JP2009167108A - Ionic compound and electrolyte liquid material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ionic compound being a liquid state at a normal temperature and excellent in heat resistance, and an electrolyte liquid material. <P>SOLUTION: This ionic compound consists of an anion expressed by formula (1) [wherein, X<SP>1</SP>to X<SP>3</SP>are each the same or different, a halogen atom, -CN, -OCN, -SCN, -NO, -NO<SB>2</SB>, -SO<SB>2</SB>R, -SO<SB>3</SB>R, -COR or a monovalent organic group containing them; R is H or a monovalent organic group; Q is an alkylene, alkenylene, arylene, alkynylene or the like; and (n) is 0 or 1] and an organic cation. The electrolyte liquid material contains the ionic compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel ionic compound and an electrolyte material.

An ionic compound is a compound composed of a combination of a cation and an anion, and since it has electrical conductivity by ions, that is, ionic conductivity, it is an ionic conductive material used in various batteries using ionic conduction. For example, in addition to batteries having charging and discharging mechanisms such as primary batteries, lithium (ion) secondary batteries and fuel cells, electrolytic capacitors, electric double layer capacitors, solar cells, etc. Used in electrochemical devices such as batteries and electrochromic display elements. In these, generally, a battery is composed of a pair of electrodes and an electrolytic solution that is an ionic conductor filling between the electrodes. Examples of such ionic conductors include organic solvents such as γ-butyrolactone, N, N-dimethylformamide, ethylene carbonate, propylene carbonate, tetrahydrofuran, lithium perchlorate, LiPF ₆ , LiBF ₄ , tetraethylammonium borofluoride, phthalate. An electrolytic solution in which an electrolyte such as tetramethylammonium acid is dissolved is used. In such an ionic conductor, when the electrolyte is dissolved, it is dissociated into a cation and an anion to conduct ions in the electrolytic solution.

  The present applicant has been researching ionic compounds from the past, and has already filed patent applications for inventions related to ionic compounds containing an anion having a cyano group (Patent Documents 1 to 5).

On the other hand, it is known that a trifluoroacetimide anion forms an ionic compound with sodium and mercury, for example (Non-patent documents 1 and 2 for sodium and Non-patent document 3 for mercury). However, all of these ionic compounds are solid at room temperature, which is difficult to use as an electrolyte material and has not been clarified as useful as an electronic material.
JP 2004-12774 A JP 2004-292350 A JP 2005-353568 A JP 2006-173014 A JP 2006-216524 A Giovanni Viti, two others, “A New Synthesis of Oxazolidin-2-ones from Triacetamides”, “Tetrahedron Letters” ", UK, 1992, Vol. 33, No. 3, p.377-380 Philip A. Harland, et al., “Synthesis of Primary Amines via Alkylation of the Sodium Salt: Synthesis of Primary Amine by Alkylation of Sodium Salt of Trifluoroacetamide: Synthesis of Primary Amines via Alkylation of the Sodium Salt of Trifluoroacetamide: An Alternative to the Gabriel Synthesis) ”,“ Synthesis (SYNTHSIS) ”, UK, November 1984, p.941-943 RH Patton, 1 other, "Mercury Derivatives of Fluorocarbon Carboxylic Acid Amides", "Journal of Organic Chemistry", USA, 1956, Volume 21, p.1199-1200

  The present applicant has made it an object to find an ionic compound and an electrolytic solution material that are liquid at room temperature, which are useful as electronic materials.

The present invention that has solved the above problems
An anion represented by the following formula (1);

(In the formula (1), X ^{1 to} X ³ are the same or different and are each a halogen atom, —CN, —OCN, —SCN, —NO, —NO ₂ , —SO ₂ R, —SO ₃ R, —COR, Alternatively, it represents a monovalent organic group containing these, R represents hydrogen or a monovalent organic group, and Q represents a halogen atom, —CN, —OCN, —SCN, —NO, —NO ₂ , —SO ₂ R , —SO ₃ R and —COR, which may have one or more selected from the group consisting of an alkylene group, an alkenylene group or an arylene group, an alkynylene group, or any one of the following formulae: A group or a group in which two or more of these divalent groups are linked, and n represents 0 or 1.)

