A-9). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-9) was a BF ₄ salt of a cationic species (a-6). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution In the same manner as in Example 1, 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-9) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 35 ppm.

<Example 14>
Synthesis of iodide salt 179 parts of [3aα, 6aα, 9aα] -dodecahydropyrido- [2,1,6-de] quinolidine obtained in Production Example 2 and 339 parts of acetone were placed in a stainless steel autoclave with a cooling condenser. The charge was uniformly dissolved. The temperature was then raised to 50 ° C., and 394 parts of a 50 wt% trifluoromethyl iodide acetone solution was added dropwise over 3 hours. Next, the reaction was carried out at 80 ° C., and after 30 hours, the solution was cooled to 30 ° C., and the solution was taken out. It was.
-Preparation of AgBF ₄ solution A methanol solution of AgBF ₄ was obtained in the same manner as in Example 1.
-Preparation of BF ₄ salt 745 parts of the above AgBF ₄ solution was slowly mixed with a mixed solution of 375 parts of the iodide salt of the cationic species (a-7) and 307 parts of methanol, and then filtered to collect the filtrate. . An AgBF ₄ solution or an iodide salt solution was added little by little to the filtrate to finely adjust the silver ion content in the solution to 10 ppm or less and the iodine ion content to 5 ppm or less, and then filtered to collect the filtrate. The filtrate was desolvated at 80 ° C. under reduced pressure to obtain 333 parts of white crystals. After adding 600 parts of methanol to the crystal and dissolving at 30 ° C., it was cooled to −5 ° C. and allowed to stand for 12 hours for recrystallization. The precipitated crystals were filtered and dried at 80 ° C. under reduced pressure to obtain 263 parts of electrolyte (A-10). As a result of analysis by 1H-NMR, 19F-NMR and 13C-NMR, the electrolyte (A-10) was a BF ₄ salt of a cationic species (a-7). From the integral value of 1H-NMR, the purity was 99%.
-Preparation of electrolyte solution In the same manner as in Example 1, 80 parts of dehydrated propylene carbonate and 20 parts of electrolyte (A-10) were uniformly mixed and dissolved at 25 ° C to obtain an electrolyte solution. The water content of the electrolytic solution was 28 ppm.

<Comparative Example 1>
Preparation of electrolyte solution As in Example 1, 80 parts of dehydrated propylene carbonate and, as a quaternary spiro ammonium salt, tetrafluoroboric acid spiro- (1,1 ′)-bipiperidinium BF ₄ salt (hereinafter “SPR”) 20 parts of the mixture was uniformly mixed and dissolved at 25 ° C. to obtain an electrolytic solution. The water content of the electrolytic solution was 36 ppm.

<Comparative example 2>
-Preparation of electrolyte solution As in Example 1, 40 parts of dehydrated propylene carbonate and 40 parts of dimethyl carbonate were uniformly mixed, and the electrolyte SPR was uniformly mixed and dissolved in this mixed solvent at 25 ° C to obtain an electrolyte solution. . The water content of the electrolytic solution was 34 ppm.

<Comparative Example 3>
-Preparation of electrolyte solution The electrolyte SPR was uniformly mixed and dissolved at 80 ° C in 80 parts of dehydrated sulfolane as in Example 1 to obtain an electrolyte solution. The water content of the electrolytic solution was 37 ppm.

<Comparative Example 4>
Preparation of electrolyte solution As in Example 1, 80 parts of dehydrated propylene carbonate and 20 parts of tetraethylammonium BF ₄ salt (hereinafter abbreviated as “TEA”) were uniformly mixed and dissolved at 25 ° C. A liquid was obtained. The water content of the electrolytic solution was 33 ppm.

In order to evaluate the characteristics of the electrolytic solution, the electrical conductivity was measured at a temperature of 30 ° C. Moreover, polarization measurement was performed using a glassy carbon electrode (manufactured by BAS, outer diameter 6 mm, inner diameter 1 mm) at a scanning potential speed of 5 mV / sec. The potential for Ag / Ag ⁺ reference electrode when a current of 10 μA / cm ² flows is an oxidation potential, and the potential for Ag / Ag ⁺ reference electrode when a current of −10 μA / cm ² flows is a reduction potential. The potential window was calculated from the difference in potential values. The results are shown in Table 4. As is clear from Table 4, it was shown that the electrolytic solutions of Examples 1 to 14 of the present invention had a larger potential window and higher electrochemical stability than the electrolytic solutions of Comparative Examples 1 to 4.

Using the electrolytic solution of the present invention and the electrolytic solution of the comparative example, a three-electrode electric double layer capacitor (manufactured by Power System Co., Ltd., FIG. 1) was prepared. A charge / discharge cycle test was performed using this capacitor, and the capacity, resistance, and leakage current were evaluated.

