JP2002252030A - Electrolyte composite and its manufacturing method, non-aqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new electrolyte composite and its manufacturing method, which shows a high ion transport number, and a non-aqueous electrolyte secondary battery, which has high battery capacity, containing this electrolyte composite. SOLUTION: The electrolyte composite and its manufacturing method, and the non-aqueous electrolyte secondary battery 1 containing the electrolyte composite, contain a high molecular compound, which has a structure expressed with a following formula (1) as a repeating unit, and a metal ion salt belonging to the 1st family or the 2nd family of the periodic law table. In the following formula (1), R<1> expresses replaced or not replaced alkyl group, or replaced or not replaced alkoxy group. R<2> expresses replaced or not replaced alkyl group. At least one among R<1> and O-R<2> , is a replaced group containing alkoxy carbonyl group. M is silicon, boron, or metallic elements. The n expresses the number of M.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyte composition, and more particularly to an electrolyte composition suitable as an antistatic agent, a battery, and a material for other electrochemical devices, a method for producing the same, and the electrolyte composition. The present invention relates to a high-capacity non-aqueous electrolyte secondary battery using the same.

[0002]

2. Description of the Related Art An electrolyte used in an electrochemical cell such as a non-aqueous secondary cell is a medium containing ions according to the purpose and having a function of transporting the ions between electrodes (called ion conduction). For example, in a lithium secondary battery, which is a typical nonaqueous secondary battery, transport of lithium ions is a problem. In the battery, generally, a solution system having high ion conductivity is often used as an electrolyte. However, there is a problem that the exhaustion or leakage of the solvent when the battery is incorporated into the battery lowers the durability of the battery. In addition, since a metal container must be used to seal the solution, the weight of the battery is increased, and it is difficult to give the battery shape flexibility.

In order to overcome the disadvantages of the above-mentioned solution-based electrolyte,
In recent years, solidification of an electrolyte (polymer electrolyte) has been proposed. A polymer electrolyte in which a salt is dissolved in a polymer such as polyethylene oxide is expected to solve the problem of a solution-based electrolyte, but has a problem that ionic conductivity is not yet sufficient. Further, in the polymer electrolytes which have been mainly reported so far, an ion transport number (for example, in the case of a lithium secondary battery, a lithium ion transport number) which is one of the important characteristics of the electrolyte is generally low. for that reason,
For example, in the case of a lithium secondary battery, the charge / discharge current decreases with time, causing problems such as a decrease in capacity,
There is a problem that it is difficult to incorporate it into general-purpose products.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a novel electrolyte composition exhibiting a high ion transport number and a method for producing the same, and further provide a non-aqueous electrolyte secondary battery containing the electrolyte composition and having a high battery capacity. And

[0005]

Means for solving the above problems are as follows. That is, <1> a polymer compound having a structure represented by the following general formula (1) as a repeating unit, and a salt of a metal ion belonging to Group 1 or 2 of the periodic table. It is an electrolyte composition.

[0006]

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In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. R ² represents a substituted or unsubstituted alkyl group. At least one of R ¹ and O—R ² is a substituent containing an alkoxycarbonyl group. M
Represents silicon, boron or a metal element. n represents the valence of M.

<2> M in the general formula (1) is:
The electrolyte composition according to <1>, wherein the composition is silicon. <3> R ¹ in the general formula (1) is an electrolyte composition according to <1> or <2> is a substituted or unsubstituted alkoxy group.

<4> The polymer compound is a product obtained by reacting a compound represented by the following general formula (2) with a carboxylic acid having a hydroxyl group, from <1> to <3>.
The electrolyte composition according to any one of the above.

[0010]

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In the general formula (2), M represents silicon, boron or a metal element. n represents a valence that the element represented by M can take. R ³ represents a substituted or unsubstituted alkyl group.

<5> The carboxylic acid having a hydroxyl group is selected from the above <1> to <4> represented by the following general formula (3).
The electrolyte composition according to any one of the above.

[0013]

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[0014] In the general formula ^{(3), R 4, R} 5 is
Each independently represents a hydrogen atom or an alkyl group. a is
B represents an integer of 0 to 30, and b represents an integer of 0 to 30.

<6> a in the general formula (3) is 1
<5>, and b is 0.
The electrolyte composition according to the above. <7> The electrolyte composition according to <5> or <6>, wherein R ⁴ and R ⁵ in the general formula (3) are hydrogen atoms.

<8> The polymer compound is a product obtained by reacting a polymer compound having a structure represented by the following general formula (4) as a repeating unit with an alcohol compound having an alkoxycarbonyl group. The electrolyte composition according to any one of <1> to <3>.

[0017]

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[0018] In the general formula (4), R ⁶ represents R ¹ as defined substituents in the general formula (1). R
⁷ represents an alkoxy group.

<9> The electrolyte composition according to <8>, wherein the alcohol compound having an alkoxycarbonyl group is represented by the following general formula (5).

[0020]

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In the general formula (5), R ⁸ represents the same substituent as R ³ in the general formula (3).

<10> The electrolyte composition according to <9>, wherein a in the general formula (5) is 1 and b is 0. <11> The electrolyte composition according to <9> or <10>, wherein R ⁴ and R ⁵ in the general formula (5) are hydrogen atoms.

<12> The electrolyte composition according to any one of <1> to <11>, wherein the electrolyte composition is reacted with a compound having at least two or more nucleophilic groups in a molecule. <13> The above <12>, wherein the nucleophilic group is a hydroxyl group.
The electrolyte composition according to the above. <14> A nonaqueous electrolyte secondary battery including a positive electrode and a negative electrode, wherein the secondary battery includes the electrolyte composition according to any one of <1> to <13>. It is a non-aqueous electrolyte secondary battery. <15> A step of preparing a polymer compound having a structure represented by the following general formula (1) as a repeating unit, and adding a salt of a metal ion belonging to Group 1 or 2 of the periodic table to the polymer compound. Wherein the step of preparing the polymer compound comprises reacting the compound represented by the following general formula (2) with a carboxylic acid having a hydroxyl group. This is a method for producing a characteristic electrolyte composition.

[0024]

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In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. R ² represents a substituted or unsubstituted alkyl group. At least one of R ¹ and O—R ² is a substituent containing an alkoxycarbonyl group. M
Represents silicon, boron or a metal element. n represents the valence of M.

[0026]

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In the general formula (2), M represents silicon, boron or a metal element. n represents a valence that the element represented by M can take. R ³ represents a substituted or unsubstituted alkyl group.

<16> a step of preparing a polymer having a structure represented by the following general formula (1) as a repeating unit, and adding a metal ion belonging to Group 1 or 2 of the periodic table to the polymer; Adding a salt of the above, wherein the step of preparing the polymer compound comprises a polymer compound having a structure represented by the following general formula (4) as a repeating unit; A method for producing an electrolyte composition, comprising reacting an alcohol compound having an alkoxycarbonyl group with an alcohol compound.

[0029]

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In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. R ² represents a substituted or unsubstituted alkyl group. At least one of R ¹ and O—R ² is a substituent containing an alkoxycarbonyl group. M
Represents silicon, boron or a metal element. n represents the valence of M.

[0031]

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In the general formula (4), R ⁶ represents the same substituent as R ¹ in the general formula (1). R
⁷ represents an alkoxy group.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an electrolyte composition of the present invention, a method for producing the same, and a non-aqueous electrolyte secondary battery will be described.
Here, first, the electrolyte composition of the present invention and the method for producing the same will be described in detail.

(Electrolyte Composition and Method for Producing the Same) The electrolyte composition of the present invention can be used for a reaction solvent such as a chemical reaction, metal plating, a CCD (charge coupled device) camera, various batteries, a photoelectric conversion element and the like. And preferably used for lithium secondary batteries.

The electrolyte composition of the present invention comprises a polymer compound having a structure represented by the following general formula (1) as a repeating unit, and a first (Ia) or second (IIa) group of the periodic table.
And a salt of a metal ion belonging to the group.

<Polymer Compound> The polymer compound having a structure represented by the following general formula (1) in the present invention as a repeating unit will be described below.

