JP2007131596A - Ionic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ionic compound which can exert excellent basic capabilities such as electrochemical stability and can be suitably used for various applications; an electrolyte suitable as a material for an ionic conductor for constituting an electrochemical device; and a lithium secondary battery, an electrolytic capacitor, an electric double-layer capacitor, etc., all prepared by using the electrolyte. <P>SOLUTION: The ionic compound comprises a dicyanotriazolate anion and a cation represented by general formula (1) (wherein L is an element selected from the group consisting of C, Si, N, P, S, and O; the R of Rs is a monovalent element or organic group being the same or different from each other and may be bonded to each other; and s is an integer of 3, 4, or 5 and is a value determined by the valency of the L element). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an ionic compound. More specifically, the ionic compound is used as an electrolyte suitable as a material of an ionic conductor constituting an electrochemical device, and a lithium secondary battery, an electrolytic capacitor, an electric double layer capacitor, or the like using the electrolyte. It can be done.

The ionic compound is composed of a cation and an anion and is widely used for various applications. Among such ionic compositions, those having ionic conductivity are suitably used as constituent materials for ionic conductors that are essential in various batteries and the like based on ionic conduction. The constituent material of the ion conductor is a material that can function as an electrolyte and / or a solvent in an electrolytic solution that constitutes the ion conductor, and can also function as a solid electrolyte. 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, electrochromic display elements, etc. Examples include chemical devices. In these, a battery is generally constituted by a pair of electrodes and an ionic conductor filling between them.

As an ionic conductor, usually, an organic solvent such as γ-butyrolactone, N, N-dimethylformamide, propylene carbonate, tetrahydrofuran, lithium perchlorate, LiPF ₆ , LiBF ₄ , tetraethylammonium borofluoride, tetramethylammonium phthalate An electrolytic solution in which an electrolyte such as an electrolyte is dissolved is used, and when the electrolyte is dissolved, it is dissociated into a cation and an anion to conduct ions in the electrolytic solution. A solid electrolyte that can conduct ions in a solid state is also used as an ion conductor.

FIG. 1 shows a schematic cross-sectional view of one form of a general lithium (ion) secondary battery. Such a lithium (ion) secondary battery has a positive electrode and a negative electrode formed from an active substance, and an electrolyte solution composed of an organic solvent in which a lithium salt such as LiPF ₆ is dissolved as a solute, An ionic conductor is formed between the negative electrode. In this case, at the time of charging, a reaction of C ₆ Li → 6C + Li + e occurs in the negative electrode, and electrons (e) generated on the negative electrode surface are ion-conducted in the electrolytic solution and move to the positive electrode surface, and on the positive electrode surface, CoO ₂ + Li + e → A reaction of LiCoO ₂ occurs, and a current flows from the negative electrode to the positive electrode. When discharging, a reverse reaction occurs during charging, and current flows from the positive electrode to the negative electrode.
However, in the electrolyte solution that constitutes such an electrochemical device, the organic solvent is likely to volatilize, the flash point is low, the liquid is liable to occur, the long-term reliability is lacking, and at low temperatures. Since the electrolytic solution is solidified and the performance as the electrolytic solution cannot be exhibited, a material capable of improving these has been demanded.

Thus, an ionic compound comprising at least one anion moiety bonded to at least one cation moiety M, sufficient to guarantee overall electronic neutrality, wherein M is hydroxonium, nitrosonium NO ⁺ , Ammonium NH ₄ ⁺ , a metal cation having a valence m, an organic cation having a valence m, or an organometallic cation having a valence m, and the anion portion is a five-membered ring or tetraazapentalene The above ionic compound characterized in that it is derived from is disclosed (for example, see Patent Document 1). In the examples, triazole, imidazole, and cyclopentadiene derivatives are described as the anion moiety. Further, an ionic liquid represented by an N-alkylimidazolium cation, an ammonium cation, a tetrazole compound anion, a triazole compound anion, and a triazole compound anion is disclosed (for example, see Patent Document 2). Furthermore, lithium dicyanotriazolate is disclosed as a lithium salt of a polymer electrolyte solution based on polyethylene oxide (see, for example, Non-Patent Document 1). However, there has been room for contrivance as anions and cations constituting ionic compounds that can be suitably used for various applications such as materials constituting electrochemical devices and exhibit excellent basic performance.
JP 2000-508676 A (Pages 2-13, 39-67) JP 2004-331521 A (page 2-3) Egashira et al., Electrochemical and Solid-State Letters, 2003, Vol. 6, No. 4, p. A71-A73

The present invention has been made in view of the above-mentioned present situation, can exhibit excellent basic performance such as electrochemical stability, and can be suitably used for various applications. An object of the present invention is to provide an electrolyte suitable as a material for an ion conductor constituting a device, and a lithium secondary battery, an electrolytic capacitor, an electric double layer capacitor, or the like using the electrolyte.

As a result of various studies on ionic compounds, the present inventors have focused on triazolate anions having triazole as an anion skeleton. Triazolate is a unique anion having a ring structure. However, since it is low in acidity, it needs to be improved, so two cyano groups (—CN) are introduced as substituents and dicyanotriazolate anion and As a result, it was found that the introduction of two cyano groups increases the electric attractiveness and can be stabilized as an anion. In addition, an electrolyte containing an ionic compound having a dicyanotriazolate anion and a matrix material can exhibit excellent basic performance such as electrochemical stability, and can solve the above-mentioned problems. did. Further, it has been found that such ionic compounds and electrolytes can be suitably applied to various uses such as materials for electrochemical devices, and the present invention has been achieved.

That is, the present invention relates to a dicyanotriazolate anion and the following general formula (1);

(In the formula, L represents one kind of element selected from the group consisting of C, Si, N, P, S and O. R is the same or different and is a monovalent element or an organic group, and S is an integer of 3, 4 or 5, and is a value determined by the valence of the element of L).
The present invention also provides a dicyanotriazolate anion and the following general formula (2):

(Wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen element or a hydrocarbon group having 1 to 8 carbon atoms. At least two of R ¹ , R ² and R ³ are carbonized. In the case of a hydrogen group, these hydrocarbon groups may be bonded directly or may have a structure bonded via at least one element selected from O, S and N.) It is also an ionic compound having a cation represented by:
The present invention is also an electrolyte containing the ionic compound and a matrix material.
The present invention is described in detail below.

The ionic compound of the present invention is a compound having a cation and an anion.
As the anion, a dicyanotriazolate anion is preferable, and the following formula (3);

It is represented by As described above, when the triazole ring has two cyano groups, the electric attractiveness is increased, the acidity can be increased, and the anion is sufficiently stable.
The cation is represented by the general formula (1). Since the ionic compound of the present invention has such a cation having a monovalent element or organic group and a dicyanotriazolate anion, it easily forms a matrix (solvent, etc.) compared to an inorganic salt such as a lithium salt. It can be dissolved and can be made into a compound excellent in various physical properties, and can be suitably applied to various uses such as materials for electrolytes and electrochemical devices.

In the general formula (1), L represents one type of element selected from the group consisting of C, Si, N, P, S, and O. N, P, and S elements are preferable, and an N element is more preferable.
Said R is the same or different, is a monovalent element or an organic group, and may be the element couple | bonded together. Examples of the monovalent element or organic group include hydrogen element, fluorine element, amino group, imino group, amide group, ether group, ester group, hydroxyl group, carboxyl group, carbamoyl group, cyano group, sulfone group, sulfide group, A vinyl group, a hydrocarbon group having 1 to 18 carbon atoms, a fluorine group having 1 to 18 carbon atoms and the like are preferable. The hydrocarbon group having 1 to 18 carbon atoms and the fluorine group having 1 to 18 carbon atoms may be linear, branched or cyclic, and may contain a nitrogen element, an oxygen element, or a sulfur element. Moreover, as these carbon number, it is preferable that it is 1-18, and it is more preferable that it is 1-8.
More preferably, the monovalent element or organic group is a hydrogen element, a fluorine element, a cyano group, a sulfone group, a hydrocarbon group having 1 to 8 carbon atoms, a hydrocarbon group having 1 to 8 carbon atoms containing an oxygen element, It is a C1-C8 fluorocarbon group, More preferably, it is a hydrogen element. Thus, in the general formula (1), an ionic compound in which at least one of R is a hydrogen element is also one of the preferred embodiments of the present invention.

The s is an integer of 3, 4 or 5, and is a value determined by the valence of the L element. When the element of L is an element of C or Si, s is 5, when the element of N or P is s is 4, and when the element of S or O is s is 3. That is, as the cation represented by the general formula (1), the following general formula:

(In formula, R is the same as that of General formula (1).) What is represented is preferable.
The cation is not particularly limited as long as it satisfies the general formula (1), and among them, the following onium cations (I) to (IV) are more preferable. The onium cation means an organic group having a cation of a nonmetallic element or a semimetallic element such as O, N, S, and P.
The ionic compound of the present invention has the cation and the anion, but an ionic composition containing other components other than the ionic compound is also one of the preferred embodiments of the present invention. Such an ionic composition is particularly suitable as a material for an ionic conductor of an electrochemical device that can withstand a long period of time.

