JP2011054463A - Electrolyte composition, method of manufacturing the same, and secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an electrolyte composition having a high ion conductivity and no liquid leakage, to provide an electrolyte having a high thermal stability and no liquid leakage and a method of manufacturing the same, to provide a secondary battery having all the above properties and having durability, and furthermore to provide a solid electrolyte having a wide range of selection of a solvent, superior in manufacturing suitability and capable of being manufactured by coating. <P>SOLUTION: The electrolyte composition contains a co-polymer compound of quaternary ammonium molten salt containing an electrolyte salt, inorganic particulates, polyimide, and a co-polymerizing group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrolyte composition, a method for producing the same, and a battery. More specifically, the present invention relates to an electrolyte composition that is flame retardant and excellent in conductivity, and a secondary battery that is excellent in repetition characteristics.

  An electrolyte used in an electrochemical battery such as a non-aqueous secondary battery is a medium that includes ions according to the purpose and has a function of transporting the ions between electrodes (referred to as ion conduction). For example, a lithium ion secondary battery, which is a typical non-aqueous secondary battery, refers to a medium having a function of transporting lithium ions between electrodes. In a secondary battery, a solution-based electrolyte with high ion conductivity is generally used, but the solution-based electrolyte is depleted due to the high volatility of the solvent when incorporated in the battery, There is a problem that leakage due to fluidity reduces the durability of the battery. Further, in order to seal the solution, a metal container must be used, the battery mass becomes heavy, and it is difficult to give the battery shape flexibility.

  A method is known in which inorganic fine particles are mixed with an ionic liquid to thicken or gel the liquid (Patent Documents 1 and 2), but the ionic conductivity is low and the electrolyte is still insufficient. Further, since the viscosity variation due to temperature variation was insufficient, it was difficult to produce by coating.

  On the other hand, a monomer composition containing a quaternary ammonium salt structure composed of a quaternary ammonium cation and a fluorine atom-containing anion and an ionic liquid monomer having a polymerizable functional group is formed into an electrochemically inert polymer reinforcement. A composite polymer electrolyte composition produced by graft polymerization in the presence of a material has been proposed (for example, Patent Documents 3 and 4). In these methods, although the electrolyte is non-volatile, it exhibits high conductivity, can be processed into a sheet by coating and film formation, is light and has improved freedom of shape and imparted nonflammability. However, the strength of the battery is insufficient, the battery is easily short-circuited during use, and the charge / discharge resistance is low. In Patent Document 3, polyimide having high thermal stability is also mentioned as a polymer reinforcing material, but there is no description regarding the specific structure of polyimide and the characteristics as an electrolyte composition.

JP 2003-257476 A JP 2006-310071 A International Publication No. 2004/88671 Pamphlet JP 2006-52362 A

  An object of the present invention is to obtain an electrolyte composition that exhibits high ionic conductivity and does not leak, and provides a solid electrolyte that has high thermal stability and does not leak, and a method for producing the same, and includes the durability. It is to provide an excellent secondary battery.

  Another object of the present invention is to provide a solid electrolyte and a secondary battery that have a wide selection range of solvents and are excellent in manufacturing suitability and can be manufactured by coating.

  The above object of the present invention is achieved by the following means.

  1. An electrolyte composition comprising an electrolyte salt, inorganic fine particles, polyimide, and a polymerized compound of a quaternary ammonium molten salt containing a polymerizable group.

  2. 2. The electrolyte composition as described in 1 above, wherein the molten quaternary ammonium salt containing the polymerizable group is at least one of the following general formula (1) or (2).

[Wherein, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, R ² represents a substituent represented by the following structure (A),

Here, L ¹ represents —COO—, —CONR ³ —, or a simple bond, R ³ represents a hydrogen atom, an alkyl group, or an aryl group, and L ² represents an alkylene group, an arylene group, or an aralkylene group. , L ³ represents a divalent linking group or a simple bond.

  N1 is 1 or 2, n2 is 2 or 3, and the sum of n1 and n2 is 4, and X represents a fluorine atom-containing anion. ]

[Wherein R ¹¹ and R ¹³ represent an alkyl group, an aryl group, a heterocyclic group, or a substituent represented by the structure (A), and at least one of R ¹¹ and R ¹³ is the structure (A). , R ¹² , R ¹⁴ and R ¹⁵ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkyloxycarbonyl group, a halogen atom, a halogenated alkyl group, a cyano group or a nitro group. , X represents a fluorine atom-containing anion. ]
3. The polyimide is at least one acid anhydride represented by the following general formula (3) or general formula (4), and at least one amine compound represented by the general formula (5) or general formula (6); 3. The electrolyte composition as described in 1 or 2 above, which is obtained by polycondensation of

[In the formula, Q ¹ and Q ² represent an atomic group necessary for forming an aromatic ring or a simple bond, but Q ¹ and Q ² do not become a simple bond at the same time, and R ²³ represents an alkyl group. Group, alkenyl group, alkynyl group, alkoxy group, aryl group, heterocyclic group, halogen atom, fluorinated hydrocarbon group, m1 represents an integer of 0-4. ]

[Wherein Q ³ represents an atomic group necessary for forming an aromatic ring, may have a condensed ring, or may have a substituent. Z represents a divalent or trivalent group, and m2 represents an integer of 2 or 3. ]

[Wherein L ¹¹ represents a divalent group, R ²⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, a halogen atom, a fluorinated hydrocarbon group, Substitution is possible at any substitutable position of L ^{11 as} a group, and m3 represents an integer of 0 to 5. ]

[Wherein L ¹² represents a trivalent group, R ²⁵ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a heterocyclic group, a halogen atom, a fluorinated hydrocarbon group, and m4 represents 0 to 6 Represents an integer. ]
4). The polyimide is obtained by polycondensation with the acid anhydride represented by the general formula (4), the general formula (5), or the amine compound represented by the general formula (6). 4. The electrolyte composition as described in 3 above.

  5. 5. The electrolyte composition according to any one of 1 to 4 above, which contains a non-polymerizable ionic liquid.

  6). 6. A method for producing the electrolyte composition according to any one of 1 to 5, wherein polymerization of a quaternary ammonium molten salt containing a polymerizable group is performed in the presence of polyimide. Manufacturing method.

  7. A secondary battery comprising the electrolyte composition according to any one of 1 to 5 above.

  According to the present invention, it was possible to obtain a solid electrolyte having high ion conductivity and thermal stability and having no liquid leakage, and providing a secondary battery excellent in durability. In addition, the solvent has a wide selection range and is excellent in manufacturing suitability, and can be manufactured by coating.

  The present invention is characterized by polymerizing a polymerizable ionic liquid in the presence of an electrolyte composition containing an electrolyte salt, inorganic fine particles, polyimide, and a polymer of a polymerizable ionic liquid, and polyimide. It is a secondary battery characterized by including the manufacturing method of an electrolyte composition, and this electrolyte composition.

[1] Electrolyte composition Hereinafter, each component of the electrolyte composition of the present invention will be described in detail.

(Quaternary ammonium molten salt containing a polymerizable group)
The quaternary ammonium molten salt used in the present invention is a salt structure composed of an aliphatic, alicyclic, aromatic, or heterocyclic quaternary ammonium cation and a counter anion.

  As used herein, “quaternary ammonium cation” means an onium cation of nitrogen, for example, pyrrolidinium cation, piperidinium cation, piperazinium cation, alkylammonium cation, pyrrolium cation, pyridinium cation, Heterocyclic onium ions such as imidazolium cation, pyrazolium cation, benzimidazolium cation, indolium cation, carbazolium cation, and quinolinium cation are included. Examples of counter anions of these cations include fluorine atom-containing anions, such as perfluoroborate ions, perfluorophosphate ions, bis (perfluoroalkylsulfonyl) imide anions, bis (fluorosulfonyl) imide anions, perfluoroalkylate ions. And perfluorosulfonate. These may be further substituted with a perfluoroalkyl group having 1 to 10 carbon atoms.

  Examples of the polymerizable group contained in the quaternary ammonium molten salt include a vinyl group, an acrylic ester group, a methacrylic ester group, an acrylamide group, a methacrylamide group, and an epoxy group.

