WO2007072763A1 - Novel cyclic fluorosulfonyl imide salt and electrolyte - Google Patents

Abstract

Disclosed are a novel cyclic fluorosulfonyl imide salt and an electrolyte. Specifically disclosed are a compound (1) shown below and an electrolyte containing a compound (1m) shown below. In this connection, n represents 1, 2, 3 or 4; [M]n+ represents an n-valent positive ion, specifically an alkali metal ion, an organic ammonium ion, a sulfonium ion, an oxonium ion or a phosphonium ion when n is 1, and an n-valent metal positive ion when n is 2, 3 or 4; [Mm]n+ represents an n-valent metal positive ion; and X and Xm respectively represent a hydrogen atom, a halogen atom, an alkyl group having 1-6 carbon atoms, a fluoroalkyl group having 1-6 carbon atoms or a fluoroalkoxy group having 1-6 carbon atoms. (1) (1m)

Description

 Specification

 Novel cyclic fluorosulfonylimide salts and electrolytes

 Technical field

 The present invention relates to a novel cyclic fluorosulfonylimide salt and an electrolyte suitably used for electrochemical devices (secondary batteries, electric double layer capacitors, fuel cells, solar cells, etc.).

 Background art

 [0002] Electrolytes used in electrochemical devices are not only superior in electrical conductivity but also in chemical stability (low corrosion resistance, heat resistance, etc.). , Operating temperature, charge / discharge cycle, durability, etc.). In order to obtain an electrolyte that achieves both electrical conductivity and chemical stability, various types of cation and anion electrolytes, and combinations thereof, have been actively studied.

[0003] Patent Document 1 and Patent Document 2, as an electrolyte used in the electrochemical device, wherein R ^F - acyclic anion represented by SO -N "-SO-R ^F, wherein R ^F - SO — N_— CO

 2 2 2

—R ^F acyclic anion, -CO-N "-CO-R ^F acyclic anion, or a 5-membered or higher ring represented by the following formula (dsi) Electrolytes with cyclic anions have been proposed.

[0004] [Chemical 1]

ただし、上記 3つの非環式陰イオンの式中の R^Fはそれぞれ独立に炭素数 1 12の 1価のペルフルォロ基を、また、上式（dsi)中の Q^Fは炭素数 2 6の 2価のペルフル ォロ基を、示す。

However, R ^F in the above three acyclic anion formulas independently represents a monovalent perfluoro group having 1 12 carbon atoms, and Q ^F in the above formula (dsi) represents 2 of 2 6 carbon atoms. The valent perfluoro group is shown.

[0005] In addition, as the fluorosulfurimides, there are known the following compounds (Ldsl), acyclic fluorosulfonylimides such as the following compounds (Lms 1), and cyclic fluorodisulfurimides such as the following compounds (Cdsl). (See Patent Document 1 and Non-Patent Document 1;). specific The salt of fluorosuldiimide is known to be an ionic substance and various applications have been attempted.

[Chemical 2] ¾

 (Lds1) (Lms1) (Cds1) On the other hand, as cyclic fluoromonosulfonylimides, only the following compound (Cms 1) and the following compound (Cms2) are known (Patent Document 3 and non-patent) See reference 2.)

 [Chemical 3]

 (Cms2) Furthermore, as physical properties of cyclic fluoromonosulfurimides, only the production method and use as a specific synthetic intermediate are known.

 [0008] Patent Document 1: Japanese Patent Publication No. 11 512653

 Patent Document 2: Japanese Patent Publication No. 01-501822

 Patent Document 3: International Publication 2005Z001979 Pamphlet

 Non-patent literature l: Chem. Commun., 1726, (2002)

 Non-Patent Document 2: J. Org. Chem., 26, 4002, (1961)

 Disclosure of the invention

 Problems to be solved by the invention

[0009] The present inventors have conducted intensive studies on the assumption that cyclic fluoromonosulfurimides can form an ionic liquid at a lower temperature because they have an asymmetric ring structure. As a result, we succeeded in obtaining a novel cyclic fluorosulfurimide salt. Furthermore, the salt is chemically And found that it is a stable ionic liquid.

 [0010] Further, the inventors of the present invention provide a 4-membered cyclic anion having a -SO-N_-CO- structure,

 2

 Since the ionic radius is small, it was considered that the mobility in the electrolyte was high and the electrical conductivity was excellent. In addition, the cyclic anion has an asymmetric molecular structure and thus has a low viscosity. Furthermore, it was considered that the cyclic anion can exist in a high molar concentration in the electrolyte because of its low molecular weight. They have also found that a novel fluorine-containing compound having a 4-membered cyclic anion is useful as an electrolyte.

 Means for solving the problem

That is, the present invention has the following gist.

 [1] A compound represented by the following formula (1).

[0012] [Chemical 4]

ただし、式中の記号は下記の意味を示す。

However, the symbol in a formula shows the following meaning.

 n: l, 2, 3, or 4.

[M] ^{n +} : an n-valent cation, and when n is 1, it is an alkali metal ion, an organic ammonium ion, a sulfone ion, a positive xanthomy ion, or a phosphorous ion. Yes, when n is 2, 3, or 4, it is an n-valent metal cation.

