JP5366460B2 - Ionic compounds - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ionic compound that exhibits excellent basic performances such as excellent electrochemical stability including excellent ionic conductivity, is excellent in pH stability and can be suitably used in various applications, and an electrolyte material, an electrolytic solution, an electrolytic capacitor, a lithium secondary battery and an electric double layer capacitor and the like each containing the ionic compound. <P>SOLUTION: The ionic compound is represented by general formula (1) and has a boiling point of 250&deg;C or lower. In the formula, A is a compound containing one element selected from the group consisting of C, Si, N, P, S and O; X is at least one element selected from the group consisting of B, C, N, O, Al, Si, P, S, As and Se; M<SP>1</SP>and M<SP>2</SP>are the same or different and are each a linking group and when multiple M<SP>1</SP>'s or M<SP>2</SP>'s exist, they may be the same or different; and Q is a monovalent element or organic group. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an ionic compound. More specifically, an ionic compound suitable as a material for an ionic conductor constituting an electrochemical device, and an electrolyte material containing the ionic compound, an electrolytic solution for driving an electrolytic capacitor, an electrolytic capacitor, a lithium secondary battery, The present invention relates to an electric double layer capacitor and the like.

  An ionic compound requires an ionic substance composed of a compound composed of a cation and an anion, and is widely used for various applications. Among ionic compounds, those having ionic conductivity are suitably used as the ionic conductive material. Specifically, it is suitably used as a constituent material of an ionic conductor that is used indispensably in various batteries using ionic conduction. The constituent material of the ion conductor can function as an electrolyte and / or a solvent in the electrolytic solution constituting the ion conductor. Moreover, the constituent material of an ion conductor can function as a solid electrolyte. Applications of constituent materials of ion conductors include, for example, primary batteries, batteries having charging and discharging mechanisms such as lithium (ion) secondary batteries and fuel cells, electrolytic capacitors, electric double layer capacitors, solar cells, electrochromic displays Electrochemical devices such as elements can be mentioned. In these electrochemical devices, a battery is generally composed of a pair of electrodes and an ionic conductor filling between them.

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

FIG. 1 shows a schematic cross-sectional view of one form of a general lithium (ion) secondary battery. In a lithium (ion) secondary battery, a positive electrode and a negative electrode formed of an active substance are used, and an electrolyte solution composed of an organic solvent in which a lithium salt such as LiPF ₆ is dissolved as a solute is used to form a positive electrode and a negative electrode. An ionic conductor is formed between them. 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 problem that the organic solvent tends to volatilize easily and the flash point is low, the problem that liquid leakage is likely to occur, and the long-term reliability is lacking, There is a problem that the electrolytic solution is solidified at a low temperature and the performance as the electrolytic solution cannot be exhibited. Therefore, a material that can improve these problems is demanded.

An ionic compound containing at least one anion moiety bound to at least one cation moiety M in a sufficient number to ensure 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 anionic moiety has the formula R _D —Y—C (C≡N) ₂ ^— Alternatively, it is disclosed that an ionic compound corresponding to one of Z—C (C≡N) ₂ ^— can be used for an ion conductive material (for example, see Patent Document 1). The anion moiety is a five-membered cyclic or tetraazapentalene derivative. In the examples, triazole, imidazole, and cyclopentadiene derivatives are described as the anion moiety. Specifically, tricyanomethide is disclosed. However, there is room for improvement in order to obtain a suitable material that constitutes an electrolytic solution that exhibits excellent basic performance.

An electrolytic solution for driving an electrolytic capacitor is disclosed in which a carboxylic acid salt of a pentaalkylguanidine is dissolved as a solute in γ-butyrolactone as an organic polar solvent (see, for example, Patent Document 2). However, the electrical conductivity of the tertiary ammonium salt electrolyte is not sufficient as compared with the quaternary ammonium salt electrolyte. For this reason, there has been room for ingenuity to develop an electrolytic solution having high reliability as an electrolyte and high electrical conductivity.
JP 2000-508676 A (Pages 2-13, 39-67) Japanese Patent Laid-Open No. 9-97749 (page 1-2)

  The present invention has been made in view of the above-mentioned present situation, and can exhibit excellent basic performance such as electrochemical stability such as having excellent ionic conductivity, excellent pH stability, and various uses. An object of the present invention is to provide an ionic compound that can be suitably used, and an electrolyte material, electrolytic solution, electrolytic capacitor, lithium secondary battery, electric double layer capacitor, and the like containing the ionic compound. It is.

  The present inventors have made various studies on ionic compounds. As a result, it has been noted that among ionic compounds composed of cations and anions, those having ionic conductivity are suitably used for various applications as ionic conductive materials.

  For example, when the cation has a hydrogen atom, the cation can react with a hydroxide ion to generate water. Due to this, for example, since it is less likely to become a strong alkali even in an environment where the hydroxide ion concentration is high, rubber or the like that easily deteriorates in an alkaline environment can be used. The present invention has been found to be suitable for use.

  It has also been found that such an ionic compound and an electrolyte material containing the ionic compound can be suitably applied to various uses such as materials for electrochemical devices.

  In a conventional electrolytic capacitor, an electrolytic solution having a high electrical conductivity using a quaternary ammonium salt as a solute in a solvent mainly composed of γ-butyrolactone has been used.

  When such a quaternary ammonium salt electrolyte is used, the base component may leak from the cathode portion. For this reason, the use of a tertiary ammonium salt electrolyte that does not cause liquid leakage has been studied.

  For example, by using a specific tertiary salt structure as the cation of the ionic compound, the electrical conductivity of the conventional tertiary ammonium salt electrolyte solution is insufficient compared to the quaternary ammonium salt electrolyte solution. It has been found that the problems that it has can be solved.

  Thereby, both long-term reliability and sufficient electrical conductivity can be achieved, and it can be suitably used for various applications such as batteries and electrochemical devices having a charging and discharging mechanism.

