JP2002298918A - Electrolyte composition and nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new electrolyte composition showing high ion conductivity and ion transference number and having remarkably low fluidity, and a nonaqueous electrolyte secondary battery of high capacity with excellent cycle stability. SOLUTION: This electrolyte composition contains fused salt of specific structure, silicon polymer and the salt of metal ion belonging to the group I or group II of the periodic table, and the nonaqueous electrolyte secondary battery contains the electrolyte composition. The fused salt is expressed by one of general formulas (1)-(3), wherein Q is an atomic group that can form the aromatic cation of 5-member ring or 6-member ring together with nitrogen atom, L<11> -L<36> are each an alkylene group, an alkyleneoxy group, an alkenyleneoxy group or a bivalent connection group formed by plurally combining these groups; R<11> -R<36> are each a hydrogen atom or a substituent which may be connected to each other to form a ring structure; n1 is 0 or 1 or more; X<-> is anion; and A is a nitrogen atom or phosphorus atom.

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, and a high capacity and excellent cycle stability. The present invention relates to a non-aqueous electrolyte secondary battery.

[0002]

2. Description of the Related Art An electrolyte used for an electrochemical cell such as a non-aqueous secondary battery 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 these batteries, 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 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, various electrolytes have been proposed. A so-called gel electrolyte in which a solution electrolyte is impregnated in a polymer matrix (see, for example, R. Koksbang et al., S.
olid State Ionics, 69, 320
(1994)) has a problem that the ion conductivity is small and the battery performance is not deteriorated with respect to the solution electrolyte, but the volatilization of the solvent cannot be completely suppressed. Further, a polymer electrolyte obtained by dissolving a salt in a polymer such as polyethylene oxide is expected to solve the problem of a solution electrolyte, but has a problem that ionic conductivity is not yet sufficient. On the other hand, if the counter anion is B
^{_{F 4 -, (CF 3 SO}} 2) 2 N - imidazolium salt or a pyridinium salt, such as a room temperature molten salt which is liquid at room temperature, as an electrolyte for lithium-ion batteries, have been proposed,
Despite high ionic conductivity, there is a problem that one of the important characteristics of the electrolyte is a decrease in lithium ion transport number, and that the electrolyte is liquid, which may cause liquid leakage.

[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, the present invention provides a novel electrolyte composition that exhibits high ionic conductivity and ion transport number, has low fluidity, or has no fluidity, and further has a high battery capacity without a decrease in capacity. An object of the present invention is to provide a nonaqueous electrolyte secondary battery having excellent cycle stability.

[0005]

Means for Solving the Problems As a result of intensive studies in view of the above object, the present inventors have found that molten salts, silicon polymers, and metal ions belonging to Group 1 (Ia) or Group 2 (IIa) of the periodic table The present inventors have found that an electrolyte composition containing a salt of (i) exhibits excellent charge transport ability and durability, and have reached the present invention. Further, a non-aqueous electrolyte secondary battery of the present invention is characterized by containing the electrolyte composition. The means for solving the above problems are as follows.

<1> An electrolyte composition comprising a molten salt, a silicon polymer, and a salt of a metal ion belonging to Group 1 or 2 of the periodic table.

<2> The electrolyte composition according to <1>, wherein the molten salt is represented by any of the following general formulas (1), (2), and (3).

[0008]

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In the general formula (1), Q represents an atomic group capable of forming a 5- or 6-membered aromatic cation together with a nitrogen atom. L ¹¹ and L ^{12 each} represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkyleneoxy group or a divalent linking group composed of a repetition thereof, a substituted or unsubstituted alkenyleneoxy group, or It represents a divalent linking group formed by repeating the above, or a divalent linking group formed by combining a plurality of these. R ¹¹ represents a hydrogen atom or a substituent. R ¹² is
Represents a hydrogen atom or a substituent. n1 is 0 or 1 or more and Q
Represents an integer equal to or less than the maximum value of the number of substitutable (L ¹² -R ¹² ). X ^- represents an anion. When n1 is 2 or more,
(L ¹² -R ¹² ) may be the same or different, and two or more of R ¹¹ and R ¹² may be linked to each other to form a ring structure.