The onium cations (I) to (IV) will be described below.
(I) the following general formula;

10 heterocyclic onium cations represented by
(II) the following general formula;

5 types of unsaturated onium cations represented by
(III) the following general formula;

9 kinds of saturated ring onium cations represented by
In the general formula, R ^{4 to} R ¹⁵ are the same or different and are a monovalent element or an organic group, and may be bonded to each other.
(IV) R is an alkyl group of _C 1 -C ₈ chain onium cations.
Among such onium cations, more preferably, L in the general formula (1) is a nitrogen element, and more preferably, the following general formula:

(Wherein R ^{4 to} R ¹⁵ are the same as above), triethylmethylammonium, dimethylethylpropylammonium, diethylmethylmethoxyethylammonium, trimethylpropylammonium, trimethylbutyl And chain onium cations such as ammonium and trimethylhexylammonium.
Examples of the monovalent element or organic group of R ^{4 to} R ¹⁵ include a hydrogen element, a fluorine element, 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, a vinyl group, a hydrocarbon group having 1 to 18 carbon atoms, a fluorine group having 1 to 18 carbon atoms, and the like are preferable. The hydrocarbon group having 1 to 18 carbon atoms and the fluorine group having 1 to 18 carbon atoms may be linear, branched or cyclic, and may contain a nitrogen element, an oxygen element, or a sulfur element. Moreover, as these carbon number, it is preferable that it is 1-18, and it is more preferable that it is 1-8.

More preferably, the monovalent element or organic group is a hydrogen element, a fluorine element, a cyano group, a sulfone group, a hydrocarbon group having 1 to 8 carbon atoms, a hydrocarbon group having 1 to 8 carbon atoms containing an oxygen element, It is a C1-C8 fluorocarbon group.
A compound composed of such an onium cation and the anion as described above becomes a room temperature molten salt that stably maintains a molten state at room temperature, and the ionic composition containing such a molten salt is used for a long time. Therefore, it is suitable as a material for an ionic conductor of an electrochemical device that can withstand high temperatures. In addition, molten salt can maintain a liquid state stably at the temperature of 80 degrees C or less.

In the ionic composition, (1) a form in which a nitrogen heterocyclic cation having a conjugated double bond is essential, or (2) in the general formula (1), L is an element of N, and R is , R ¹ , R ² and R ^3, which are the same or different and each represents a hydrogen element or a hydrocarbon group having 1 to 8 carbon atoms, are preferred.
In the form of (1) above, examples of the nitrogen heterocyclic cation having a conjugated double bond include 10 types of heterocyclic onium cations represented by the above general formula (I) and 5 represented by the above general formula (II). Among the kinds of unsaturated onium cations and the like, those having a conjugated double bond and L in the general formula (1) being a nitrogen element are suitable.
In the form of (2) above, when at least two of R ¹ , R ² and R ³ are hydrocarbon groups, these hydrocarbon groups are directly bonded or O, S and N It may have a structure bonded through at least one element selected from among the above. Thus, dicyanotriazolate anion and the following general formula (2);

(Wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen element or a hydrocarbon group having 1 to 8 carbon atoms. At least two of R ¹ , R ² and R ³ are carbonized. In the case of a hydrogen group, these hydrocarbon groups may be bonded directly or may have a structure bonded via at least one element selected from O, S and N.) An ionic compound having a cation represented by the formula is also one aspect of the present invention.

The ionic composition may also contain an anion other than the above-described dicyanotriazolate anion, and an anion or cation other than the above-described cation.
The ionic composition may further contain an organic compound having an onium cation other than the organic salt of an anion essentially comprising the onium cation described above. Examples of the organic compound having such an onium cation include a halogen anion (fluoro anion, chloro anion, bromo anion, iodo anion), tetrafluoroborate anion, hexafluorophosphate anion, tetrafluoroaluminate anion. , Hexafluoroarsenate anion, sulfonylimide anion represented by the following general formula (4), sulfonylmethide anion represented by the following general formula (5), organic carboxylic acid (acetic acid, trifluoroacetic acid, phthalic acid, Fluorinated inorganic ions such as hexafluorophosphate ion, hexafluoroarsenate ion, hexafluoroantimonate ion, hexafluoroniobate ion, hexafluorotantalate ion; Hydrogen ion, maleic acid hydrogen ion, salicylic acid Carboxylic acid ions such as benzene, benzoic acid and adipic acid ions; sulfonic acid ions such as benzene sulfonic acid ions, toluene sulfonic acid ions, dodecyl benzene sulfonic acid ions, trifluoromethane sulfonic acid ions, perfluorobutane sulfonic acid; boric acid Inorganic oxo acid ions such as ions and phosphate ions; bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion, perfluoroalkylfluoroborate ion, perfluoroalkylfluorophosphate ion , Borodicatecholate, borodiglycolate, borodisalicylate, borotetrakis (trifluoroacetate), bis (oxalato) borate, etc. And anions of c acid ion or the like, an organic compound having an onium cation is preferable.

In said general formula, R <^16> , R <^17> and R <^18> are the same or different, and represent the C1-C4 perfluoroalkyl group which may have one or two ether groups.

In the ionic composition, the abundance of the onium cation is preferably 0.5 mol with respect to 1 mol of the anion. More preferably, it is 0.8 mol. Moreover, it is preferable that an upper limit is 2.0 mol. More preferably, it is 1.2 mol.

The ionic composition may further contain an alkali metal salt and / or an alkaline earth metal salt. An ionic composition comprising such an alkali metal salt and / or alkaline earth metal salt contains an alkali metal salt and / or alkaline earth metal salt as an electrolyte, and is an ionic conductor of an electrochemical device. It becomes more suitable as a material for the above. 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 an ionic substance which essentially requires an anion as described above, or other compounds.
In the case of the ionic substance essentially containing the anion, an alkali metal salt and / or alkaline earth metal salt of a dicyanotriazolate anion is preferable. For example, it can be used in the form of a lithium salt. As other alkali metal salts and / or alkaline earth metal salts, for example, lithium salts can be used, and as such lithium salts, LiC (CN) ₃ , LiSi (CN) ₃ , LiB (CN) ₄ , LiAl (CN) ₄ , LiP (CN) ₂ , LiP (CN) ₆ , LiAs (CN) ₆ , LiOCN, LiSCN and the like are suitable.

When the compound is other than the ionic substance, it is preferably an electrolyte salt having a large dissociation constant in the electrolytic solution or the solid polymer electrolyte. For example, LiCF ₃ SO ₃ , NaCF ₃ SO ₃ , KCF ₃ Alkali metal salts and alkaline earth metal salts of trifluoromethanesulfonic acid such as SO ₃ ; alkali metals of perfluoroalkanesulfonic acid imide such as LiN (CF ₃ SO ₃ ) ₃ and LiN (CF ₃ CF ₃ SO ₂ ) ₂ Salts and alkaline earth metal salts; alkali metal salts and alkaline earth metal salts of hexafluorophosphoric acid such as LiPF ₆ , NaPF ₆ and KPF ₆ ; alkali metal salts and alkaline earth perchlorates such as LiClO ₄ and NaClO ₄ metal _salts; LiBF 4, Tetorafuroro borates NaBF _{4 such; LiAsF 6, LiI, NaI,} NaAsF 6, KI Alkali metal salts of are preferred. Among these, from the viewpoint of solubility and ionic conductivity, LiPF ₆ , LiBF ₄ , LiAsF ₆ , and alkali metal salts or alkaline earth metal salts of perfluoroalkanesulfonic acid imide are preferable.

The ionic composition may contain other electrolyte salts, such as quaternary ammonium salts of perchloric acid such as tetraethylammonium perchlorate; tetrafluoroboric acid such as (C ₂ H ₅ ) ₄ NBF ₄ Quaternary ammonium salts, quaternary ammonium salts such as (C ₂ H ₅ ) ₄ NPF ₆ ; quaternary phosphonium salts such as (CH ₃ ) ₄ P · BF ₄ , (C ₂ H ₅ ) ₄ P · BF _4, etc. Quaternary ammonium salts are more preferable from the viewpoint of solubility and ionic conductivity.
As the abundance of the electrolyte salt, it is preferable that the lower limit value is 0.1% by mass and the upper limit value is 50% by mass with respect to 100% by mass of the ionic composition. If the amount is less than 0.1% by mass, the absolute amount of ions may not be sufficient, and the ionic conductivity may be reduced. If the amount exceeds 50% by mass, the migration of ions may be greatly inhibited. is there. A more preferable upper limit is 30% by mass.