  It has also been found that such an ionic compound and an electrolyte material containing the ionic compound can be suitably applied to various uses such as materials for electrochemical devices.

（一般式（２）中、Ｌは、Ｃ、Ｓｉ、Ｎ、Ｐ、Ｓ及びＯからなる群より選ばれる１種類の元素を表す。Ｒは、同一又は異なって、１価の元素、官能基又は有機基であり、互いに結合した元素となっていてもよい。ｓは、２、３又は４の整数であり、Ｌの元素の価数によって決まる値である。）で表されるカチオンと対アニオンを有し、
２５℃でのイオン伝導度が１０ｍＳ／ｃｍ以上である。 The ionic compound of the present invention is
General formula (2);

(In general formula (2), L represents one 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 functional group. Or an organic group which may be an element bonded to each other, and s is an integer of 2, 3 or 4, and is a value determined by the valence of the element of L. Having an anion,
The ionic conductivity at 25 ° C. is 10 mS / cm or more.

  According to another aspect of the present invention, an electrolyte material is provided. The electrolyte material of the present invention contains the ionic compound.

  In a preferred embodiment, the electrolyte material includes a matrix material.

  The ionic compound of the present invention has the above-described configuration, can exhibit excellent basic performance such as electrochemical stability, and can be suitably used for various applications. In addition to batteries having charging and discharging mechanisms such as batteries, lithium (ion) secondary batteries, and fuel cells, the present invention is suitably applied to electrochemical devices such as electrolytic capacitors, electric double layer capacitors, solar cells, and electroluminescent display elements. It is something that can be done.

  In the present specification, the ionic compound has a compound represented by the above general formula (1), but is in the form of an ionic compound-containing composition (ionic composition) containing other than the above compound. Also good.

  In the present specification, the “ionic compound” may mean an “ionic composition”.

  In the present specification, the “organic group” means a group having at least one carbon atom. That is, the “organic group” in the present specification is a group having at least one carbon atom, and includes an amino group, an imino group, an amide group, a group having an ether bond, a group having a thioether bond, an ester group, and a hydroxyl group. , A functional group such as a carboxyl group, a carbamoyl group, a cyano group, and a sulfide group, and another group or atom such as a halogen atom.

  The present invention is described in detail below.

<< A-1. First Embodiment of Ionic Compound of the Present Invention >>
The ionic compound of the present invention is a compound having a boiling point of 250 ° C. or lower while having excellent ionic conductivity by requiring the cation (AH ⁺ ) and the anion represented by the general formula (1) described above as essential. Therefore, leakage of the liquid is sufficiently suppressed, the corrosiveness to the electrode or the like is sufficiently suppressed, and a material that is stable with time can be obtained. The boiling point of the compound represented by the general formula (1) is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.

  In the general formula (1), A represents a compound containing one kind of element selected from the group consisting of C, Si, N, P, S and O. The element contained in the cation containing A is an element of C, Si, N, P, S, or O, preferably an element of N, P, or S, and more preferably an element of N. It is an element. When L is an element of N, it is chemically and electrochemically stable. Thus, an ionic compound which is an amine compound for A in the general formula (1) is also one of the preferred embodiments of the present invention.

As said cation (AH ^<+> ) which consists of A and a hydrogen atom, what is represented by following General formula (2) is preferable.

  In the general formula (2), L represents one element selected from the group consisting of C, Si, N, P, S, and O. N, P, and S are preferable, and N is more preferable. When L is N, it is chemically and electrochemically stable.

  In the general formula (2), Rs are the same or different and are monovalent elements, functional groups, or organic groups, and may be elements bonded to each other. Examples of the monovalent element, functional group, 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, 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.

  The monovalent element, functional group or organic group is more preferably a hydrogen element, a fluorine element, a cyano group, a sulfone group, a hydrocarbon group having 1 to 8 carbon atoms, an oxygen or nitrogen element containing 1 to 8 carbon atoms. A hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and a saturated hydrocarbon group having 1 to 8 carbon atoms containing oxygen or nitrogen element. . In addition, in the case of containing a nitrogen element, the nitrogen element preferably has no hydrogen element (the hydrogen element is not bonded or coordinated to the nitrogen element).

  In the ionic compound, because of excellent heat resistance, (1) a form in which a nitrogen cation having no conjugated double bond is essential, or (2) an element in which L is N in the general formula (2) And the other is the same or different hydrocarbon having 1 to 8 carbon atoms which may contain nitrogen, and the nitrogen element is preferably a tertiary amine.

The s is an integer of 1, 2 or 3, 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 3, when the element of N or P is s is 2, and when the element of S or O is s is 1. That is, as the cation represented by the general formula (2), the following general formula:

(Wherein R is the same as in formula (2), but at least one is a hydrogen element) is preferred.

  Any appropriate cation may be adopted as the cation as long as it satisfies the general formula (2). Especially, the form whose L is a nitrogen element and the form which is an onium cation are more preferable.

で表されるものが好適である。 That is, the cation (AH ⁺ ) composed of A and a hydrogen atom is represented by the following general formula (3);

What is represented by these is suitable.

  The onium cation means an organic group having a cation of a nonmetal atom or a semimetal atom such as O, N, S, and P.

Examples of the monovalent element, functional group or organic group of R ^{1 to} R ³ 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, functional group 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, or a carbon atom having 1 to 8 carbon atoms containing an oxygen element. A hydrogen group, a hydrocarbon group having 1 to 8 carbon atoms, and more preferably a hydrocarbon group having 1 to 8 carbon atoms, an oxygen element, or a hydrocarbon group having 1 to 8 carbon atoms containing a nitrogen element. .

  Examples of A include methylamine, ethylamine, propylamine, butylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, ethylmethylamine, butylmethylamine, trimethylamine, triethylamine, and tripropylamine. , Tributylamine, dimethylethylamine, diethylmethylamine, cyclohexylamine, dicyclohexylamine, pyrrolidine, methylpyrrolidine, methylmorpholine, methylpiperidine and other aliphatic amines, aniline, dimethylaniline, nitroaniline, dimethyltoluidine, naphthylamine, pyridine, methylpyridine , Aromatic amines such as quinoline and methylpyrrole, tetramethylethylenediamine, diazabicycloocta , Diethylenetriamine, methylimidazole, amines having two or more nitrogen atoms in the molecule pyrimidine, and the like, guanidine and its alkyl substituted derivatives are preferred.