In the general formula (2), L ²¹ , L ²² ,
L ²³ and L ²⁴ have the same meaning as L ¹¹ in the formula (1). R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrogen atom or a substituent. Of R ²¹ , R ²² , R ²³ and R ²⁴ , 2
Two or more may be connected to each other to form a ring structure. A
Represents a nitrogen atom or a phosphorus atom.

In the general formula (3), L ^{31 to} L
³⁶ has the same meaning as L ¹¹ in the formula (1). R
³¹ to R ³⁶ represents a hydrogen atom or a substituent. Two or more of R ^{31 to} R ³⁶ may be linked to each other to form a ring structure.

<3> Q in the general formula (1) is:
The electrolyte composition according to <2>, which is an atomic group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. <4> The electrolyte according to <2> or <3>, wherein the 5-membered or 6-membered aromatic cation formed by Q in the general formula (1) together with the nitrogen atom is an imidazolium cation or a pyridinium cation. A composition.

<5> The molten salt represented by the general formula (1) is the electrolyte composition according to any one of <2> to <4> represented by the following general formula (4).

[0014]

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In the general formula (4), L ⁴¹ , L ⁴² ,
And L ⁴³ each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group composed of a repetition thereof, a substituted or unsubstituted alkenyleneoxy group; A divalent linking group consisting of a group or a repetition thereof, or a divalent linking group obtained by combining a plurality of these groups. R
⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom or a substituent. n4 represents an integer of 0 to 3. X ^- represents an anion. When n4 is 2 or 3, (R ⁴³ -L ⁴³ ) may be the same or different, and R ⁴¹ , R ⁴² and R ⁴³
Two or more of them may be connected to each other to form a ring structure.

<6> The molten salt represented by the general formula (1) is the electrolyte composition according to any one of <2> to <4> represented by the following general formula (5).

[0017]

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In the general formula (5), L⁵¹, And L
⁵²Is each independently a substituted or unsubstituted alkylene
Group, substituted or unsubstituted alkenylene, substituted or unsubstituted
Is an unsubstituted alkyleneoxy group or a repeat thereof.
Divalent linking group, substituted or unsubstituted alkenylene
A divalent linking group consisting of
It represents a divalent linking group formed by combining a plurality of these. R⁵¹,
And R⁵²Each independently represents a hydrogen atom or a substituent. n
5 represents the integer of 0-5. X^-Represents an anion.
When n5 is 2 or more, (L⁵²-R⁵²) Are the same but different
May be R ⁵¹And R⁵²Two or more of
They may be linked to form a ring structure.

<7> The electrolyte composition according to any one of <1> to <6>, wherein the silicon polymer has a structure represented by the following general formula (6) as a repeating unit.

[0020]

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In the above general formula (6), R ¹ and R
² represents an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. X represents an oxygen atom, a nitrogen atom, an alkylene group, a phenylene group, a silicon atom, a metal atom, or an atomic group consisting of a combination thereof.

<8> The electrolyte according to <7>, wherein the silicon polymer having the structure represented by the general formula (6) as a repeating unit has the structure represented by the following general formula (7) as a repeating unit. A composition.

[0023]

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In the general formula (7), R ³ represents an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. R ⁴ represents an alkyl group or an aryl group.

<9> R in the general formula (7)
The electrolyte composition according to the item <8>, wherein ³ is an alkoxy group.

<10> R ³ in the general formula (7)
And at least one of OR ⁴ is the electrolyte composition according to any one of the above <8> or <9>, having an alkoxycarbonyl group as a substituent.

<11> A silicon polymer having a structure represented by the above general formula (7) as a repeating unit is formed by reacting a compound represented by the following general formula (8) with a carboxylic acid having a hydroxyl group. The electrolyte composition according to any one of <8> to <10>, wherein the electrolyte composition is a substance.

[0028]

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[0029] In the general formula (8), R ³ has the same meaning as R ³ in Formula (7). R ⁵ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

<12> The carboxylic acid having a hydroxyl group is a compound represented by the following general formula (9):
1> The electrolyte composition according to any one of the above.

[0031]

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In the general formula (9), R ⁶ and R
⁷ represents a hydrogen atom or an alkyl group. a represents an integer of 1 to 5. b represents an integer of 0 to 30.