[0037]

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In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. R ² represents a substituted or unsubstituted alkyl group. At least one of R ¹ and O—R ² is a substituent containing an alkoxycarbonyl group. M
Represents silicon, boron or a metal element. n represents the valence of M.

In the above general formula (1), M represents silicon, boron or a metal element, such as titanium, aluminum, zirconium, germanium, iron, gallium, phosphorus, tin, vanadium and the like. Are preferred. In addition, the metal elements shown in the raw material of the sol-gel method described in "Science of the sol-gel method" (written by Ms. Sakuhana) (issued by Agne Shofusha in 1988) can be used. .

Among the above M, silicon, boron, titanium and aluminum are preferred, and silicon is more preferred.

In the general formula (1), n represents a possible valence of the element represented by M.

In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. The alkyl group represented by R ¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and among them, for example, methyl group, ethyl group, propyl group, n -Butyl group, t-butyl and the like are more preferred.

The alkoxy group represented by R ¹ is preferably an alkoxy group having 1 to 8 carbon atoms.
The alkoxy groups of Nos. To 4 are more preferable, and among them, for example, methoxy group, ethoxy group, propoxy group, n-butoxy group, t-butoxy and the like are further preferable. Among the groups represented by R ¹ , an alkoxy group is more preferred.

In the general formula (1), R ² represents a substituted or unsubstituted alkyl group, and the alkyl group represented by R ² has the same meaning as the alkyl group represented by R ¹ .

The alkyl group represented by R ¹ and R ² and the alkoxy group represented by R ¹ may be unsubstituted or may have a substituent. As the substituent,
The following are preferred. For example, a halogen atom,
Alkyl group, aryl group, heterocyclic group, cyano group, nitro group, alkoxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group,
Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group,
Arylthio group, heterocyclic thio group, sulfamoyl group,
Examples thereof include an alkyl and aryl sulfinyl group, an alkyl and aryl sulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, and a silyl group.

As the halogen atom, for example, a chlorine atom, a bromine atom and an iodine atom are preferable.

Examples of the alkyl group include a linear, branched or cyclic alkyl group. Among them, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n- Octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl and the like are preferred.

Among the above aryl groups, for example, a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group and the like are preferable.

Among the above heterocyclic groups, 5-membered or 6-membered
A monovalent group obtained by removing one hydrogen atom from a member-substituted or unsubstituted aromatic or non-aromatic heterocyclic compound is preferable. Among them, for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl Group, 2-benzothiazolyl group, and the like are more preferred.

Among the above alkoxy groups, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy,
—O (CH ₂ CH ₂ O) nCH ₃ is more preferred.

Among the above silyloxy groups, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, a trimethoxysilyloxy group and the like are more preferable.

Among the above acyloxy groups, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-
A methoxyphenylcarbonyloxy group is more preferred.

Among the carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy group, N, N-
More preferred are a diethylcarbamoyloxy group, a morpholinocarbonyloxy group, an N, N-di-n-octylaminocarbonyloxy group, a Nn-octylcarbamoyloxy group, and the like.

Among the above alkoxycarbonyloxy groups, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group,
An n-octylcarbonyloxy group is more preferred.

Among the above aryloxycarbonyloxy groups, for example, phenoxycarbonyloxy group, p-
A methoxyphenoxycarbonyloxy group and a pn-hexadecyloxyphenoxycarbonyloxy group are more preferred.

Among the above amino groups, for example, amino group, methylamino group, dimethylamino group, anilino group,
An N-methyl-anilino group, a diphenylamino group and the like are preferred.

Among the above acylamino groups, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,3
A 4,5-tri-n-octyloxyphenylcarbonylamino group is more preferred.

Among the above aminocarbonylamino groups,
For example, a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group, a morpholinocarbonylamino group, and the like are more preferable.

Among the above alkoxycarbonylamino groups, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group,
More preferred are an n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group and the like.

Among the above aryloxycarbonylamino groups, for example, phenoxycarbonylamino group, p-
A chlorophenoxycarbonylamino group, a mn-octyloxyphenoxycarbonylamino group and the like are more preferred.

Among the above sulfamoylamino groups, for example, a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, a Nn-octylaminosulfonylamino group and the like are more preferable.

Among the above-mentioned alkyl and arylsulfonylamino groups, for example, methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group and the like Is more preferred.

Among the above alkylthio groups, for example, a methylthio group, an ethylthio group, an n-hexadecylthio group and the like are more preferable.

As the arylthio group, for example, a phenylthio group, a p-chlorophenylthio group, an m-methoxyphenylthio group and the like are more preferable.

Among the above heterocyclic thio groups, those having 2 to 2 carbon atoms
30 substituted or unsubstituted heterocyclic thio groups are preferable, and for example, a 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group and the like are more preferable.

Among the sulfamoyl groups, for example,
N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N '-Phenylcarbamoyl) sulfamoyl and the like are more preferred.

Among the above-mentioned alkyl and arylsulfinyl groups, for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group and the like are more preferable.

Among the alkyl and arylsulfonyl groups, for example, a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-methylphenylsulfonyl group and the like are more preferable.

Among the above acyl groups, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl and the like are more preferable.

Among the above aryloxycarbonyl groups, for example, phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt-butylphenoxycarbonyl group and the like are more preferable.

Among the above alkoxycarbonyl groups, for example, a methoxycarbonyl group, an ethoxycarbonyl group,
A t-butoxycarbonyl group, an n-octadecyloxycarbonyl group and the like are preferable.

Among the carbamoyl groups, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group and the like are exemplified. preferable.

Among the above silyl groups, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms is preferable, and for example, a trimethylsilyl group, a t-butyldimethylsilyl group, a phenyldimethylsilyl group and the like are more preferable.

Hereinafter, specific examples (A-1 to 10) of the repeating unit in the polymer compound having the structure represented by the general formula (1) as a repeating unit according to the present invention will be shown. It is not limited at all.

[0075]

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[0076]

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In the present invention, the polymer compound having the structure represented by the general formula (1) as a repeating unit is obtained by reacting a compound represented by the following general formula (2) with a carboxylic acid having a hydroxyl group. Preferably,

[0078]

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In the general formula (2), M represents silicon, boron or a metal element. n represents a valence that the element represented by M can take. R ³ represents a substituted or unsubstituted alkyl group.

In the general formula (2), M, n, R ¹
Has the same meaning as that represented by M, n, and R ¹ in the general formula (1). R ³ represents a substituted or unsubstituted alkyl group. Alkyl group represented by R ³ has the same meaning as the alkyl group represented by R ¹ in the general formula (1).

Hereinafter, specific examples (2-1 to 11) of the compound represented by formula (2) of the present invention will be shown, but the present invention is not limited thereto.

[0082]

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Examples of the carboxylic acid having a hydroxyl group include:
The compound represented by the following general formula (3) is more preferred.

[0084]

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In the general formula (3), R ⁴ and R ⁵ are
Each independently represents a hydrogen atom or an alkyl group. R ⁴ , R ⁵
Is an alkyl group represented by the general formula (1)
It has the same meaning as the alkyl group represented by ¹ . Among the above R ⁴ and R ⁵ , a hydrogen atom is preferable.

In the general formula (3), a is 1 to 5
And b represents an integer of 0 to 30. When a is 2 or more, R ⁴ and R ⁵ may be the same or different. Of the above a and b, a is 1 and b
Is preferably 0.

Hereinafter, specific examples (3-1 to 10) of the carboxylic acid having a hydroxyl group and the compound represented by the general formula (3) in the present invention are shown, but the present invention is not limited thereto. Not something.

[0088]

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In the present invention, the polymer compound having the structure represented by the general formula (1) as a repeating unit is the same as the polymer compound having a structure represented by the following formula (4) as a repeating unit: And more preferably an alcohol compound having an alkoxycarbonyl group.

[0090]

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In the general formula (4), R ⁶ represents the same substituent as R ¹ in the general formula (1);
⁷ represents an alkoxy group. The alkoxy group represented by R ⁶ and R ⁷ has the same meaning as the alkoxy group represented by R ¹ in the general formula (1).