  The ionic compound may also contain other anions other than the organic salt of an anion essentially comprising the onium cation described above as long as the effects of the present invention are exhibited.

  Examples of the organic compound having an onium cation include a halogen anion (fluoro anion, chloro anion, bromo anion, iodo anion), tetrafluoroborate anion, hexafluorophosphate anion, tetrafluoroaluminate anion, 6 Fluoroarsenate 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, maleic acid , Fluorine-containing inorganic ions such as hexafluorophosphate ion, hexafluoroarsenate ion, hexafluoroantimonate ion, hexafluoroniobate ion and hexafluorotantalate ion; hydrogen phthalate ion , Hydrogen maleate ion, salicylate ion, Carboxylic acid ions such as benzoic acid ions and adipic acid ions; sulfonic acid ions such as benzenesulfonic acid ions, toluenesulfonic acid ions, dodecylbenzenesulfonic acid ions, trifluoromethanesulfonic acid ions, perfluorobutanesulfonic acid; boric acid ions Inorganic oxoacid ions such as phosphate ion; bis (trifluoromethanesulfonyl) imide ion, bis (pentafluoroethanesulfonyl) imide ion, tris (trifluoromethanesulfonyl) methide ion, perfluoroalkylfluoroborate ion, perfluoroalkylfluorophosphate ion, Tetracoordinate boric acid such as borodicatecholate, borodiglycolate, borodisalicylate, borotetrakis (trifluoroacetate), bis (oxalato) borate And anions on such an organic compound having an onium cation is preferable.

In said general formula, R < ⁴ >, R < ⁵ > and R < ⁶ > are the same or different, and represent the C1-C4 perfluoroalkyl group which may have one or two ether groups.

  In the ionic compound, 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.

In the general formula (1), the anion forming a cation (AH ⁺ ) pair is preferably an anion represented by the following general formula (6).

(Wherein X is at least one element selected from the group consisting of B, C, N, O, Al, Si, P, S, As and Se, and M ¹ and M ² are the same or different. A plurality of linking groups, which may be the same or different, and Q represents a monovalent element or an organic group, a is an integer of 1 or more, b, c, d and e Is an integer greater than or equal to 0.)

In the general formula (1), X represents at least one element selected from the group consisting of B, C, N, O, Al, Si, P, S, As, and Se. O is preferred. More preferably, it is C or N. Thus, an ionic compound in which X in the general formula (1) is C or N is also one of the preferred embodiments of the present invention. X is more preferably C as described later. M ¹ and M ² are the same or different and each represent a linking group, but each independently represents at least one kind selected from the group consisting of —S—, —O—, —SO ₂ — and —CO—. A group is preferred. More preferred are —SO ₂ — and —CO—. Q represents a monovalent element or an organic group, and is a hydrogen element; a halogen element; an alkyl group, an allyl group, an acyl group, a substituted derivative thereof; C _p F _{(2p + 1-q)} H _q , OC _p F ₍ during _{2p + 1-q) H q} , SO 2 C p F (2p + 1-q) H q, CO 2 C p F (2p + 1-q) H q, SO 3 C 6 F 5-r H r, NO 2 ( wherein, 1 ≦ p ≦ 6, 0 <q ≦ 13, and 0 <r ≦ 5). It is preferable that the element is at least one monovalent element or organic group selected from the group consisting of: More preferably a fluorine element, elemental _{chlorine, C p F (2p + 1} -q) H q, SO 2 C p F (2p + 1-q) H q. Further, a is an integer of 1 or more, and b, c, d, and e are integers of 0 or more, but a, d, and e are determined by the valence of the element X, for example, X When X is a sulfur element, a = 1, d = 0, e = 0, and when X is a nitrogen element, (1) a = 2, d = 0, e = 0, (2) a = 1, d = 1, e = 0, or (3) a = 1, d = 0, or e = 1. Also, b and c are preferably 0. That is, a form in which a cyano group is directly bonded to X is preferable, and in this case, there is no group represented by M ¹ and M ² .

（式中、Ｍ^１、Ｍ^２、Ｑ、ａ、ｂ、ｃ、ｄ及びｅは、上述したとおりである。） In the anion represented by the general formula (6), X in the general formula (6) is preferably N or C, and more preferably C. That is, an ionic compound in which X in the general formula (1) is a carbon element is also one of the preferred embodiments of the present invention. In this case, the anion represented by the general formula (6) is an anion represented by the following general formula (7) in which X is C in the general formula (6).

(Wherein M ¹ , M ² , Q, a, b, c, d and e are as described above.)

  As the anion represented by the general formula (6), an anion represented by the following general formula (8) in which e is 0 in the general formula (6) is preferable. More preferred are a tricyanomethide anion, a dicyanoamide anion, a thioisocyanate anion, and a cyanooxy anion, and further preferred are a dicyanoamide anion and a tricyanomethide anion. It is preferable because it is excellent. Particularly preferred is a tricyanomethide anion. Moreover, what is represented by the following general formula (9) or (10) is also a preferable anion.

  In the ionic compound, the lower limit of the content of the anion-derived compound is preferably 1% by mass, and the amount of anion present is preferably 5% by mass with respect to 100% by mass of the ionic compound. Is more preferable, and it is further more preferable that it is 10 mass%. The upper limit of the content of the compound from which the anion is derived is preferably 99.5% by mass, more preferably 95% by mass, and even more preferably 90% by mass.

  The ionic compound may further contain an alkali metal salt and / or an alkaline earth metal salt. Such an ionic compound containing an alkali metal salt and / or an alkaline earth metal salt contains an alkali metal salt and / or an alkaline earth metal salt as an electrolyte, and is used as a material for an ionic conductor of an electrochemical device. It becomes more suitable. 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.