<13> The electrolyte composition according to <1212>, wherein a in the general formula (9) is 1 and b is 0. <14> The electrolyte composition according to <12> or <13>, wherein R ⁶ and R ⁷ in the general formula (9) are hydrogen atoms.

<15> A silicon polymer having a structure represented by the general formula (7) as a repeating unit is a combination of a silicon polymer having a structure represented by the following general formula (10) as a repeating unit and an alcohol compound. The electrolyte composition according to any one of <8> to <10>, which is a product obtained by reacting.

[0035]

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In the general formula (10), R ⁸ has the same meaning as R ³ in the general formula (7). R ⁹ represents an alkoxy group.

<16> The above <15> wherein the alcohol compound has an alkoxycarbonyl group as a substituent.
The electrolyte composition according to the above.

<17> The electrolyte composition according to <16>, wherein the alcohol compound is represented by the following general formula (11).

[0039]

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In the general formula (11), R ¹⁰ represents an alkyl group or an aryl group.

<18> a in formula (11)
Is 1 and b is 0, the electrolyte composition according to <17> above. <19> R ⁶ and R ⁷ in the general formula (11) are:
The electrolyte composition according to any one of the items <17> to <18>, which is a hydrogen atom.

<20> The electrolyte composition according to any one of <8> to <19>, wherein the electrolyte composition is reacted with a compound having at least two or more nucleophilic groups in a molecule.

<21> The electrolyte composition according to <20>, wherein the nucleophilic group is a hydroxyl group.

<22> 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 <1> to <21>. Is a non-aqueous electrolyte secondary battery.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The electrolyte composition of the present invention and a non-aqueous electrolyte secondary battery will be described below. Here, first, the electrolyte composition of the present invention will be described in detail.

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

The electrolyte composition of the present invention comprises a molten salt, a silicon polymer, and a Group 1 (Ia) or Group 2 (II)
a) It is characterized by containing a salt of a metal ion belonging to the group.

<Molten Salt> The molten salt contained in the electrolyte composition of the present invention will be described below. The salt contained in the electrolyte composition of the present invention is preferably a low-melting salt, a so-called molten salt, from the viewpoint of exhibiting high ionic conductivity and having low volatility, and normal temperature (around 25 ° C.) More preferably, the compound is a liquid that is a liquid at room temperature, that is, a so-called room temperature molten salt.

The molten salt used in the present invention is preferably a compound represented by any one of the following general formulas (1), (2) and (3). ° C or lower, more preferably 80 ° C or lower, and particularly preferably 60 ° C or lower.

[0050]

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-Compound represented by Formula (1)-Here, the compound represented by Formula (1) will be described. In the general formula (1), Q represents an atomic group capable of forming a 5- or 6-membered aromatic cation together with a nitrogen atom. Q is preferably an atomic group composed of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, and a sulfur atom. A 5-membered ring or 6 which Q forms together with a nitrogen atom
The membered ring aromatic cation is preferably an imidazolium cation or a pyridinium cation.

The 5-membered ring formed by Q with a nitrogen atom is preferably an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an isoxazole ring, a thiadiazole ring, an oxadiazole ring or a triazole ring. It is more preferably a ring, a triazole ring or an imidazole ring, particularly preferably an imidazole ring.

The 6-membered ring formed by Q with a nitrogen atom includes a pyridine ring, a pyrimidine ring, a pyridazine ring,
It is preferably a pyrazine ring or a triazine ring, and more preferably a pyridine ring.

In the general formula (1), L ¹¹ and L ¹²
Is a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkyleneoxy group or a divalent linking group consisting of a repetition thereof, a substituted or unsubstituted alkenyleneoxy group or a repetition thereof Represents a valent linking group or a divalent linking group obtained by combining a plurality of these.

Specific examples of L ¹¹ include a methylene group,
An ethylene group, a propylene group, a vinylene group, a propenylene _{group, - (CH 2 CH 2 O} ) n -, - (CH 2 CH 2 O) n -C
_{H 2 -, - (C 3} H 6 O) n -, - (C 3 H 6 O) n -CH
_2- , combinations thereof, and the like. Where n
Represents an integer of 1 to 20, respectively. L ¹¹ is a methylene group, an ethylene group, a propylene group,-(CH ₂ CH ₂ O) _n- or-(CH ₂ CH ₂ O) _{n-
CH 2 -, - (C 3} H 6 O) n -, - (C 3 H 6 O) n -CH 2
Is preferable, and an alkylene group such as a methylene group, an ethylene group, and a propylene group is more preferable.