Hereinafter, specific examples of the polymer compound having the structure represented by the general formula (4) as a repeating unit (4-
1 to 5), but the present invention is not limited to these.

[0093]

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As the alcohol compound having an alkoxycarbonyl group, a compound represented by the following general formula (5) is more preferable.

[0095]

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In the general formula (5), R ⁸ represents the same substituent as R ³ in the general formula (2). R ⁴ ,
R ⁵ , a and b are the same as R ⁴ , R in the general formula (3).
Synonymous with ⁵ , a and b. Among the above R ⁴ and R ⁵ , a hydrogen atom is preferable, a is 1 and b
Is preferably 0.

Hereinafter, specific examples of the alcohol compound having an alkoxycarbonyl group according to the present invention (5-1 to 1)
Although 3) is shown, the present invention is not limited to these.

[0098]

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<Method for Producing Electrolyte Composition> The method for producing an electrolyte composition according to the present invention comprises the steps of preparing a polymer having a structure represented by the above general formula (1) as a repeating unit, Adding a salt of a metal ion belonging to Group 1 (Ia) or Group 2 (IIa) of the periodic table to the compound; and preparing the polymer compound according to the general formula (2). Preferably, the step is a step of reacting the compound represented by the formula with the carboxylic acid having a hydroxyl group. Further, the step of preparing the polymer compound may be a step of reacting the polymer compound having the structure represented by the general formula (4) as a repeating unit with the alcohol compound having an alkoxycarbonyl group. preferable.

A reaction between the general formula (2) and the carboxylic acid having a hydroxyl group (hereinafter sometimes referred to as “reaction A”), and the structure represented by the general formula (4) as a repeating unit Reaction of a high molecular compound having the above with an alcohol compound having an alkoxycarbonyl group (hereinafter referred to as
It may be referred to as "Reaction B". ) May be performed in the presence or absence of a solvent, but is preferably performed without using a solvent, that is, in the absence of a solvent.

The reaction temperature in the reaction A and the reaction B is preferably not lower than room temperature and not higher than the reflux starting temperature of the reaction mixture. The reaction time in the reaction A and the reaction B is preferably from 30 minutes to 7 days, more preferably from 1 hour to 2 days. The reaction temperature and the reaction time are not limited to the above because the reaction rate is adjusted.

In the reaction A and the reaction B, after the reaction,
Preferably, volatile components are distilled off from the reaction product. The distillation of volatile components is preferably performed under reduced pressure by heating, preferably 10
Under a condition of 0 ° C./5 mmHg (667 Pa), the reaction product is preferably distilled off until the weight reduction rate of the reaction product becomes 50% or less, more preferably 30% or less. .

In the method for producing an electrolyte composition according to the present invention, a step of preparing a polymer compound having the structure represented by the general formula (1) as a repeating unit (the above-mentioned reaction A or reaction B); Periodic Table 1 (Ia)
The step of adding a salt of a metal ion belonging to Group 2 or II (IIa) may be performed simultaneously, or a salt of a metal ion may be added after preparing a polymer. That is, the preparation of the polymer compound (the reaction A or the reaction B) is carried out according to the Periodic Table 1 (I
The reaction may be performed in the presence of a salt of a metal ion belonging to Group a) or Group 2 (IIa), and the salt of the metal ion may be added to the prepared polymer compound later.

In the reaction A in the step of preparing the polymer compound, the compound represented by the general formula (2) (A
¹ ) and the ratio of the carboxylic acid having a hydroxyl group (A ² ) is such that A ² / A ¹ is 0.1 to n (molar ratio) (n is the same as n in the general formula (1)) ), More preferably 0.2 to 2, more preferably 0.5 to 1.
Is more preferred.

In the reaction B in the step of preparing the polymer compound, the alcohol compound having an alkoxycarbonyl group (B ¹ ) is a polymer compound having a structure represented by the general formula (4) as a repeating unit. to (B ^2), it is preferably 1 wt% to 300 wt%,
10 mass%-200 mass% is more preferable, and 30 mass%.
~ 150 mass% is more preferred.

In the electrolyte composition of the present invention, a solvent can be used up to the same mass as the compound, but from the viewpoint of storage stability, it is preferable not to use a solvent. The electrolyte composition of the present invention may be dissolved by heating, or, if necessary, a method of permeating the electrode under reduced pressure, using a low-boiling solvent (methanol, acetonitrile, methylene chloride, etc.) to permeate the electrode, Thereafter, it can be incorporated into the battery by a method of removing the solvent by heating or the like.

As the solvent used in the electrolyte composition of the present invention, a solvent having a low viscosity and improving ionic mobility, or a substance having a high dielectric constant and an effective carrier concentration can be used.
It is preferable that the compound be capable of exhibiting excellent ion conductivity. Such solvents include, for example, 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, and propylene glycol dialkyl ether. Chain ethers such as polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether,
Methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether,
Alcohols such as polypropylene glycol monoalkyl ether, polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol and glycerin, acetonitrile, glutarodinitrile, methoxyacetonitrile,
Preferable examples include nitrile compounds such as propionitrile and benzonitrile, esters such as carboxylate, phosphate and phosphonate, and aprotic polar substances such as dimethyl sulfoxide and sulfolane. Among them, ethylene carbonate, carbonate compounds such as propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, nitrile compounds such as benzonitrile, esters are particularly preferable. preferable. These may be used alone or in combination of two or more.

From the viewpoint of improving durability due to volatility, the preferable solvent has a boiling point at normal pressure (1 atm) of 200 ° C. or higher, and preferably 250 ° C.
The temperature is more preferably at least 270 ° C.

<Salts of Metal Ions belonging to Group 1 or 2 of the Periodic Table> Here, the salts of the first (Ia) group or the second (IIa) group of the periodic table contained in the electrolyte composition of the present invention. The salt of the metal ion to which it belongs will be described.

The periodic table contained in the electrolyte composition of the present invention
Metal ions belonging to Group 1 (Ia) or Group 2 (IIa)
Lithium, sodium, and potassium ions
Preferably, a representative metal ion salt is LiCF
_ThreeSO_Three, LiPF₆, LiClO_Four, LiI, LiB
F_Four, LiCF_ThreeCO_Two, LiSCN, LiN (SO_TwoCF
_Three)_Two, NaI, NaCF_ThreeSO_Three, NaClO_Four, NaB
F_Four, NaAsF₆, KCF _ThreeSO_Three, KSCN, KP
F₆, KCLO_Four, KAsF₆And the like. The gold
Among the specific examples of the salts of the genus ions, the above-mentioned Li salts are more preferable.
New

The metal ion salts may be used alone or in a combination of two or more. The concentration of the salt is from 3% by mass to 300% with respect to the polymer compound.
It is preferably 5% by mass, more preferably 5% by mass to 200% by mass.

<Compound having at least two or more nucleophilic groups in the molecule> The electrolyte composition of the present invention further comprises a compound having at least two or more nucleophilic groups in the molecule (hereinafter referred to as "nucleophilic agent"). ) In some cases.) And solidified before use. From the viewpoint of preventing liquid leakage and volatilization, it is preferable to use the electrolyte composition after solidifying it.

As the nucleophilic group in the compound having at least two or more nucleophilic groups, a hydroxyl group, an amino group, a mercapto group, a sulfide group, a sulfino group, or a sulfinato group is preferable. preferable.

Specific examples (a to j) of the compound having at least two or more nucleophilic groups in the molecule are shown below.
The present invention is not limited to these.

[0115]

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The compound having at least two or more nucleophilic groups in the molecule is preferably used in an amount of 0.1% by mass or more and 70% by mass or less based on the whole electrolyte composition. It is more preferably used at 0.3% by mass or more and 50% by mass or less, and further preferably used at 0.5% by mass or more and 30% by mass or less.

The reaction temperature when the above compound is added is preferably from 0 ° C. to 150 ° C., and preferably from 10 ° C. to 10 ° C.
0 ° C. or lower is more preferable. The reaction time when the compound is added is preferably from 5 minutes to 2 days, more preferably from 10 minutes to 1 day. The reaction temperature and the reaction time are not limited to the above because the reaction rate is adjusted.