When the alkali metal salt and / or alkaline earth metal salt is an ionic substance essentially containing the anion, the alkali metal salt and / or alkaline earth metal of the anion represented by the general formula (1) A salt is preferred. 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 alkali metal salt and / or alkaline earth metal salt is a compound other than the ionic substance, the electrolyte salt is preferably an electrolyte salt having a large dissociation constant in the electrolytic solution or the polymer solid electrolyte. For example, alkali metal salts or alkaline earth metal salts of trifluoromethanesulfonic acid such as LiCF ₃ SO ₃ , NaCF ₃ SO ₃ , KCF ₃ SO ₃ ; LiN (CF ₃ SO ₃ ) ₃ , LiN (CF ₃ CF ₃ SO ₂ ) Alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid imide such as ₂ ; Alkali metal salt or alkaline earth metal salt of hexafluorophosphoric acid such as LiPF ₆ , NaPF ₆ , KPF ₆ ; LiClO ₄ , Preferred are alkali metal salts and alkaline earth metal salts of perchloric acid such as NaClO ₄ ; tetrafluoroborate salts such as LiBF ₄ and NaBF ₄ ; alkali metal salts such as LiAsF ₆ , LiI, NaI, NaAsF ₆ and KI; . 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.

  When the ionic compound contains a polymer, it can be solidified and suitably used as a polymer solid electrolyte.

  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 compound is used as a polymer solid electrolyte, the abundance of the polymer is such that the lower limit is 0.1% by mass and the upper limit is 5000% by mass with respect to 100% by mass of the ionic compound. 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.

  When the ionic compound contains a solvent, the ionic conductivity is further improved.

  Any appropriate solvent can be adopted as the solvent as long as the ion conductivity can be improved. For example, water or an organic solvent is suitable. As the organic solvent, the compatibility with the components in the ionic compound 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 stability range. Are broad compounds. 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 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 , 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6-dimethyltetrahydrofuran, tetrahydropyran and other ethers; dimethyl sulfoxide, methyl ethyl sulfoxide, diethyl sulfoxide and other sulfoxides; 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; and the like, 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 compound containing compositions. That is, the content of the solvent is preferably 1 to 99% by mass when the total mass of the ionic compound and the solvent is 100% by mass. When the content of the solvent is less than 1% by mass, the ionic conductivity is not sufficiently improved, and when it exceeds 99% by mass, the stability is not 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 compound preferably has a reduced volatile content, and does not freeze even at a low temperature of −55 ° C., for example, and has excellent ionic conductivity. When such an ionic compound is used as an electrolytic solution, excellent electrical characteristics can be exhibited.

  The ionic compound may contain various additives. 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 Phosphorous compounds such as phosphorous acid and hypophosphorous acid; 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; Aluminic acid compounds; Nitric acid and nitrous acid compounds; Benzoic acids such as 2-hydroxy-N-methylbenzoic acid and di (tri) hydroxybenzoic acid; Gluconic acid and dichromium Acid, sorbic acid, dicarboxylic acid, EDTA, fluorocarboxylic acid, picric acid Suberic acid, adipic acid, sebacic acid, heteropolyacid (tungstic acid, molybdic acid), gentisic acid, borodigenticic acid, salicylic acid, N-aminosalicylic acid, borodiprotocatechuic acid, borodipyrrocatechol, bamonic acid, bonic acid, borodiresorcyl Acids, resorcylic acid, borodiprotocaquelic acid, glutaric acid, dithiocarbamic acid and other acids, esters, amides and salts thereof; silane coupling agents; silica, silica compounds such as aminosilicates; triethylamine, hexamethylenetetramine, etc. L-amino acids; benzol; polyhydric phenol; 8-oxyquinoline; sulfur compounds such as hydroquinone, N-methylpyrocatechol, quinoline and thioanisole, thiocresol, thiobenzoic acid; sorbitol; - histidine; can be used one or more such.

  Arbitrary appropriate quantity can be employ | adopted for content of the said additive. For example, the range of 0.1-20 mass% is preferable with respect to 100 mass% of ionic compounds, and the range of 0.5-10 mass% is more preferable.

  In the ionic compound, the impurity content is preferably 0.1% by mass (1000 ppm) or less in 100% by mass of the ionic compound. 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.

  The said impurity does not contain water, For example, what mixes when manufacturing an ionic compound or transporting it is mentioned. Specifically, when an ionic compound having an anion represented by the general formula (1) as an essential component is produced, for example, when the ionic compound is obtained using a halogen compound, the halogen compound is There is a possibility of contamination as an impurity, and when the ionic compound is derived using a silver salt, the silver salt may be contaminated as an impurity. In addition, manufacturing raw materials, by-products, and the like may be mixed as impurities.

  In the present invention, by setting the impurity content in the ionic compound as described above, for example, it is possible to sufficiently inhibit the halogen compound from poisoning the electrode of the electrochemical device and reducing the performance, It is possible to sufficiently suppress the performance of iron ions or the like from affecting the ion conductivity and degrading the performance. 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, sulfate 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 compound, the water content is preferably 0.05 to 10% by mass in 100% by mass of the ionic compound. 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 compound, The manufacturing method which comprises the process of inducing | guiding an ionic substance from the compound which has an anion represented by General formula (6) 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 structure of an anion represented by the general formula (6) using a halide or a carbonate. A step of reacting a compound having an anion represented by the formula (6) with a halide or a carbonate compound, wherein the halide or the carbonate compound is an onium cation, an alkali metal atom, or an alkaline earth metal. It is preferable to have a cation that essentially contains at least one metal atom selected from an atom, a transition metal atom, and a rare earth 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 may be used as the production method.