 X: A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms.

[0013] [2] A compound represented by the following formula (11):

[0014] [Chemical 5] [0015] [0016]

ただし、式中の記号は下記の意味を示す。

However, the symbol in a formula shows the following meaning.

 n: l, 2, 3, or 4.

[M] ^{n +} : an n-valent cation, and when n is 1, it is an alkali metal ion, an organic ammonium ion, a sulfone ion, a positive xanthomy ion, or a phosphorous ion. Yes, when n is 2, 3, or 4, it is an n-valent metal cation.

 X: A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms.

 [4] An electrolyte comprising a compound represented by the following formula (lm):

 [0018] [Chemical 7]

ただし、式中の記号は下記の意味を示す。 [Mm (1 m)

However, the symbol in a formula shows the following meaning.

 n: l, 2, 3, or 4.

[Mm] ^{n +} : n-valent metal cation.

 Xm: a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluorinated alkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms.

[5] The electrolyte according to [4] above, wherein n is 1 and [Mm] ^{n +} is a monovalent metal cation.

 [6] An electrolytic solution comprising the electrolyte according to [4] or [5] above and a nonaqueous solvent.

[7] The electrolytic solution according to [6], wherein the electrolyte contains 0. OlmolZdm ³ or more with respect to the non-aqueous solvent.

 [8] The electrolytic solution according to the above [6] or [7], wherein the non-aqueous solvent is a polar aprotic solvent.

 [9] An electrochemical device using the electrolytic solution according to any one of [6] to [8] above. The invention's effect

 According to the present invention, there is provided a novel compound which is a chemically stable ionic liquid and has low volatility, high compatibility, high conductivity, and flame retardancy. Furthermore, according to the present invention, a novel electrolyte excellent not only in electrical conductivity but also in chemical stability (low corrosion resistance, heat resistance, etc.), an electrolyte containing the electrolyte, and the electrolyte The used electrochemical device is provided.

 BEST MODE FOR CARRYING OUT THE INVENTION

 In the present specification, a compound represented by the formula (1) is also referred to as a compound (1), and an ion represented by the formula (im) is also referred to as an ion (im). The same applies to compounds represented by other formulas and ions represented by other formulas. Moreover, the symbols in the formula are as defined above unless otherwise specified.

 The present invention provides the following compound (1).

[0021] [Chemical 8]

[0022] Compound (1) is a salt of [M] ^{n +} which is an n-valent cation and n anions. In the compound (1), n is preferably 1, and [M] + is a monovalent cation.

 The monovalent cation is particularly preferably an alkali metal ion, an organic ammonium ion or a phosphonium ion! /.

 The alkali metal ion is preferably lithium ion! /.

 The organic ammonium ion is not particularly limited, and may be an acyclic organic ammonium ion or a cyclic organic ammonium ion. The organic ammonium ion preferably has 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms.

[0023] An acyclic organic ammonium ion is an ion represented by the formula [(R ^A ) N] + (where R ^A is

 Four

A monovalent hydrocarbon group having 1 to 10 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 10 carbon atoms. ) (Hereinafter referred to as ions (Ai)). The four R ^A in the ion (Ai) may be the same or different. In addition, when a carbon atom-carbon atom bond is present in R ^A , an etheric oxygen atom, a carbon group, or an oxycarbol group may be inserted between the carbon atom-carbon atom bond. .

[0024] R ^A is preferably an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms. Among them, an alkyl group having 1 to 6 carbon atoms is more preferably a methyl group, an ethyl group, an n propyl group, an iso propyl group, an n butyl group, an iso butyl group, or a tert-butyl group. Is particularly preferred.

 [0025] The cyclic organic ammonium ion is preferably an ion having a ring structure containing a positively charged nitrogen atom. Especially preferred is quinolinium or triazinium! /.

[0026] The carbon atom forming the ring of the cyclic organic ammonium ion contains 1 to 6 carbon atoms. An alkyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms is bonded.

The power of imidazolium is the following ion (im—1) The power of virazolium is the following ion (pi 1), while the power of pyradium is the following ion (pi—2). ion (Py- 1) a is the force Piridaji - © beam is of the the following ions (py- 2), pyrimidine - © beam is of the the following ions _(P y- 3), pyrrolidine - © Is the following ion (pr 1), but Piberidi-um is the following ion (pp-1), and quinolium is the following ion (qu-1). Triazolium is the following ion. (tr—l) or the ion (tr 2) below is preferred U, respectively.

[0027] [Chemical 9]

お よび Ζ¹⁷は、それぞれ独立に、炭素数 1〜20の 1価炭化水素基、または炭素数 1〜20 の 1価フッ素化炭化水素基を示す。 [0028]

Contact and Zeta ¹⁷ each independently represent a monovalent hydrocarbon group or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms.

ζ¹²、 ζ¹³、 ζ¹⁴、 ζ¹⁵、 ζ¹⁶、およ び ζ¹⁷中に、炭素原子 炭素原子結合が存在する場合、該炭素原子 炭素原子結 合間には、エーテル性酸素原子、カルボ-ル基、またはォキシカルボ-ル基が挿入 されていてもよい。 Also,

When a carbon atom-carbon atom bond exists in ζ ¹² , ζ ¹³ , ζ ¹⁴ , ζ ¹⁵ , ζ ¹⁶ , and ζ ¹⁷ , an etheric oxygen atom, carbo- Or an oxycarbonyl group may be inserted.