The electrolyte composition of the present invention comprises a polymer,
It can be gelled (solidified) by a technique such as addition of an oil gelling agent, polymerization containing a polyfunctional monomer, or crosslinking reaction of a polymer. When gelation is performed by adding the polymer, "Polymer Electro
lyte Reviews-1 and 2 "(JR Ma
cCallum and C.I. A. Vincent co-editing, E
Compounds described in LSEVIER APPLIED SCIENCE can be used, and particularly, polyacrylonitrile, polyvinylidene fluoride, polyethylene oxide, polysiloxane and the like are suitably used.

When gelation is carried out by adding the oil gelling agent, use is made of an industrial science magazine (J. Chem Soc. Ja).
pan, Ind. Chem. Sec. ), 46, 779
(1943), J.M. Am. Chem. Soc. , 11
1, 5542 (1989); Chem. Soc. ,
Chem. Com mun. , 1993, 390, An
gew. Chem. Int. Ed. Engl. , 35,
1949 (1996), Chem. Lett. , 199
6,885, J. Chm. Soc. Chem. Com
mun. , 1997, 545 can be suitably used, but a compound having an amide structure in the molecular structure is more preferable.

(Non-Aqueous Electrolyte Secondary Battery) Here, the non-aqueous electrolyte secondary battery of the present invention will be described. <Positive electrode active material> When the electrolyte composition of the present invention is used in a secondary battery, a transition metal oxide capable of reversibly inserting and releasing lithium ions can be used as the positive electrode active material. Preferably, an oxide is used. In the present invention, the lithium-containing transition metal oxide preferably used as the positive electrode active material includes lithium-containing Ti, V, Cr, Mn, Fe, Co, Ni, Cu, M
Oxides containing o and W are preferred. Alkali metals other than lithium (elements of the first (Ia) group and second (IIa) group of the periodic table) and / or Al, Ga, In,
Ge, Sn, Pb, Sb, Bi, Si, P, B and the like may be mixed. The mixing amount is 0 to transition metal.
30 mol% is preferred.

Among the lithium-containing transition metal oxides preferably used as the positive electrode active material, lithium compounds / transition metal compounds (where transition metals are Ti, V, C
It means at least one selected from r, Mn, Fe, Co, Ni, Mo and W. ) Is 0.3
Those synthesized by mixing so as to be 2.2 are more preferable.

Further, among the lithium compounds / transition metal compounds, Li _g M ³ O ₂ (M ³ is Co, Ni, Fe,
And one or more elements selected from Mn. g is
Represents 0 to 1.2. Materials containing), or Li _h M ⁴ ₂ O
(.H M ⁴ is representative of the Mn represents. 0-2) material particularly preferably has a spinel structure represented by. As the M ³ and M ⁴ , other than transition metals, Al, Ga, In,
Ge, Sn, Pb, Sb, Bi, Si, P, B and the like may be mixed. The mixing amount is 0 to 30 mo relative to the transition metal.
1% is preferred.

The material containing Li _g M ³ O ₂ , Li _h M ⁴ O ₂
In Among the materials having the spinel structure represented, Li _g
CoO ₂ , Li _g NiO ₂ , Li _g MnO ₂ , Li _g Co _j N
_{i 1-j O 2, Li} h Mn 2 O 4 ( where g is 0.02-1.
2 is represented. j represents 0.1 to 0.9. h represents 0 to 2. Is particularly preferred. Here, the g value and the h value are
This is a value before the start of charging and discharging, and is a value that increases and decreases due to charging and discharging.

The positive electrode active material can be synthesized by a method in which a lithium compound and a transition metal compound are mixed and fired, or a solution reaction, but a firing method is particularly preferable. In the calcination method used in the present invention, the calcination temperature may be a temperature at which a part of the mixed compound is decomposed and melted.
0 to 1500 ° C is more preferable. When firing,
It is preferable to calcine at 250 to 900 ° C. In the firing method, the firing time is preferably 1 to 72 hours, more preferably 2 to 20 hours. The method of mixing the raw materials may be a dry method or a wet method. After firing, 20
Annealing may be performed at 0 to 900 ° C.

In the firing method, the firing gas atmosphere is not particularly limited, and any of an oxidizing atmosphere and a reducing atmosphere can be used. For example, air, gas whose oxygen concentration is adjusted to an arbitrary ratio, hydrogen, carbon monoxide, nitrogen, argon, helium, krypton, xenon, carbon dioxide and the like can be mentioned.

In the non-aqueous electrolyte secondary battery of the present invention, the average particle size of the positive electrode active material used is not particularly limited, but is preferably 0.1 to 50 μm. The specific surface area is not particularly limited, but is 0.01 to 50 m by the BET method.
^It is preferably ² / g. The pH of the supernatant when 5 g of the positive electrode active material is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.

In order to make the positive electrode active material have a predetermined particle size, a well-known pulverizer or classifier is used. For example, mortar, ball mill, vibration ball mill, vibration mill,
A satellite ball mill, a planetary ball mill, a swirling air jet mill, a sieve, and the like are used. Positive electrode active material obtained by the firing method is water, an acidic aqueous solution, an alkaline aqueous solution,
It may be used after washing with an organic solvent.

<Negative Electrode Active Material> In the nonaqueous electrolyte secondary battery of the present invention, one of the negative electrode active materials is preferably a carbonaceous material capable of inserting and extracting lithium. The carbonaceous material is a material substantially composed of carbon. Examples thereof include carbonaceous materials obtained by firing petroleum pitch, natural graphite, artificial graphite such as vapor-grown graphite, and various synthetic resins such as PAN-based resins and furfuryl alcohol resins. Furthermore, PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PV
A-based carbon fiber, lignin carbon fiber, glassy carbon fiber,
Various carbon fibers such as activated carbon fibers, mesophase microspheres, graphite whiskers, and flat graphite can also be mentioned.

These carbonaceous materials can be classified into non-graphitizable carbon materials and graphite-based carbon materials according to the degree of graphitization. Further, the carbonaceous material preferably has a plane spacing, a density, and a crystallite size described in JP-A-62-22066, JP-A-2-6856, and JP-A-3-45473. The carbonaceous material does not need to be a single material, and a mixture of natural graphite and artificial graphite described in JP-A-5-90844, graphite having a coating layer described in JP-A-6-4516, or the like is used. Can also.

In the non-aqueous electrolyte secondary battery of the present invention, as the other negative electrode active material, oxides and / or chalcogenides are preferably exemplified.

Of these, amorphous oxides and / or chalcogenides are particularly preferred. The term amorphous here means
X-ray diffractometry using CuKα ray, 20 ° to 4 in 2θ value
It means a material having a broad scattering band having an apex in a region of 0 °, and may have a crystalline diffraction line. The strongest intensity of the crystalline diffraction lines observed at 40 ° or more and 70 ° or less in 2θ value is 100 times or less of the diffraction line intensity at the top of the broad scattering band observed at 20 ° or more and 40 ° or less in 2θ value. Is preferably 5 times or less, particularly preferably no crystalline diffraction line.

Among the amorphous oxides and / or chalcogenides, an amorphous oxide of a metalloid element and / or a chalcogenide are more preferable.
Group B) to Group 15 (VB) elements, Al, Ga, Si, S
Oxides consisting of n, Ge, Pb, Sb, Bi alone or in combination of two or more thereof, and chalcogenides are particularly preferred.

The preferred amorphous oxide and / or calcium
As a cogenide, for example, Ga _TwoO_Three, SiO, Ge
O, SnO, SnO_Two, PbO, PbO_Two, Pb_TwoO_Three, P
b_TwoO_Four, Pb_ThreeO_Four, Sb_TwoO_Three, Sb_TwoO_Four, Sb_TwoO_Five, B
i_TwoO_Three, Bi_TwoO_Four, SnSiO_Three, GeS, SnS, S
nS_Two, PbS, PbS_Two, Sb_TwoS_Three, Sb_TwoS_Five, SnS
iS_ThreeAre preferred. These are also lithium oxide
And a composite oxide such as Li_TwoSnO_TwoMay be
No.