  The production method may include a step of producing a compound having an anion represented by the general formula (6) used in the step of deriving an ionic substance from the compound having an anion represented by the general formula (6). Well, in this case, the compound having the anion represented by the general formula (6) by reacting the compound having the anion represented by the general formula (6) as described above with a halide or carbonate. It is preferable to manufacture. Thereby, the structure of the anion represented by the general formula (6) in the ionic substance can be appropriately set according to the performance required for the ionic compound. In this case, the general formula (6) The anion possessed by the compound having an anion, which is a production raw material in the step of producing the compound having an anion represented by formula (1), and the anion represented by the general formula (6) in the ionic substance are not the same. Become. In addition, a step of reacting a compound such as a tertiary amine and an acid type compound of the general formula (6) is also a preferable production method.

  In the above step, one form of a chemical reaction formula in the step of deriving an ionic substance from the compound having an anion represented by the general formula (6) is shown in the following reaction formula.

  In the above step, when the number of moles of the compound having an anion represented by the general formula (6) is x and the number of moles of the halide is y, the molar ratio (x / y) in the reaction is 100/1 to It is preferably 0.1 / 1. If the compound having an anion is less than 0.1, the halide may be excessive and the product may not be obtained efficiently, and the halogen is mixed in the ionic compound, which poisons the electrode and the like. There is a risk of causing. If it exceeds 100, the anion-containing compound may be excessive, and further improvement in yield may not be expected. Also, metal ions may be mixed into the ionic compound and deteriorate the performance of the electrochemical device. . 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) Cyclohexene and other alicyclic unsaturated hydrocarbons; (4) Aromatic hydrocarbons such as benzene, toluene and xylene; (5) Ketones such as acetone and methyl ethyl ketone; (6) Methyl acetate, ethyl acetate, butyl acetate, γ- Esters such as butyrolactone; (7) Halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; (8) Ethers such as diethyl ether, dioxane and dioxolane, (9) Alkylene such as propylene glycol monomethyl ether acetate and diethylene glycol monomethyl ether acetate Glycol A (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) Sulfones such as dimethyl sulfoxide (13) Carbonic acid esters such as dimethyl carbonate and diethyl carbonate; (14) Alicyclic carbonic acid esters such as ethylene carbonate and propylene carbonate; (15) Nitriles such as acetonitrile; (16) Water and the like are suitable. is there. 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), (6), (10), (14), (15), and (16).

In the method for producing the ionic compound, 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 substance under vacuum conditions, etc., it is washed by dissolving in a solvent such as dichloromethane, dehydrated by adding a substance having a dehydrating effect such as MgSO ₄ , and the pressure is reduced after removing the solvent. An ionic compound may be obtained by drying. 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.

<< A-2. Second Embodiment of Ionic Compound of the Present Invention >>
The ionic compound of the present invention has a cation and a counter anion represented by the general formula (2), and has an ionic conductivity at 25 ° C. of 10 mS / cm or more.

  Up to now, the tertiary salt has a structure that is difficult to dissociate when used as an electrolytic solution for a capacitor as compared with the quaternary salt, although it does not cause a problem of liquid leakage from the cathode portion. The grade salt could not achieve an ionic conductivity (25 ° C.) of 10 mS / cm or more. In the present invention, the problem was achieved by designing and optimizing an anion having an excellent degree of dissociation.

About the cation represented by the said General formula (2), the description in item A-1 is used.
Any appropriate anion can be adopted as the counter anion. Preferably, the anion represented by the general formula (6) described in item A-1 and the other anions described in item A-1.

The ionic conductivity at 25 ° C. is 10 mS / cm or more, preferably 15 mS / cm or more, more preferably 20 mS / cm or more, and further preferably 25 mS / cm or more. When the ionic conductivity at 25 ° C. is less than 10 mS / cm, it is not possible to provide excellent ionic conductivity, and there is a possibility that an ionic compound that can be suitably used for various applications cannot be provided.
It is preferable that the ionic compound contains a cation (AH ⁺ ) represented by the general formula (1) represented by the item A-1 described above from the viewpoints of suppressing liquid leakage and inhibiting corrosion on the electrode.

≪B. Electrolyte material >>
The present invention is also an electrolyte material containing the ionic compound. Since the ionic compound can exhibit the above-described characteristics, it can be suitably applied to various applications. Among them, primary batteries, lithium (ion) secondary batteries, fuel cells, etc. Particularly suitable as an electrolyte constituting an electrochemical device such as a battery having a charge / discharge mechanism, an electrolytic solution for an electrolytic capacitor, an electrolytic capacitor, an electric double layer capacitor, a solar cell or an electrochromic display element, and a material for such an electrolyte It is a thing. A lithium secondary battery, an electrolytic solution for an electrolytic capacitor, an electrolytic capacitor, or an electric double layer capacitor using the electrolyte of the present invention 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 only needs to include an electrolyte material, and preferably includes an electrolyte material and a matrix material. Thus, the electrolyte material including the matrix material is also one aspect of the present invention.

  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 lithium 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 consisting of 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. By mixing these, 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.

（式中、Ａは、Ｃ、Ｓｉ、Ｎ、Ｐ、Ｓ及びＯからなる群より選ばれる一種類の元素を含む化合物を表す。Ｘは、Ｂ、Ｃ、Ｎ、Ｏ、Ａｌ、Ｓｉ、Ｐ、Ｓ、Ａｓ及びＳｅからなる群より選ばれる少なくとも１種類の元素であり、Ｍ^１及びＭ^２は、同一又は異なって、連結基を表し、複数ある場合は、同一又は異なっていてもよい。Ｑは、１価の元素又は有機基を表す。ａは、１以上の整数であり、ｂ、ｃ、ｄ及びｅは、０以上の整数である。）で表され、沸点が２５０℃以下の化合物を有するイオン性化合物を含んでなる。 ≪C. Electrolytic solution for electrolytic capacitor drive >>
The electrolyte for driving the electrolytic capacitor of the present invention is
General formula (1);

(In the formula, A represents a compound containing one kind of element selected from the group consisting of C, Si, N, P, S and O. X represents B, C, N, O, Al, Si, P , S, As, and Se. At least one element selected from the group consisting of S, As, and Se. M ¹ and M ² may be the same or different and each represent a linking group, and when there are a plurality of elements, they may be the same or different. Q represents a monovalent element or organic group, a is an integer of 1 or more, and b, c, d, and e are integers of 0 or more. It comprises an ionic compound having a compound.