When the ionic composition contains a proton, it can be suitably used as a material for an ionic conductor constituting a hydrogen battery. In the present invention, by including a compound that can dissociate to generate protons, protons are present in the ionic composition according to the present invention.
As for the abundance of the proton, it is preferable that the lower limit is 0.01 mol / L and the upper limit is 10 mol / L with respect to the ionic composition. If the amount is less than 0.01 mol / L, the absolute amount of protons may not be sufficient, and the proton conductivity may decrease. If the amount exceeds 10 mol / L, proton transfer may be significantly inhibited. is there. A more preferable upper limit is 5 mol / L or less.

As the ionic composition, by including a polymer, it becomes solidified and can be suitably used as a polymer solid electrolyte. Moreover, ion conductivity will improve more by including a solvent.
Examples of the polymer include polyvinyl polymers such as polyacrylonitrile, poly (meth) acrylates, polyvinyl chloride, and polyvinylidene fluoride; polyoxymethylene: polyether polymers such as polyethylene oxide and polypropylene oxide. Polyamide polymers such as nylon 6 and nylon 66; polyester polymers such as polyethylene terephthalate; polystyrene, polyphosphazenes, polysiloxane, polysilane, polyvinylidene fluoride, polytetrafluoroethylene, polycarbonate polymers, ionene One or more polymers are preferred.
When the ionic composition is a solid polymer electrolyte, the polymer is present in a lower limit of 0.1% by mass and an upper limit of 5000% by mass with respect to 100% by mass of the ionic composition. It is preferable. If it is less than 0.1% by mass, the effect of solidification may not be sufficiently obtained, and if it exceeds 5000% by mass, the ionic conductivity may be lowered. A more preferred lower limit is 1% by mass and an upper limit is 1000% by mass.

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. As the organic solvent, the compatibility with the constituents in the ionic composition described above is good, the dielectric constant is large, the solubility of the electrolyte salt is high, the boiling point is 60 ° C. or higher, and the electrochemical A compound having a wide dynamic stability range is preferred. More preferably, it is an organic solvent (non-aqueous solvent) having a low water content. Examples of such organic solvents include ethers such as 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, crown ether, triethylene glycol methyl ether, tetraethylene glycol dimethyl ether, dioxane; ethylene carbonate, propylene carbonate Carbonates such as diethyl carbonate and methyl ethyl carbonate; chain carbonates such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, diphenyl carbonate and methyl phenyl carbonate; ethylene carbonate, propylene carbonate, 2,3-dimethyl ethylene carbonate, Cyclic carbonates such as butylene carbonate, vinylene carbonate, 2-vinylethylene carbonate; methyl formate, methyl acetate, propionic acid, methyl propionate, ethyl acetate, propyl acetate, acetic acid Aliphatic carboxylic acid esters such as chill and amyl acetate; Aromatic carboxylic acid esters such as methyl benzoate and ethyl benzoate; Carboxylic acid esters such as γ-butyrolactone, γ-valerolactone and δ-valerolactone; Phosphate esters such as trimethyl acid, ethyldimethyl phosphate, diethylmethyl phosphate, triethyl phosphate; nitriles such as acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile, adiponitrile, 2-methylglutaronitrile, etc. Amides such as N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone, N-methylpyrrolidone, N-vinylpyrrolidone; dimethylsulfone, ethylmethylsulfone , Diethyl Sulfur compounds such as luphone, sulfolane, 3-methylsulfolane, 2,4 dimethylsulfolane: alcohols such as ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethers such as 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6-dimethyltetrahydrofuran, tetrahydropyran; sulfoxides such as dimethyl sulfoxide, methylethyl sulfoxide, diethyl sulfoxide; benzonitrile, Aromatic nitriles such as tolunitrile; nitromethane, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4 , 5,6-tetrahydro-2 (1H) -pyrimidinone, 3-methyl-2-oxazolidinone, etc., and one or more of these are preferred. Among these, carbonates, aliphatic esters, and ethers are more preferable, carbonates such as ethylene carbonate and propylene carbonate are more preferable, and cyclic esters such as γ-butyrolactone and γ-valerolactone are most preferable.

As content of the said solvent, it is preferable that it is 1-99 mass% in 100 mass% of ionic compositions. If it is less than 1% by mass, the ionic conductivity will not be sufficiently improved, and if it exceeds 99% by mass, the stability will not be sufficiently improved due to volatilization of the solvent or the like. As a lower limit, Preferably, it is 1.5 mass%, More preferably, it is 20 mass%, More preferably, it is 50 mass%. As an upper limit, Preferably, it is 85 mass%, More preferably, it is 75 mass%, More preferably, it is 65 mass%. As a range, the solvent amount is preferably 50 to 85% by mass.
The ionic composition has a reduced volatile content, and does not freeze even at a low temperature of −55 ° C., for example, has excellent ionic conductivity, and has excellent basic performance when used as an electrolyte. Can be demonstrated.

The said ionic composition may contain 1 type, or 2 or more types of components other than the above, as long as there exists an effect of this invention. For example, by including various inorganic oxide fine particles, it can also be used as a composite electrolyte, thereby not only improving strength and film thickness uniformity, but also providing fine voids between the inorganic oxide and the above-described polymer. In particular, when a solvent is added, free electrolyte will be dispersed in the composite electrolyte in the pores, and the ion conductivity and mobility will be increased without deteriorating the strength improvement effect. It can also be made.
As the inorganic oxide fine particles, non-electron conductive and 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, γ-alumina, silica, titania, zirconia, magnesia, barium titanate, titanium oxide, and hydrotalcite are suitable.

The specific surface area of the inorganic oxide fine particles is preferably as large as possible from the viewpoint of increasing the amount of the electrolyte-containing liquid in the polymer solid electrolyte and increasing the ionic conductivity and mobility. For example, the BET method Is preferably 5 m ² / g or more, and more preferably 50 m ² / g or more. The crystal particle size of such inorganic oxide fine particles may be any as long as it can be mixed with other components in the ionic composition. For example, the size (average crystal particle size) has a lower limit value. It is preferable that the upper limit value is 0.01 μm and 20 μm. A more preferable lower limit value is 0.01 μm, and an upper limit value is 2 μm.
As the shape of 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.
The addition amount of the inorganic oxide fine particles is preferably 50% by mass with respect to 100% by mass of the polymer solid electrolyte. On the other hand, if it exceeds 50% by mass, the strength and ion conductivity of the polymer solid electrolyte may be lowered, or film formation may be difficult. More preferably, it is 30 mass%. The lower limit is preferably 0.1% by mass.

The ionic composition may also contain various additives in addition to the salts and solvents 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 phosphorus compounds such as boric acid or boric acid and 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, 2-hydroxy-N-methylbenzoic acid, benzoic acids such as di (tri) hydroxybenzoic acid, gluconic acid, dichromic acid, sorbic acid, dicarboxylic acid, EDTA , Fluorocarboxylic acid, picric acid, suberic acid, adipine , Sebacic acid, heteropolyacid (tungstic acid, molybdic acid), gentisic acid, borodigentisic acid, salicylic acid, N-aminosalicylic acid, borodiprotocatechuic acid, borodipyrocatechol, bamonic acid, boric acid, borodiresorcylic acid, resorcylic acid, Borodiprotocaquelic acid, glutaric acid, acids such as dithiocarbamic acid, esters thereof, amides and salts thereof, silane coupling agents, silicon compounds such as silica and aminosilicate, amine compounds such as triethylamine and hexamethylenetetramine, L- Amino acids, benzoles, polyphenols, 8-oxyquinoline, hydroquinone, N-methylpyrocatechol, quinoline and thioanisole, thiocresol, thiobenzoic acid and other sulfur compounds, sorbitol, L-histidine, etc. It may be used or 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 ionic compositions. More preferably, it is the range of 0.5-10 mass%.

As said ionic composition, it is preferable that the ionic conductivity in 0 degreeC is 0.5 mS / cm or more. If it is less than 0.5 mS / cm, the ionic conductor using the ionic composition may not be able to sufficiently function stably with time while maintaining excellent ionic conductivity. More preferably, it is 2.0 mS / cm or more. At −55 ° C., it is preferably 1 × 10 ⁻⁷ S / cm or more. If it is less than 1 × 10 ⁻⁷ S / cm, the electrolytic solution using the ionic composition may not be able to sufficiently function with time while maintaining excellent ionic conductivity. is there. More preferably, it is 1 × 10 ⁻⁶ S / cm or more, further preferably 5 × 10 ⁻⁵ S / cm or more, and particularly preferably 1 × 10 ⁻⁴ S / cm or more.
The ion conductivity is measured by a complex impedance method using an impedance analyzer HP4294A (trade name, manufactured by Toyo Technica Corp.) or an impedance analyzer SI1260 (trade name, manufactured by Solartron Corp.) using a SUS electrode. Is preferred.