In the general formula (1), R ¹¹ represents a hydrogen atom or a substituent. R ¹² represents a hydrogen atom or a substituent. Examples of the substituent represented by R ¹¹ or R ¹² include, for example, an alkyl group, an alkenyl group, an aryl group, a silyl group, a silyloxy group, an alkoxy group, an amino group, an amide group, a guanidino group, a carbamoyl group, a cyano group, Examples include an alkylthio group, a heterocyclic group, and a halogen atom.

Among the above alkyl groups, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an octyl group, a 2-carboxyethyl group, a benzyl group and the like are preferable. Among the alkenyl groups, for example, a vinyl group, an allyl group, a propenyl group and the like are preferable. Among the aryl groups, for example, a phenyl group, a methoxyphenyl group and the like are preferable.

Among the above silyl groups, those having 3 to 3 carbon atoms
A substituted or unsubstituted silyl group preferably 0, for example, a trimethylsilyl group, t- butyl dimethyl silyl group, a phenyl dimethylsilyl group, - (Si (CH _3)
2 O) _n Si (CH ₃ ) _{3 and the} like are more preferred. Among the silyloxy groups, a silyloxy group having 3 to 20 carbon atoms is preferable. For example, a trimethylsilyloxy group, t-
A butylsilyloxy group is more preferred. Among the alkoxy groups, for example, methoxy group, ethoxy group,-
_{(OCH 2 CH 2) n -OCH} 3, - (OCH 2 CH 2) n -
OCH ₂ CH _{3 and the} like are preferred.

Among the above-mentioned amino groups, for example, a dimethylamino group, a diethylamino group and the like are preferable. Among the amide groups, for example, an acetylamino group, a benzoylamino group and the like are preferable. Among the carbamoyl groups, for example, an N, N-dimethylcarbamoyl group, an N-phenylcarbamoyl group and the like are preferable. Among the alkylthio groups, for example, a methylthio group, an ethylthio group and the like are preferable. Among the above heterocyclic groups, for example, a pyridyl group, an imidazolyl group and the like are preferable. Among the halogen atoms,
For example, a chlorine atom, a bromine atom, an iodine atom and the like are preferable.

Among the above preferred substituents, an alkyl group, an alkenyl group, an aryl group, a silyl group, a silyloxy group, an alkoxy group, an amino group, a guanidino group, a cyano group, a heterocyclic group and a halogen atom are preferred. The preferred substituent may further have a substituent. In the specific examples of the preferable substituents, n is 1 to
Represents an integer of 20.

In the general formula (1), n1 is 0 or an integer of 1 or more and not more than the maximum value of the number of (L ¹² -R ¹² ) which can be substituted on Q. n1 is preferably an integer of 0 to 2. When n1 is 2 or more, (L ¹² -R ¹²⁾
May be the same or different.

In the general formula (1), R ¹¹ and R ¹²
Of these, two or more may be connected to each other to form a ring structure. The ring structure is preferably a 5- to 7-membered ring, more preferably a 5- to 6-membered ring.

The compound represented by the general formula (1) may form a multimer via R ¹¹ and / or R ¹² . As the formed multimer, a dimer to a tetramer is preferable, and a dimer is more preferable.

In the general formula (1), X ⁻ represents an anion. As the X ⁻ , for example, SCN ⁻ , B
F ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , SbF ₆ ⁻ , (CF ₃ SO ₂ ) _{2
^{N -, (CF 3 CF 2}} 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 S
O ₃ ⁻ , C ₆ F ₅ SO ₃ ^{— and the} like are preferred.

[0065] The X ^- the Among the preferred embodiment, SC
N ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , SbF ₆ ⁻ , (CF ₃ S
O ₂ ) ₂ N ⁻ , (CF ₃ CF ₂ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ )
₃ C ⁻ and CF ₃ SO ₃ ⁻ are more preferred.

Among the compounds represented by the general formula (1), which are preferable as the molten salt contained in the electrolyte composition of the present invention, the compound represented by the following general formula (4) and the compound represented by the following general formula (5) The compounds represented are more preferred.