The electrolytic solution for driving the electrolytic capacitor according to the present invention includes the above formula (2), and the cation (AH ⁺ ) and the anion represented by the general formula (1) described above are essential, so that ions Since it is excellent in conductivity and is a compound having a temperature of 250 ° C. or lower, liquid leakage is sufficiently suppressed, corrosiveness to electrodes and the like is sufficiently suppressed, and a material that is stable over time can be obtained. In addition, as represented by the general formula (2), the ionic compound of the present invention has a hydrogen atom as a cation. However, since it does not become a strong alkali, it can be sufficiently excellent in performance, durability and quality, and can be suitably used for various applications such as materials for electrochemical devices.

  Preferred forms and illustrations of the cation are the same as described above. That is, A in the general formula (1) is preferably an amine compound. Thus, the electrolytic solution for driving an electrolytic capacitor in which A in the general formula (1) is an amine compound is also the present invention. This is one of the preferred forms.

In the general formula (1), X represents at least one element selected from the group consisting of B, C, N, O, Al, Si, P, S, As, and Se. O or S is preferred. More preferably, X in the general formula (1) is C or N. The more preferable form of X in the general formula (1), the more preferable form, and the preferable forms and examples of M ¹ , M ² , Q, a, b, c, d and e are the same as described above.

In the general formula (1), X represents at least one element selected from the group consisting of B, C, N, O, Al, Si, P, S, As, and Se. O or S is preferred. More preferably, X in the general formula (1) is C or N. More preferred forms of X in the general formula (1), further preferred forms, preferred forms of M ¹ , M ² , Q, a, b, c, d and e, preferred forms of the cations, examples, etc. It is the same.

≪D. Lithium secondary battery, electrolytic capacitor, electric double layer capacitor >>
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 components. . 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. _{6 Li → 6C + Li + e} - occurs in the reaction, the electrons generated in the negative electrode surface (e ^-) are moved to the positive electrode surface in the electrolyte solution by ion conduction, the positive electrode ^{_{surface, CoO 2 + Li + e -}} → the reaction of LiCoO ₂ is Occurs and 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. 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 negative electrode current collector, 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. In addition, as the positive electrode active material, a transition metal chalcogenide, a 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 trapezoid used for an electric vehicle.

(2) Electrolytic Capacitor As the electrolytic capacitor, it is preferable to use the above-mentioned electrolytic solution, but among them, an electrolytic capacitor using the above-described electrolytic solution for driving the electrolytic capacitor is preferable. This is one of the preferred forms.

  The electrolytic capacitor includes an anode foil, a cathode foil, a capacitor element composed of electrolytic paper and a lead wire as a separator sandwiched between the anode foil and the cathode foil, and an ion conductor using the electrolyte of the present invention. A bottomed cylindrical outer case and a 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 impregnated with an electrolytic solution that is an ionic conductor using the above electrolyte material in a capacitor element, the capacitor element is accommodated in a bottomed cylindrical outer case, and sealed in an opening of the outer case. It can be obtained by attaching the body and sealing the outer case by drawing the end of the outer case. 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 dielectric having a thin oxide film (aluminum oxide) formed by electrolytic anodic oxidation on the surface of an aluminum foil roughened by making fine irregularities by electrolytic etching or vapor deposition is suitable. It is.

  Further, FIG. 2C shows a cross section of the main part of the aluminum electrolytic capacitor. FIG. 2C shows a capacitor element 6 in which the anode foil 1 and the cathode foil 2 subjected to the roughening treatment and the oxide film formation treatment are wound through the separator 3, and this capacitor element is an electrolyte for driving. After impregnating (hereinafter referred to as an electrolytic solution), it is housed in a bottomed cylindrical outer case 8. The anode and cathode lead-out leads 4 and 5 are inserted into a through-hole formed in the elastic sealing body 7 and pulled out, and the elastic sealing body 7 is attached to the opening of the outer case and sealed by drawing. .

  An aluminum electrolytic capacitor generally has a structure as shown in FIGS. A capacitor element 6 is formed by winding the anode foil 1 and the cathode foil 2 subjected to the roughening treatment and the oxide film formation treatment with the separator 3 interposed therebetween. The capacitor element is impregnated with an electrolytic solution, and then has a bottomed cylindrical shape. In the outer case 8. A sealing body 9 is attached to the opening of the outer case 8 and sealed by drawing. An element fixing agent 17 for fixing the capacitor element 6 to the outer case 8 may be included. An anode terminal 13 and a cathode terminal 14 are formed on the outer end surface of the sealing body 9, and the lower end portions of these terminals 13 and 14 are anode tabs drawn out from the capacitor element 6 as anode internal terminals 15 and cathode internal terminals 16. The terminal 11 and the cathode tab terminal 12 are electrically connected. Here, the anode tab terminal 11 is subjected to a chemical conversion treatment, while the cathode tab terminal 12 is not subjected to a chemical conversion treatment. For any of the tab terminals 11 and 12, an aluminum foil that is not subjected to surface processing is used.

  With the progress of downsizing, thinning, and high-density surface mounting technology of electronic components, aluminum electrolytic capacitors are also required to be chip-shaped, and chip-shaped aluminum electrolytic capacitors have a structure as shown in FIG. Become. A capacitor element 6 is formed by winding an anode foil and a cathode foil that have been subjected to roughening treatment and oxide film formation treatment through a separator, and this capacitor element is impregnated with an electrolytic solution, and then has a bottomed cylindrical outer case. 8, and the opening is sealed with an elastic sealing body 7 to constitute an aluminum electrolytic capacitor. The aluminum electrolytic capacitor lead terminal 18 is disposed so as to be in contact with the drawn end surface, and an insulating plate 19 having a through-hole through which the lead terminal 18 passes is attached to provide stability in board mounting. It is configured to

  The structure of the aluminum electrolytic capacitor using the electrolytic solution provided with the ionic compound of the present invention may also be used in the structure of the newly proposed aluminum electrolytic capacitor, for example, roughening treatment and oxide film formation treatment. Examples thereof include an aluminum electrolytic capacitor having a structure in which an anode foil and a cathode foil are laminated via a separator.