And an ionic compound comprising an organic cation.

X ^{1 to} X ³ in formula (1) are all the same and are preferably a halogen atom, —CN, —NO or —NO ₂ . In particular, an embodiment in which X ^{1 to} X ³ in formula (1) are all fluorine atoms and n is 0 is preferable. The organic cation is preferably an onium cation.

  The present invention also includes an electrolyte solution material containing the ionic compound.

  The ionic compound of the present invention is a room temperature molten salt that stably maintains a molten state at room temperature, and also has excellent heat resistance. Therefore, it has become possible to provide an electrolyte material that is stable over a long period of time.

  The ionic compound of the present invention contains an anion represented by the following formula (1) as an essential component.

(In the formula (1), X ^{1 to} X ³ are the same or different and are each a halogen atom, —CN, —OCN, —SCN, —NO, —NO ₂ , —SO ₂ R, —SO ₃ R, —COR, Alternatively, it represents a monovalent organic group containing these, R represents hydrogen or a monovalent organic group, and Q represents a halogen atom, —CN, —OCN, —SCN, —NO, —NO ₂ , —SO ₂ R , —SO ₃ R and —COR, which may have one or more selected from the group consisting of an alkylene group, an alkenylene group or an arylene group, an alkynylene group, or any one of the following formulae: A group or a group in which two or more of these divalent groups are linked, and n represents 0 or 1.)

R in —SO ₂ R, —SO ₃ R, and —COR in the formula (1) is hydrogen or a monovalent organic group, and examples of the organic group include a fluorine atom, an amino group, an imino group, an amide group, and an ether. Group, ester group, hydroxyl group, carboxyl group, carbamoyl group, cyano group, sulfone group, sulfide group, straight chain, branched chain or cyclic, which may contain a nitrogen atom, an oxygen atom, a sulfur atom, etc. 18 hydrocarbon groups and fluorocarbon groups are represented. Preferably they are a hydrogen atom, a fluorine atom, a cyano group, a sulfone group, and a C1-C8 hydrocarbon group.

Moreover, all of X < ¹ > -X < ³ > in Formula (1) are electron withdrawing groups. A halogen atom, —CN, —NO or —NO ₂ is preferable from the viewpoint of performance as an electronic material, and an embodiment in which X ^{1 to} X ³ are all F (fluorine atoms) and n is 0 is the most. preferable. The halogen atom means F, Cl, Br and I.

Q is a divalent linking group selected from the group consisting of (a) a halogen atom, —CN, —OCN, —SCN, —NO, —NO ₂ , —SO ₂ R, —SO ₃ R, and —COR. An alkylene group, an alkenylene group or an arylene group, which may have one or more of these as a substituent; (b) an alkynylene group; (c) any group represented by the above structural formula; (d) (a) A group in which two or more of the groups shown in (c) are linked. In order to make it difficult to stop electrons at the Q portion, any group represented by the above structural formula of (c) is preferred.

  The organic cation serving as the partner of the anion is not particularly limited as long as it forms a liquid ionic compound at room temperature, but an onium cation having a hetero atom such as N, P, S, or O is preferable.

  Examples of the onium cation include cations represented by the following formula.

  R in the above formula is the same or different and is a hydrogen atom, a fluorine atom, an amino group, an imino group, an amide group, an ether group, an ester group, a hydroxyl group, a carboxyl group, a carbamoyl group, a cyano group, a sulfone group, a sulfide group, Represents a C1-C18 hydrocarbon group or fluorine-containing group which is linear, branched or cyclic and may contain a nitrogen atom, an oxygen atom, a sulfur atom or the like. Preferably they are a hydrogen atom, a fluorine atom, a cyano group, a sulfone group, and a C1-C8 hydrocarbon group.

More specifically, for example, a cation having a heterocyclic structure having the following structure can be used. R ^{1 to} R ⁶ in the following formula have the same meaning as R above.

Moreover, the onium cation which has a saturated ring represented by a following formula may be sufficient. R ^{1 to} R ¹² in the following formula have the same meaning as R above.

  Among the above, cations represented by the following six formulas are preferable.