[0067]

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In the general formula (4), L ⁴¹ , L ⁴² ,
And L ⁴³ each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group composed of a repetition thereof, a substituted or unsubstituted alkenyleneoxy group; A divalent linking group consisting of a group or a repetition thereof, or a divalent linking group obtained by combining a plurality of these groups. R
⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom or a substituent. n4 represents an integer of 0 to 3. X ^- represents an anion. When n4 is 2 or 3, (R ⁴³ -L ⁴³ ) may be the same or different, and R ⁴¹ , R ⁴² and R ⁴³
Two or more of them may be connected to each other to form a ring structure.

[0069]

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In the general formula (5), L⁵¹, And L
⁵²Is each independently a substituted or unsubstituted alkylene
Group, substituted or unsubstituted alkenylene, substituted or unsubstituted
Is an unsubstituted alkyleneoxy group or a repeat thereof.
Divalent linking group, substituted or unsubstituted alkenylene
A divalent linking group consisting of
It represents a divalent linking group formed by combining a plurality of these. R⁵¹,
And R⁵²Each independently represents a hydrogen atom or a substituent. n
5 represents the integer of 0-5. X^-Represents an anion.
When n5 is 2 or more, (L⁵²-R⁵²) Are the same but different
May be R ⁵¹And R⁵²Two or more of
They may be linked to form a ring structure.

In the general formulas (4) and (5), specific examples and preferred embodiments of L ⁴¹ , L ⁴² , L ⁴³ , L ⁵¹ and L ⁵² include L ¹¹ in the general formula (1).
Is the same as The general formula (4) and the general formula (5)
In the formula, specific examples and preferred embodiments of R ⁴¹ , R ⁴² , R ⁴³ , R ^51, and R ⁵² include R in formula (1).
^Same as ¹¹ . Formula (4) and the general formula (5), X ^- is the X in the general formula (1) ^-
And the preferred embodiment is also the same.

In the general formula (4), R ⁴¹ and R ⁴²
And two or more of R ⁴³ and two or more of R ⁵¹ and R ^{52 in} the formula (5) may be connected to each other to form a ring structure. As this ring structure,
A 5- to 7-membered ring is preferred, and a 5- to 6-membered ring is more preferred.

-Compound represented by the general formula (2) and compound represented by the general formula (3)-Next, a compound represented by the following general formula (2), which is preferable as a molten salt contained in the electrolyte composition of the present invention. The compound represented by the formula and the compound represented by the following formula (3) will be described.

[0074]

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In the general formula (2), L ²¹ , L ²² ,
L ²³ and L ²⁴ have the same meaning as L ¹¹ in the formula (1). R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrogen atom or a substituent. Of R ²¹ , R ²² , R ²³ and R ²⁴ , 2
Two or more may be connected to each other to form a ring structure. A
Represents a nitrogen atom or a phosphorus atom.

[0076]

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In the general formula (3), L ^{31 to} L
³⁶ has the same meaning as L ¹¹ in the formula (1). R
³¹ to R ³⁶ represents a hydrogen atom or a substituent. Two or more of R ^{31 to} R ³⁶ may be linked to each other to form a ring structure.

In the general formulas (2) and (3), L ²¹ , L ²² , L ²³ , L ²⁴ , L ³¹ , L ³² , L ³³ ,
Specific examples and preferred embodiments of L ³⁴ , L ³⁵ and L ³⁶ are the same as L ¹¹ in the general formula (1). In the general formulas (2) and (3), R ²¹ , R ²² , R
^23, specific examples and preferred embodiments of ^{R 24, R 31, R 32} , R 33, R 34, R 35 and R ^36, is the same as R ¹¹ in the formula (1). In the general formulas (2) and (3), X ⁻ has the same meaning as X ⁻ in the general formula (1), and the preferred embodiments are also the same.

In the general formula (2), R ²¹ ,
In the general formula (3), two or more of R ²² , R ²³ and R ²⁴ are two or more of R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are each other They may be linked to form a ring structure. As this ring structure, a 5- to 7-membered ring is preferable, and a 5- to 6-membered ring is more preferable.