  Of these quaternary ammonium salts containing a polymerizable group, a compound represented by the general formula (1) or (2) is preferable.

In the compound represented by the general formula (1), R ¹ represents an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group), cycloalkyl group (for example, cyclopentyl group, Cyclohexyl group), aryl group (for example, phenyl group, naphthyl group), heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group) Group, benzimidazolyl group, benzooxazolyl group, quinazolyl group, phthalazyl group, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group and the like.

R ¹ may further have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and an alkoxy group (for example, a methoxy group, an ethoxy group, a propyloxy group, Pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group), aryloxy group (for example, phenoxy group, naphthyloxy group), alkylthio group (for example, , Methylthio group, ethylthio group, propylthio group), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group), arylthio group (for example, phenylthio group, naphthylthio group), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbon group) Rubonyl, butyloxycarbonyl), aryloxycarbonyl (eg, phenyloxycarbonyl, naphthyloxycarbonyl, etc.), sulfamoyl (eg, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl) Group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, Pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group), acyloxy (For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, phenylcarbonyloxy group), acylamino group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonyl) Amino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, trifluoromethylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group), sulfonylamino group (for example, methyl) Sulfonylamino group, ethylsulfonylamino group, hexylsulfonylamino group, phenylsulfonylamino group), carbamoyl group (for example, amino Bonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), sulfinyl group (for example, methylsulfinyl group) Group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, Nylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl) Group, 2-pyridylsulfonyl group), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, anilino group, naphthylamino group, 2-pyridylamino group), cyano group, nitro group Group, halogen atom (fluorine, chlorine, bromine, iodine, etc.), alkyl halide (eg, methyl fluoride group, trifluoromethyl group, chloromethyl group, trichloromethyl group, perfluoropropyl group) and the like.

  Preferred examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, an acylamino group, a carbamoyl group, a sulfamoyl group, an amino group, a cyano group, a halogenated alkyl group, and a halogen atom.

A plurality of R ¹ may be bonded to each other to form a ring.

In the compound represented by the general formula (1), R ² represents a substituent represented by the structure (A).

L ¹ represents —CO—O—, —CO—NR ³ —, or a simple bond, and R ³ represents a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom.

L ² represents an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, etc.), an arylene group (for example, a phenylene group), an aralkylene group (a group in which an alkylene group and an arylene group are bonded), and a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, a halogenated alkyl, and a cyano group.

L ³ represents a divalent linking group or a simple bond. Examples of the divalent linking group include an alkylene group, an arylene group, an oxygen atom, a sulfur atom, —SO ² —, —NR ³ —, and a divalent group obtained by bonding a plurality of these divalent linking groups. The substituent represented by the structure (A) is bonded to the nitrogen atom of the general formula (1) at the portion *. n1 is 1 or 2, n2 is 2 or 3, and the sum of n1 and n2 is 4.

Specifically, the fluorine atom-containing anion represented by X is represented by general formulas (A-1) to (A-5).
Formula ^{(A-1) R 31 -L} 21 -N - -L 22 -R 32
Formula (A-2) B ^- F _n11 (R ³³ ) _n12
Formula (A-3) P ^- F _n13 (R ³⁴ ) _n14
Formula (A-4) R ³⁵ COO ⁻
Formula (A-5) R ³⁶ SO ₂ O ⁻
In General Formula (A-1), R ³¹ and R ³² represent a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. R ³¹ and R ³² may be the same or different. R ³¹ and R ³² may be bonded to each other to form a 5-membered ring or a 6-membered ring. L ²¹ and L ²² represent —SO ₂ — and —C (═O) —, and L ²¹ and L ²² may be the same or different.

R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represents a C 1-4 perfluoroalkyl group.

In general formula (A-2), n11 represents an integer of 1 to 4, and the sum of n11 and n12 is 4. When n12 is 2 or more, the plurality of R ³³ may be the same or different, and the plurality of R ³³ may be bonded to each other to form a ring.

In general formula (A-3), n13 represents an integer of 1 to 4, and the sum of n13 and n14 is 6. When n14 is 2 or more, the plurality of R ³⁴ may be the same or different, and the plurality of R ³⁴ may be bonded to each other to form a ring.

  The fluorine atom-containing anion represented by X is preferably general formulas (A-1) to (A-3), more preferably general formulas (A-1) and (A-2).

  Next, the polymerizable compound represented by the general formula (2) will be described.

In General Formula (2), R ¹¹ and R ¹³ represent an alkyl group, an aryl group, a heterocyclic group, or a substituent represented by the structure (A), and at least one of R ¹¹ and R ¹³ has a structure (A ). It is bonded to one of the nitrogen atoms of the general formula (2) at the site represented by * in the structure (A).

R ¹¹ and R ¹³ may further have a substituent, and examples of the substituent include the same groups as the groups that can be substituted on R ¹ .

R ¹¹ and R ¹³ are preferably an alkyl group and a substituent represented by the structure (A).

R ¹² , R ¹⁴ and R ¹⁵ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkyloxycarbonyl group, a halogen atom, a halogenated alkyl group, a cyano group or a nitro group. R ¹² is preferably a hydrogen atom or an alkyl group. R ¹⁴ and R ¹⁵ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

  X represents a fluorine atom-containing anion, and specifically has the same meaning as X in formula (1).

  Specific examples of the compounds represented by the general formulas (1) and (2) are shown below, but the present invention is not limited thereto.

  The blending amount of the polymerizable compound represented by the general formulas (1) and (2) in the electrolyte composition is preferably 10 to 90% by mass, and particularly preferably 30 to 80% by mass.

(Polyimide)
The polyimide used in the present invention includes a compound obtained by polymerizing at least one of tetracarboxylic dianhydride and hexacarboxylic dianhydride with diamine and / or triamine, or a polymerizable group such as a vinyl group. After synthesizing an imide compound using the dicarboxylic acid anhydride and diamine and / or triamine contained as raw materials, a polyimide that is common to those skilled in the art such as a polymerized compound can be used.

  The polyimide is preferably made from at least one acid anhydride represented by the general formula (3) or (4) and at least one amine compound represented by the general formula (5) or (6) as a raw material. It is a polycondensation product.

In General formula (3), Q < ¹ >, Q < ² > represents the atomic group required in order to form an aromatic ring with the carbon-carbon bond of two acid anhydrides, or a mere bond.

The aromatic ring formed from the carbon-carbon bond of Q ¹ , Q ² and an acid anhydride may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a condensed ring. Aromatic hydrocarbon rings (for example, benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, etc.), aromatic heterocyclic rings (for example, furan ring, thiophene ring, thianthrene ring, phenoxathiin ring, pyridine ring, pyrrole ring) , pyridazine ring, pyrazine ring, naphthyridine ring, a quinoline ring, an acridine ring, phenazine ring, a quinazoline ring, a phthalazine ring, anti lysine ring, benzimidazole ring, benzoxazole ring, but benzothiazole ring, etc.) and the like, Q ¹ and Q ² is not be a single bond simultaneously. The aromatic ring formed from the carbon-carbon bond of Q ¹ and Q ² and an acid anhydride is preferably a benzene ring, a naphthalene ring, an anthracene ring, or a pyridine ring, more preferably a benzene ring or a naphthalene ring. It is.

In the general formula (3), R ²³ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a heterocyclic group, a halogen atom, or a fluorinated hydrocarbon group. R ²³ is preferably an alkyl group or an alkenyl group, and more preferably an alkenyl group polymerizable with an ionic liquid containing a polymerizable group represented by the general formulas (1) and (2).

  m1 represents an integer of 0 to 4, preferably 0 to 2.

In the general formula (4), Q ³ represents an atomic group necessary for forming an aromatic ring together with the carbon-carbon double bond of the acid anhydride, and Q ³ together with the carbon-carbon double bond of the acid anhydride. The aromatic ring to be formed may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a condensed ring, for example, an aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, an anthracene ring) , Tetracene ring, pentacene ring, etc.), aromatic heterocycle (eg furan ring, thiophene ring, thianthrene ring, phenoxathiin ring, pyridine ring, pyrrole ring, pyridazine ring, pyrazine ring, naphthyridine ring, quinoline ring, acridine ring Phenazine ring, quinazoline ring, phthalazine ring, anti-lysine ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, etc.). Q ³ may have a substituent, and examples of the substituent include the same groups as the groups that can be substituted on R ¹ .