  More specifically, a pyrrolidinium cation having the following structure,

A piperidinium cation having the structure

Etc. are also suitable. Moreover, the alkyl quaternary ammonium cation of the following structure is also mentioned as a suitable thing. In addition, m represents the integer of 1-4.

  The ionic compound of the present invention is composed of an organic cation, particularly preferably an onium cation and an anion represented by the above formula (1). This ionic compound has a melting point of 10 ° C. or lower and is liquid at room temperature (ionic liquid). Also, the viscosity is as low as 400 mPa · s or less. On the other hand, it can be seen that the thermal decomposition starting temperature is as high as 100 ° C. or higher, and the heat resistance is excellent. Therefore, it can be applied to a wide range of applications other than the electrolyte material described later. For example, it is generally known that ionic liquids are liquid while having ionic bonds, and thus have high electrochemical and thermal stability, and also selectively absorb specific gases such as carbon dioxide. The ionic compound of the present invention also has these characteristics. From this, it is preferable that the ionic compound in the present invention has a solvent for reaction, a sealant and a lubricant for a machine sliding portion, electrochemical characteristics and thermal stability in addition to the electrochemical material. Therefore, a conductivity imparting agent for the polymer, a gas absorbent such as carbon dioxide, and the like can be mentioned.

  Next, the electrolyte material of the present invention will be described. The electrolyte solution material of the present invention contains an ionic compound composed of an organic cation, particularly preferably the above-described onium cation, and the anion represented by the above formula (1). This ionic compound is a room temperature molten salt that stably maintains a molten state at room temperature, and also has excellent heat resistance. Therefore, it becomes a material of an ionic conductor of an electrochemical device that is stable for a long period of time. In addition, molten salt can maintain a liquid state stably in the temperature range of room temperature (25 degreeC) to 80 degreeC.

  The abundance of the cation in the electrolyte material of the present invention is preferably 0.5 mol or more, more preferably 0.8 mol or more with respect to 1 mol of anion present in the electrolyte material. Moreover, 2.0 mol or less is preferable, More preferably, it is 1.2 mol or less.

  The electrolyte material of the present invention may contain an anion other than that represented by the above formula (1) as long as it works suitably when used as an electrolyte solution. For example, bistrifluoromethanesulfonyl Contains imide anions (TFSI), tetrafluoroborate anions, monocarboxylic acids such as acetic acid and benzoic acid, dicarboxylic acid anions such as phthalic acid, maleic acid and succinic acid anions, and sulfate ester anions such as methyl sulfate and ethyl sulfate You may do it.

  Fluorine-containing inorganic ions such as hexafluorophosphate ion, hexafluoroarsenate ion, hexafluoroantimonate ion, hexafluoroniobate ion, hexafluorotantalate ion; hydrogen phthalate ion, hydrogen maleate ion, salicylate ion Carboxylic acid ions such as benzoic acid ion and adipic acid ion; sulfonic acid ions such as benzenesulfonic acid ion, toluenesulfonic acid ion, dodecylbenzenesulfonic acid ion, trifluoromethanesulfonic acid ion, perfluorobutanesulfonic acid; boric acid ion Inorganic oxoacid ions such as phosphate ion; bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion Tetracoordinate borate ions such as perfluoroalkylfluoroborate ion, perfluoroalkylfluorophosphate ion, borodicatecholate, borodiglycolate, borodisalicylate, borotetrakis (trifluoroacetate), bis (oxalato) borate 1 type or 2 types or more, such as these, may be contained.

  The electrolyte material of the present invention contains a solvent in addition to the ionic compound described above. It is preferable that a solvent is 1-99 mass% in 100 mass% of electrolyte material. If it is less than 1% by mass, the ionic conductivity may be too small, and if it exceeds 99% by mass, the stability may decrease due to volatilization of the solvent or the like. The amount of the solvent is more preferably 1.5% by mass or more, further preferably 20% by mass or more, and most preferably 50% by mass or more. Moreover, 85 mass% or less is more preferable, 75 mass% or less is further more preferable, and 65 mass% or less is the most preferable.

  The electrolyte material of the present invention has reduced volatile content and excellent ionic conductivity, and can exhibit excellent basic performance when used as an electrolyte.