 Λ Ί

および Ζ¹ は、それぞれ独立に、炭素数 1 10のアルキル基、または炭素数 1 10のフルォロ アルキル基であるのが好ましい。中でも、炭素数 1 6のアルキル基であるのがより好 ましぐメチル基、ェチル基、 n—プロピル基、 iso プロピル基、 n—ブチル基、 iso— ブチル基、または tert ブチル基であるのが特に好まし 、。 [0029]

And Ζ ¹ Are preferably each independently an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms. Among them, the alkyl group having 16 carbon atoms is more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, or a tert-butyl group. Especially preferred.

[0030] The phosphonium ion is preferably a quaternary phosphonium ion with the formula [(R ^s ) P] +

4 is particularly preferably an ion represented by (wherein represents a monovalent hydrocarbon group having 120 carbon atoms or a monovalent halogenated hydrocarbon group having 120 carbon atoms). Further, when a carbon atom-carbon atom bond is present in R ^S , an etheric oxygen atom, a carbonyl group, or an oxycarbonyl group may be inserted between the carbon atom-carbon atom bond.

[0031] R ^s is preferably an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms. Among these, a methyl group, an ethyl group, an _n -propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a tert-butyl group is more preferable as an alkyl group having 16 carbon atoms. Especially preferred!

[0032] In addition, in the compound (1), when n is 2, the compound (1) is preferably the following compound (12) ([M ² ] ²⁺ represents a divalent metal cation. ) When ₀ n is 3, the compound (1) is preferably the following compound (13) ([M ³ ] ³⁺ represents a trivalent metal cation.) some cases, the compound (1) is the following compound (14) is preferably ([M ^{4] 4+} indicates a tetravalent metal cation.) ₀

 [0033] [Chemical 10]

M

し

Shi

 (12) (13) (14)

[Μ ² ] ^{2 It} is preferable to use calcium ions, magnesium ions, or copper (Π) ions.

[Μ ³ ] ³⁺ is preferably an aluminum (ΠΙ) ion.

In the compound (1), X is preferably a halogen atom or a perfluoroalkyl group having 14 carbon atoms. Among them, chlorine atom, fluorine atom, or trifluoromethyl Particularly preferred is a fluorine atom, which is more preferably a group! /.

 [0034] A preferred embodiment of the compound (1) of the present invention includes the following compound (11).

[0035] [Chemical 11]

[M ¹ ] is a monovalent cation, which is a lithium ion, the ion (Ai), the ion (im 1), the ion (pi-1), the ion (pi-2), or the ion (py — 1), the ion (py—2), the ion (py—3), the ion (pr—1), the ion (pp—1), the ion (qu—1), the ion (tr—1) Or the above-mentioned ion (tr-2). Among these, lithium ions, the ions (Ai), the ions (im-1), the ions (py-1), or the ions (pr-1) are particularly preferable.

[0036] Specific examples of the compound (11) in which [M ¹ ] is an alkali metal ion include the following compounds.

 [0037] [Chemical 12]

 [Specific examples of compound (11) in which Mif is an organic ammonium ion include the following compounds.

[Chemical 13] o

 II

[(CH ₃ ) ₄ N] c.

> F ₂ [(CH ₃ CH2) (CH ₃ ) ₃ N]

 0

 0 O

 II II

 c

[(CH ₃ CH ₂ CH ₂ CH ₂ ) ₄ N] [(CH ₃ CH ₂ ) ₂ (CH ₃ ) (CH ₃ OCH ₂ CH2) N]

> ²

O <KU S) ^F2 0 KU S).

Specific examples of the compound (11) in which [M ¹ ] is imidazolium include the following compounds.

[0039] [Chemical 14]

-s one //, / 0

Specific examples of the compound (11) wherein [M ¹ ] is virazolium include the following compounds.

[0040] [Chemical 15]

Specific examples of the compound (11) in which [M ¹ ] is pyradium include the following compounds.

[0041] [Chemical 16]

Specific examples of the compound (11) in which [M ¹ ] is pyridinium include the following compounds.

[0042] [Chemical 17]

Specific examples of the compound (11) in which [Μ ¹ ] is pyridadi-um include the following compounds.

 [Chemical 18]

Specific examples of the compound (11) in which [Μ ¹ ] is pyrimidium-um include the following compounds.

[0044] [Chemical 19]

Specific examples of the compound (11) wherein [M ¹ ] is pyrrolidinium include the following compounds.

[Chemical 20]

Specific examples of the compound (11) in which [M ¹ ] is piberidinium include the following compounds.

[Chemical 21]

Specific examples of the compound (11) in which [M ¹ ] ⁺ is l, 2,4-triazolium include the following compounds.

[Chemical 22]

Specific examples of compound (11) wherein [M ¹ ] is 1,2,3-triazolium include the following compounds: Things.

 [0048] [Chemical 23]

Specific examples of the compound (11) in which [M ¹ ] is quinolium include the following compounds.