Hereinafter, specific examples (Y1 to 29) of the compounds represented by formulas (1), (2) and (3) of the present invention will be shown. It is not limited at all.

[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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<Silicon Polymer> Here, the silicon polymer contained in the electrolyte composition of the present invention will be described.

The silicon polymer in the present invention is a polymer in which an atomic group containing a silicon atom is present on a side chain of a polymer skeleton (for example, poly (p-trimethylsilylstyrene), poly (1-trimethylsilyl-1-propyne)).
Etc.), or containing a silicon atom in the polymer main chain. Among them, those containing a silicon atom in the polymer main chain are preferred.

Examples of the polymer containing silicon in the polymer main chain include a linear, branched, cyclic or polycyclic polymer having a structure represented by the following general formula (6) as a repeating unit. Preferred are mentioned.

[0090]

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In the general formula (6), R ¹ and R
² represents an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. In the general formula (6), X
Represents an oxygen atom, a nitrogen atom, an alkylene group, a phenylene group, a silicon atom, a metal atom, or an atomic group composed of a combination thereof. Examples of the atomic group represented by X include polysiloxane, polysilazane, polysilmethylene, polysilphenylene, polysilane, and polymetallosiloxane. Among them, oxygen atom,
Alternatively, an atomic group composed of a combination of an oxygen atom and an alkylene group is more preferable, and an oxygen atom is particularly preferable.

Among the polymers having the structure represented by the general formula (6) as a repeating unit, those having a structure represented by the following general formula (7) as a repeating unit include a linear, branched, cyclic, Polycyclic polymers are more preferred.

[0093]

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In the general formula (7), R ³ represents an alkyl group, an alkoxy group, an aryl group or an aryloxy group. R ⁴ represents an alkyl group or an aryl group.
As the alkyl group represented by R ³ or R ⁴ , an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. For example, methyl group, ethyl group, propyl group, n -Butyl group, t-butyl group and the like are particularly preferred.

The aryl group represented by R ³ or R ⁴ is preferably an aryl group having 1 to 10 carbon atoms, for example, more preferably a phenyl group, a naphthyl group and the like.

The alkoxy group represented by R ³ is preferably an alkoxy group having 1 to 8 carbon atoms.
~ 4 alkoxy groups are more preferable, for example, methoxy group, ethoxy group, propoxy group, n-butoxy group, t-
Butoxy groups and the like are particularly preferred.

The aryloxy group represented by R ³ is preferably an aryloxy group having 6 to 20 carbon atoms.
An aryloxy group having 6 to 10 carbon atoms is more preferable, and for example, a phenoxy group, a p-methylphenoxy group, a p-methoxyphenoxy group, a naphthoxy group and the like are particularly preferable.

The alkyl group and aryl group represented by R ³ or R ⁴ , and the alkoxy group and aryloxy group represented by R ³ may have a substituent. Specific examples of the substituent are preferably those described below. For example, 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 An aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group,
Alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group,
Examples include 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, and among them, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-butyl group 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 group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group,
—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-mentioned 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, methoxycarbonylamino group, ethoxycarbonylamino group, 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 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 alkyl and aryl sulfonylamino 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 above-mentioned 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 acyl groups, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl and the like are more preferred.

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, methoxycarbonyl group, ethoxycarbonyl group,
A t-butoxycarbonyl group, an n-octadecyloxycarbonyl group and the like are preferable.

Among the carbamoyl groups, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl 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.

In the general formula (7), R ³ is more preferably an alkoxy group. More preferably, at least one of R ³ and OR ⁴ has an alkoxycarbonyl group as a substituent.

Hereinafter, specific examples (A) of the silicon polymer according to the present invention and a silicon polymer having a structure represented by the general formula (6) or (7) as a repeating unit will be described.
-1 to 15), but the present invention is not limited thereto.

[0129]

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[0130]

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[0131]

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The silicon polymer having the structure represented by the general formula (7) as a repeating unit is preferably obtained by reacting a compound represented by the following general formula (8) with a carboxylic acid having a hydroxyl group. .

[0133]

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[0134] In the general formula (8), R ³ has the same meaning as R ³ in Formula (7). R ⁵ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. The alkyl groups represented by R ⁵ may be the same or different. The alkyl group represented by R ⁵ has the same meaning as the alkyl group represented by R ⁴ in Formula (7). The aryl groups represented by R ⁵ may be the same or different. The aryl group represented by R ⁵ has the same meaning as the aryl group represented by R ⁴ in Formula (7).