Z represents a divalent or trivalent group. Examples of the divalent group include the same groups as the divalent groups mentioned in the above L ³ and simple bonds.

  Specific examples of the trivalent group include the following structures.

L ¹³ is the same group as the divalent group represented by L ³ above, or a divalent group in which these groups are linked to each other. A plurality of L ¹³ may be the same or different. good. L ¹³ may further have a substituent, and examples of the substituent include the same groups as the groups capable of substituting for R ¹ described above. R ″ represents a hydrogen atom or a monovalent substituent, and examples of the substituent include the same groups as those that can be substituted for R ¹ .

A ² represents a nitrogen atom or a phosphorus atom.

The plurality of L ¹³ are preferably the same, and R ″ is preferably a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an alkyloxycarbonyl group.

  Of (L3-1) to (L3-3), (L3-1) and (L3-3) are preferred.

  m2 represents an integer of 2 or 3.

In the general formula (5), L ¹¹ represents a divalent group, and examples of the divalent group include the same groups as the divalent groups listed for L ³ . Preferably, an alkylene group, an arylene group, or a divalent group formed by combining a plurality of divalent groups is a group in which a portion bonded to a nitrogen atom is an alkylene group or an arylene group.

R ²⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, a halogen atom or a fluorinated hydrocarbon group, and can be substituted at any substitutable position of L ¹¹ . R ²⁴ is preferably an alkyl group, an alkenyl group, or an aryl group, and more preferably an alkenyl group that can be polymerized with an ionic liquid containing a polymerizable group represented by the general formulas (1) and (2). m3 represents an integer of 0 to 5, preferably 0 to 2.

In the general formula (6), L ¹² represents a trivalent group, and specific examples thereof include the same groups as the trivalent groups listed for Z.

R ²⁵ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a heterocyclic group, a halogen atom, or a fluorinated hydrocarbon group, and is exemplified as the above-described trivalent groups (L3-1) to ( It can bind to any substitutable site of L3-5). R ²⁵ is preferably an alkyl group or an alkenyl group. m4 represents an integer of 0 to 6, preferably 0 to 3.

  Polyimide obtained by polymerizing at least one acid anhydride represented by general formulas (3) and (4) and at least one amine compound represented by general formulas (5) and (6) Of these, preferred are polyimides obtained by polymerizing the general formulas (3), (5) and (6), and polyimides obtained by polymerizing the general formulas (4), (5) and (6). . When only general formulas (3) and (5), and only general formulas (4) and (5) are polymerized, a linear polyimide is obtained, and polymerized by adding general formula (6) having a triamine structure to these. Thus, since a branched polyamide having a network structure is formed, the ability to maintain the shape of the electrolyte can be further enhanced, which is preferable. In addition to improving heat resistance, solubility in a solvent is improved, and manufacturing suitability such as coating properties is excellent.

  The polymerization ratios of general formulas (3), (5), (6), and general formulas (4), (5), (6) can be any ratio as long as the acid anhydride structure and the amine are 1: 1. For example, when 10 mol of the triamine of the general formula (6) is added to 100 mol of the acid anhydride structure of the general formula (3) or (4), the diamine of the general formula (5) Is calculated to be 85 moles reduced by 15 moles.

  Although the specific compound example of General formula (3)-(6) preferably used for this invention below and the structure of the polyimide obtained from these are shown, this invention is not limited to these.

  Moreover, the example of the polyimide obtained from this is shown below.

  The constituent components of the polyimide can be easily synthesized by those skilled in the art using known methods.

  Moreover, the polyimide which consists of General formula (3) or (4) and (5) and (6) is Unexamined-Japanese-Patent No. 2006-131706, Unexamined-Japanese-Patent No. 2006-265496, Unexamined-Japanese-Patent No. 2008-50694, Chemistry Letters, Vol. 37, No. 1, pages 86-87 (2008), etc., and can be easily synthesized by known production methods.

(Electrolyte salt)
As the electrolyte salt of the present invention, a salt of a metal ion belonging to Group Ia or IIa of the periodic table is used. As the metal ions belonging to Group Ia or Group IIa of the periodic table, ions of lithium, sodium and potassium are preferable. As anions of metal ion salts, halide ions (I ⁻ , Cl ⁻ , Br ⁻ etc.), SCN ⁻ , BF ₄ ⁻ , BF ₃ (CF ₃ ) ⁻ , BF ₃ (C ₂ F ₅ ) ⁻ , PF _{^{6 -, ClO 4 -, SbF}} 6 -, (FSO 2) 2 N -, (CF 3 SO 2) 2 N -, (C 2 F 5 SO 2) 2 N -, Ph 4 B -, (C 2 H ^{_{4 O 2) 2 B -,}} (CF 3 SO 2) 3 C -, CF 3 COO -, CF 3 SO 2 O -, C 6 F 5 SO 2 O - , and the like.

Examples of anions include SCN ⁻ , BF ₄ ⁻ , BF ₃ (CF ₃ ) ⁻ , BF ₃ (C ₂ F ₅ ) ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , SbF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ^−. , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , and CF ₃ SO ₂ O ⁻ are preferable.

Typical electrolyte salts include LiOSO ₂ CF ₃ , LiPF ₆ , LiClO ₄ , LiI, LiBF ₄ , LiBF ₃ (CF ₃ ), LiBF ₃ (C ₂ F ₅ ), LiCF ₃ COO, LiSCN, LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ F) ₂ , NaI, NaOSO ₂ CF ₃ , NaClO ₄ , NaBF ₄ , NaAsF ₆ , KOSO ₂ CF ₃ , KSCN, KPF ₆ , KClO ₄ , KAsF _{6 and the} like are preferable. Is the Li salt. These may be used alone or in combination. The amount of the electrolyte salt in the electrolyte composition is preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass.

(Inorganic fine particles)
Any inorganic fine particles can be used as the inorganic fine particles of the present invention as long as they are inert to the electrolyte. Among these, inorganic oxide fine particles are preferable, and as the metal constituting the inorganic oxide particles, Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi and rare earth metals Selected from the group of Specifically, for example, silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide, niobium oxide, tantalum oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, indium oxide, tin oxide, oxide Inorganic oxide fine particles composed of lead and the like can be mentioned. In addition, rare earth oxides can also be used as the oxide fine particles used in the present invention, specifically, scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, Fine particles containing gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and the like can be given. Among these, neutral or acidic metal inorganic oxide fine particles are effective in improving ion conductivity. Examples thereof include iron oxide, zirconium oxide, clay, tin oxide, tungsten oxide, titanium oxide, aluminum phosphate, silicon oxide, zinc oxide, and aluminum oxide. The hydroxyl group on the surface of the inorganic oxide interacts with the ion conductive compound or the salt of the secondary battery to form an ion path that transports ions at a high speed.

  The shape of the fine particle powder may be spherical, but even mesoporous, flat or needle-like particles can be preferably used.

  The mesoporous inorganic particles are porous inorganic particles having a plurality of pores having a pore diameter of 2 to 50 nm (hereinafter abbreviated as mesopores), which is a region to which Kelvin's capillary condensation theory can be applied.

  The pore diameter and pore distribution can be measured by a mercury intrusion method, a gas adsorption method, or the like. The pore diameter of the present invention refers to the median diameter of the pore distribution calculated by analyzing the hysteresis pattern of the adsorption / desorption isotherm obtained by the gas adsorption method using a pore distribution measuring device.

The composition of the mesoporous inorganic particles is not particularly limited as long as it has mesopores, but mesoporous inorganic particles having mesopores regularly arranged with a metal oxide as a skeleton are preferable. As the metal oxide, SiO ₂ , Al ₂ O ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ , TiO ₂ , ZrO ₂ , SnO ₂ or a composite oxide thereof can be preferably used.