[0049] [Chemical 24]

化合物（1)は、下記の化合物（2)と式 [Μ]^η+ ( [ΟΗΓ) で される化合物 (以下、 化合物（3)とも 、う。 )とを反応させて製造するのが好ま 、。

Compound (1) is preferably produced by reacting the following compound (2) with a compound represented by the formula [Μ] ^{η +} ([ΟΗΓ) (hereinafter, also referred to as compound (3)). .

[0050] [Chemical 25]

[0051] In the reaction, it is preferable to react 1.00 Xn to 2.OOXn times mol of compound (3) to n mol of compound (2). It is particularly preferable to react 50 × n mole. The temperature in the reaction is preferably 0 to 200 ° C, particularly preferably 40 to 120 ° C. The pressure in the reaction is not particularly limited. The reaction may be performed in the presence of a solvent or may be performed in the absence of a solvent.

[0052] Specific examples of the compound (3) include lithium hydroxide, tetramethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and hydroxy acid. Yttrimethyl methylammonium, decylmethylmethoxymethoxyethyl ammonium hydroxide, 1-hydroxyl Rheo 3—Methylimidazolium, Hydroxyl-1-Methyl-3 Propylimidazole, Hydroxyl 1,2-Dimethyl-3 Butylimidazole, Hydroxyl 1-Ethylru 2-Methylvirazolium, Hydroxyl-1-Methyl-2- Propyl bisazolium hydroxide, 1-methylpyridinium hydroxide, hydroxylated 1-hexylpyridinium hydroxide, 1-butylpyridinium hydroxide, hydroxylated 1 ethylpyridinum, hydroxylated 1 propyl-3 methylpyridinum , Water Oxidation — 1-ethyl 1-methylpyrrolidinium, hydroxyl — 1-methyl 1-propyl pyridium, 1-hydroxyl 1-methyl biveridium, 1-methyl 1-propyl pyridium, water Oxygen 1-methyl-2 propyl-1,2,4-tria zolycum, hydroxy-a- 1-ethino lei 2-methinolay 1, 2, 4 tri-zolicum, hydroxy-a- 1 propyl-2 Methyl-1, 2, 3 Triazolium, Hydroxyl-1-ethyl-2-methyl-1,2,3 Triazolium, Hydroxyl 1 Methylpyridazinium, Hydroxyl-1 Monohexyl pyridazinum, Hydroxyl 1 Butylpyridazinium 1-hydroxypyridazinium hydroxide, 1-propyl 3-methylpyridazinium hydroxide, 1-methylpyrimidinium hydroxide, 1-hexylpyrimidinium hydroxide, 1-butylpyrimidinium hydroxide, water 1-ethyl pyrimidium oxide, 1-propyl 3-methyl pyrimidium hydroxide, 1-methyl villajum hydroxide, 1-hexyl viradjum hydroxide, 1-butyl pyrazidium hydroxide, 1-butyl pyrazidium hydroxide, 1-ethyl pyrazidium hydroxide And 1-propyl 3-methyl villainum hydroxide, 1-ethyl quinolinium hydroxide, 1-ethyl 4-methyl quinolium hydroxide and the like. As the compound (3), a hydrate may be used.

[0053] The compound (1) of the present invention is a novel compound unknown in the literature.

 The present inventors have found that the compound (1) is a chemically stable molten salt and ionic liquid over a wide temperature range (from 1700C to + 300C). Furthermore, it was found that the compound (1) has low volatility, high compatibility with other compounds, and excellent conductivity and flame retardancy.

[0054] The present invention provides a composition comprising compound (1) as an active ingredient. The composition of the present invention may be a composition comprising compound (1) and may be a composition comprising compound (1) and another compound. The composition of the present invention preferably contains 1 to L00% by mass of the compound (1). When the composition of the present invention contains other compounds, it is more than 0 to 99% by mass of the other compounds. Is preferably included. The other compound may be a liquid compound or a solid compound. Further, the other compound may be an organic compound or an inorganic compound.

 [0055] The type of the compound (1) in the composition of the present invention, the types of other compounds, and their blending amounts are appropriately changed according to the use of the composition of the present invention.

For example, when the composition of the present invention is used as an electrolyte for a lithium secondary battery, the composition preferably contains a compound (1) in which [M] ^{n +} is a lithium ion.

 [0056] When the composition of the present invention is used as an electrolyte for an electric double layer capacitor, the composition is

[M] It is preferable to contain a compound (1) in which ^{n +} is an organic ammonium ion or a phosphonium ion, and an organic carbonate. The composition preferably comprises 40-80% by weight of compound (1) and 20-60% by weight of organic carbonate.

 The organic carbonate is preferably ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, or methyl ethyl carbonate.

When the composition of the present invention is used as an antistatic agent, the composition of the present invention contains a compound (1) in which [M] n ⁺ is a lithium ion, an organic ammonium ion, or a phosphonium ion. Is preferred.

[0057] The composition of the present invention may be used in various forms according to the application. The composition of the present invention may be used alone or in combination with other materials.