  The solvent is not particularly limited as long as it can improve the ionic conductivity. For example, water, an organic solvent, or the like is preferable. Examples of the organic solvent include 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, crown ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1,4-dioxane, 1,3-dioxolane, 2,6-dimethyl. Ethers such as tetrahydrofuran, tetrahydropyran, triethylene glycol methyl ether, tetraethylene glycol dimethyl ether; chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate, methyl phenyl carbonate; ethylene carbonate, Cyclic carbonates such as propylene carbonate, 2,3-dimethylethylene carbonate, butylene carbonate, vinylene carbonate, 2-vinylethylene carbonate; methyl formate, methyl acetate, methyl propionate, Aliphatic carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate and amyl acetate; Aromatic carboxylic acid esters such as methyl benzoate and ethyl benzoate; γ-butyrolactone, γ-valerolactone, δ-valerolactone, etc. Cyclic carboxylic acid esters of: phosphoric acid esters such as trimethyl phosphate, ethyl dimethyl phosphate, diethyl methyl phosphate, triethyl phosphate; acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2- Nitriles such as methylglutaronitrile; aromatic nitriles such as benzonitrile and tolunitrile; N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone, N -Methylpyrrolidone Amides such as N-vinylpyrrolidone; sulfur compounds such as dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, sulfolane, 3-methyl sulfolane, 2,4-dimethyl sulfolane, dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide: ethylene glycol , Alcohols such as propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; nitromethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazolidinone and the like can be mentioned, and one or more of these can be used. Among these, carbonate esters, aliphatic esters, cyclic esters, and ethers are preferable, and carbonate esters, and cyclic esters such as γ-butyrolactone and γ-valerolactone are more preferable.

  The electrolyte material of the present invention may further contain an alkali metal salt and / or an alkaline earth metal salt. Since the electrolytic solution material containing an alkali metal salt and / or an alkaline earth metal salt contains an electrolyte, it is suitable as a material for an electrolytic solution of an electrochemical device. As the alkali metal salt, a lithium salt, a sodium salt, and a potassium salt are preferable, and as the alkaline earth metal salt, a calcium salt and a magnesium salt are preferable. More preferably, it is a lithium salt.

The alkali metal salt and / or alkaline earth metal salt may be a compound that requires an anion as described above, or other compounds. Further, an electrolyte salt having a large dissociation constant in the electrolytic solution is preferable. For example, alkali metal salts of trifluoromethanesulfonic acid such as LiCF ₃ SO ₃ , NaCF ₃ SO ₃ , KCF ₃ SO ₃ , and alkalis thereof. Earth metal salts; alkali metal salts of perfluoroalkanesulfonic imides such as LiN (CF ₃ SO ₃ ) ₃ , LiN (CF ₃ CF ₃ SO ₂ ) _2, and alkaline earth metal salts thereof; LiPF ₆ , NaPF ₆ Alkali metal salts of hexafluorophosphoric acid such as KPF ₆ and alkaline earth metal salts thereof; Alkali metal salts of perchloric acid such as LiClO ₄ and NaClO ₄ and alkaline earth metal salts thereof; LiBF ₄ and NaBF ₄ alkali metal salts and the alkali earth metal salt of tetrafluoroboric acid and the _{like; LiAsF 6, LiI, NaI,} NaAsF 6, KI , etc. Al of Potassium metal salts are preferred. Among these, from the viewpoint of solubility and ionic conductivity, LiPF ₆ , LiBF ₄ , LiAsF ₆ , alkali metal salts of perfluoroalkanesulfonic imides, and alkaline earth metal salts thereof are preferable.

The electrolyte material may contain other electrolyte salt, and quaternary ammonium salt of perchloric acid such as tetraethylammonium perchlorate; quaternary ammonium of tetrafluoroboric acid such as (C ₂ H ₅ ) ₄ NBF ₄ Quaternary ammonium salts such as (C ₂ H ₅ ) ₄ NPF ₆ ; quaternary phosphonium salts such as (CH ₃ ) ₄ P · BF ₄ and (C ₂ H ₅ ) ₄ P · BF ₄ are suitable. From the viewpoints of solubility and ionic conductivity, quaternary ammonium salts are preferred.