As the negative electrode active material used in the nonaqueous electrolyte secondary battery of the present invention, the preferable amorphous oxide and / or
Alternatively, among the chalcogenides, an amorphous oxide mainly composed of Sn, Si, and Ge is more preferable, and among them, a compound represented by the following general formula (6) is particularly preferable.

[0135] In the general formula _{^{(6) SnM 1 d M 2}} e O f the formula (6), M ¹ is, Al, B, P, G
represents at least one element selected from e. M
² represents at least one element selected from Group 1 (Ia), Group 2 (IIa), Group 3 (IIIa), and halogen elements of the periodic table. d is 0.2 or more 2
E represents a number of 0.01 or more and 1 or less,
0.2 <d + e <2. f represents a number of 1 or more and 6 or less. Is preferably an amorphous oxide represented by the formula:

Hereinafter, specific examples (C-1 to C-18) of the amorphous oxide mainly containing Sn will be shown, but the present invention is not limited thereto.

C-1 SnSiO ₃ C-2 Sn _0.8 Al _0.2 B _0.3 P _0.2 Si _0.5 O _3.6 C-3 SnAl _0.4 B _0.5 Cs _0.1 P _0.5 O _3.65 C-4 SnAl _0.4 B _0.5 Mg _0.1 P _0.5 O _3.7 C -5 SnAl _0.4 B _0.4 Ba _0.08 P _0.4 O _3.28 C-6 SnAl _0.4 B _0.5 Ba _0.08 Mg _0.08 P _0.3 O
_3.26 C-7 SnAl _0.1 B _0.2 Ca _0.1 P _0.1 Si _0.5 O _3.1 C-8 SnAl _0.2 B _0.4 Si _0.4 O _2.7 C-9 SnAl _0.2 B _0.1 Mg _0.1 P _0.1 Si _0.5 O _2.6 C-10 SnAl _0.3 B _0.4 P _0.2 Si _0.5 O _3.55 C-11 SnAl _0.3 B _0.4 P _0.5 Si _0.5 O _4.3 C-12 SnAl _0.1 B _0.1 P _0.3 Si _0.6 O _3.25 C-13 SnAl _0.1 B _0.1 Ba _0.2 P _0.1 Si _0.6 O
_2.95 C-14 SnAl _0.1 B _0.1 Ca _0.2 P _0.1 Si _0.6 O
_2.95 C-15 SnAl _0.4 B _0.2 Mg _0.1 Si _0.6 O _3.2 C-16 SnAl _0.1 B _0.3 P _0.1 Si _0.5 O _3.05 C-17 SnB _0.1 K _0.5 P _0.1 SiO _3.65 C-18 SnB _0.5 F _0.1 Mg _0.1 P _0.5 O _3.05

As a method for synthesizing the amorphous oxide and / or chalcogenite of the present invention, any of a firing method and a solution method can be employed, but the firing method is more preferable. In the firing method, oxides of the corresponding elements,
It is preferable to mix the chalcogenite or compound well and then calcinate to obtain an amorphous oxide and / or chalcogenite.

The firing temperature in the firing method is 5
The temperature is preferably from 00 ° C to 1500 ° C, and the firing time is preferably from 1 hour to 100 hours.

In the above firing method, the temperature after firing may be cooled in a firing furnace, or may be taken out of the firing furnace and put into, for example, water to cool. Also, the gun method, Hammer-Anvil method, slap method, and the like described on page 217 of ceramics processing (Gihodo Shuppan 1987).
Gas atomizing method, plasma spray method, centrifugal quenching method,
An ultra-quenching method such as a melt drag method can also be used. Also New Glass Handbook (Maruzen 1991)
The cooling may be performed using a single roller method or a twin roller method described on page 172. In the case of a material that melts during firing, a fired product may be continuously taken out while supplying raw materials during firing. In the case of a material that melts during firing, it is preferable to stir the melt.

The firing gas atmosphere in the firing method is preferably an atmosphere having an oxygen content of 5% by volume or less, and more preferably an inert gas atmosphere. Preferred examples of the inert gas include nitrogen, argon, helium, krypton, and xenon. Among them, pure argon is particularly preferred.

In the non-aqueous electrolyte secondary battery of the present invention, the negative electrode active material used has an average particle size of 0.1 to 0.1.
60 μm is preferred. To obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a sand mill, a vibration ball mill, a satellite ball mill, a planetary ball mill, a swirling air jet mill, a sieve, and the like are suitably used. At the time of pulverization, wet pulverization in the presence of water or an organic solvent such as methanol can also be performed if necessary. Classification is preferably performed to obtain a desired particle size. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be performed both in a dry type and a wet type.

The chemical formula of the compound obtained by the calcination method can be calculated by an inductively coupled plasma (ICP) emission spectroscopic analysis method as a measuring method and a mass difference between powder before and after calcination as a simple method.

Examples of the negative electrode active material which can be used in combination with the amorphous oxide negative electrode active material mainly composed of Sn, Si, and Ge of the present invention include a carbon material capable of inserting and extracting lithium ions or lithium metal, Lithium, lithium alloy,
A metal that can be alloyed with lithium is preferably exemplified.

<Electrode mixture> The electrode mixture of the present invention includes:
In addition to the conductive agent, the binder, the filler, and the like, a polymer network having a structure represented by the general formula (1) as a repeating unit, a lithium salt, an aprotic organic solvent, and the like are added.

As the conductive agent, any material may be used as long as it does not cause a chemical change in the configured secondary battery. Usually, natural graphite (scale graphite, flaky graphite, earthy graphite, etc.), artificial graphite, carbon black, acetylene black, ketjen black, carbon fibers and metal powders (copper, nickel, aluminum, silver (Japanese Unexamined Patent Publication No.
148,554), a metal fiber or a polyphenylene derivative (described in JP-A-59-20971), or a mixture thereof. Among them, the combined use of graphite and acetylene black is particularly preferred. The addition amount of the conductive agent is preferably 1 to 50% by mass, and 2 to 30% by mass.
Is more preferred. In the case of carbon or graphite, the content is particularly preferably 2 to 15% by mass.

In the present invention, a binder for holding the electrode mixture is used. Examples of the binder include polysaccharides, thermoplastic resins and polymers having rubber elasticity, among which, for example, starch, carboxymethylcellulose, cellulose, diacetylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, sodium alginate Water-soluble polymers such as polyacrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer, and polyvinyl Chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylide (Meth) acrylic such as fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate (Meth) acrylate copolymer containing acid ester, (meth) acrylate-acrylonitrile copolymer, polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene-butadiene copolymer, acrylonitrile -Butadiene copolymer, polybutadiene, neoprene rubber, fluoro rubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, polycarbonate resin Urethane 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 above binders can be used alone or in combination of two or more. If the amount of the binder is small, the holding power and the cohesive strength of the electrode mixture are weakened. If it is too large, the electrode volume increases, and the capacity per unit volume or unit mass of the electrode decreases. For these reasons, the amount of the binder added is preferably 1 to 30% by mass, and more preferably 2 to 10% by mass.

As the filler, in the secondary battery of the present invention, any fibrous material that does not cause a chemical change can be used. Usually, fibers such as olefin-based polymers such as polypropylene and polyethylene, glass, and carbon are used. The amount of the filler added is not particularly limited, but is preferably 0 to 30% by mass.

<Separator> The electrolyte composition of the present invention can be used in combination with a separator to ensure safety. To ensure safety, the separator used in combination must have a function of blocking the following gap at 80 ° C or higher to increase the resistance and cut off the current. If the blocking temperature is 90 ° C or higher and 180 ° C or lower, Preferably, there is.

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

The separator may be one using a single material such as polyethylene or polypropylene, or one using two or more composite materials. What laminated | stacked two or more types of microporous films which changed the pore diameter, the porosity, the pore closing temperature, etc. is preferable.