Hereinafter, specific examples (2-1 to 8) of the compound represented by the general formula (8) will be shown, but the present invention is not limited thereto.

[0136]

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Examples of the carboxylic acid having a hydroxyl group include:
A compound represented by the following general formula (9) is preferred.

[0138]

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In the general formula (9), R ⁶ and R ⁷ are
Each independently represents a hydrogen atom or an alkyl group. R ⁶ , R ⁷
Is an alkyl group represented by the general formula (7)
It has the same meaning as the alkyl group represented by ³ . Among the above R ⁶ and R ⁷ , a hydrogen atom is preferable.

In the general formula (9), a represents 1 to 5
And b represents an integer of 0 to 30. When a is 2 or more, R ⁶ and R ⁷ may be the same or different.

Hereinafter, specific examples (3-1 to 10) of the carboxylic acid having a hydroxyl group and the compound represented by the general formula (9) in the present invention are shown, but the present invention is not limited thereto. Not something.

[0142]

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In the present invention, the compound represented by the general formula (7)
The silicon polymer having a repeating unit represented by the following formula (I) is preferably obtained by reacting a silicon polymer having a structure represented by the following general formula (10) as a repeating unit with an alcohol compound. More preferably, it is an alcohol compound having a carbonyl group.

[0144]

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In the general formula (10), R ⁸ has the same meaning as R ³ in the general formula (7). That is, it represents an alkyl group, an alkoxy group, an aryl group or an aryloxy group. R ⁹ represents an alkoxy group. Alkoxy group represented by R ⁸ and R ^9, the general formula (7) R
It has the same meaning as the alkoxy group represented by ³ .

Hereinafter, specific examples (4-1 to 4) of the silicon polymer having the structure represented by the general formula (10) as a repeating unit are shown, but the present invention is not limited thereto.

[0147]

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As the alcohol compound having an alkoxycarbonyl group, a compound represented by the following formula (11) is more preferable.

[0149]

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In the general formula (11), R ⁶ , R ⁷ ,
a and b have the same meanings as R ⁶ , R ⁷ , a and b in the general formula (9). R ¹⁰ has the same meaning as R ⁵ in the general formula (8), and is a substituted or unsubstituted alkyl group;
Represents a substituted or unsubstituted aryl group. Alkyl and aryl groups represented by R ¹⁰ has the same meaning as the alkyl group and aryl group represented by R ³ in the general formula (7).

Hereinafter, specific examples (5-1 to 13) of the alcohol compound in the present invention will be shown, but the present invention is not limited thereto.

[0152]

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<Production of Electrolyte Composition> The general formula (8)
And the above-mentioned carboxylic acid having a hydroxyl group (hereinafter sometimes referred to as “reaction A”), and a silicon polymer having a structure represented by the general formula (10) as a repeating unit With the alcohol compound (hereinafter may be referred to as "reaction B").
May be performed in the presence of a solvent or in the 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 from room temperature to 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 Reaction A and 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 production of the electrolyte composition of the present invention, a step of preparing a silicon polymer having the structure represented by the general formula (7) as a repeating unit (reaction A or reaction B); And the step of adding the molten salt and the salt of a metal ion belonging to Group 1 (Ia) or Group 2 (IIa) of the Periodic Table may be performed simultaneously. An ionic salt may be added. That is, the preparation of the silicon polymer (the above-mentioned reaction A or reaction B) is carried out by using the molten salt and the periodic table 1 (I
The treatment may be carried out in the presence of a salt of a metal ion belonging to the group a) or the group 2 (IIa), and the molten salt and the salt of the metal ion may be added to the prepared silicon polymer later.

In the reaction A in the step of preparing the silicon polymer, the ratio of the compound (A ¹ ) represented by the general formula (8) to the carboxylic acid (A ² ) having a hydroxyl group is represented by A ² / A ¹ is 0.1 to n (molar ratio) (n
Has the same meaning as n in the general formula (1). ), More preferably 0.2 to 2,
More preferably, it is 0.5 to 1.