  As a method for producing mesoporous inorganic particles, a conventionally known method such as hydrothermal synthesis using a surfactant or an organic compound as a template can be used. For example, as described in JP-A-2005-53737 A method is mentioned. The mesoporous inorganic particles can hold a solvent inside the mesopores or on the surface of the porous body.

As the mesoporous inorganic particles of the present invention, those having a specific surface area of 300 to 1000 m ² / g are particularly preferred from the viewpoint of safety and charge / discharge durability.

  The specific surface area of the mesoporous inorganic particles of the present invention is a value calculated as a BET specific surface area using a BET isotherm adsorption equation from an adsorption isotherm obtained by adsorbing nitrogen gas or the like to a particle powder using a specific surface area meter. .

  The content of mesoporous inorganic particles in the battery composition is preferably 5 to 40% with respect to the fluorine-containing compound from the viewpoint of safety and voltage characteristics.

  Further, the average particle diameter of the mesoporous inorganic particles is preferably 1 to 50 μm, more preferably 5 to 20 μm, from the viewpoint of safety and voltage characteristics.

  The average particle diameter is a volume average value of the diameter (sphere converted particle diameter) when each particle is converted into a sphere having the same volume, and this value can be evaluated from an electron micrograph. That is, by taking a transmission electron micrograph of the battery composition or particle powder, measuring 200 or more particles in a certain visual field range, obtaining a spherical equivalent particle diameter of each particle, and obtaining an average value thereof. Value.

  Furthermore, the mesoporous inorganic particles of the present invention are preferably subjected to surface hydrophobization treatment from the viewpoint of uniform mixing with the fluorine-containing compound.

  Further, the inorganic fine particles of the present invention may be a mixture of two or more types of inorganic oxide fine particles uniformly, or may be one in which two or more types of inorganic oxides are separated inside like a core-shell type. Examples of the inorganic oxide include IIA to VA groups such as magnesium, silicon, zirconium, and titanium, and two or more of these inorganic oxides are combined.

  For example, composite fine particles of an inorganic oxide having a high ion conductivity improving effect and an inorganic oxide having a good compatibility with the dispersant can have both an ion conductivity improving effect and a dispersibility. These particles can be prepared using a flame method or a plasma method using a plurality of alkoxides or chlorides. Moreover, it can also granulate in a liquid using catalysts, such as ammonia. Furthermore, the surface of these inorganic compounds can be surface-treated by using a silane coupling agent or a dispersant. Depending on the degree of surface treatment, the surface can be classified into hydrophilic and hydrophobic, but can be used in either case.

  The composite oxide fine particles of the present invention preferably contain silica, and the silica content is preferably 10 to 90%, more preferably 15 to 85%.

  The inorganic fine particles according to the present invention preferably have a hydrophobic surface.

  As the hydrophobizing agent, hexamethyldisilazane, trimethylmethoxysilane, trimethylethoxysilane, trimethylsilyl chloride and the like can be preferably used.

  As the surface treatment method, there are a dry method in which the powder is directly sprayed to heat and fixed, and a wet method in which particles are dispersed in a solution and a surface treatment agent is added to carry out the surface treatment. A wet method in which is dispersed is desirable. For example, the method is as described in Japanese Patent Publication No. 2007-264581, and wet-treated particles have high dispersibility and can be preferably used.

  The particle size of the inorganic fine particles according to the present invention is desirably 100 nm or less, and more desirably 20 nm or less. In the case of fine particles having a particle diameter of 100 nm or more, the ionic liquid may not be gelled with sufficient strength.

  The content of the inorganic fine particles according to the present invention is not particularly limited, but is preferably 5 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the ionic liquid. .

  In the present invention, the solvent can be used up to 50% by mass in combination with the above electrolyte constituent elements. However, from the viewpoint of storage stability, it is more preferable not to use a solvent.

(Non-polymerizable ionic liquid)
In addition to the polymerizable compounds represented by the general formulas (1) and (2), the electrolyte composition of the present invention includes a low melting point compound in which a cation having no polymerizable group is a quaternary ammonium cation or an imidazolium cation. (So-called room temperature molten salt / ionic liquid) may be added. These compounds can often be used as an electrolyte with almost no solvent, and may be used alone as an electrolyte, but they are poorly compatible with polyimide and cause phase separation due to phase separation from the ionic liquid. Sometimes. In the present invention, micro phase separation is facilitated by the combined use with a polymer of a quaternary ammonium molten salt, and high ionic conductivity can be maintained.

  Specific examples of the non-polymerizable ionic liquid are shown below, but the present invention is not limited thereto.

  The blending amount of the ionic liquid in the electrolyte composition is preferably 10 to 90% by mass, particularly 30 to 80% by mass, together with the polymerizable compounds represented by the general formulas (1) and (2). It is preferable to do.

(solvent)
In the present invention, the solvent can be used up to 50% by mass in combination with the above electrolyte constituent elements. However, from the viewpoint of storage stability, it is more preferable not to use a solvent.

  The solvent used in the electrolyte of the present invention should be a compound that has low viscosity and improved ion mobility, or has a high dielectric constant and improved effective carrier concentration, and can exhibit excellent ion conductivity. desirable. Examples of such a solvent include carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether compounds such as dioxane and diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, and polyethylene. Chain ethers such as glycol dialkyl ether and polypropylene glycol dialkyl ether, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile, esters such as carboxylic acid ester, phosphoric acid ester and phosphonic acid ester And aprotic polar substances such as dimethyl sulfoxide and sulfolane. Among these, carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, nitrile compounds such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, and benzonitrile, and esters are particularly preferred. preferable. These may be used alone or in combination of two or more.

  The solvent preferably has a boiling point of 200 ° C. or higher, more preferably 250 ° C. or higher, more preferably 270 ° C. or higher, from the viewpoint of improving durability due to volatility.

(Other additives)
In the present invention, the electrolyte can be used after adding a polymer, an oil gelling agent or the like. In the case of adding a polymer, the compounds described in “Polymer Electrolyte Reviews-1 and 2” (J.R. MacCallum and CA Vincent co-edit, ELSEVIER APPLIED SCIENCE) can be used. Acrylonitrile and polyvinylidene fluoride can be preferably used. When adding an oil gelling agent, it is recommended that ChemSoc. Japan, Ind. Chem. Sec. 46, 779 (1943), J. Am. Am. Chem. Soc. 111, 5542 (1989), J. Am. Chem. Soc. , Chem. Commun. 1993, 390, Angew. Chem. Int. Ed. Engl. , 35, 1949 (1996), Chem. Lett. 1996, 885, J. et al. Chm. Soc. , Chem. Commun. , 1997, 545 can be used, but preferred compounds are those having an amide structure in the molecular structure.

(Method for polymerizing molten salt monomer)
The monomer of the quaternary ammonium molten salt containing a polymerizable group is homopolymerized (in the case of using a plurality of monomers, a plurality of monomers can be polymerized separately or mixed). It is possible to copolymerize with a monomer that can be copolymerized with. Examples of the copolymerizable monomer include (meth) acrylic acid, (meth) acrylic acid ester (meth) acrylonitrile, (meth) acrylamide, vinyl compounds such as styrene derivatives, and allyl compounds. Furthermore, compounds containing a plurality of polymerizable functional groups such as vinyl groups, allyl groups, and acrylic acid derivatives can also be preferably used. The copolymerizable monomer can be added in an amount of 0.5 to 20 mol% of the quaternary ammonium salt monomer.

  As a method for polymerizing the molten salt monomer, after polymerizing only by the molten salt monomer (or in combination with a monomer copolymerizable therewith) by heat or actinic ray irradiation, an electrolyte salt, inorganic fine particles, A solid electrolyte may be prepared by mixing with polyimide (and non-polymerizable ionic liquid), or all of molten salt monomer, electrolyte salt, inorganic fine particles, polyimide, (and non-polymerizable ionic liquid) are mixed. Then, it may be polymerized to produce a solid electrolyte.

  Preferably, the molten salt monomer, electrolyte salt, inorganic fine particles, and polyimide are all mixed and polymerized to produce a solid electrolyte. In this method, compared to the case where a molten salt polymer is formed and then mixed with the polyimide, the polyimide chain and the molten salt polymer are intertwined in a complicated manner, and further, there are polymerizable groups such as vinyl groups in the polyimide. It becomes possible to introduce a quaternary ammonium salt into the polyimide as a side chain, and micro phase separation becomes more possible.