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

The current collector of the negative electrode is preferably copper, stainless steel, nickel, or titanium, and more preferably copper or a copper alloy.

As the shape of the current collector, a film sheet is usually used, but a net, a punch, a lath, a porous body, a foam, a fiber group formed body and the like may also be used. Can be. The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. Also,
It is also preferable that the current collector surface is provided with irregularities by surface treatment.

<Preparation of Nonaqueous Electrolyte Secondary Battery>
The production of the nonaqueous electrolyte secondary battery of the present invention will be described.
As the shape of the nonaqueous electrolyte secondary battery of the present invention, a sheet,
It can be applied to any shape such as corners and cylinders. The mixture of the positive electrode active material and the negative electrode active material is mainly used after being applied (coated), dried, and compressed on the current collector.

As the method of applying the mixture, for example, 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, a squeeze method and the like are preferably used. No. Among them, a blade method, a knife method and an extrusion method are preferred. In addition, application is 0.1 to
It is preferably carried out at a speed of 100 m / min. At this time, by selecting the above coating method in accordance with the solution physical properties and drying properties of the mixture, a good surface state of the coated layer can be obtained. The application may be performed simultaneously on one side or simultaneously on both sides.

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

As a method for drying and dewatering the electrode sheet coating material, a method using hot air, vacuum, infrared ray, far infrared ray, electron beam and low humidity air alone or in combination can be used. The drying temperature is preferably from 80 to 350 ° C.
~ 250 ° C is more preferred. The water content is preferably 2000 ppm or less for the whole battery, and is preferably 500 ppm or less for each of the positive electrode mixture, the negative electrode mixture and the electrolyte. As a method for pressing the sheet, a method generally used can be used, but a calendar press method is particularly preferable. The pressing pressure is not particularly limited.
3 t / cm ² is preferred. The press speed of the calender 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 width of the negative electrode sheet to the width of the negative electrode sheet is preferably 0.9 to 1.1, and particularly preferably 0.95 to 1.0. The content ratio between the positive electrode active material and the negative electrode active material varies depending on the type of compound and the formulation of the mixture.

After the positive and negative electrode sheets produced by the above method are overlapped via a separator, they are directly processed into a sheet battery or folded and inserted into a rectangular can. After the connection, an electrolyte is injected, and a prismatic battery is formed using a sealing plate. In addition, the positive and negative electrode sheets are overlapped and wound via a separator, inserted into a cylindrical can, electrically connected to the can and the sheet, injected with electrolyte, and formed into a cylindrical battery using a sealing plate. I do. At this time, a safety valve can be used as a sealing plate. In addition to the safety valve, various conventionally known safety elements may be provided. For example, a fuse, a bimetal, a PTC element, or the like is preferably used as the overcurrent prevention element.

In addition to the above-mentioned safety valve, as a countermeasure against an increase in the internal pressure of the battery can, a method of making a cut in the battery can, a gasket cracking method, a sealing plate cracking method, or a cutting method with a lead plate can be used. Further, the charger may be provided with a protection circuit incorporating measures for overcharging or overdischarging, or may be connected independently.

As a measure against overcharging, a method of interrupting the current by increasing the internal pressure of the battery may be provided. At this time, a compound for increasing the internal pressure can be contained in the mixture or the electrolyte. Compounds used to increase the internal pressure include Li ₂ CO ₃ , LiHCO ₃ , Na ₂ C
Carbonates such as O ₃ , NaHCO ₃ , CaCO ₃ and MgCO ₃ can be mentioned.

For the can or the lead plate, a metal or an alloy having electrical conductivity can be used. For example, metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum or alloys thereof are suitably used.

As a method for welding the cap, the can, the sheet, and the lead plate, known methods (eg, DC or AC electric welding, laser welding, ultrasonic welding) can be used. A conventionally known compound or mixture such as asphalt can be used as the sealing agent for closing.

The application of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited.
Notebook PC, pen input PC, mobile PC, e-book player, mobile phone, cordless phone handset, pager, handy terminal, mobile fax, mobile copy, mobile printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CD , Mini disk, electric shaver, transceiver, electronic organizer, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, etc. For other consumer use, automobiles, electric vehicles, motors, lighting equipment, toys,
Game equipment, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder massagers, etc.). Furthermore, it can be used for various military purposes and space applications. Further, it can be combined with a solar cell.

[0166]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1) <Synthesis of polymer compound having structure represented by general formula (1) as a repeating unit-reaction between general formula (2) and carboxylic acid having a hydroxyl group-> Exemplified compound (2) -1) 52.
0 g and 26.0 g of Exemplified Compound (3-1) were mixed and reacted with heating under reflux for 10 hours. After the reaction, 150 ° C / 5
After removing volatile components with mmHg (667 Pa), (A-
37.0 g of a polymer compound colorless liquid (Si-1) having the structure represented by 1) as a repeating unit was obtained. Furthermore, except that the compound represented by the general formula (2) and the carboxylic acid having a hydroxyl group were changed as shown in Table 1, (Si)
(Si-2) to (Si-6) were synthesized in the same manner as in -1).

[0168]

[Table 1]

Comparative Example 1 <Synthesis of Poly (dimethoxysiloxane)> 15.2 g of Exemplified Compound (2-1), 6 g of acetic acid, 3.2 g of methanol
Were mixed and reacted under heating to reflux for 10 hours. After the reaction,
After volatile components were distilled off at 150 ° C./5 mmHg (667 Pa), 1.3 g of a colorless liquid for comparison (Si-9) was obtained.

Example 2 <Synthesis of High Molecular Compound Having Structure Represented by General Formula (1) as Repeating Unit—Polymer Compound Having Structure Represented by General Formula (4) as Repeating Unit and General Reaction with Compound Represented by Formula (5) >> 5.3 g of Poly (dimethoxysiloxane), 4.5 g of Exemplified Compound (5-1)
Were mixed and reacted under heating to reflux for 10 hours. After the reaction,
After volatile components were distilled off at 150 ° C./5 mmHg (667 Pa), 3 g of a colorless liquid (Si-7) was obtained. Except that the exemplified compound (5-1) was changed to 9.5 g of the exemplified compound (5-6), 7 g of a colorless liquid (Si-8) was obtained in the same manner as in the above (Si-7).

(Example 3) <Preparation of electrolyte composition> Compound (Si-1) 1 of the present invention
A mixture of 6 g and 7 g of N-lithiotrifluoromethanesulfonimide (LiNTf ₂ ) was dissolved in an acetonitrile solution (10 ml), and acetonitrile was distilled off under reduced pressure.
An electrolyte composition (SiE-1) was produced. Further, (SiE-1) was prepared in the same manner as (SiE-1) except that the polymer compound having the structure represented by the general formula (1) as a repeating unit and the metal ion salt were changed as shown in Table 2.
-2) to (SiE-14) were obtained.

[0172]

[Table 2]

Example 4 <Preparation of Solid Electrolyte> To 10 g of the electrolyte composition (SiE-1) prepared in Example 3, Exemplified Compound d as a nucleophilic agent was added.
0.5 g was mixed. This mixture was cast on Teflon (registered trademark). The casting solution was heated at 100 ° C. for 4 hours under an argon gas atmosphere to obtain a solid electrolyte membrane (SPE-1). Solid electrolyte thin films (SPE-2) to (SPE-13) having the compositions shown in Table 3 in the same manner as described above, except that the types of the electrolyte composition and the nucleophile were changed.
I got

[0174]

[Table 3]

(Example 5) <Measurement of ionic conductivity and transport number> The direct current polarization measurement method of the electrolyte prepared in Example 3 or 4 was sandwiched between two lithium electrodes each having 0.5 mm polypropylene as a spacer. And complex impedance measurement,
The ion transport number was measured. The results are shown in Tables 2 and 3.

As shown in Tables 2 and 3, it was confirmed that the electrolyte using the compound of the present invention exhibited a higher Li ion transport number than the comparative example, and was useful as a lithium ion conductive material.