The ionic composition 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.
The 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.

In the ionic substance, the impurity content is preferably 0.1% by mass (1000 ppm) or less in 100% by mass of the ionic substance. If it exceeds 0.1% by mass, sufficient electrochemical stability may not be obtained. More preferably, it is 0.05 mass% or less, More preferably, it is 0.01 mass% or less.
In addition, the said impurity does not contain water, For example, what is mixed when manufacturing an ionic substance is mentioned. Specifically, in the case of producing an ionic substance having the above-mentioned dicyanotriazolate anion as an example, for example, when the ionic substance is derived using a halogen compound, the halogen compound is There is a possibility that it is mixed as an impurity, and when it is obtained by inducing the ionic substance using a silver salt, the silver salt may be mixed as an impurity. In addition, manufacturing raw materials and by-products may be mixed as impurities.
In the present invention, by setting the impurity content in the ionic substance as described above, for example, it is possible to sufficiently inhibit the halogen compound from poisoning the electrode in the electrochemical device and reducing the performance, It is possible to sufficiently suppress the deterioration of performance due to the influence of ion conductivity on the ion conductivity. The impurity content is preferably measured by the following measurement method.

(Measurement method of impurities)
(1) ICP (Measurement of cations such as silver ion and iron ion)
Instrument: ICP emission spectroscopic analyzer SPS4000 (manufactured by Seiko Electronics Co., Ltd.)
Method: Dilute 0.3 g of sample 10 times with ion-exchanged water, and measure the solution. (2) Ion chromatography (measurement of anions such as nitrate ion, bromine ion, chloride ion)
Equipment: Ion chromatograph system DX-500 (manufactured by Nippon Dionex)
Separation mode: Ion exchange detector: Electrical conductivity detector CD-20
Column: AS4A-SC
Method: Dilute 0.3g of sample 100 times with ion-exchanged water and measure the solution

In the ionic substance, the water content is preferably 0.05 to 10% by mass in 100% by mass of the ionic substance. If it is less than 0.05% by mass, moisture management becomes difficult, which may lead to an increase in cost. Moreover, when it exceeds 10 mass%, there exists a possibility that electrical stability cannot fully be exhibited. The preferred lower limit is 0.1% by mass and the upper limit is 5% by mass, the more preferred lower limit is 0.5% by mass, and the upper limit is 3% by mass.
The water content is preferably measured by the following measurement method.
(Moisture measurement method)
For sample preparation, 0.25 g of a measurement sample and 0.75 g of dehydrated acetonitrile are mixed in a glow box with a dew point of -80 ° C. or lower, and mixed with a Terumo syringe (trade name, 2.5 ml) that is sufficiently dried in the glow box. This is done by collecting 0.5 g. Thereafter, moisture measurement is performed with a Karl Fischer moisture meter AQ-7 (trade name, manufactured by Hiranuma Sangyo Co., Ltd.).

Although it does not specifically limit as a manufacturing method of the said ionic composition, The manufacturing method which comprises the process of inducing | guiding an ionic substance from the compound which has a dicyano triazolate anion is suitable. Thereby, it becomes possible to make an ionic substance into a suitable form as a molten salt or a salt constituting a solid electrolyte. Such a production method preferably includes a step of deriving an ionic substance from a compound having a dicyanotriazolate anion structure using a halide or a carbonate, for example, having a dicyanotriazolate anion. A step of reacting a compound with a halide or a carbonate compound, wherein the halide or carbonate compound is selected from an onium cation, or an alkali metal atom, an alkaline earth metal atom, a transition metal atom, and a rare earth metal atom. It is preferable to have a cation which essentially contains at least one kind of metal atom. These production raw materials can be used alone or in combination of two or more. In the present invention, an anion exchange resin is preferably used as the production method.

The production method may include a step of producing a compound having a dicyanotriazolate anion used in the step of deriving an ionic substance from a compound having a dicyanotriazolate anion. In this case, as described above, It is preferable to produce a compound having a dicyanotriazolate anion by reacting a compound having a dicyanotriazolate anion with a halide or a carbonate. This makes it possible to appropriately set the structure of the dicyanotriazolate anion in the ionic substance according to the performance required for the ionic composition. In this case, a compound having a dicyanotriazolate anion is used. The anion possessed by the compound having the anion as the production raw material in the production step and the dicyanotriazolate anion in the ionic substance are not the same.

In the above process, one form of a chemical reaction formula in the process of deriving an ionic substance from a compound having a dicyanotriazolate anion is shown in the following formula (1).

In the above step, assuming that the number of moles of the compound having a dicyanotriazolate anion is a and the number of moles of the halide is b, the molar ratio (a / b) in the reaction is 100/1 to 0.1 / 1. It is preferable that If the compound having an anion is less than 0.1, the halide may be excessive and the product may not be obtained efficiently. Also, halogen may be mixed into the ionic composition, and the electrode or the like may be covered. There is a risk of poisoning. If it exceeds 100, there is a possibility that the compound having an anion becomes excessive and further improvement in the yield cannot be expected, and there is a possibility that metal ions are mixed in the ionic composition and deteriorate the performance of the electrochemical device. is there. More preferably, it is 10/1 to 0.5 / 1.

The reaction conditions for the above steps can be appropriately set depending on the production raw materials and other reaction conditions, but the reaction temperature is preferably -20 to 200 ° C, more preferably 0 to 100 ° C, and more preferably 10 to 60 ° C. Is more preferable. The reaction pressure is preferably 1 × 10 ² to 1 × 10 ⁸ Pa, more preferably 1 × 10 ³ to 1 × 10 ⁷ Pa, and still more preferably 1 × 10 ⁴ to 1 × 10 ⁶ Pa. As reaction time, 48 hours or less are preferable, 24 hours or less are more preferable, and 12 hours or less are still more preferable.

In the above step, a reaction solvent is usually used. As the reaction solvent, (1) aliphatic hydrocarbons such as hexane and octane; (2) alicyclic saturated hydrocarbons such as cyclohexane; (3) Cycloaliphatic unsaturated hydrocarbons such as cyclohexene; (4) aromatic hydrocarbons such as benzene, toluene, xylene; (5) ketones such as acetone and methyl ethyl ketone; (6) methyl acetate, ethyl acetate, butyl acetate, Esters such as γ-butyrolactone; (7) Halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride; (8) Ethers such as diethyl ether, dioxane, dioxolane, (9) Propylene glycol monomethyl ether acetate, Diethylene glycol monomethyl ether acetate Etc. of alkylene glycol (10) Alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol monomethyl ether; (11) Amides such as dimethylformamide and N-methylpyrrolidone; (12) Sulfonic acids such as dimethyl sulfoxide (13) Carbonic esters such as dimethyl carbonate and diethyl carbonate; (14) Alicyclic carbonates such as ethylene carbonate and propylene carbonate; (15) Nitriles such as acetonitrile; (16) Water and the like are suitable. . These can use 1 type (s) or 2 or more types. Among these, (5), (6), (10), (11), (12), (13), (14), (15), and (16) are preferable. More preferred are (5), (10), (15) and (16).

In the method for producing the ionic composition, after the above step, the precipitate may be filtered, the solvent may be removed, dewatered, dried under reduced pressure, or the like. After removing the solvent from the solvent containing the volatile substance under conditions such as vacuum, it is washed by dissolving in a solvent such as dichloromethane, and then dehydrated by adding a substance having a dehydrating effect such as MgSO ₄ , and after removing the solvent. You may obtain the ionic composition which makes an ionic substance essential by drying under reduced pressure. The number of times of washing treatment with a solvent may be appropriately set. As the solvent, in addition to dichloromethane, ketones such as chloroform, tetrahydrofuran and acetone, ethers such as ethylene glycol dimethyl ether, acetonitrile, water and the like are suitable. In addition to MgSO ₄ , molecular sieves, CaCl ₂ , CaO, CaSO ₄ , K ₂ CO ₃ , activated alumina, silica gel, and the like are preferable as the substance having a dehydrating effect. What is necessary is just to set suitably according to a kind etc.

Since the ionic compound and the ionic composition of the present invention can exhibit the above-described characteristics, they can be suitably applied to various uses. Among them, primary batteries, lithium (ion) 2 Particularly suitable as an electrolyte constituting an electrochemical device such as a secondary battery or a fuel cell having a charging / discharging mechanism, an electrolytic solution for an electrolytic capacitor, an electrolytic capacitor, an electric double layer capacitor, a solar cell or an electrochromic display element It is. That is, an electrolyte containing the ionic compound and the matrix material is also one aspect of the present invention, and a lithium secondary battery, an electrolytic solution for an electrolytic capacitor, an electrolytic capacitor, or an electric capacitor using the electrolyte of the present invention. A double layer capacitor is also a preferred embodiment of the present invention. The ionic compound is preferably used as an electrolyte, but can be used as a material other than the electrolyte.