  When the electrolytic solution material of the present invention contains an electrolyte salt, the amount of the electrolyte salt is preferably 0.1% by mass or more and preferably 50% by mass or less in 100% by mass of the electrolytic solution material. If it is less than 0.1% by mass, the absolute amount of ions may be insufficient and the ionic conductivity may be reduced. If it exceeds 50% by mass, the movement of ions may be greatly inhibited. More preferably, it is 30 mass% or less.

  The electrolyte material of the present invention can be suitably used as an ion conductor material constituting a hydrogen battery by containing protons. Such an electrolyte material further containing protons is one of the preferred embodiments of the present invention. In the present invention, the inclusion of a compound that can dissociate to generate a proton causes the proton to be present in the electrolytic solution.

  The abundance of protons in the electrolyte material of the present invention is preferably 0.01 mol / L or more, more preferably 10 mol / L or less, with respect to the electrolyte material. If it is less than 0.01 mol / L, the absolute amount of protons may be insufficient and proton conductivity may be reduced. When it exceeds 10 mol / L, there is a possibility that proton transfer is greatly inhibited. More preferably, it is 5 mol / L or less.

  The electrolyte material of the present invention may contain one or more components other than those described above as long as the effects of the present invention are exhibited, and may contain, for example, various inorganic oxide fine particles. As the inorganic oxide fine particles, non-electron conductive electrochemically stable particles are preferable, and those having ion conductivity are more preferable. As such fine particles, ion conductive or nonconductive ceramic fine particles such as α, β or γ-alumina, silica, titania, zirconia, magnesia, barium titanate, titanium oxide, hydrotalcite and the like are suitable.

The specific surface area of the inorganic oxide fine particles is preferably as large as possible, preferably 5 m ² / g or more, more preferably 50 m ² / g or more by the BET method. The size of the inorganic oxide fine particles is not particularly limited as long as it can be mixed with other components in the electrolytic solution. However, the size (average particle size) is preferably 0.01 μm or more, and preferably 20 μm or less. . More preferably, it is 0.1 μm or more and 2 μm or less. The average particle size is measured by, for example, preparing a particle dispersion by dispersing the particles in ion-exchanged water, etc., and using a precision particle size distribution analyzer (“Multisizer II” manufactured by Beckman Coulter, Inc.). And calculating the average particle size on a volume basis. As the inorganic oxide fine particles, those having various shapes such as a spherical shape, an oval shape, a cubic shape, a rectangular parallelepiped shape, a cylindrical shape, and a rod shape can be used.

  As addition amount of the said inorganic oxide microparticles | fine-particles, 0.1-100 mass parts is preferable with respect to 100 mass parts of electrolyte material. If it exceeds 100 parts by mass, the ion conductivity may be reduced. A more preferable upper limit is 20 parts by mass.

  In addition, acid anhydrides such as acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, pyromellitic anhydride, acid compounds thereof, and basic compounds such as triethylamine and methylimidazole may be added. As addition amount, 50 mass% or less is preferable in 100 mass% of electrolyte material. More preferably, it is 0.01 mass% or more and 20 mass% or less.

  The electrolyte material of the present invention may also contain various additives in addition to the salt and solvent described above. The purpose of adding the additive is various, and includes improvement of electrical conductivity, improvement of thermal stability, suppression of electrode deterioration due to hydration and dissolution, suppression of gas generation, improvement of withstand voltage, improvement of wettability, etc. it can. Examples of such additives include nitro compounds such as p-nitrophenol, m-nitroacetophenone, and p-nitrobenzoic acid; dibutyl phosphate, monobutyl phosphate, dioctyl phosphate, monooctyl phosphonate, monophosphate Boron compounds such as complex compounds of boric acid or boric acid with polyhydric alcohols (ethylene glycol, glycerin, mannitol, polyvinyl alcohol, etc.) and polysaccharides; nitroso compounds; urea compounds; arsenic compounds; titanium compounds; Silicic acid compounds; aluminate compounds; nitric acid and nitrous acid compounds; benzoic acids such as 2-hydroxy-N-methylbenzoic acid and di (tri) hydroxybenzoic acid; gluconic acid, dichromic acid, sorbic acid, dicarboxylic acid, EDTA , Fluorocarboxylic acid, picric acid, suberic acid, azide Acid, sebacic acid, heteropolyacid (tungstic acid, molybdic acid), gentisic acid, borodigentisic acid, salicylic acid, N-aminosalicylic acid, borodiprotocatechuic acid, borodipyrocatechol, bamonic acid, boronic acid, borodiresorcillic acid, resorcil Acids, acids such as borodiprotocaeric acid, glutaric acid, dithiocarbamic acid, esters thereof, amides and salts thereof; silane coupling agents, silicon compounds such as silica and aminosilicates; amine compounds such as triethylamine and hexamethylenetetramine; L-amino acids; sulfur compounds such as benzol, polyhydric phenol, 8-oxyquinoline, hydroquinone, N-methylpyrocatechol, quinoline; thioanisole, thiocresol, thiobenzoic acid, etc .; 1 such as sorbitol, L-histidine, etc. Or it may be used two or more.