  Powdered activated carbon (“MSP-20” manufactured by Kansai Thermal Chemical Co., Ltd.) was mixed with carbon black and polytetrafluoroethylene powder (PTFE). The weight ratio was 10: 1: 1.

  The obtained mixture was kneaded for about 5 minutes in a mortar and rolled with a roll press to obtain an activated carbon sheet. The thickness of the activated carbon sheet was 400 μm. This activated carbon sheet was punched into a 20 mmφ disk shape to obtain an activated carbon electrode.

  Using the obtained activated carbon electrodes (positive electrode, negative electrode and reference electrode), a three-electrode electric double layer capacitor (manufactured by Power System Co., Ltd., FIG. 1) was assembled. These cells were dried in vacuum at 170 ° C. for 7 hours and cooled to 30 ° C. In a dry atmosphere, the electrolytic solutions of <Examples 1 to 14> and <Comparative Examples 1 to 4> were injected into the cell, followed by vacuum impregnation to produce an electric double layer capacitor.

  Connect the charge / discharge test device (“CDT-5R2-4” manufactured by Power System Co., Ltd.) to the created electric double layer capacitor, perform constant current charging at 25 mA to the set voltage, and 25 mA 7200 seconds after the start of charging. A constant current discharge was performed at. This was carried out for 50 cycles at a set voltage of 3.3 V and 45 ° C., and the capacitance value and the rate of decrease in capacitance (%) at the initial stage and after 50 cycles of the cell, and the internal resistance and internal resistance after the initial and 50 cycles. The rate of increase (%) was calculated. Moreover, the leakage current at the time of constant voltage charge at 50 cycles was measured and used as an indicator of voltage resistance. The test results are shown in Table 5.

As is apparent from Table 5, the electric double layer capacitors using the electrolytic solutions of Examples 1 to 14 of the present invention have a capacity after a cycle test as compared with the electric double layer capacitors using the electrolytic solutions of Comparative Examples 1 to 4. The withstand voltage is high because the retention rate is high and the internal resistance increase rate is low. Furthermore, since the leakage current was significantly low, the electrochemical stability of the electrolyte was high. Therefore, it is clear that the electrolytic solution of the present invention can drastically improve the deterioration of performance of the electrochemical capacitor over time and constitute a highly reliable electrochemical element.

Since the quaternary ammonium salt electrolyte of the present invention has a very high withstand voltage, an electrolytic solution using the quaternary ammonium salt electrolyte can produce an electrochemical device with little performance deterioration over time. Therefore, by using the electrolyte of the present invention, an electrochemical element having a large energy density and excellent charge / discharge cycle characteristics can be obtained. The electrochemical element can be applied to an electrochemical capacitor, a secondary battery, a dye-sensitized solar cell, and the like.

3 electrode type electric double layer capacitor

Claims (9)

An electrolyte (B) containing the compound (A) represented by the general formula (1).

[R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have at least one group selected from the group consisting of a halogen atom, a hydroxyl group, a nitro group, a cyano group and a group having an ether bond. is there. R ^{2 to} R ⁴ are each a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have at least one group selected from the group consisting of a halogen atom, a nitro group, a cyano group and a group having an ether bond, A hydrogen atom or a halogen atom, which may be the same or different. R ^{5 to} R ⁷ are an alkylene group having 1 to 5 carbon atoms or a fluoroalkylene group having 1 to 5 carbon atoms, and may be the same or different. X ⁻ represents a counter ion. ] ^2. The electrolyte according to claim 1, wherein in the general formula (1), R ¹ is a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group, and R ^{2 to} R ⁴ are a hydrogen atom or a halogen atom. B). In the general formula (1), the counter ion X ⁻ represents I ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , N (RfSO ₃ ) ₂ ⁻ , C (RfSO ₃ ) ₃ ⁻ and RfSO _3. ^- (Rf is a fluoroalkyl group having 1 to 12 carbon atoms) electrolyte according to claim 1 or 2 is at least one selected from the group consisting of (B). The electrolyte solution containing the electrolyte (B) and nonaqueous solvent (C) of any one of Claims 1-3. Non-aqueous solvent (C) is propylene carbonate, ethylene carbonate, butylene carbonate, sulfolane, methyl sulfolane, acetonitrile, γ-butyrolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, xylene, chlorobenzene, 1,2-dichlorobenzene, 1, The electrolytic solution according to claim 4, which is at least one selected from the group consisting of 3-dichlorobenzene and 1,4-dichlorobenzene. An electrolytic solution for an electrochemical device comprising the electrolytic solution according to claim 4 or 5. An electrochemical element using the electrolytic solution according to claim 6. An electrochemical capacitor using the electrolytic solution according to claim 6. An electric double layer capacitor using the electrolytic solution according to claim 6.

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