  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.

  As the cathode foil, one or more metal nitrides selected from titanium nitride, zirconium nitride, tantalum nitride, and niobium nitride are formed on a part or all of the surface of the aluminum foil that has been subjected to surface expansion treatment by chemical or electrochemical etching. And / or an aluminum foil formed with a film composed of one or more metals selected from titanium, zirconium, tantalum, and niobium 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 ionic conductor using the electrolyte of the present invention as basic constituent elements. In addition, an electrolyte solution that is an ionic conductor is included in an electrode element composed of a negative electrode. FIG. 6 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. 6, 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.

  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]
41.2 g (0.24 mol) of silver nitrate and 250 ml of ion-exchanged water were added to a flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, a stirrer, and a dropping funnel and stirred to completely dissolve the silver nitrate. . Next, a 30% aqueous solution of 26.1 g (0.20 mol) of potassium tricyanomethide (hereinafter referred to as KTCM) was placed in the dropping funnel and added dropwise to the silver nitrate solution at room temperature for 1 hour. The resulting white solid was filtered off and washed with 300 ml of ion exchange water. This washing process was repeated 5 times.
Next, 300 ml of ion-exchanged water was added to the white solid, put into a separable flask and stirred to form a slurry, and 27.3 g (0.15 mol) of a 50% aqueous solution of triethylammonium bromide in the dropping funnel was added for 1 hour at room temperature. It was dripped over. Furthermore, after stirring at room temperature for 1 hour, the obtained reaction liquid was filtered with a membrane filter (hydrophilic type, pore diameter 0.2 μm). The obtained aqueous solution was concentrated with an evaporator to obtain 27.0 g (0.14 mol) of triethylammonium tricyanomethide (hereinafter referred to as TEATCM). The yield was 94%.

[Example 2]
An ion-exchange resin (product name: Amberlite IR120-H (120 ml)) thoroughly washed with ion-exchanged water is packed in a column tube, and KTCM 19.3 g (0.15 mol) 0.2 mol / l aqueous solution is taken over 4 hours. The obtained aqueous solution was put into a beaker, and a 50% methanol solution of 30.2 g (0.30 mol) of triethylamine was added thereto at room temperature, and the resulting aqueous solution was stirred with an evaporator. By concentrating, 28.5 g (0.15 mol) of TEATCM was obtained, and the yield was 99%.

[Example 3]
Pyridinium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to pyridine. The yield was 93%.

[Example 4]
1-methylpyrrolidinium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to methylpyrrolidine. The yield was 95%.

[Example 5]
N, N-dimethylhexylammonium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to N, N-dimethylhexylamine. The yield was 93%.

[Example 6]
Dimethylphenylammonium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to dimethylphenylamine. The yield was 95%.

[Example 7]
N-methylimidazolium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to N-methylimidazole. The yield was 98%.

[Example 8]
Trimethylammonium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to trimethylamine. The yield was 97%.

[Example 9]
Dimethylethylammonium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to dimethylethylamine. The yield was 97%.

[Example 10]
1-Butylpyrrolidinium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to 1-butylpyrrolidine. The yield was 90%.

[Example 11]
Diethylammonium tricyanomethide was obtained using the same type of spikelet, except that the triethylammonium bromide in Example 1 was changed to diethylammonium bromide. The yield was 90%.

[Example 12]
Dibutylammonium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to dibutylamine. The yield was 95%.

[Example 13]
N-octylammonium tricyanomethide was obtained using the same method except that triethylamine in Example 2 was changed to n-octylamine. The yield was 97%.

[Example 14]
Triethylammonium dicyanoamide was obtained using the same method except that potassium tricyanomethide in Example 1 was changed to sodium dicyanoamide. The yield was 88%.
Table 1 shows the ion conductivity, ¹ H-NMR, ¹³ C-NMR spectrum data and boiling points (bp) of Examples 2 to 14 at 25 ° C. Table 1 shows the ion conductivity, ¹ H-NMR, ¹³ C-NMR spectrum data and boiling point (bp) of triethylammonium phthalate as Comparative Example 1 and imidazolium tricyanomethide as Comparative Example 2 at 25 ° C. Show. In addition, the measurement conditions of ion conductivity, ¹ H-NMR and ¹³ C-NMR are as follows.

(Ionic conductivity)
Measuring device: Impedance analyzer SI1260 (manufactured by Solartron)
Method: SUS electrode, complex impedance method

⁽¹ H-NMR measurement conditions)
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

( ^13C -NMR measurement conditions)
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

  Although the test result of the product which provided the said ionic compound represented by Example 2 and 7 as an electrolyte solution of an aluminum electrolytic capacitor as an Example is shown below, this invention is not limited to these Examples. .

[Examples 15 to 43 and Comparative Examples 3 and 4]
Hereinafter, as an example of the present invention, an electrolytic solution used for an aluminum electrolytic capacitor provided with the substances shown in Examples 2 and 7 was prepared with the formulation shown in Tables 2 and 3, and the specific resistance at 30 ° C. was measured. The specific resistance measurement conditions are as follows. The results are shown in Tables 2 and 3.

(Resistivity)
Equipment: HIOKI 3522 LCR HiTESTER
Measurement frequency: 1 kHz
Measurement temperature: 30 ° C

  As is clear from Tables 2 and 3, it can be seen that the specific examples of the electrolyte using the ionic compound in the present invention have a lower specific resistance than the comparative example. In the electrolytic solution using the ionic compound in the present invention, the solute concentration decreases and the specific resistance value increases. However, in Example 15 where the solute concentration is 3% by weight, the ratio is lower than that in Comparative Example 3. Resistance is achieved, and a satisfactory reduction in specific resistance is realized as compared with Example 19 having the same solute concentration.