  Although content of the said additive is not specifically limited, For example, it is preferable that it is the range of 0.1-20 mass% with respect to 100 mass% of electrolyte material. More preferably, it is the range of 0.5-10 mass%.

The ionic conductivity of the electrolyte material of the present invention is preferably 1 × 10 ⁻⁷ S / cm or more at 25 ° C. If it is less than 1 × 10 ⁻⁷ S / cm, the electrolytic solution using the electrolytic solution material of the present invention may not function stably over time while maintaining excellent ionic conductivity. More preferably, it is 1 × 10 ⁻⁶ S / cm or more, still more preferably 5 × 10 ⁻⁵ S / cm or more, and particularly preferably 1 × 10 ⁻⁴ S / cm or more.

  The ion conductivity is measured by, for example, a complex impedance method using an impedance analyzer HP4294A (trade name, manufactured by Toyo Technica) using a SUS electrode or an impedance analyzer SI1260 (trade name, manufactured by Solartron). Is preferred.

  The electrolyte material preferably has a viscosity at 25 ° C. of 300 mPa · s or less. If it exceeds 300 mPa · s, the ionic conductivity may not be sufficiently improved. More preferably, it is 200 mPa * s or less, More preferably, it is 100 mPa * s or less, Most preferably, it is 50 mPa * s or less. A method for measuring the viscosity is not particularly limited, but a method of measuring at 25 ° C. using a TV-20 viscometer: cone plate type (manufactured by Tokimec) is preferable.

  The electrolyte material of the present invention is a primary battery, a battery having a charging / discharging mechanism such as a lithium (ion) secondary battery or a fuel cell, an electrolytic capacitor, an electric double layer capacitor, a solar cell, an electrochromic display element, or the like It is suitable as a material for an ionic conductor constituting the device.

  When an electrochemical device is configured using the electrolytic solution material of the present invention, a preferred form of the electrochemical device has an ionic conductor, a negative electrode, a positive electrode, a current collector, a separator, and a container as basic components. .

  As the ionic conductor, a mixture of an electrolyte and an organic solvent is suitable. If an organic solvent is used, this ionic conductor is generally called an electrolytic solution. The electrolytic solution material of the present invention can be suitably applied as an alternative to the electrolyte or organic solvent in the electrolytic solution in such an ionic conductor, and the electrolytic solution material of the present invention is used as a material for the ionic conductor. In the chemical device, at least one of these is constituted by the electrolyte material of the present invention. Among these, it is preferable to use as an alternative of the organic solvent in electrolyte solution.

  The organic solvent may be an aprotic solvent that can dissolve the electrolytic solution material of the present invention, and the same organic solvents as described above are suitable. However, when two or more kinds of mixed solvents are used, when the electrolyte contains Li ions, among these organic solvents, an aprotic solvent having a dielectric constant of 20 or more and an aprotic solvent having a dielectric constant of 10 or less It is preferable to prepare an electrolytic solution by dissolving in a mixed solvent. In particular, when a lithium salt is used, the solubility in an aprotic solvent having a dielectric constant of 10 or less, such as diethyl ether or dimethyl carbonate, is low, and sufficient ionic conductivity cannot be obtained by itself. Although the aprotic solvent alone has high solubility but high viscosity, ions are difficult to move and sufficient ionic conductivity cannot be obtained. If these are mixed, appropriate solubility and mobility can be ensured, and sufficient ionic conductivity can be obtained.