  A quaternary ammonium molten salt containing a polymerizable group can be polymerized and cured by heat or / and actinic ray irradiation to form a lithium ion conductive cured film.

  When polymerizing, all components may be polymerized without using a solvent, or may be polymerized by dissolving in a dissolving solvent. Usable solvents include N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), various diethylene glycol dialkyl ethers, and the like. It is done. The usage-amount of a solvent is 0.1-30 mass parts with respect to 1 mass part of electrolyte composition components, Preferably it is 0.3-10 mass parts. After polymerization, the solvent is removed by drying under heat or reduced pressure.

  When polymerizing and curing by heat, 0.1 to 5 parts by mass, particularly 0.3 to 1 part by mass of the thermal polymerization initiator is contained with respect to 100 parts by mass of the polymerizable component of the electrolyte composition. preferable.

  The thermal polymerization initiator is not particularly limited. For example, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, ethyl methyl ketone peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl Examples include peroxydicarbonates such as peroxydicarbonate.

Polymerization with actinic rays is usually carried out with light, ultraviolet rays, electron beams, X-rays, etc. Among them, ultraviolet rays are preferred, and when irradiating with ultraviolet rays, high pressure mercury lamps, ultrahigh pressure mercury lamps, carbon arc lamps, xenon lamps, metal halides are used as light sources. A lamp, a chemical lamp, etc. are used. The irradiation amount is not particularly limited, but is preferably 100 to 1000 mJ / cm ² , more preferably 200 to 700 mJ / cm ² .

  Moreover, it is also preferable to heat after actinic ray irradiation in order to accelerate hardening.

  When polymerizing and curing by irradiation with these actinic rays, the photopolymerization initiator is 0.3 parts by mass or more, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polymerizable component of the electrolyte composition. Let

  The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used, and examples thereof include benzophenone, P, P′-bis (dimethylamino) benzophenone, P, P′-bis (diethylamino). ) Benzophenone, P, P'-bis (dibutylamino) benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoylbenzoic acid, benzoylbenzoic acid methyl Benzyl diphenyl disulfide, benzyl dimethyl ketal, dibenzyl, diacetyl, anthraquinone, naphthoquinone, 3,3'-dimethyl-4-methoxybenzophenone, dichloroacetophenone, 2 Chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone, phenylglyoxylate, α-hydroxyisobutylphenone, dibenzoparone, 1- (4-Isopropylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, tribromophenylsulfone, tribromomethylphenylsulfone Methylbenzoylformate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylmethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and Are 2, 4, 6- [tris (trichloromethyl)]-1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (4'-methoxyphenyl) -1,3,5-triazine, 2, 4- [bis (trichloromethyl)]-6- (4'-methoxynaphthyl) -1,3,5-triazine, 2,4- [bis (trichloromethyl)]-6- (piperonyl) -1,3 5-triazine, 2,4- [bis (trichloromethyl)]-6- (4'-methoxystyryl) -1,3,5-triazine and other triazine derivatives, acridine and 9-phenylacridine and other acridine derivatives, , 2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-chlorophenyl) -4,5,4' , 5'-Tetra Phenyl-1,1'-biimidazole, 2,2'-bis (o-fluorophenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (O-methoxyphenyl) -4,5,4 ', 5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis (p-methoxyphenyl) -4,5,4', 5 ' -Tetraphenyl-1,1'-biimidazole, 2,4,2 ', 4'-bis [bi (p-methoxyphenyl)]-5,5'-diphenyl-1,1'-biimidazole, 2, 2'-bis (2,4-dimethoxyphenyl) -4,5,4 ', 5'-diphenyl-1,1'-biimidazole, 2,2'-bis (p-methylthiophenyl) -4,5 4 ', 5'-diphenyl-1,1'-biimidazole, bis (2,4,5 Triphenyl) -1,1′-biimidazole and the like, and tautomerism covalently bonded at 1,2′-, 1,4′-, 2,4′-disclosed in Japanese Examined Patent Publication No. 45-37377 Hexaarylbiimidazole derivatives, triphenylphosphine, 2-benzoyl-2-dimethylamino-1- [4-morpholinophenyl] -butane, and the like, especially in terms of handling. Particularly preferred are 2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylmethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and the like.

  Moreover, when it superposes | polymerizes and hardens | cures using light and a heat together, it is preferable to use said photoinitiator and said thermal polymerization initiator together.

[2] Secondary Battery Here, the electrolyte secondary battery of the present invention will be described.

<Positive electrode active material>
Examples of the positive electrode active material include an inorganic active material, an organic active material, and a composite thereof. However, the energy density of an inorganic active material or a composite of an inorganic active material and an organic active material is particularly large. It is preferable from the point.

Examples of inorganic active materials include metal oxides such as Li _0.3 MnO ₂ , Li ₄ Mn ₅ O ₁₂ , V ₂ O ₅ , LiCoO ₂ , LiMn ₂ O ₄ , LiNiO ₂ , LiFePO ₄ , TiS ₂ , MoS. ₂ and metal sulfides such as FeS, and complex oxides of these compounds and lithium.

  Examples of the organic active material include conductive polymers such as polyacetylene, polyaniline, polypyrrole, polythiophene, and polyparaphenylene, sulfur-based positive electrode materials such as organic disulfide compounds, carbon disulfides, and active sulfur, and organic radical compounds. It is done.

  Moreover, it is preferable that the surface of the positive electrode active material is coated with an inorganic oxide from the viewpoint of extending the life of the battery. In coating the inorganic oxide, a method of coating the surface of the positive electrode active material is preferable, and examples of the coating method include a method of coating using a surface modifying apparatus such as a hybridizer.

Examples of the inorganic oxide include IIA to VA groups such as magnesium oxide, silicon oxide, alumina, zirconia, and titanium oxide, transition metals, IIIB and IVB oxides, barium titanate, calcium titanate, lead titanate, Examples include γ-LiAlO ₂ and LiTiO ₃ , and silicon oxide is particularly preferable.

  In the present invention, the inorganic oxide is preferably fine particles, and the particle size is preferably 1 μm or less from the viewpoint of improving the mechanical strength. A more preferable particle size is 7 to 500 nm, particularly 7 to 40 nm.

  Moreover, it is preferable that content of an inorganic oxide is 2-15 mass parts normally with respect to 100 mass parts of active materials, especially 3-10 mass parts.

<Negative electrode active material>
There is no restriction | limiting in particular about a negative electrode, What adhered the negative electrode active material to the electrical power collector can be utilized. Powders such as graphite and tin alloys can be applied as pastes together with binders such as styrene butadiene rubber and polyvinylidene fluoride on the current collector, dried, and press-molded. . A silicon-based thin film negative electrode in which a 3-5 μm silicon-based thin film is directly formed on a current collector by physical vapor deposition (such as sputtering or vacuum deposition) can also be used. In the case of a lithium metal negative electrode, a material obtained by attaching a 10 to 30 μm lithium foil on a copper foil is suitable. From the viewpoint of increasing the capacity, it is preferable to be composed of a silicon-based thin film negative electrode or a lithium metal negative electrode.

<Electrode mixture>
Examples of the electrode mixture used in the present invention include those to which a lithium salt, an aprotic organic solvent, or the like is added in addition to a conductive agent, a binder, a filler, and the like.

  As the conductive agent, any material may be used as long as it is an electron conductive material that does not cause a chemical change in the constituted secondary battery. Usually, natural graphite (scale-like graphite, scale-like graphite, earth-like graphite, etc.), artificial graphite, carbon black, acetylene black, ketjen black, carbon fiber or metal powder (copper, nickel, aluminum, silver (Japanese Patent Laid-Open No. Sho 63-63)) 148, 554), etc.), metal fibers or polyphenylene derivatives (described in JP-A-59-20971) can be contained as one kind or a mixture thereof. Among these, the combined use of graphite and acetylene black is particularly preferable. As addition amount of the said electrically conductive agent, 1-50 mass% is preferable and 2-30 mass% is more preferable. In the case of carbon or graphite, 2 to 15% by mass is particularly preferable.