 Applications for using the composition of the present invention alone include electrolytes for electrochemical devices (electrolytes for lithium secondary batteries, electrolytes for electric double layer capacitors, electrolytes for fuel cells, etc.), solvents (solvents for chemical reactions) , Solvent for extraction, solvent for electrolytic bath, etc.), heat medium, optical resolution agent, lubricant, gas detector for gas sensor, temperature sensor for temperature sensor, gas absorbent, chemical (transdermal absorption enhancer, enzyme coating) And the like in the immersion exposure method.

[0058] The composition of the present invention is particularly useful as an electrolyte for an electrochemical device, a solvent, or a heat medium from the viewpoint of its physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.). It is. Applications for combining the composition of the present invention with other materials include electrochemical device components ( Lithium secondary battery member, electric double layer capacitor member, fuel cell member, etc. ), Antistatic agents, dispersants and the like.

 [0059] Specific examples of articles obtained by combining the composition of the present invention with other materials include a carrier obtained by impregnating a porous carrier with the composition of the present invention, and the composition of the present invention as another material. And composite materials obtained by kneading or adding to the above.

 [0060] Specific examples of the porous carrier include porous carbon materials (activated carbon and the like), porous inorganic materials (inorganic glass, silica gel, ceramics and the like), and porous resin.

 The carrier is a carrier to which the physical properties (low volatility, high compatibility, high conductivity, flame retardancy, etc.) of the composition of the present invention are imparted, and is particularly useful as a member for an electrochemical device.

 [0061] Specific examples of other materials in the composite material include carbon materials (carbon nanotubes, fullerenes, diamonds, etc.), thermoplastic resins (fluorine-containing resin, polychlorinated resin, cellulose, polyolefins). System resin (polyethylene, polypropylene, polyacetate butyl, etc.), styrene resin (polystyrene, ABS, etc.), polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), (meth) acrylic resin Polyacrylate, polymethylenomethacrylate, etc.), polyamide-based resin (nylon 6, nylon 66, Naiton MXD6, etc.), polycarbonate-based resin (bisphenol A polycarbonate, etc.), polyether-based resin (Polyphenylene ether, polyacetal, etc.).

 [0062] A composite material in which the other material is a carbon material can be a composite carbon material with improved flowability and excellent workability.

 The composite material in which the other material is thermoplastic resin is a composite material imparted with low volatility, high compatibility, high conductivity, and flame retardancy, and is an electrochemical device member, a display element member, It is useful as an optically anisotropic film, a conductive film, an antistatic film, a photoelectric conversion element, an actuator element, a photosensitive element, and the like.

 [0063] The present invention provides an electrolyte containing the following compound (lm).

化合物（lm)は、 1個の n価の金属陽イオンである [Mm]ⁿ⁺と、 n個の陰イオンとの 塩である。 [0064] [Chemical 26]

The compound (lm) is a salt of [Mm] ^{n +} which is one n-valent metal cation and n anions.

 [0065] Xm is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Among these, a fluorine atom is particularly preferable from the viewpoint of the molecular weight of the compound (lm) in which a fluorine atom or a trifluoromethyl group is more preferable.

[0066] In the compound (lm), when n is 1, the compound (lm) is represented by the following compound (11m) ([Mm ¹ ] + represents a monovalent metal cation), and n is The compound (lm) when 2 is represented by the following compound (12m) ([Mm ² ] ²⁺ represents a divalent metal cation), and the compound (lm) when n is 3 is The following compound (13m) ([Mm ³ ] ³⁺ represents a trivalent metal cation), and when n is 4, compound (1) is represented by the following compound (14m) ([Mm ⁴ ] ⁴ + represents a tetravalent metal cation.

 However, in any compound (l lm, 12m, 13m, and 14m), Xm has the same meaning as described above.

 [0067] [Chemical 27]

[0068] [Mm ¹ ] is particularly preferably a lithium ion, preferably a lithium ion, a sodium ion, or a potassium ion. [Mm ² ] is preferably calcium ion, magnesium ion, or copper (II) ion.

[Mm ³ ] ³⁺ is preferably an aluminum (ΠΙ) ion.

In compound (lm), n is 1 and [Mm] ^{n +} is preferably a monovalent metal cation. Compound (lm) is preferably compound (11m).

[0069] Specific examples of the compound (11m) include the following compounds.

[0070] [Chemical 28]

0 O o

 II II II

[Li] V ^CF2 [Na l> F ₂ [> ₂

 Specific examples of the compound (12m) include the following compounds.

[0071] [Chemical 29]

l ²⁺ l

化合物（13m)の具体例としては、下記の化合物が挙げられる。

Specific examples of the compound (13m) include the following compounds.

[0072] [Chemical 30]

本発明の電解質は、化合物（lm)のみ力もなつていてもよぐ化合物（lm)と化合 物（lm)以外の電解質 (他の電解質ともいう。）とからなっていてもよい。他の電解質 は、フッ素原子を含む化合物であっても、フッ素原子を含まない化合物であってもよ い。他の電解質は、有機化合物であっても、無機化合物であってもよい。

The electrolyte of the present invention may be composed of a compound (lm) that may have only the compound (lm) and an electrolyte other than the compound (lm) (also referred to as other electrolyte). The other electrolyte may be a compound containing a fluorine atom or a compound not containing a fluorine atom. The other electrolyte may be an organic compound or an inorganic compound.