The electrolyte includes an ionic compound, and preferably includes an ionic compound and a matrix material.
The electrolyte means an electrolyte material or an electrolyte material, and (1) a solvent constituting the electrolyte and / or (2) an electrolyte material (ion conductor material) and (3) As a solid electrolyte material (electrolyte material), it can be suitably used for an ionic conductor of an electrochemical device. For example, in the case of (1), an electrolyte solution (or solid electrolyte) is constituted by containing a substance exhibiting ionic conductivity in a solvent together with the electrolyte of the present invention. In the case of (2), the electrolyte material is constituted by containing the electrolyte of the present invention in a solvent. In the case of (3), the electrolyte of the present invention is used as it is or contains other components to form a solid electrolyte.
The matrix material is preferably an electrolyte that requires an organic solvent. As such an organic solvent, the thing similar to the above-mentioned organic solvent is suitable.

When an electrochemical device is configured using the electrolyte of the present invention, the electrochemical device preferably has an ion conductor, a negative electrode, a positive electrode, a current collector, a separator, and a container as basic components.
As the ion conductor, a mixture of an electrolyte and an organic solvent or a polymer is suitable. If an organic solvent is used, this ionic conductor is generally called an electrolytic solution, and if a polymer is used, it is called a polymer solid electrolyte. The polymer solid electrolyte includes those containing an organic solvent as a plasticizer. The electrolyte of the present invention can be suitably applied to such an ion conductor as a substitute for an electrolyte or an organic solvent in an electrolytic solution or as a polymer solid electrolyte. The electrolyte of the present invention can be used as a material for an ion conductor. In the electrochemical device used as, at least one of these is constituted by the electrolyte of the present invention. Among these, it is preferable to use as an alternative to the organic solvent in the electrolytic solution or as a polymer solid electrolyte.

The organic solvent may be an aprotic solvent that can dissolve the electrolyte 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 are used. 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.

As the polymer that dissolves the electrolyte, one or more of the above-described polymers can be suitably used. Among these, a polymer or copolymer having polyethylene oxide in the main chain or side chain, a homopolymer or copolymer of polyvinylidene fluoride, a methacrylic acid ester polymer, and polyacrylonitrile are preferable. When a plasticizer is added to these polymers, the above-mentioned aprotic organic solvent can be used.

The electrolyte concentration in the ion 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.

In the case of a lithium battery, the negative electrode material is preferably lithium metal or an alloy of lithium and another metal. In the case of a lithium ion battery, a material using a phenomenon called intercalation of carbon, natural graphite, metal oxide, or the like obtained by firing a polymer, an organic substance, pitch, or the like is preferable. In the case of the electric double layer capacitor, activated carbon, porous metal oxide, porous metal, and conductive polymer are suitable.

As the positive electrode material, in the case of lithium batteries and lithium ion batteries, lithium-containing oxides such as LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ ; oxides such as TiO ₂ , V ₂ O ₅ , MoO ₃ ; Sulfides such as TiS ₂ and FeS; conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole are suitable. In the case of the electric double layer capacitor, activated carbon, porous metal oxide, porous metal, and conductive polymer are suitable.

Hereinafter, (1) a lithium secondary battery, (2) an electrolytic capacitor, and (3) an electric double layer capacitor using the electrolyte of the present invention will be described in more detail.
(1) Lithium secondary battery A lithium secondary battery is composed of a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an ionic conductor using the electrolyte of the present invention as basic constituent elements. . In this case, the electrolyte of the present invention contains a lithium salt as a substance exhibiting ionic conductivity. Such a lithium secondary battery is preferably a non-aqueous electrolyte lithium secondary battery that is a lithium secondary battery other than the water electrolyte. A schematic cross-sectional view of one embodiment of a lithium secondary battery is shown in FIG. This lithium secondary battery uses coke as a negative electrode active material, which will be described later, and uses a compound containing Co as the positive electrode active material. The reaction of ₆ Li → 6C + Li + e occurs, and the electron (e) generated on the negative electrode surface is ion-conductive in the electrolyte and moves to the positive electrode surface. On the positive electrode surface, the reaction of CoO ₂ + Li + e → LiCoO ₂ occurs. Current flows from the positive electrode to the positive electrode. When discharging, a reverse reaction occurs during charging, and current flows from the positive electrode to the negative electrode. Thus, electricity is stored or supplied by a chemical reaction by ions.

The negative electrode is preferably prepared by applying a negative electrode mixture containing a negative electrode active material, a negative electrode conductive agent, a negative electrode binder, and the like to the surface of the negative electrode current collector. The negative electrode mixture may contain various additives in addition to the conductive agent and the binder.
As the negative electrode active material, metallic lithium, a material capable of inserting and extracting lithium ions, and the like are suitable. Suitable materials that can occlude and release lithium ions include metallic lithium; pyrolytic carbon; coke such as pitch coke, needle coke, and petroleum coke; graphite; glassy carbon; phenol resin, furan resin, and the like. Organic polymer compound fired body fired at temperature and carbonized; carbon fiber; carbon material such as activated carbon; polymer such as polyacetylene, polypyrrole, polyacene; Li _4/3 Ti _5/3 O ₄ , TiS ₂ etc. Lithium-containing transition metal oxides or transition metal sulfides; metals such as Al, Pb, Sn, Bi, and Si that are alloyed with alkali metals; AlSb, Mg ₂ Si, in which alkali metals can be inserted between lattices, and cubic intermetallic compounds of NiSi _{2, etc., Li 3-f G f N} : lithium nitrogen compounds in (G transition metals), etc. Etc. are preferred. These can use 1 type (s) or 2 or more types. Among these, metallic lithium and carbon materials that can occlude / release alkali metal ions are more preferable.

The negative electrode conductive agent may be an electronic conductive material, such as natural graphite such as flake graphite, graphite such as artificial graphite; acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, etc. Carbon black; conductive fibers such as carbon fibers and metal fibers; metal powders such as carbon fluoride, copper and nickel; organic conductive materials such as polyphenylene derivatives are suitable. These can use 1 type (s) or 2 or more types. Among these, artificial graphite, acetylene black, and carbon fiber are more preferable. The amount of the negative electrode conductive agent used is preferably 1 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the negative electrode active material. Further, since the negative electrode active material has electronic conductivity, a negative electrode conductive agent need not be used.

The binder for the negative electrode may be either a thermoplastic resin or a thermosetting resin. Polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, styrene butadiene rubber, tetrafluoroethylene-hexafluoropropylene Polymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotri Fluoroethylene, vinylidene fluoride-pentafluoropropylene copolymer, propylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene -Tetrafluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether-tetrafluoroethylene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, An ethylene-methyl methacrylate copolymer, polyamide, polyurethane, polyimide, polyvinyl pyrrolidone, and a copolymer thereof are preferable. These can use 1 type (s) or 2 or more types. Among these, styrene butadiene rubber, polyvinylidene fluoride, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, polyamide, polyurethane, More preferred are polyimide, polyvinylpyrrolidone and copolymers thereof.

The current collector for the negative electrode may be an electronic conductor that does not cause a chemical change inside the battery. Stainless steel, nickel, copper, titanium, carbon, conductive resin, carbon on the surface of copper or stainless steel, Those having nickel or titanium adhered or coated thereon are suitable. Among these, copper and alloys containing copper are more preferable. These can use 1 type (s) or 2 or more types. Further, the surface of the negative electrode current collector can be oxidized and used. Furthermore, it is desirable to make the current collector surface uneven. As the shape of the current collector for the negative electrode, a foil, a film, a sheet, a net, a punched one, a lath body, a porous body, a foamed body, a molded body of a fiber group, and the like are suitable. The thickness of the current collector is preferably 1 to 500 μm.

The positive electrode is preferably prepared by coating a positive electrode mixture containing a positive electrode active material, a positive electrode conductive agent, a positive electrode binder, and the like on the surface of the positive electrode current collector. The positive electrode mixture may contain various additives in addition to the conductive agent and the binder.
Examples of the positive electrode active material include metal Li, Li _x CoO ₂ , Li _x NiO ₂ , Li _x MnO ₂ , Li _x Co _y Ni _1-y O ₂ , Li _x Co _y J _1-y O _z , and Li _x Ni. _{1-y J y O z,} Li x Mn 2 O 4, Li x Mn 2-y J y O 4; MnO 2, V g O h, Cr g O h (g and h is an integer of 1 or more) such as An oxide containing no lithium is suitable. These can use 1 type (s) or 2 or more types.
J represents at least one element selected from Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B. X is 0 ≦ x ≦ 1.2, y is 0 ≦ y ≦ 0.9, z is 2.0 ≦ z ≦ 2.3, and x is charge / discharge of the battery. Will increase or decrease. Further, as the positive electrode active material, a transition metal chalcogenide, vanadium oxide or niobium oxide which may contain lithium, an organic conductive material composed of a conjugated polymer, a chevrel phase compound, or the like may be used. The average particle diameter of the positive electrode active material particles is preferably 1 to 30 μm.