  In the present invention, a binder for holding the electrode mixture is used. Examples of such a binder include polysaccharides, thermoplastic resins, and polymers having rubber elasticity. Among them, for example, starch, carboxymethylcellulose, cellulose, diacetylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, Water-soluble polymers such as sodium alginate, polyacrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer , Polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer , Vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate, etc. (Meth) acrylic acid ester-containing (meth) acrylic acid ester copolymer, (meth) acrylic acid ester-acrylonitrile copolymer, polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene-butadiene copolymer Polymer, acrylonitrile-butadiene copolymer, polybutadiene, neoprene rubber, fluororubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, Polycarbonate polyurethane resins, polyester resins, phenolic resins, emulsion (latex) or a suspension such as an epoxy resin is preferable, a latex of polyacrylate, carboxymethyl cellulose, polytetrafluoroethylene, polyvinylidene fluoride is more preferable.

  The said binder can be used individually by 1 type or in mixture of 2 or more types. When the amount of the binder added is small, the holding power and cohesive force of the electrode mixture are weakened. If the amount is too large, the electrode volume increases and the capacity per electrode unit volume or unit mass decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.

  As the filler, any fibrous material that does not cause a chemical change in the secondary battery of the present invention can be used. Usually, olefin polymers such as polypropylene and polyethylene, fibers such as glass and carbon are used. Although the addition amount of a filler is not specifically limited, 0-30 mass% is preferable.

<separator>
The electrolyte composition of the present invention can be used in combination with a separator. The separator used in combination for ensuring safety must have a function of blocking the current by blocking the gap at 80 ° C or higher and blocking the current, and the blocking temperature is 90 ° C or higher and 180 ° C or lower. Is preferred.

  The shape of the holes of the separator is usually circular or elliptical, and the size is 0.05 to 30 μm, preferably 0.1 to 20 μm. Furthermore, it may be a rod-like or irregular-shaped hole as in the case of making by a stretching method or a phase separation method. The ratio of these gaps, that is, the porosity, is 20 to 90%, preferably 35 to 80%.

  The separator may be a single material such as polyethylene or polypropylene, or two or more composite materials. What laminated | stacked 2 or more types of microporous film which changed the hole diameter, the porosity, the obstruction | occlusion temperature of a hole, etc. is preferable.

<Current collector>
As the positive / negative current collector, an electron conductor that does not cause a chemical change in the nonaqueous secondary battery of the present invention is used. As the current collector of the positive electrode, in addition to aluminum, stainless steel, nickel, titanium, etc., the surface of aluminum or stainless steel is preferably treated with carbon, nickel, titanium, or silver. Among them, aluminum and aluminum alloys are preferable. More preferred.

  As the negative electrode current collector, copper, stainless steel, nickel, and titanium are preferable, and copper or a copper alloy is more preferable.

  As the shape of the current collector, a film sheet is usually used, but a porous body, a foam, a molded body of a fiber group, and the like can also be used. Although it does not specifically limit as thickness of the said electrical power collector, 1-500 micrometers is preferable. Moreover, it is also preferable that the current collector surface is roughened by surface treatment.

<Preparation of non-aqueous electrolyte secondary battery>
Here, production of the nonaqueous electrolyte secondary battery of the present invention will be described. The shape of the non-aqueous secondary battery of the present invention can be applied to any shape such as a sheet, a corner, and a cylinder. A positive electrode active material or a mixture of negative electrode active materials is mainly used after being applied (coated), dried and compressed on a current collector.

  Preferable examples of the method for applying the mixture include a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion method, a curtain method, a gravure method, a bar method, a dip method, and a squeeze method. Of these, the blade method, knife method and extrusion method are preferred. Moreover, it is preferable that application | coating is implemented at the speed | rate of 0.1-100 m / min. Under the present circumstances, the surface state of a favorable coating layer can be obtained by selecting the said application | coating method according to the solution physical property and dryness of a mixture. Application may be performed one side at a time or both sides simultaneously.

  Furthermore, the application may be continuous, intermittent or striped. The thickness, length and width of the coating layer are determined by the shape and size of the battery, but the thickness of the coating layer on one side is preferably 1 to 2000 μm in a compressed state after drying.

As a method for drying and dehydrating the electrode sheet coated product, a method of combining hot air, vacuum, infrared rays, far infrared rays, electron beams and low-humidity air alone or in combination can be used. The drying temperature is preferably 80 to 350 ° C, more preferably 100 to 250 ° C. The water content is preferably 2000 ppm or less for the entire battery, and preferably 500 ppm or less for each of the positive electrode mixture, the negative electrode mixture and the electrolyte. As a sheet pressing method, a generally adopted method can be used, but a calendar pressing method is particularly preferable. Although a press pressure is not specifically limited, 0.2-3 t / cm < ² > is preferable. The press speed of the calendar press method is preferably 0.1 to 50 m / min, and the press temperature is preferably room temperature to 200 ° C. The ratio of the negative electrode sheet width to the positive electrode sheet is preferably 0.9 to 1.1, particularly preferably 0.95 to 1.0. The content ratio of the positive electrode active material and the negative electrode active material varies depending on the compound type and the mixture formulation.

  Although the form of the secondary battery of the present invention is not particularly limited, it can be enclosed in various battery cells such as coins, sheets, and cylinders.

  The use of the secondary battery of the present invention is not particularly limited. For example, as an electronic device, a notebook computer, a pen input personal computer, a mobile personal computer, an electronic book player, a mobile phone, a cordless phone, a pager, a handy terminal, a mobile phone Fax, portable copy, portable printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD, mini-disc, electric shaver, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, memory card Etc. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game equipment, road conditioners, watches, strobes, cameras, medical equipment (such as pacemakers, hearing aids, and shoulder grinders). Furthermore, it can be used for various military use and space use. Moreover, it can also combine with a solar cell.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.

(1) Preparation of inorganic fine particles (Preparation of Mg-Si particles)
Using a nano creator manufactured by Hosokawa Micron Co., Ltd., a raw material gas stream containing polydimethylsiloxane and a magnesium compound prepared so that MgO has a mass ratio shown in Table 1 and oxygen gas flow into the reaction space in a high-temperature atmosphere. In this way, white fine powdery inorganic fine particles 1 and 2 were formed. Table 4 shows the particle diameter measurement result of the obtained particles by TEM observation, the presence or absence of an absorption peak derived from silica by IR measurement, the composition analysis result by TEM / EDX of the particle cross section, and the crystal structure analysis result by XRD measurement. As a result, the inorganic fine particles 1 were particles in which magnesium silicate crystals were uniformly dispersed in amorphous silica. The inorganic fine particles 2 were particles in which the presence of amorphous silica could not be confirmed, and magnesium oxide crystals and magnesium silicate crystals were uniformly mixed.

(Creation of mesoporous silica particles)
3.645 g of cetyltrimethylammonium bromide was dissolved in 100 ml of pure water, and 4.41 ml of 1 mol / L hydrochloric acid was put therein. Next, while this solution was stirred at room temperature, a solution of 11 g of tetraethoxysilane (TEOS) dissolved in 44 ml of pure water was added over 5 min.

Then, stirring was performed for 24 hours under irradiation with a high-pressure mercury lamp lamp (100 W) with a light amount of about 2.5 × 10 ¹⁶ / sec / cm ² .

  The resulting precipitate was filtered, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 100 ° C. for 12 hours to obtain 3.2 g of a complex.

The obtained composite was calcined in air at 500 ° C. for 8 hours, then heated to 200 ° C., 0.5 g of hexamethyldisilazane was added, and surface treatment was performed for 2 hours to obtain mesoporous inorganic particles MP having mesopores. -1 was obtained 2g. The mesoporous inorganic particles 1 had a pore diameter of 4 nm, a specific surface area of 800 m ² / g, and an average particle diameter of 7 μm.

  The pore diameter and specific surface area were measured using an automatic specific surface area / pore distribution measuring device BELSORP-miniII manufactured by Nippon Bell Co., Ltd. The average particle size was obtained by measuring 200 or more particles with a scanning electron microscope and determining the average value of the sphere equivalent particle size of each particle.