[0073] Specific examples of other electrolytes include LiCl LiF Lil LiPF LiBF LiSbF LiCIO

 Inorganic electrolyte such as 6 4 6 4; LiSO CF LiN (SO CF) LiN (SO CF CF) LiC (SO CF

 3 3 2 3 2 2 2 3 2 2 ί

Organic electrolytes such as CF) LiC (SO CF) LiPF (SO CF), LiPF (SO CF) I can get lost.

 [0074] When the electrolyte of the present invention contains another electrolyte, the electrolyte of the present invention contains 0.1 to 80% by mass of the compound (lm) with respect to the total amount of the compound (lm) and the other electrolyte. It is especially preferred to contain 1-40% by weight.

 [0075] The compound (lm) is a molten salt that is chemically stable in a wide temperature range (from 70 ° C to + 150 ° C). The compound (lm) has high compatibility with other compounds and low volatility. A solution obtained by dissolving the compound (lm) in a liquid solvent capable of dissolving the compound (lm) (hereinafter also simply referred to as a liquid solvent) becomes an electrolytic solution containing the compound (lm) as an electrolyte. The electrolytic solution is excellent in electrical conductivity.

 [0076] The present invention provides an electrolytic solution comprising the electrolyte of the present invention and a liquid solvent.

 The liquid solvent is not particularly limited as long as it has a boiling point of 25 ° C or higher, preferably 50 ° C or higher. The liquid solvent is preferably a non-aqueous solvent from the viewpoint of compatibility with the electrolyte of the present invention. The non-aqueous solvent is a solvent excluding water and a solvent containing water, and is not particularly limited as long as it is a solvent that does not substantially contain water. The non-aqueous solvent is preferably a polar aprotic solvent from the viewpoint of compatibility with the electrolyte of the present invention.

[0077] polar aprotic solvents, there is self-proton dissociation constant of 10 ^_2 molZdm ³ or less and a specific dielectric constant of 1 or more, is not preferable in particular if also a made solvates force is 10 or more limited. In addition, the liquid solvent may be used alone or in combination of two or more.

 [0078] The liquid solvent is preferably ethers, esters, nitriles, nitrohydrocarbons, amides, sulfoxides, carbonates, and at least one kind of solvent that is selected from the group power of sulfones. Among them, from the viewpoint of compatibility with the electrolyte of the present invention, the ability of at least one solvent selected from the group power of esters and carbonates is more preferred.

 [0079] Specific examples of ethers include acyclic ethers such as jetyl ether, diethylene glycol dimethyl ether, 1,2-dimethoxyethane; tetrahydrofuran, 2-methyltetrahydrofuran, dimethyltetrahydrofuran, dioxane, dioxolane And cyclic ethers such as 4-methyldioxolane.

Specific examples of esters include acyclic ethers such as methyl formate, ethyl formate, and methyl acetate. Steal; y Cyclic esters such as butyrololataton and γ-valerolataton. Specific examples of carbonates include acyclic carbonates such as dimethyl carbonate, jetyl carbonate, and methylethyl carbonate; and cyclic carbonates such as propylene carbonate, ethylene carbonate, and butylene carbonate.

 Specific examples of nitriles include acetonitrile, propio-tolyl, and benzo-tolyl.

 Specific examples of the nitro hydrocarbons include nitromethane and nitrobenzene. Specific examples of amides include Ν, ジ メ チ ル dimethylformamide, Ν, ジ ェ jetyl amide, and Ν-methylpyrrolidone.

 Specific examples of the sulfoxides include dimethyl sulfoxide.

 Specific examples of the sulfones include dimethyl sulfone and tetramethylene sulfone.

[0080] electrolytic solution of the present invention, the electrolyte of the present invention with respect to the liquid solvent, preferably to include 0. OlmolZdm ³ or more instrument 0. ImolZdm ³ or more preferably contain instrument 0. 4 mol / dm ³ It is particularly preferable to include the above. The electrolyte solution of the present invention preferably contains 5. Omol / dm ³ or less of the electrolyte of the present invention in a liquid solvent, and particularly preferably contains 2.5 mol Zdm ³ or less.

 [0081] The compound (lm) has a low molecular weight as compared with a conventional electrolyte. Therefore, the electrolytic solution of the present invention is an electrolytic solution containing a high molar concentration of the electrolyte even if the absolute amount of the electrolyte of the present invention is small. Moreover, the electrolytic solution of the present invention becomes an electrolytic solution containing a desired molar concentration of the electrolyte by appropriately adjusting the absolute amount of the electrolyte of the present invention.

 [0082] The electrolytic solution of the present invention is useful as an electrolytic solution used in an electrochemical device. The electrochemical device of the present invention is not particularly limited as long as it has at least a pair of electrodes and a structure filled with the electrolytic solution of the present invention between the electrodes.

 Specific examples of the electrochemical device of the present invention include a primary battery, a secondary battery, an electric double layer capacitor, a fuel cell, and a solar cell.

 The compound (lm) has sufficient electrical conductivity.