The positive electrode conductive agent may be any electron conductive material that does not cause a chemical change in the charge / discharge potential of the positive electrode active material used, and is the same as the negative electrode conductive agent described above; metal powder such as aluminum and silver Conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide are suitable. These can use 1 type (s) or 2 or more types. Among these, artificial graphite, acetylene black, and nickel powder are more preferable. The amount of the positive electrode conductive agent used is preferably 1 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the positive electrode active material. When carbon black or graphite is used, the amount is preferably 2 to 15 parts by weight with respect to 100 parts by weight of the positive electrode active material.

The positive electrode binder may be either a thermoplastic resin or a thermosetting resin, other than the styrene butadiene rubber in the negative electrode binder described above, and tetrafluoroethylene-hexafluoroethylene copolymer. A coalescence or the like is preferred. These can use 1 type (s) or 2 or more types. Among these, polyvinylidene fluoride and polytetrafluoroethylene are more preferable.
The positive electrode current collector may be any electron conductor that does not cause a chemical change in the charge / discharge potential of the positive electrode active material to be used. The surface of stainless steel, aluminum, titanium, carbon, conductive resin, aluminum or stainless steel Those having carbon or titanium adhered or coated thereon are suitable. These can use 1 type (s) or 2 or more types. Among these, aluminum or an alloy containing aluminum is preferable. Further, the surface of the positive electrode current collector can be oxidized and used. Furthermore, it is desirable to make the current collector surface uneven. The shape and thickness of the positive electrode current collector are the same as those of the negative electrode current collector described above.

The separator is preferably an insulating microporous thin film having a large ion permeability and a predetermined mechanical strength when an electrolytic solution is used as an ionic conductor. It preferably has a function of closing and increasing resistance. Materials include porous synthetic resin films of polyolefin polymers such as polyethylene and polypropylene, woven or non-woven fabrics made of organic materials such as polypropylene and fluorinated polyolefins, glass fibers, and inorganic materials from the viewpoint of organic solvent resistance and hydrophobicity. A woven fabric or a non-woven fabric is preferably used. The pore diameter of the pores of the separator is preferably in a range in which the positive electrode active material, the negative electrode active material, the binder, and the conductive agent detached from the electrode do not pass through, and is preferably 0.01 to 1 μm. The thickness of the separator is preferably 10 to 300 μm. Moreover, as a porosity, it is preferable that it is 30 to 80%.
Further, the surface of the separator is preferably modified in advance by corona discharge treatment, plasma discharge treatment, or other wet treatment using a surfactant so as to reduce the hydrophobicity. As a result, the wettability of the separator surface and the inside of the pores is improved, and the increase in the internal resistance of the battery can be suppressed as much as possible.

As the lithium secondary battery, a positive electrode mixture or a negative electrode mixture containing a gel holding an electrolyte solution in a polymer material, or a porous separator made of a polymer material holding an electrolyte solution is used as a positive electrode or a negative electrode. You may be comprised by integrating. The polymer material is not particularly limited as long as it can hold an electrolytic solution, and a copolymer of vinylidene fluoride and hexafluoropropylene is preferable.
Examples of the shape of the lithium secondary battery include a coin shape, a button shape, a sheet shape, a laminated shape, a cylindrical shape, a flat shape, a square shape, and a large size used for an electric vehicle.

(2) Electrolytic Capacitor An electrolytic capacitor is composed of an anode foil, a cathode foil, an electrolytic paper that is a separator sandwiched between the anode foil and the cathode foil, and a capacitor element composed of a lead wire and the electrolyte of the present invention. The ion conductor, the bottomed cylindrical outer case, and the sealing body that seals the outer case are configured as basic constituent elements. A perspective view of one embodiment of the capacitor element is shown in FIG. The electrolytic capacitor in the present invention is obtained by impregnating a capacitor element with an electrolytic solution that is an ionic conductor using the above ionic composition, housing the capacitor element in a bottomed cylindrical outer case, and opening the outer case. The sealing body can be attached to the outer casing and the end of the outer casing can be drawn to seal the outer casing. As such an electrolytic capacitor, an aluminum electrolytic capacitor, a tantalum electrolytic capacitor, and a niobium electrolytic capacitor are suitable. A schematic cross-sectional view of one embodiment of the aluminum electrolytic capacitor is shown in FIG. As such an aluminum electrolytic capacitor, a thin oxide film (aluminum oxide) formed by electrolytic anodic oxidation on the surface of an aluminum foil roughened by producing fine irregularities by electrolytic etching is suitable. .

As the anode foil, an aluminum foil having a purity of 99% or more is chemically or electrochemically etched in an acidic solution and subjected to a surface expansion treatment, and then in an aqueous solution such as ammonium borate, ammonium phosphate, or ammonium adipate. A material obtained by performing a chemical conversion treatment and forming an anodized film layer on the surface thereof can be used.
The cathode foil is selected from one or more metal nitrides selected from titanium nitride, zirconium nitride, tantalum nitride and niobium nitride, and / or titanium, zirconium, tantalum and niobium on part or all of the surface. An aluminum foil formed with a film composed of one or more metals can be used.
Examples of the method for forming the film include a vapor deposition method, a plating method, a coating method, and the like. As a portion for forming the film, the entire surface of the cathode foil may be coated, or if necessary, For example, only one surface of the cathode foil may be coated with metal nitride or metal.

The lead wire is preferably composed of a connection part in contact with the anode foil and the cathode foil, a round bar part, and an external connection part. The lead wires are electrically connected to the anode foil and the cathode foil by means such as stitching and ultrasonic welding at the connection portions. Further, the connecting portion and the round bar portion in the lead wire are preferably made of high-purity aluminum, and the external connecting portion is preferably made of a copper-plated steel wire subjected to solder plating. In addition, an aluminum oxide layer formed by anodizing with an aqueous ammonium borate solution, an aqueous ammonium phosphate solution, or an aqueous ammonium adipate solution may be formed on part or all of the surface of the connecting portion with the cathode foil and the round bar portion. An insulating layer such as a ceramic coating layer made of Al ₂ O ₃ , SiO ₂ , ZrO ₂ or the like can be formed.

The exterior case is preferably made of aluminum.
The sealing body is preferably provided with a through hole through which each lead wire is led out, and is preferably composed of an elastic rubber such as butyl rubber, and the butyl rubber is, for example, a copolymer of isobutylene and isoprene. After adding and kneading a reinforcing rubber (carbon black, etc.), a bulking agent (clay, talc, calcium carbonate, etc.), a processing aid (stearic acid, zinc oxide, etc.), a vulcanizing agent, etc. A molded rubber elastic body can be used. Examples of vulcanizing agents include alkylphenol formalin resins; peroxides (dicumyl peroxide, 1,1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5- Di- (t-butylperoxy) hexane etc.); quinoids (p-quinone dioxime, p, p'-dibenzoylquinone dioxime etc.); sulfur etc. can be used. Note that it is more preferable to coat the surface of the sealing body with a resin such as Teflon (registered trademark) or to attach a plate such as bakelite because the permeability of the solvent vapor is reduced.
As the separator, paper such as manila paper or kraft paper is usually used, but non-woven fabrics such as glass fiber, polypropylene and polyethylene can also be used.

The electrolytic capacitor may have a hermetic seal structure or a structure sealed in a resin case (for example, described in JP-A-8-148384). In the case of an aluminum electrolytic capacitor with a rubber seal, gas permeates through rubber to some extent, so that the solvent evaporates from the inside of the capacitor to the atmosphere in a high temperature environment, and from the atmosphere to the inside of the capacitor in a high temperature and high humidity environment. Moisture may be mixed into the capacitor, and under these harsh environments, the capacitor may cause undesirable characteristic changes such as a decrease in capacitance. On the other hand, a capacitor with a hermetic seal structure or a structure sealed in a resin case has a very small amount of gas permeation, and thus exhibits stable characteristics even in such a harsh environment.

(3) Electric Double Layer Capacitor The electric double layer capacitor is composed of a negative electrode, a positive electrode, and an ion conductor using the electrolyte of the present invention as a basic constituent element. In addition, an electrolyte solution that is an ionic conductor is included in an electrode element composed of a negative electrode. FIG. 3 shows a schematic cross-sectional view of one embodiment of such an electric double layer capacitor and an enlarged schematic view of the electrode surface.

The positive electrode and the negative electrode are polarizable electrodes, and are composed of activated carbon fibers, activated carbon particle molded bodies, activated carbon particles such as activated carbon particles, a conductive agent, and a binder material as an electrode active material. It is preferable to use it as a plate-shaped molded body. In the electric double layer capacitor having such a configuration, as shown in the enlarged view of FIG. 3, the electric double layer generated at the interface between the polarizable electrode and the electrolytic solution due to physical adsorption / desorption of ions is charged. Will be stored.