  Similarly, mesoporous inorganic particles MP-2 to MP-4 having different pore sizes, specific surface areas, and average particle sizes were prepared by changing the amount of cetyltrimethylammonium bromide and the amount of TEOS.

  Table 5 shows the pore diameter, specific surface area, and average particle diameter of each mesoporous inorganic particle.

(2) Synthesis of diamine compound (Synthesis of compound (P2-15))

(I) Synthesis of intermediate (1) In a 1 L eggplant flask, 37.1 g (0.2 mol) of 2-chloro-5-nitrobenzaldehyde, 22.9 g (0.22 mol) of malonic acid, 500 ml of 95% ethanol, 50 ml of pyridine Was heated to reflux for 8 hours. The reaction solution was ice-cooled, and the precipitated crystals were filtered, washed twice with 200 ml of cold ethanol and then with 200 ml of cold diisopropyl ether, and then added with 600 ml of ethanol, and suspended hot at reflux temperature for 2 hours. The suspension was ice-cooled and then filtered, and the solid was dried to obtain 34.1 g of intermediate (1) (yield 75%).

(Ii) Synthesis of intermediate (2) An air-cooled tube and a thermometer were attached to a 250 ml three-head flask, and 30.0 g (0.13 mol) of intermediate (1), 1.65 g (26 mmol) of copper powder and 50 ml of dried quinoline were added. Heated at 195 ° C. for 3 hours. The reaction solution was allowed to cool and then slowly poured into a mixture of 63 ml of concentrated hydrochloric acid and 147 g of ice. The resulting oil was extracted three times with ethyl acetate, the organic layer was washed with water, dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The obtained oil was distilled under reduced pressure to obtain 13.8 g of intermediate (2) (yield 58%, boiling point 108-116 ° C./400 Pa).

(Iii) Synthesis of intermediate (3) In a 300 ml eggplant flask, 12.85 g (0.07 mol) of intermediate (2) was dissolved in 77 ml of N, N-dimethylacetamide, and 5.32 g of potassium carbonate was added thereto at 150 ° C. And stirred for 18 hours. The reaction solution was allowed to cool and then poured little by little into 500 ml of ice water and recrystallized with ethanol to obtain 13.4 g of intermediate (3) (yield 61%).

Synthesis of (P2-15) 38.6 g (0.17 mol) of tin chloride dihydrate was dissolved in 39 ml of concentrated hydrochloric acid, and 12.5 g (0.04 mol) of intermediate (3) was added while stirring the reaction vessel with water. I added it little by little. After reacting at room temperature for 30 minutes, the mixture was heated and stirred at 100 ° C. for 2 hours. The reaction solution was allowed to cool while stirring 375 ml of an ice-cooled 20% aqueous sodium hydroxide solution with a mechanical stirrer, and the mixture was further stirred on ice for 30 minutes. The precipitated solid was filtered and washed with water until the washing liquid became neutral. The solid was dissolved in 30 ml of ethanol and treated with activated carbon. After filtration, 35 ml of water was added and left in the refrigerator overnight. The obtained crystals were filtered to obtain 7.4 g of (P2-15) (yield 73%). The structure was identified by 1N-NMR and MS spectrum.

(4) Synthesis of polyimide (Synthesis of polyimide (P-12))
17.0 g (0.085 mol) of 4,4′-oxydianiline (P2-1) and 32 ml of triethylamine were dissolved in 70 ml of N-methyl-2-pyrrolidinone, and then pyromellitic anhydride (P1-9) 21. 8 g (0.1 mol) and 17.1 g of benzoic acid were added, and the mixture was stirred with heating under a nitrogen atmosphere at 80 ° C. for 4 hours and then at 180 ° C. for 20 hours. The solution was cooled to room temperature, and 3.5 g (0.01 mol) of 1,3,5-tri (4-aminophenyl) benzene (P3-2) and 70 ml of N-methyl-2-pyrrolidinone were further added at 60 ° C. Stir for 4 hours. The obtained solution was added to 1 L of water and reprecipitated, and the solid was further washed with 1 L of water and vacuum dried at 150 ° C. for 10 hours to obtain polyimide (P-12).

(Synthesis of polyimide (P-14))
(P2-15) 6.43 g (25.5 mmol) and triethylamine 9.6 ml were dissolved in 30 ml of N-methyl-2-pyrrolidinone, and then 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride ( 6.5-1 g (30 mmol) of P1-1) and 5.13 g of benzoic acid were added, and the mixture was heated and stirred at 80 ° C. for 4 hours and then at 180 ° C. for 20 hours under a nitrogen atmosphere. The solution was cooled to room temperature, and 7.0 g (0.02 mol) of 1,3,5-tri (4-aminophenyl) benzene (P3-2) and 70 ml of N-methyl-2-pyrrolidinone were further added at 60 ° C. Stir for 4 hours. The obtained solution was added to 300 ml of water and reprecipitated, and the solid was further washed with 300 ml of water and vacuum dried at 150 ° C. for 10 hours to obtain polyimide (P-14).

(4) Preparation of electrolyte composition (i) Electrolyte compositions (1) to (11)
Polymerizable ionic liquid (M-5) 3.2 g, lithium bis (trifluoromethanesulfonyl) imide 0.29 g, inorganic fine particle 1 0.96 g, polyimide (P-11) (Pier MLRC-5019: Jun Wako) 3.2 g, 0.1 g of polymerization initiator lauroyl peroxide was dissolved in 20 ml of N, N-dimethylacetamide, and this solution was applied onto a glass plate having a thickness of 3 mm. Heating and drying and polymerization reaction were performed. The coating film was peeled from the glass plate to obtain a film-like electrolyte composition (1) having a film thickness of 30 μm.

  Similarly, electrolyte compositions (2) to (11) were obtained except that the polymerizable ionic liquid, inorganic fine particles, and polyimide were changed from (1) to Table 6, respectively. When the polymerizable ionic liquid and the non-polymerizable ionic liquid were mixed, the total mass was 3.2 g and the mass ratio was 75:25. The amount of polymerization initiator added was also reduced to 75% in accordance with the ratio of the polymerizable ionic liquid.

(Ii) Preparation of electrolyte compositions (12) and (13) The polyimide of (1) was changed to a modified polyvinylidene fluoride resin (PVdF) prepared by the method of Example 2 of International Patent Publication No. 2004-88671. Further, electrolyte compositions (12) and (13) were obtained in the same manner as (1) except that the polymerizable ionic liquid and the inorganic fine particles were changed as shown in Table 4.

(Iii) Preparation of electrolyte composition (14) Non-polymerizable ionic liquid (IL-51) 3.2 g, RX300 (silica, Nippon Aerosol average particle size of about 7 nm) 0.96 g, lithium bis (trifluoromethanesulfonyl) imide 0.29 g was dissolved in 15 ml of N, N-dimethylacetamide, and this solution was applied on a glass plate having a thickness of 3 mm and dried together with the glass plate at 130 ° C. for 30 minutes. An attempt was made to peel the coating film from the glass plate, but it failed to be obtained as a film.

(Iv) Preparation of electrolyte composition (15) 3.2 g of ionic liquid (IL-51) and 0.29 g of lithium bis (trifluoromethanesulfonyl) imide were dissolved in 15 ml of N, N-dimethylacetamide, and the thickness of this solution was increased. It apply | coated on a 3 mm glass plate, and it heat-dried at 130 degreeC with the glass plate for 30 minutes. An attempt was made to peel the coating film from the glass plate, but it could not be obtained as a film because it was liquid.

RX300 (silica, manufactured by Nippon Aerosol, average particle size of about 7 nm)
PVdF: Polyvinylidene fluoride resin Kynar461 manufactured by Arkema Co., Ltd. modified by the method of Example 2 of International Patent Publication No. 2004-88671 (5) Measurement of ionic conductivity About the electrolyte composition prepared in (4), a dry box The ionic conductivity was measured by a complex impedance measurement method between two platinum electrodes. In addition, since electrolyte composition (13) and (14) was not obtained as a film, the electrolyte composition peeled off from the glass plate was similarly measured by sandwiching it between two platinum electrodes.