The electrolyte concentration in the ionic conductor is preferably 0.01 mol / dm ³ or more, and more preferably a saturation concentration or less. If it is less than 0.01 mol / dm ³ , the ionic conductivity is low, which is not preferable. More preferably, 0.1 mol / dm ³ or more, it is 1.5 mol / dm ³ or less.

  As the constituent elements of the negative electrode, the positive electrode, the current collector, the separator, and the container, any of known materials and forms in various electrochemical devices can be used.

  The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the present invention.

  In the following examples, NMR was measured with an NMR measuring apparatus “Unity Plus” (manufactured by Varian). The IR spectrum was measured with an FT-IR measuring apparatus “Nexus-670” (manufactured by Thermo Electron).

Example 1 [Synthesis of triethylammonium trifluoroacetimide (TEATFAI)]
To a 500 ml beaker equipped with a stirrer were added 15.8 g (140 mmol) of trifluoroacetamide and 100 ml of water, and the mixture was stirred at room temperature for 5 minutes, and then cooled in an ice bath. The mixture was stirred for 10 minutes while immersed in an ice bath, and 17 g (168 mmol) of triethylamine was added little by little with a pipette. After all the triethylamine was added, the beaker was taken out of the ice bath and stirred for 30 minutes. The obtained solution was concentrated and dried to obtain a colorless and transparent liquid (TEATFAI). The obtained TEATFAI was 30 g (140 mmol), and the yield was 100%. The analysis results are shown below.
¹ H-NMR (400 MHz: DMSO-d ₆ : TMS standard)
δ 9.28 (bs, 1H), δ 7.19 (m, 1H), δ 3.09 (m, 6H), δ 1.20 (m, 9H)
¹³ C-NMR (100 MHz: DMSO-d ₆ : TMS standard)
δ 158.0 (t), 116.7 (q), 45.6 (s), 8.5 (s)
¹⁹ F-NMR (376 MHz: DMSO-d ₆ : TMS standard)
δ 69.3 (s)
FT-IR (ATR method)
2997, 1666, 1478, 1199, 1127 cm ^-1

Example 2 [Synthesis of 1-ethyl-3-methylimidazolium trifluoroacetimide (EMImTFAI)]
A column tube was filled with 96 ml of an ion exchange resin (“Amberlite (registered trademark) IRA-400-OH”: manufactured by Rohm and Haas), and 830 ml of a 3% aqueous solution of 25 g of TEATFAI synthesized in Example 1 was taken for 1 hour. I passed slowly. The liquid after passing was discarded. After passing the TEATFAI aqueous solution, ultrapure water was passed through the column tube for 1 hour to wash the ion exchange resin in the column. 610 ml of 1% aqueous solution of 5.1 g (27 mmol) of 1-ethyl-3-methylimidazolium bromide (EMImBr) was slowly passed through the column tube after washing over 2 hours. The solution collected after passing through the solution was concentrated and dried to obtain a colorless transparent liquid EMImTFAI. The obtained EMImTFAI was 5.4 g (24 mmol), and the yield was 91% (based on EMImBr). The analysis results are shown below.
¹ H-NMR (400 MHz: DMSO-d ₆ : TMS standard)
δ 9.14 (s, 1H), δ 7.78 (d, ΔJ = 1.6 Hz, 1H), δ 7.69 (d, ΔJ = 1.6 Hz, 1H), δ 4.20 (q, ΔJ) = 7.2 Hz, 2H), δ 3.84 (s, 3H), δ 1.41 (t, ΔJ = 7.2 Hz, 3H)
¹³ C-NMR (100 MHz: DMSO-d ₆ : TMS standard)
δ 136.3, 123.6, 122.0, 118.9, 115.9, 44.1, 35.7, 15.1
¹⁹ F-NMR (376 MHz: DMSO-d ₆ : TMS standard)
δ 69.1 (s)
FT-IR (ATR method)
3090, 1771, 1688, 1199, 1168, 1118, 822, 717 cm ^-1

  Below, each characteristic of TEATFAI obtained in Example 1 and EMImTFAI obtained in Example 2 was evaluated.