As the activated carbon, those having an average pore diameter of 2.5 nm or less are preferable. The average pore diameter of the activated carbon is preferably measured by the BET method using nitrogen adsorption. The specific surface area of the activated carbon varies depending on the capacitance per unit area (F / m ² ) depending on the carbonaceous species, the decrease in bulk density accompanying the increase in the specific surface area, etc., but the specific surface area determined by the BET method by nitrogen adsorption as is preferably ^{500~2500m 2 / g, 1000~2000m 2 /} g is more preferable.

As the method for producing the activated carbon, plant-based wood, sawdust, coconut husk, pulp waste liquid, fossil fuel-based coal, heavy petroleum oil, or pyrolyzed coal and petroleum-based pitch, petroleum coke, Carbon aerogel, mesophase carbon, tar pitched fiber, synthetic polymer, phenol resin, furan resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyimide resin, polyamide resin, ion exchange resin, liquid crystal polymer, plastic disposal It is preferable to use an activation method in which a raw material such as a product or a waste tire is carbonized and then activated.

The activation method includes (1) a gas activation method in which a carbonized raw material is contact-reacted with water vapor, carbon dioxide gas, oxygen, and other oxidizing gas at a high temperature, and (2) zinc chloride and phosphoric acid are added to the carbonized raw material. An inert gas atmosphere that is uniformly impregnated with sodium phosphate, calcium chloride, potassium sulfide, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium sulfate, potassium sulfate, calcium carbonate, boric acid, nitric acid, etc. The chemical activation method which heats in and obtains activated carbon by the dehydration and oxidation reaction of a chemical | medical agent is mentioned, Any may be used.

Activated carbon obtained by the above activation method is preferably heat treated at 500 to 2500 ° C., more preferably 700 to 1500 ° C. in an inert gas atmosphere such as nitrogen, argon, helium, xenon, etc. The electron conductivity may be increased by removing functional groups or by developing carbon crystallinity. Examples of the shape of the activated carbon include crushing, granulation, granule, fiber, felt, woven fabric, and sheet shape. In the case of particles, the average particle diameter is preferably 30 μm or less in terms of improving the bulk density of the electrode and reducing the internal resistance.
As the electrode active material, in addition to activated carbon, a carbon material having the above-described high specific surface area may be used. For example, carbon nanotubes or diamond produced by plasma CVD may be used.

As the conductive agent, carbon black such as acetylene black and ketjen black, natural graphite, thermally expanded graphite, carbon fiber, metal fiber such as ruthenium oxide, titanium oxide, aluminum, and nickel are preferable. These can use 1 type (s) or 2 or more types. Among these, acetylene black and ketjen black are more preferable in that the conductivity is effectively improved with a small amount. The blending amount of the conductive agent varies depending on the bulk density of the activated carbon, but when the activated carbon is 100% by mass, 5 to 50% by mass is preferable, and 10 to 30% by mass is more preferable.

As the binder material, polytetrafluoroethylene, polyvinylidene fluoride, carboxymethyl cellulose, fluoroolefin copolymer crosslinked polymer, polyvinyl alcohol, polyacrylic acid, polyimide, petroleum pitch, coal pitch, phenol resin, and the like are suitable. These can use 1 type (s) or 2 or more types. The blending amount of the binder substance varies depending on the type and shape of the activated carbon, but when the activated carbon is 100% by mass, 0.5 to 30% by mass is preferable, and 2 to 30% by mass is more preferable.

The positive electrode and negative electrode are formed by, for example, (1) a method obtained by adding polytetrafluoroethylene to a mixture of activated carbon and acetylene black and then press-molding. (2) activated carbon and pitch, tar, phenol resin, etc. A method of mixing and molding the binder material and then heat-treating it under an inert atmosphere to obtain a sintered body, and (3) a method of sintering only activated carbon and the binder material or activated carbon to form an electrode are preferred. When using activated carbon fiber cloth obtained by activating carbon fiber cloth, it may be used as an electrode as it is without using a binder substance.

In the electric double layer capacitor, the polarizable electrode is prevented from contacting or short-circuiting by a method in which the separator is sandwiched between the polarizable electrodes or a method in which the polarizable electrodes are opposed to each other by using a holding means. It is preferable. As the separator, it is preferable to use a porous thin film that does not cause a chemical reaction with molten salt or the like in the operating temperature range. As the material of the separator, paper, polypropylene, polyethylene, glass fiber, and the like are suitable.
Examples of the shape of the electric double layer capacitor include a coin type, a wound type, a square type, and an aluminum laminate type, and any shape may be used.

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

The ionic compound and electrolyte of the present invention have the above-described configuration, can exhibit excellent basic performance such as electrochemical stability, and can be suitably used for various applications. Suitable for electrochemical devices such as electrolytic capacitors, electric double layer capacitors, solar cells and electrochromic display elements, as well as batteries having charging and discharging mechanisms such as primary batteries, lithium (ion) secondary batteries and fuel cells It can be applied.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

[Example 1]
[Step 1] Synthesis of 1-ethyl-3-methylimidazolium bromide thermometer, nitrogen gas introduction tube, reflux condenser, stirrer, and flask equipped with a dropping funnel 82 g (1.0 mol) of methyl imidazole ) And 2-butanone (hereinafter referred to as MEK) 400 g, 163.5 g (1.5 mol) of ethyl bromide was added dropwise over 2 hours while maintaining the temperature at 50 ° C. under a nitrogen stream, and further 2 hours. The temperature was kept at 80 ° C. to complete the reaction. Next, the reaction solution was filtered to obtain slightly brownish white crystals of 1-ethyl-3-methylimidazolium bromide (hereinafter referred to as EMImBr). Thereafter, the crystals were washed twice with MEK in a nitrogen-substituted glove box to obtain 172 g of white EMImBr (yield 90%).

[Step 2] Synthesis of 4,5 dicyanotriazolate silver thermometer, nitrogen gas introduction tube, reflux condenser, stirrer, and flask equipped with a dropping funnel are referred to as dicyanomale noniol (hereinafter referred to as DAMN). ) 216 g (2.0 mol), 98 g of sulfuric acid and 400 g of ion-exchanged water were charged, and 138 g (2.0 mol) of sodium nitrite and 400 g of water were added dropwise over 1 hour while maintaining 0 ° C. under a nitrogen stream. The reaction was completed after maintaining at 25 ° C. for 1 hour.
Next, an extraction process was performed using diethyl ether and ion-exchanged water to obtain a brown solid. The obtained solid was sublimated at 80 ° C. and 30 Pa to obtain 160 g of white 4,5-dicyanotriazole (hereinafter referred to as HDCTA).
Next, 119 g (1.0 mol) of HDCTA was dissolved in 500 g of ion-exchanged water, and 40 g of a 30 wt% sodium hydroxide aqueous solution was added thereto while cooling to obtain a sodium ginanotriazolate aqueous solution.

Subsequently, the sodium dicyanotriazolate aqueous solution was charged into a 2 L separable flask equipped with a thermometer, a nitrogen gas introduction tube, a reflux condenser, a stirring device, and a dropping funnel, and stirred at 25 ° C. Next, 169 g (1.0 mol) of silver nitrate was dissolved in 360 g of ion-exchanged water, and this aqueous solution was added dropwise over 1 hour. At this time, the temperature in the system was kept at 40 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred for 3 hours, and a cake-like white product having a slightly silvery color was obtained by suction filtration. Furthermore, this cake-like product was dispersed in ion-exchanged water, and then suction filtration was performed. This operation was performed three times to obtain a cake-like silver dicyanotriazolate (hereinafter referred to as AgDCTA). This AgDCTA had a solid content of 85%.

[Step 3] Synthesis of 1-ethyl-3-methylimidazolium dicyanotriazolate Next, 120 g of cake-like AgDCTA (0 g) was added to a flask equipped with a thermometer, a nitrogen gas introduction tube, a reflux condenser, and a stirrer. .45 mol) and 500 g of ion-exchanged water were added and dispersed at room temperature. Subsequently, 57.3 g (0.30 mol) of EMImBr was dissolved in 200 g of ion-exchanged water and added dropwise to the above AgDCTA-dispersed aqueous solution over 2 hours. At this time, the inside of the system was kept at 30 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred at room temperature for 24 hours. Thereafter, the precipitate was removed by suction filtration (filter: membrane cellulose mixed ester type pore system 0.2 μm), and the filtrate was subjected to removal of volatile components at 50 ° C. and 10 to 200 mmHg using a rotary evaporator. Subsequently, it was dried under reduced pressure at 60 ° C. for 3 days to obtain 1-ethyl-3-methylimidazolium dicyanotriazolate (hereinafter abbreviated as EMImDCTA) having a water content of 50 ppm or less (65 g, yield 95%). . FIG. 4 shows the ¹ H-NMR of the obtained EMImDCTA, and FIG. 5 shows the ¹³ C-NMR. The measurement was performed under the conditions shown below. This EMImDCTA was a pale yellow solid, and the thermal decomposition temperature in nitrogen was 218 ° C. The ionic conductivity at 25 ° C. of EMImDCTA propylene carbonate (hereinafter abbreviated as PC) 2 mol / kg was 3.0 × 10 ⁻² S / cm.