(Example 6) <Preparation of cylinder type battery> Preparation of positive electrode mixture paste 200 g of LiCoO ₂ and 10 g of acetylene black were mixed with a homogenizer as a positive electrode active material, and then ₂ g of a binder was prepared. -Ethylhexyl acrylate,
8 g of an aqueous dispersion of a copolymer of acrylic acid and acrylonitrile (solid content concentration: 50% by weight), 60 g of a 2% by mass aqueous solution of carboxymethylcellulose were added, kneaded and mixed, 50 g of water was further added, and the mixture was stirred and mixed with a homogenizer. Then, a positive electrode mixture paste was produced.

Preparation of Negative Electrode Mix Paste As negative electrode active material, SnGe _0.1 B _0.5 P _0.58 Mg _0.1 K
200 g of _0.1 O _3.35 and 30 g of conductive agent (artificial graphite) were mixed with a homogenizer, and 50 g of a 2% by mass aqueous solution of carboxymethylcellulose as a binder and 10 g of polyvinylidene fluoride were added and mixed. 30 g was added and further kneaded and mixed to prepare a negative electrode mixture paste.

Preparation of Positive and Negative Electrode Sheets The positive electrode mixture paste prepared above was coated on both surfaces of a 30 μm-thick aluminum foil current collector with a blade coater at an application amount of 400 g / m ² and the compressed sheet thickness was 280 μm. And dried, then compression-molded with a roller press and cut into a predetermined size to produce a belt-shaped positive electrode sheet. Furthermore, in a dry box (dew point; dry air of -50 ° C or less), dehydration and drying are performed sufficiently with a far-infrared heater.
A positive electrode sheet was produced. Similarly, paste the negative electrode mixture into 2
A negative electrode sheet having a coating amount of 70 g / m ² and a compressed sheet thickness of 90 μm was prepared in the same manner as in the preparation of the positive electrode sheet.

Production of Cylinder-Type Battery A method of producing a battery will be described with reference to FIG. The positive electrode sheet prepared above, a 30 μm-thick Tonen Tapyrus Co., Ltd. non-woven fabric TAPYRUS P22FW-OCS, a negative electrode sheet, and a 30 μm-thick Tonen Tapyrus Co., Ltd. non-woven fabric TAPYRUS P22FW-OCS in this order. The layers were laminated, and this was spirally wound. The wound electrode group 2 was housed in a nickel-plated iron bottomed cylindrical battery can 1 also serving as a negative electrode terminal, and the above-mentioned electrolyte SiE-1 was injected at 70 ° C. under reduced pressure. Then, the upper insulating plate 3
Was further inserted. A stack of the positive electrode terminal 6, the insulating ring, the PTC element 63, the current interrupter 62, and the pressure-sensitive valve element 61 was caulked via the gasket 5 to produce a cylinder (cylindrical) battery D-1. Batteries D-2 to D-13 using the electrolytes shown in Table 4 were produced in the same manner as the cylinder type (cylindrical) battery D-1. Ten batteries were produced.

Example 7 Cylinder-type (cylindrical) batteries D-14 to D-20 were produced in the same manner as in Example 6 except that graphite powder was used as the negative electrode active material.

<Evaluation of Battery Characteristics> The battery fabricated by the above method was repeatedly charged and discharged 10 times under the conditions of 0.2 C, end-of-charge voltage 4.1 V, and end-of-discharge voltage 2.7 V.
The discharge capacity at the 0th cycle was determined. This was examined for 10 batteries of the same prescription, and the average was taken as the capacity of the battery. Thus, the battery capacity of each battery was obtained, and this value was divided by the capacity of the battery of the battery number D-1 to obtain the relative capacity. The values are shown in Table 4.

[0183]

[Table 4]

From the results shown in Table 4, it can be seen that when the compound (electrolyte composition) of the present invention was used as an electrolyte, the battery capacity was large.

When the positive electrode active material is LiNiO ₂ or LiNiO ₂
In the case of MnO ₂ , the same result as above was obtained.

Example 8 <Preparation of Sheet Type Battery> Preparation of Positive Electrode Sheet 1 As a positive electrode active material, 43 parts by mass of LiCoO ₂ , 2 parts by mass of flaky graphite, 2 parts by mass of acetylene black, and as a binder A slurry obtained by adding 3 parts by mass of polyacrylonitrile and kneading with 100 parts by mass of acrylonitrile as a medium is applied to an aluminum foil having a thickness of 20 μm by using an extrusion type applicator, and then dried and compressed by a calender press. After the molding, a lead plate made of aluminum was welded to the end to prepare a positive electrode sheet (CA-1) having a thickness of 95 μm, a width of 54 mm and a length of 49 mm.

Preparation of positive electrode sheet 43 As a positive electrode active material, 43 parts by mass of LiMn ₂ O ₄ , 2 parts by mass of flaky graphite, 2 parts by mass of acetylene black, and 3 parts by mass of polyacrylonitrile as a binder were added, and acrylonitrile 100 parts was added. The slurry obtained by kneading the mass part as a medium was applied to an aluminum foil having a thickness of 20 μm using an extrusion coating machine, dried, compression-molded by a calender press, and then made of aluminum at the end. Weld the lead plate, thickness 114μm, width 54mm ×
A positive electrode sheet (CA-2) having a length of 49 mm was produced.

Preparation of positive electrode sheet 3 As a positive electrode active material, 43 parts by mass of LiNiO ₂ , 2 parts by mass of flaky graphite, 2 parts by mass of acetylene black, and 3 parts by mass of polyacrylonitrile as a binder were added, and 100 parts by mass of acrylonitrile were added. The slurry obtained by kneading with a medium as a medium is applied to an aluminum foil having a thickness of 20 μm using an extrusion coating machine, and after drying and compression-molding with a calendar press machine, an aluminum lead plate is attached to the end. By welding, a positive electrode sheet (CA-3) having a thickness of 75 μm, a width of 54 mm and a length of 49 mm was produced.

Preparation of Negative Electrode Sheet 1 43 parts by mass of SnSiO ₃ as a negative electrode active material, 2 parts by mass of acetylene black and 2 parts by mass of graphite as a conductive agent, and 3 parts by mass of polyacrylonitrile as a binder were mixed. And N-methylpyrrolidone 10
The mixture was kneaded using 0 parts by mass as a medium to obtain a negative electrode mixture slurry. Next, 45 parts by mass of α-alumina, 7 parts by mass of graphite, 3 parts by mass of polyacrylonitrile, and 100 parts by mass of N-methylpyrrolidone were mixed to obtain an auxiliary layer slurry. Using a negative electrode mixture slurry as a lower layer and an auxiliary layer slurry as an upper layer, a 10 μm-thick copper foil is applied using an extrusion coater, dried, and compression-molded with a calender press to obtain a thickness of 46 μm and a width of 55 mm × A negative electrode sheet having a length of 50 mm was prepared. After welding a lead plate made of nickel to the end of the negative electrode sheet, heat treatment was performed at 230 ° C. for 1 hour in dry air having a dew point of −40 ° C. or less. The heat treatment was performed using a far-infrared heater. 4 across the negative electrode sheet after heat treatment
Lithium foil (purity: 99.8%) having a thickness of 35 μm and cut to a size of 55 mm × 55 mm was attached at an interval of 10 mm at right angles to the sheet length direction (AN-1).

Preparation of Negative Electrode Sheet In preparation of the negative electrode sheet 1, SnSiO ₃ was converted to Sn _0.8 A
_{l 0.2 B 0.3 P 0.2 Si 0} .5 O 3.6, SnAl 0.4 B 0.5 Cs
A negative electrode sheet (AN-2) having a width of 55 mm and a length of 50 mm in which a lithium foil obtained by welding a nickel-made lead plate to the end was similarly applied, except that _0.1 P _0.5 O _3.65 was used.
(AN-3) was produced.