 [0083] In addition, the compound (lm) contains a conventional electrolyte (one SO—N_—SO— structure-containing anion).

 twenty two

Having compound. The electrode of the electrochemical device of the present invention has a lower acidity than The material is not easily corroded. Therefore, the electrochemical device of the present invention is an electrochemical device that has not only sufficient electrochemical performance but also excellent durability so that the electrode material is not easily corroded.

 [0084] Specific examples of electrochemical devices include secondary batteries such as lithium primary batteries, lithium ion batteries, and polymer secondary batteries, electric double layer capacitors, fuel cells, solar cells, and the like. As a specific example of the battery, a positive electrode formed on both surfaces of an aluminum foil and a foil-shaped negative electrode are laminated or wound via a separator, and the gap between the positive electrode and the negative electrode is the present invention. Examples include a primary battery having a configuration filled with an electrolytic solution.

[0085] Examples of the material for the positive electrode include one or more metal oxides selected from the group force consisting of manganese, conoleto, nickel, niobium, and vanadium.

 A specific example of the lithium secondary battery of the present invention has a configuration in which a positive electrode and a negative electrode face each other via a separator, and a configuration in which a space between the positive electrode and the negative electrode is filled with the electrolytic solution of the present invention. Examples include lithium secondary batteries.

 Examples of the material for the positive electrode include composite oxides of lithium and metal atoms selected from conoretol, nickel, and iron.

 Examples of the material for the negative electrode include lithium, aluminum, graphite, amorphous carbon material, silicon, germanium, and a composite material made of lithium and a material selected from gold.

[0086] As a specific example of the electric double layer capacitor of the present invention, each has two or more positive electrodes and negative electrodes, each of which has a configuration in which the positive electrode and the negative electrode are stacked or wound via a separator, and each of them. An electric double layer capacitor having a structure in which the space between the positive electrode and the negative electrode is filled with the electrolytic solution of the present invention.

 Each of the positive electrode and negative electrode materials is preferably a polarizable material. The polarizable material is particularly preferably glassy carbon, carbon black, carbon fiber, activated carbon microbeads, or activated carbon fiber, which is preferred for carbon materials having a large specific surface area.

 Examples of the material for the separator include organic polymers such as polyethylene, polypropylene, beylene copolymer, butylene, and polyvinylidene fluoride.

[0087] In the electrochemical device of the present invention, only the electrolytic solution of the present invention is provided between the positive electrode and the negative electrode. Or may be filled with a carrier obtained by impregnating the electrolytic solution of the present invention. Examples of the carrier material include organic polymers such as polyvinylidene fluoride, polyacrylonitrile, and polyethylene oxide. Example

 [0088] The present invention will be specifically described below with reference to examples, but the present invention should not be construed as being limited thereto.

[Example 1 (Synthesis example)] Production example of compound (2 ¹ )

 Place the following compound (s) (540 g) in a three-necked flask (with an internal volume of 1 L) equipped with a condenser, and then add N (CH) (50 mL) while maintaining the flask internal temperature at 20 ° C or lower. Yutsu

 3 3

 It was dripped. After completion of dropping, the inside of the flask was stirred for 12 hours while maintaining the internal temperature at 25 ° C. The contents of the flask were distilled to obtain CF (COF) (SO F) (513 g).

 twenty two

オートクレーブ（内容積 500mL)に、 CF (COF) (SO F) (50. 4g)とテトラヒドロフ [0089] [Chemical 31]

In an autoclave (with an internal volume of 500 mL), CF (COF) (SO F) (50.4 g) and tetrahydrofluoro

 twenty two

 Run (200mL) and then hold liquid NH at 0.34m while maintaining the internal temperature at 30 ° C.

 Three

 It was introduced at a flow rate of olZ for 4 hours. Next, the autoclave was sealed and stirred at 25 ° C. for 12 hours, after which excess NH was purged. Remove the autoclave contents by filtration.

 Three

The collected filtrate was concentrated and further dried under vacuum to obtain the following compound (2 ¹ ) (42. 79 g, purity 90%).

 [Chemical 32]

[Example 2 (Example)] Production Example of Compound (I ¹ )

Into the reactor, compound (2 ¹ ) (5.20 g), lithium hydroxide hydrate (1.33 g), and acetate Nitrile (50 mL) was added and reacted at 80 ° C. for 4 hours. Then, after cooling to lower the temperature in the container, the filtrate obtained by filtering the reactor contents was concentrated and further dried to obtain a solid. The solid was recrystallized and purified in dioxane to obtain the following high purity compound (I ¹ ) (4.17 g).

¹⁹ F—NMR (283 MHz, CD CN) of compound (I ¹ ) δ (ppm): — 103.7 (s, CF)

[0092] [Chemical 33]

[0093] [Example 3 (Example)] Production Example of Compound (l ² )

Into the reactor, compound (2 ¹ ) (6.97 g), and [(CH CH CH CH) N] + [OH] _

 3 2 2 2 4

An aqueous solution (103 mL) containing 4 mol ZL was added and reacted at 70 ° C for 3 hours. Subsequently, after cooling the inside of the container to 25 ° C., the filtrate obtained by filtering the reactor contents was concentrated and further dried to obtain the following high purity compound (I ² ) (5.76 g). The melting point of the compound (I ² ) is 77-79. C.