(Figure 4 measurement conditions)
Standard ¹ H measurement solvent: DMSO
Temperature: Room temperature Device: GEMINI-200BB gemini2000
Pulse sequence:
Relaxation delay: 1.254 seconds Pulse: 45.4 degrees Acquisition time: 2.741 seconds Spectral range: 3000.3 Hz
Integration count: 16 observations H1,199.93229029MHz
Number of data processing data points 32768
Measurement time 1 minute

(Fig. 5 Measurement conditions)
¹³ C measurement solvent: DMSO
Temperature: Room temperature Device: GEMINI-200BB gemini2000
Pulse sequence:
Relaxation delay: 1.000 seconds Pulse: 44.6 degrees Acquisition time: 1.498 seconds Spectral range: 12500.0 Hz
Integration count: 13712 observations C13, 50.723453MHz
Decouple H1,199.933090MHz
power 41dB
continuously on
WALTZ-16 modulated
Data processing line width: 1.0 Hz
Number of data points 65536
Measurement time 9.5 hours

[Example 2]
In a flask equipped with a thermometer, a nitrogen gas introduction tube, a reflux condenser, a stirrer, and a dropping funnel, 35.7 g (0.3 mol) of HDCTA obtained in Step 2 of Example 1 was dissolved in 200 g of methanol. . Next, the inside of the system was kept at 30 ° C. or lower, and 30.3 g (0.3 mol) of triethylamine was dropped over 1 hour. Then, the volatile matter was removed from the obtained solution at 50 degreeC and 10-200 mmHg using the rotary evaporator. Subsequently, it was dried under reduced pressure at 60 ° C. for 3 days to obtain triethylammonium dicyanotriazolate (hereinafter abbreviated as TEADCTA) having a water content of 50 ppm or less (65 g, yield 98%). FIG. 6 shows the ¹ H-NMR of the obtained TEADCTA, and FIG. 7 shows the ¹³ C-NMR. The measurement was performed under the conditions shown below. This TEADCTA is a pale yellow solid, has a thermal decomposition temperature of 93 ° C. in nitrogen, and the ionic conductivity at 25 ° C. of TEADCTA PC 2 mol / kg is 1.8 × 10 ⁻² S / cm. It was.

(Fig. 6 Measurement conditions)
Standard ¹ H measurement pulse sequence: s2pul
Solvent: DMSO
Temperature: Room temperature Device: Varian's UNITY plus-400
Relaxation delay: 3.000 seconds Pulse: 45.0 degrees Acquisition time: 4.000 seconds Spectral range: 8000.0 Hz
Integration count: 16 observations H1,399.969491 MHz
Number of data processing data points 65536
Measurement time 1 minute 52 seconds

(Fig. 7 measurement conditions)
¹³ C measurement solvent: DMSO
Temperature: Room temperature Device: GEMINI-200BB gemini2000
Pulse sequence:
Relaxation delay: 1.000 seconds Pulse: 44.6 degrees Acquisition time: 1.498 seconds Spectral range: 12500.0 Hz
Integration count: 20432 observations C13, 50.723453MHz
Decouple H1,199.933090MHz
power 41dB
continuously on
WALTZ-16 modulated
Data processing line width: 1.0 Hz
Number of data points 65536
Measurement time 14.2 hours

Example 3
A 500 mL SUS stirred autoclave was charged with 135 g of dimethyl carbonate, 2-methylimidazoline (42.1 g), and 100 g of methanol as a solvent, and reacted at a reaction temperature of 130 ° C. and a reaction pressure of 0.7 MPa for 24 hours. After the reaction, the autoclave was cooled, the reaction solution was taken out, and 1,2,3-trimethylimidazolinium methyl carbonate was obtained (90.0 g, yield 95.5%). Next, 37.6 g of 1,2,3-trimethylimidazolinium methyl carbonate was dissolved in 200 g of methanol, and 23.8 g of dicyanotriazole was gradually added, and carbon dioxide gas was generated vigorously. Subsequently, the volatile matter was removed using an evaporator at 75 ° C. and 20 mmHg to obtain 1,2,3-trimethylimidazolinium dicyanotriazolate (44.3 g, yield 95.8%). The obtained 1,2,3-trimethylimidazolinium dicyanotriazolate solution in heavy water (D ₂ O) was measured by ¹ H-NMR, and the DMSO-d6 solution was measured by ¹³ C-NMR. However, the following signal was obtained.
¹ H-NMR
δ = 2.22 ppm (3H), 3.05 ppm (6H), 3.78 ppm (2H)
¹³ C-NMR
δ = 10.7 ppm, 34.0 ppm, 114.2 ppm, 121.9 ppm, 166.9 ppm
Moreover, the ionic conductivity at 25 ° C. of 1,2,3-trimethylimidazolinium dicyanotriazolate propylene carbonate (hereinafter abbreviated as PC) 2 mol / kg was 2.5 × 10 ⁻² S / cm. .

Example 4
A SUS stirred autoclave was charged with 135 g of dimethyl carbonate, 2,4-dimethylimidazoline (49.1 g) and 100 g of methanol as a solvent, and reacted at a reaction temperature of 130 ° C. and a reaction pressure of 0.7 MPa for 24 hours. After the reaction, the autoclave was cooled, and the reaction solution was taken out to obtain 1,2,3,4-tetramethylimidazolinium methyl carbonate (95.6 g, yield 94.5%).
Next, 40.5 g of 1,2,3,4-tetramethylimidazolinium methyl carbonate was dissolved in 200 g of methanol, and 23.8 g of ginanotriazole was gradually added, and carbon dioxide gas was generated vigorously. Then, using an evaporator, volatile components were removed at 75 ° C. and 20 mmHg to obtain 1,2,3,4-tetramethylimidazolinium dicyanotriazolate (45.1 g, yield 97.5%). It was.

[Comparative Example 1]
HDCTA 35.7 g (0.3 mol) obtained in Step 2 in Example 1 was dissolved in 200 g of methanol. Next, the solution obtained above was added to a dispersion obtained by dispersing 11.1 g (0.15 mol) of lithium carbonate in 300 g of methanol over 1 hour. Then, the volatile matter was removed from the obtained solution at 50 degreeC and 10-200 mmHg using the rotary evaporator. Subsequently, it was dried under reduced pressure at 80 ° C. for 3 days to obtain lithium dicyanotriazolate (hereinafter abbreviated as LiDCTA). Next, an attempt was made to prepare a solution of LiDCTA PC 1 mol / L, but it was difficult to dissolve in PC, and a large amount of undissolved residue was observed, so that the ionic conductivity could not be measured.

It is a cross-sectional schematic diagram which shows one form of a lithium secondary battery. (A) is a perspective view which shows one form of an electrolytic capacitor, (b) is a cross-sectional schematic diagram which shows one form of an aluminum electrolytic capacitor. It is the cross-sectional schematic diagram which shows one form of an electrical double layer capacitor, and the enlarged schematic diagram of the electrode surface. ^{1 is} a ¹ H-NMR chart of EMImDCTA. It is a ³ C-NMR chart of EMImDCTA. ^{1 is} a ¹ H-NMR chart of TEADCTA. It is a ¹³ C-NMR chart of TEADCTA.

Claims (5)

Dicyanotriazolate anion and the following general formula (1);

(In the formula, L represents one kind of element selected from the group consisting of C, Si, N, P, S and O. R is the same or different and is a monovalent element or an organic group, and An ion having a cation represented by the following: s is an integer of 3, 4 or 5 and is a value determined by the valence of the element of L) Sex compounds. 2. The ionic compound according to claim 1, wherein in the general formula (1), at least one of R is a hydrogen element. Dicyanotriazolate anion and the following general formula (2);

(Wherein R ¹ , R ² and R ³ are the same or different and represent a hydrogen element or a hydrocarbon group having 1 to 8 carbon atoms. At least two of R ¹ , R ² and R ³ are carbonized. In the case of a hydrogen group, these hydrocarbon groups may be bonded directly or may have a structure bonded via at least one element selected from O, S and N.)
An ionic compound having a cation represented by the formula: An electrolyte comprising the ionic compound according to claim 1, 2 or 3 and a matrix material. The electrolyte according to claim 4, wherein the matrix material essentially contains an organic solvent.

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