Preparation of Negative Electrode Sheet 3 43 parts by mass of a mesoface pitch-based carbon material (Petoka) as a negative electrode active material, and 2 parts by mass of acetylene black and 2 parts by mass of graphite as conductive agents were mixed and bound. 3 parts by mass of polyacrylonitrile as an agent were added and kneaded with 100 parts by mass of N-methylpyrrolidone as a medium to obtain a negative electrode mixture slurry. The negative electrode mixture slurry,
A 10-μm-thick copper foil was applied using an extrusion-type coating machine, dried, and compression-molded with a calender press to produce a negative electrode sheet having a thickness of 46 μm, a width of 55 mm and a length of 50 mm. After welding a lead plate made of nickel to the end of the negative electrode sheet, it was dried in a dry air having a dew point of −40 ° C. or less.
Heat treatment was performed at 30 ° C. for 1 hour. The heat treatment was performed using a far-infrared heater. (AN-4).

Manufacturing of Sheet Type Battery The manufacturing of a sheet type battery will be described with reference to FIGS.
First, the negative electrode sheet and the positive electrode sheet each have a dew point of -40 ° C.
It was dehydrated and dried at 230 ° C. for 30 minutes in the following dry air. In a dry atmosphere, a dehydrated and dried positive electrode sheet (CA-1) 21 having a width of 54 mm × length 49 mm, a solid electrolyte 22 having a width of 60 mm × length 60 mm and a thickness of 30 μm, and a width of 55 m
Dehydrated and dried negative electrode sheet of mx 50 mm length (AN-
1) and 23 were laminated in this order, and polyethylene (50 μm)
m) -An exterior material made of a laminated film of polyethylene terephthalate (50 μm) was used, and the four edges were heat-sealed under vacuum to form a sheet-type battery (SB-1). In the same manner as in the production of the sheet-type battery (SB-1), the sheet-type battery (SB-2) having the configuration shown in Table 5
To (SB-16).

[0193]

[Table 5]

<Evaluation of Battery Performance> With respect to the sheet-type battery produced by the above method, 0.2 C and end-of-charge voltage 4.2.
The charge and discharge were repeated 10 times under the conditions of V and a discharge end voltage of 2.6 V, and the discharge capacity at the 10th cycle was determined. This was examined for 10 batteries of the same prescription, and the average was taken as the capacity of the battery. In this way, the capacity of each battery is obtained, and this value is set to SB-2 to SB-5 for SB-2.
-1 and SB-12 for SB-12 and SB-13
Is SB-7 for SB-14 and SB-8 for SB-14
Then, SB-15 was divided by SB-9 for SB-15 and SB-10 for SB-16 to obtain the relative capacitance between the same electrode compositions. Table 5 shows the values.

From the above results, it was confirmed that when the compound (electrolyte composition) of the present invention was used as an electrolyte, the battery capacity was larger than that of the comparative example.

[0196]

According to the present invention, there is provided a novel electrolyte composition exhibiting a high ion transport number, a method for producing the same, and a non-aqueous electrolyte secondary battery containing the electrolyte composition and having a high battery capacity. Can be provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a cylinder battery manufactured in Examples 6 and 7.

FIG. 2 shows a conceptual diagram of a sheet-type battery manufactured in Example 8.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Battery can also serve as a negative electrode 2 Wound electrode group 3 Upper insulating plate 4 Positive electrode lead 5 Gasket 6 Battery lid also serving as a positive electrode terminal 61 Pressure sensitive valve element 62 Current cutoff element (switch) 63 PTC element 21 Positive sheet 22 Nonwoven fabric 23 Negative sheet 24 Positive terminal 25 Negative terminal

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Takeshi Chiga 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film F-term (reference) 5H029 AJ03 AJ06 AK03 AL02 AL03 AL04 AL06 AL07 AM02 AM03 AM04 AM05 AM07 AM16 BJ02 BJ04 BJ14 DJ09 DJ18 HJ02

Claims (16)

[Claims] 1. A polymer compound having a structure represented by the following general formula (1) as a repeating unit, and a salt of a metal ion belonging to Group 1 or 2 of the periodic table. Electrolyte composition. Embedded image In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. R ² represents a substituted or unsubstituted alkyl group. At least one of R ¹ and O—R ² is a substituent containing an alkoxycarbonyl group. M is silicon,
Represents boron or a metal element. n represents the valence of M. 2. The electrolyte composition according to claim 1, wherein M in the general formula (1) is silicon. 3. The electrolyte composition according to claim 1, wherein R ¹ in the general formula (1) is a substituted or unsubstituted alkoxy group. 4. The polymer compound represented by the following general formula (2)
The electrolyte composition according to any one of claims 1 to 3, which is a product obtained by reacting a compound represented by the formula with a carboxylic acid having a hydroxyl group. Embedded image In the general formula (2), M represents silicon, boron or a metal element. n represents a valence that the element represented by M can take. R ³ represents a substituted or unsubstituted alkyl group. 5. The electrolyte composition according to claim 1, wherein the carboxylic acid having a hydroxyl group is represented by the following general formula (3). Embedded image In the general formula (3), R ⁴ and R ⁵ are each independently:
Represents a hydrogen atom or an alkyl group. a represents an integer of 1 to 5, and b represents an integer of 0 to 30. 6. The electrolyte composition according to claim 5, wherein a in the general formula (3) is 1 and b is 0. 7. R ⁴ and R in the general formula (3)
7. The electrolyte composition according to claim ⁵ , wherein ⁵ is a hydrogen atom. 8. The polymer compound represented by the following general formula (4):
The electrolyte composition according to any one of claims 1 to 3, which is a product obtained by reacting a polymer compound having a structure represented by the following formula as a repeating unit with an alcohol compound having an alkoxycarbonyl group. Embedded image In the general formula (4), R ⁶ represents the general formula (1)
Represents a substituent having the same meaning as R ¹ . R ⁷ represents a substituted or unsubstituted alkoxy group. 9. The electrolyte composition according to claim 8, wherein the alcohol compound having an alkoxycarbonyl group is represented by the following general formula (5). Embedded image In the general formula (5), R ⁸ represents the general formula (2)
Represents a substituent having the same meaning as R ³ . 10. The electrolyte composition according to claim 9, wherein a in the general formula (5) is 1 and b is 0. 11. R ⁴ and R ⁵ in the general formula (5)
Is a hydrogen atom, The electrolyte composition according to claim 9 or 10. 12. The electrolyte composition according to claim 1, which is reacted with a compound having at least two or more nucleophilic groups in a molecule. 13. The electrolyte composition according to claim 12, wherein the nucleophilic group is a hydroxyl group. 14. A non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode, wherein the secondary battery contains the electrolyte composition according to any one of claims 1 to 13. Water electrolyte secondary battery. 15. A step of preparing a polymer compound having a structure represented by the following general formula (1) as a repeating unit;
Adding a salt of a metal ion belonging to Group 1 or Group 2 of the periodic table to the polymer compound, wherein the step of preparing the polymer compound comprises the following general method: A method for producing an electrolyte composition, comprising reacting a compound represented by the formula (2) with a carboxylic acid having a hydroxyl group. Embedded image In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. R ² represents a substituted or unsubstituted alkyl group. At least one of R ¹ and O—R ² is a substituent containing an alkoxycarbonyl group. M is silicon,
Represents boron or a metal element. n represents the valence of M. Embedded image In the general formula (2), M represents silicon, boron or a metal element. n represents a valence that the element represented by M can take. R ³ represents a substituted or unsubstituted alkyl group. 16. A step of preparing a polymer having a structure represented by the following general formula (1) as a repeating unit:
Adding a salt of a metal ion belonging to Group 1 or Group 2 of the periodic table to the polymer compound, wherein the step of preparing the polymer compound comprises the following general method: A method for producing an electrolyte composition, comprising reacting a polymer compound having a structure represented by the formula (4) as a repeating unit with an alcohol compound having an alkoxycarbonyl group. Embedded image In the general formula (1), R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxy group. R ² represents a substituted or unsubstituted alkyl group. At least one of R ¹ and O—R ² is a substituent containing an alkoxycarbonyl group. M is silicon,
Represents boron or a metal element. n represents the valence of M. Embedded image In the general formula (4), R ⁶ represents the general formula (1)
Represents a substituent having the same meaning as R ¹ . R ⁷ represents an alkoxy group.