¹⁹ F—NMR (283 MHz, CD CN) of compound (I ² ) δ (ppm): — 104.1 (s, CF)

3 2 δ (ppm) of ¹ H-NMR (300 MHz, CD CN) of compound (l ² ): 3. 88 (t, J = 9 Hz,

 Three

8H), 3.07 (m, 8H), 1.58 (tt, J = 7Hz, 8H), 1.34 (tq, J = 7Hz, 8H), 0. 96 (t, J = 7Hz, 12H) ₀

[0094] [Chemical 34]

0

 II

[(CH ₃ CH ₂ CH ₂ CH ₂ ) ₄ N]> F ₂

 (0 S)

[0095] [Example 4 (Example)] Production example of electrolyte Compound (l ¹ ) (1.63 g) was dissolved in propylene carbonate to obtain a solution (total volume lOmL). Thereafter, while maintaining the solution temperature at 40 ° C., the solution was vacuum-reduced to completely distill off the recrystallization solvent dioxane. Next, until the total volume of the solution became 10 mL, propylene carbonate was added to the solution to obtain an electrolytic solution containing 1. OmolZdm ^{3 of} compound (I ¹ ) with respect to propylene carbonate. The electrical conductivity of the obtained electrolyte was measured at 20 ° C, 40 ° C, and 60 ° C, respectively. The results are shown in Table 1.

以上の結果から、化合物（1)は電解質として有用な材料であり、化合物（1)を非水 溶媒に溶解させて得られた電解液は、電気伝導性と化学的安定性を両立した電解 液であることがわかる。 [0096] [Table 1]

From the above results, the compound (1) is a useful material as an electrolyte, and an electrolyte obtained by dissolving the compound (1) in a non-aqueous solvent is an electrolyte having both electrical conductivity and chemical stability. It can be seen that it is.

 Industrial applicability

 [0097] According to the present invention, a solvent (a solvent for chemical reaction, a solvent for extraction, a solvent for electrolytic bath, etc.), a heat medium, an optical resolution agent, a lubricant, a gas detection agent for a gas sensor, a temperature sensor for a temperature sensor, a gas Absorber, drug (percutaneous absorption enhancer, enzyme coating agent, etc.), immersion liquid for immersion exposure method, electrolyte for electrochemical device (electrolyte for secondary battery, electrolyte for electric double layer capacitor, electrolyte for fuel cell) Etc.), electrochemical device members (secondary battery members, electric double layer capacitor members, fuel cell members, etc.), display element members, optical anisotropic films, conductive films, antistatic films, photoelectric conversion elements, Cyclic fluorosulfonylimides useful for applications such as actuator elements and photosensitive elements are provided.

In addition, the electrolyte solution used in electrochemical devices such as secondary batteries such as primary batteries and lithium ion batteries, electric double layer capacitors, fuel cells and solar cells using the cyclic fluorosulfonylimides of the present invention. A suitable electrolyte is provided. The specifications and claims of Japanese patent application 2005-365117 filed on December 19, 2005 and Japanese Patent Application 2006-0664279 filed March 9, 2006 The entire contents of the scope and abstract are hereby incorporated by reference as disclosure of the specification of the present invention.

Claims

The scope of the claims  A compound represented by the following formula (1): .

However, the symbol in a formula shows the following meaning.  n: l, 2, 3, or 4. [M] ^{n +} : an n-valent cation, and when n is 1, it is an alkali metal ion, an organic ammonium ion, a sulfone ion, a positive xanthomy ion, or a phosphorous ion. Yes, when n is 2, 3, or 4, it is an n-valent metal cation.  X: A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms.  A compound represented by the following formula (11): [Chemical 2]

However, the symbol in a formula shows the following meaning. [M ¹ ]: Alkali metal ion, organic ammonium ion, or phosphonium ion. A method for producing a compound represented by the following formula (1), comprising reacting a compound represented by the following formula (2) with a compound represented by the formula [M] ^{n +} ([OH] "). [Chemical 3]

However, the symbol in a formula shows the following meaning.  n: l, 2, 3, or 4. [M] ^{n +} : an n-valent cation, and when n is 1, it is an alkali metal ion, an organic ammonium ion, a sulfone ion, a positive xanthomy ion, or a phosphorous ion. Yes, when n is 2, 3, or 4, it is an n-valent metal cation.  X: a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. Shiki.  [4] An electrolyte containing a compound represented by the following formula (lm):  [Chemical 4]

However, the symbol in a formula shows the following meaning.  n: l, 2, 3, or 4. [Mm] ^{n +} : n-valent metal cation.  Xm: a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluorinated alkyl group having 1 to 4 carbon atoms, or a fluoroalkoxy group having 1 to 4 carbon atoms. [5] The electrolyte according to claim 4, wherein n is 1, and [Mm] ^{n +} is a monovalent metal cation.  [6] An electrolytic solution comprising the electrolyte according to claim 4 or 5 and a nonaqueous solvent. [7] The electrolyte according to [6], wherein the electrolyte contains 0. OlmolZdm ³ or more with respect to the nonaqueous solvent. Electrolytic solution on the list.  The electrolytic solution according to claim 6 or 7, wherein the non-aqueous solvent is a polar aprotic solvent. An electrochemical device using the electrolytic solution according to claim 6.