(6) Evaluation of flammability The prepared electrolyte composition was placed 10 cm above the tip of the flame of the gas burner, and evaluated whether or not ignition occurred. The evaluation criteria are as follows.

Does not ignite electrolytes: ○
Fire extinguishing within 2-3 seconds after ignition: △
Continue to burn without extinguishing fire: ×
(7) Evaluation of membrane strength Using the tensile tester Tensilon RT1350 manufactured by A & D, the membrane of the prepared electrolyte composition was measured at 25 ° C. and 5 cm / min. Measured with

(8) Production of secondary battery (Production of positive electrode sheet)
It is obtained by adding 43 parts by mass of LiCoO ₂ as a positive electrode active material, ₂ parts by mass of flaky graphite, 2 parts by mass of acetylene black, and 3 parts by mass of polyacrylonitrile as a binder, and kneading 100 parts by mass of acrylonitrile as a medium. The slurry was coated on an aluminum foil with a thickness of 20μm using an extrusion coater, dried and compression-molded with a calendar press, and then welded with an aluminum lead plate at the end, with a thickness of 95μm and a width. A positive electrode sheet of 54 mm × length 49 mm was prepared and dehydrated and dried at 230 ° C. for 30 minutes in dry air having a dew point of −40 ° C. or lower.

(Creation of sheet batteries (D-1) to (D-13))
In the dry box, except that the solvent before the heating and polymerization of the electrolyte composition (1) was changed to N-methyl-pyrrolidone, the prepared solution was similarly dissolved into a dehydrated and dried positive electrode sheet having a width of 54 mm and a length of 49 mm. After soaking, it was heated at 130 ° C. for 30 minutes. A negative electrode sheet (lithium-laminated copper foil (lithium film thickness 30 μm, copper foil film thickness 20 μm)) having a width of 55 mm and a length of 50 mm welded to the lead plate was laminated thereon and heated to 80 ° C. under reduced pressure for 3 hours. Thereafter, an exterior material made of a laminate film of polyethylene (50 μm) -polyethylene terephthalate (50 μm) was used, and the four edges were heat-sealed under vacuum to be sealed, thereby producing a sheet type battery (D-1). Moreover, sheet type batteries (D-2 to D-13) were prepared in the same manner as the sheet battery (D-1) except that the electrolyte composition (1) was changed to the electrolyte compositions (2) to (13).

(Preparation of sheet battery (D-14))
The same positive electrode sheet as (D-1), with a 30 μm thick Tonen Tapirs non-woven fabric TAPYRUS P22FW-OCS cut into a width of 60 mm and a length of 60 mm, and the solvent of the electrolyte composition (14) removed. After immersing 3.2 g of ionic liquid (IL-51) and 0.29 g of lithium bis (trifluoromethanesulfonyl) imide into the positive electrode from the top of the nonwoven fabric, the same as in the sheet type battery (D-1) A sheet battery (D-14) was produced.

(Preparation of sheet battery (D-15))
The same positive electrode sheet as (D-1), with a 30 μm thick Tonen Tapirs non-woven fabric TAPYRUS P22FW-OCS cut into a width of 60 mm and a length of 60 mm, and the solvent of the electrolyte composition (15) removed. After immersing 3.2 g of ionic liquid (IL-51) and 0.29 g of lithium bis (trifluoromethanesulfonyl) imide into the positive electrode from the top of the nonwoven fabric, the same as in the sheet type battery (D-1) A sheet battery (D-15) was produced.

(Evaluation of battery performance)
(I) Repetitive characteristics About the sheet-type lithium secondary battery created by the above method, from a voltage of 2.0 V to 4.2 V at a current of 0.2 mA / cm ² using a charge / discharge measuring device manufactured by Keiki Keiki Center. After charging for 10 minutes, the battery was discharged to a battery voltage of 3.0 V with a current of 0.2 mA / cm ² . This charging / discharging was repeated 500 cycles. The discharge capacity at the 500th cycle was obtained, and the ratio to the discharge capacity at the 10th cycle was calculated as an initial value and expressed as the cycle capacity.

(Ii) Battery weather resistance evaluation For battery weather resistance evaluation, sheet batteries (D-1) to (D-14) charged from a voltage of 2.0 V to 4.2 V with a current of 0.2 mA / cm ^2. A sheet-like organic EL surface light emitter produced by the method described in Example 1 of Japanese Patent Application Laid-Open No. 2008-159741 (the organic EL element number 104 and the same shape and the same area as the produced sheet-like secondary battery) And a sheet-like lighting device was produced. After leaving these in the A environment room (room temperature 40 ° C., humidity 50%) and the B environment room (room temperature −20 ° C., humidity 20%) for 24 hours, the voltage drops and the initial emission luminance decreases to ¼. The time to complete (τ1 / 4) was measured.

  From the results of Table 7, it was found that the solid electrolyte of the present invention was excellent in production suitability, high in ionic conductivity, and high in strength. From the results in Table 8, it can be seen that the secondary battery using the electrolyte composition of the present invention has good cycle characteristics and excellent durability.

Claims (7)

  An electrolyte composition comprising an electrolyte salt, inorganic fine particles, polyimide, and a polymerized compound of a quaternary ammonium molten salt containing a polymerizable group. The electrolyte composition according to claim 1, wherein the molten quaternary ammonium salt containing the polymerizable group is at least one of the following general formula (1) or (2).

[Wherein, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, R ² represents a substituent represented by the following structure (A),

Here, L ¹ represents —COO—, —CONR ³ —, or a simple bond, R ³ represents a hydrogen atom, an alkyl group, or an aryl group, and L ² represents an alkylene group, an arylene group, or an aralkylene group. , L ³ represents a divalent linking group or a simple bond.
N1 is 1 or 2, n2 is 2 or 3, and the sum of n1 and n2 is 4, and X represents a fluorine atom-containing anion. ]

[Wherein R ¹¹ and R ¹³ represent an alkyl group, an aryl group, a heterocyclic group, or a substituent represented by the structure (A), and at least one of R ¹¹ and R ¹³ is the structure (A). , R ¹² , R ¹⁴ and R ¹⁵ represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkyloxycarbonyl group, a halogen atom, a halogenated alkyl group, a cyano group or a nitro group. , X represents a fluorine atom-containing anion. ] The polyimide is at least one acid anhydride represented by the following general formula (3) or general formula (4), and at least one amine compound represented by the general formula (5) or general formula (6); The electrolyte composition according to claim 1, wherein the electrolyte composition is obtained by polycondensation.

[In the formula, Q ¹ and Q ² represent an atomic group necessary for forming an aromatic ring or a simple bond, but Q ¹ and Q ² do not become a simple bond at the same time, and R ²³ represents an alkyl group. Group, alkenyl group, alkynyl group, alkoxy group, aryl group, heterocyclic group, halogen atom, fluorinated hydrocarbon group, m1 represents an integer of 0-4. ]

[Wherein Q ³ represents an atomic group necessary for forming an aromatic ring, may have a condensed ring, or may have a substituent. Z represents a divalent or trivalent group, and m2 represents an integer of 2 or 3. ]

[Wherein L ¹¹ represents a divalent group, R ²⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, a halogen atom, a fluorinated hydrocarbon group, Substitution is possible at any substitutable position of L ^{11 as} a group, and m3 represents an integer of 0 to 5. ]

[Wherein L ¹² represents a trivalent group, R ²⁵ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a heterocyclic group, a halogen atom, a fluorinated hydrocarbon group, and m4 represents 0 to 6 Represents an integer. ]   The polyimide is obtained by polycondensation with the acid anhydride represented by the general formula (4), the general formula (5), or the amine compound represented by the general formula (6). The electrolyte composition according to claim 3.   The electrolyte composition according to claim 1, comprising a non-polymerizable ionic liquid.   A method for producing the electrolyte composition according to any one of claims 1 to 5, wherein polymerization of a quaternary ammonium molten salt containing a polymerizable group is performed in the presence of polyimide. A method for producing the composition.   A secondary battery comprising the electrolyte composition according to claim 1.