[Ionic conductivity]
Each sample was a 35% by mass solution of γ-butyrolactone. The impedance was measured by a complex impedance method using an SUS electrode in an atmosphere of 25 ° C., 0 ° C., and −20 ° C. with an impedance analyzer (“SI1260”; manufactured by Solartron). The results are shown in Table 1.

[Potential window]
Using cyclic voltammetry tool “HSV-100” (Hokuto Denko), working electrode: glassy carbon electrode, reference electrode: Ag electrode, counter electrode: Pt electrode, sweep speed: 100 mV / s, sweep range: The potential window was measured under the condition of natural potential to 3V. The results are also shown in Table 1.

[Measurement of melting point]
Using a differential scanning calorimeter (“EXSTAR6000 DSC” manufactured by Seiko Instruments Inc.), the sample was placed in an aluminum pan and measured at a temperature drop rate of 5 ° C./min and a measurement temperature range of 30 to −100 ° C. The results are also shown in Table 1.

[Measurement of thermal decomposition start temperature]
Using a differential thermothermal gravimetric simultaneous measurement device (“EXSTAR6000 TG / DTA”: manufactured by Seiko Instruments Inc.), the sample is placed in an aluminum pan, and the temperature is raised at a heating rate of 10 ° C./min and a measurement temperature range of 30 to 500 ° C. The temperature at which a mass decrease of 2% from the initial mass was observed was defined as the thermal decomposition start temperature. The results are also shown in Table 1.

[Measurement of viscosity]
Using a rheometer ("Programmable rheometer DV-III +": manufactured by Brookfield), the temperature of the sample was adjusted to 25 ° C and measured. The results are also shown in Table 1.

  It was confirmed that all of the ionic compounds of the present invention exhibited good ionic conductivity and a wide potential window. In addition, it is liquid at room temperature and has high heat resistance. Furthermore, it was confirmed that the viscosity was low.

  The electrolyte material of the present invention is suitable as an electrolyte material constituting an ion conductor because it has high ionic conductivity, excellent heat resistance, and is stable over time. Ion) In addition to batteries having a charge / discharge mechanism such as secondary batteries and fuel cells, the present invention can be suitably applied to electrochemical devices such as electrolytic capacitors, electric double layer capacitors, solar cells and electrochromic display elements.

  In particular, electrochemical devices such as lithium secondary batteries, electrolytic capacitors, and electric double layer capacitors using the electrolyte material according to the present invention include portable information terminals, portable electronic devices, small household electric power storage devices, motorcycles, and electric vehicles. It can be suitably used for various applications such as hybrid electric vehicles.

  Also, since it is liquid and non-volatile at normal temperature and has high thermal stability, it absorbs gases such as solvents for reaction, sealants and lubricants for machine sliding parts, conductivity enhancers for polymers, and carbon dioxide. Application to agents is possible.

Claims (5)

An anion represented by the following formula (1);
(In the formula (1), X ^{1 to} X ³ are the same or different and are each a halogen atom, —CN, —OCN, —SCN, —NO, —NO ₂ , —SO ₂ R, —SO ₃ R, —COR, Alternatively, it represents a monovalent organic group containing these, R represents hydrogen or a monovalent organic group, and Q represents a halogen atom, —CN, —OCN, —SCN, —NO, —NO ₂ , —SO ₂ R , —SO ₃ R and —COR, which may have one or more selected from the group consisting of an alkylene group, an alkenylene group or an arylene group, an alkynylene group, or a group represented by the following formula: Or represents a group in which two or more of these divalent groups are linked, and n represents 0 or 1.)
And an organic cation. _2. The ionic compound according to claim 1, wherein X ^{1 to} X ³ in formula (1) are all the same and are a halogen atom, —CN, —NO, or —NO ₂ . The ionic compound according to claim 1 or 2, wherein X ^{1 to} X ³ in formula (1) are all fluorine atoms and n is 0.   The ionic compound according to any one of claims 1 to 3, wherein the organic cation is an onium cation. An electrolytic solution material comprising the ionic compound according to claim 1.