  In Tables 2 and 3, Examples 32-34 using sulfolanes as solvents have a lower specific resistance than Comparative Example 3.

  In Tables 2 and 3, in Example 35 using ethylene glycol as the solvent, the specific resistance is reduced as compared with Comparative Example 3.

  In Tables 2 and 3, Examples 36 to 40, which contain nitro compounds as additives, showed no rapid increase in specific resistance, and were reduced in specific resistance compared to Comparative Examples 3 and 4. Yes.

  In Tables 2 and 3, Examples 41 to 43, which are cases where a phosphorus compound is contained as an additive, show no rapid increase in specific resistance, and have a lower specific resistance than Comparative Examples 3 and 4. .

Next, the aluminum electrolytic capacitor of the present invention was manufactured by the following procedure.
A capacitor element is formed by winding a cathode foil subjected to etching treatment and oxide film formation treatment and a cathode foil through a Manila hemp separator, and the capacitor element is impregnated with the electrolytic solution, and then has a bottomed tube made of aluminum. In an outer case. The anode and cathode lead leads are pushed into a through-hole formed in an elastic sealing body made of butyl rubber and pulled out, and an elastic sealing body made of butyl rubber is attached to the opening of the outer case, which is sealed by drawing and aluminum electrolytic A capacitor was produced.

  Although the present invention can be applied to any structure, a structure as shown in FIG. 2C will be described as a representative in the embodiment. Hereinafter, all the aluminum electrolytic capacitors used in the examples have the same structure.

  Using electrolytic solutions of Tables 2 and 3 (Examples 17 to 21, 26 to 30 and Comparative Examples 3 and 4), an aluminum electrolytic capacitor having a capacitor element specification of 6.3 V-1000 μF (φ10 × 12.5 mmL) 10 pieces of each were prepared.

  For Examples 17 to 21 and 26 to 30 and Comparative Examples 3 and 4, the impedance values at 20 ° C. and 100 kHz, and the equivalent series resistance values at 20 ° C. and 100 kHz were measured using HEWLETT PACKARD 4284A PRECISION LCR METER (manufactured by Hewlett-Packard Company). ). The results are shown in Table 4.

  As is apparent from Table 4, it can be seen that the embodiment of the present invention has lower impedance and lower equivalent series resistance than the comparative example. Therefore, the present invention can be used as an aluminum electrolytic capacitor for low impedance.

  Subsequently, by using the electrolytic solutions of Examples 2 and 3 (Examples 17 to 21, 26 to 30 and Comparative Example 4), aluminum electrolysis with a capacitor element specification of 6.3 V-1000 μF (φ10 × 12.5 mmL) was performed. Ten capacitors were manufactured, and DC 6.3 V was applied for 2000 hours under high temperature and high humidity conditions of 85 ° C. and 85% relative humidity, and the presence or absence of liquid leakage from the lead hole portion of the sealing portion was examined. The results are shown in Table 5.

  As is apparent from Table 5, the examples of the present invention showed excellent reliability with no liquid leakage even under high humidity conditions, as compared with Comparative Example 4 using a solute having a boiling point exceeding 250 ° C. I understand that.

[Example 44]
To a flask equipped with a stirrer and a dropping funnel, 3.7 g (13 mmol) of trifluoromethylsulfonimide and 15 ml of methanol were added and stirred at room temperature, and a 20 ml methanol solution of 1.6 g (16 mmol) of triethylamine was added thereto at room temperature. It was added dropwise over time. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and then the solution was concentrated and dried to obtain 4.9 g of a flesh-colored solid (triethylammonium (bis (trifluoromethanesulfonimide)): TEATFSI). The yield was 98%.
Next, 35 parts of TEATFSI were dissolved in 65 parts of γ-butyrolactone and the ionic conductivity was measured to find 29.8 mS / cm.
¹ H-NMR of TEATFSI was as follows.
¹ H-NMR (solvent: d6-DMSO): δ 8.82 (bs, 1H), δ 3.10 (q, ΔJ = 5.2 Hz, 6H), δ 1.17 (t, ΔJ = 5.2 Hz, 9H)

  In addition, this invention is not limited to an Example, It can apply to the electrolytic capacitor which consists of any material and structure using the electrolyte solution which melt | dissolved various compounds described previously individually or in multiple. In any electrolytic capacitor of any structure, the same effect as in the embodiment can be obtained.

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. (C) is a principal part cutting front view of an aluminum electrolytic capacitor. It is a disassembled perspective view of the aluminum electrolytic capacitor element of other forms. It is a principal part cutting front view of the aluminum electrolytic capacitor of other forms. It is a principal part cutting front view of a chip-type 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Anode foil 2 Cathode foil 3 Separator 4 Anode drawer lead 5 Cathode drawer lead 6 Capacitor element 7 Elastic sealing body 8 Exterior case 9 Sealing body 10 Clamping (or welding)
11 Anode Tab Terminal 12 Cathode Tab Terminal 13 Anode Terminal 14 Cathode Terminal 15 Anode Internal Terminal 16 Cathode Internal Terminal 17 Element Fixing Agent 18 Lead Terminal 19 Insulating Plate

Claims (2)

A tricyanomethide anion, and
A cation of triethylamine, pyridine, methylpyrrolidine, N, N-dimethylhexylamine, dimethylphenylamine, N-methylimidazole, trimethylamine, dimethylethylamine, 1-butylpyrrolidine, diethylamine, dibutylamine, n-octylamine;
Containing only one ionic compound having
The ionic compound state, and are ionic conductivity 10 mS / cm or more at 25 ° C., and a boiling point of 250 ° C. or less,
Electrolyte material . The electrolyte material comprises a matrix material, the electrolyte material according to claim 1.

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