In the reaction B in the step of preparing the silicon polymer, the alcohol compound (B ¹ ) is reacted with the silicon polymer (B ² ) having a structure represented by the general formula (10) as a repeating unit. 1% by mass to 30
0 mass% is preferable, 10 mass%-200 mass% is more preferable, and 30 mass%-150 mass% is still more preferable.

The electrolyte composition of the present invention can use a solvent up to the same mass as the compound, but it is preferable not to use a solvent from the viewpoint of storage stability. 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.

The solvent used in the electrolyte composition of the present invention may have a low viscosity to improve ionic mobility, or a high dielectric constant to improve the effective carrier concentration.
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 solvent preferably has a boiling point at normal pressure (1 atm) of 200 ° C. or higher, and 250 ° C. or higher.
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 salts of the metal ions may be used alone or in combination of two or more. The concentration (addition amount) of the salt of the metal ion contained in the electrolyte composition of the present invention is 1% by mass to 30% with respect to the molten salt.
0 mass% is preferable, and 3 mass%-200 mass% is more preferable.

The silicon polymer contained in the electrolyte composition of the present invention was 3% by mass based on the molten salt.
To 300% by mass is preferable, and 5% to 200% by mass is more preferable.

<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.

[0169]

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The compound having at least two 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 in an amount of 0.3% by mass or more and 50% by mass or less, and further preferably used in an amount of 0.5% by mass or more and 30% by mass or less.

The reaction temperature when the 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 above 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, and 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 nonaqueous 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.

[0183] 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 above-mentioned amorphous oxides and / or chalcogenides, amorphous oxides of semimetal elements and / or chalcogenides are more preferable, and the periodic table 13 (III
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 preferred 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 (12) is particularly preferable.

[0189] general formula _{^{(12) SnM 1 d M 2}} e O f

In the general formula (12), M ¹ represents A
Represents at least one or more elements selected from l, B, P, and Ge. 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
Represents a number of 0.2 or more and 2 or less, e represents a number of 0.01 or more and 1 or less, and has a relation of 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 composed of 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 _{-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 adopted, 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-mentioned 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 inductively coupled plasma (ICP) emission spectroscopy as a measuring method, and from the mass difference of 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> As the electrode mixture of the present invention,
In addition to a conductive agent, a binder, a filler, and the like, a polymer network having a structure represented by the general formula (6) 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 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 as a mixture 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 positive / negative current collector, an electron conductor which 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.

As the current collector of the negative electrode, 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 net, a punched material, a lath, a porous material, a foam, a molded product of a fiber group, 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 for 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.

Furthermore, 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 dehydrating the electrode sheet coated 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.

The positive / negative electrode sheets produced by the above-described method are overlapped with a separator interposed therebetween, then processed into a sheet battery as it is, 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 can 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, can, sheet, and 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.

[0221]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (a) Synthesis of Silicon Polymer <Reaction of Compound Represented by Formula (8) with Carboxylic Acid Having Hydroxyl Group> 52.0 g of Exemplified Compound (2-1) and 52.0 g of Exemplified Compound ( 3-1) 26.0 g was mixed, and the mixture was reacted with heating under reflux for 10 hours. After the reaction, 150 ℃ / 5mmHg
After evaporating volatile components at (667 Pa), 37.0 g of a silicon polymer (Si-1) having a structure represented by (A-1) as a repeating unit was obtained. Furthermore, the general formula (8)
And a carboxylic acid having a hydroxyl group,
(Si-2) to (Si-6) were obtained in the same manner as (Si-1) except for the change as shown in Table 1.

[0223]

[Table 1]

(B) Synthesis of silicon polymer <Reaction of silicon polymer having structure represented by general formula (10) as a repeating unit with alcohol compound represented by general formula (11)> poly (dimethoxysiloxane)
5.3 g and 4.5 g of Exemplified Compound (5-1) were mixed and reacted under heating and reflux for 10 hours. After the reaction, 150 ° C / 5
After removing volatile matter with mmHg (667 Pa), 3 g of a colorless liquid (Si-7) was obtained. Except that the exemplified compound (5-1) was replaced with 9.5 g of the exemplified compound (5-6), 7 g of a colorless liquid (Si-8) was obtained by the same operation.

(C) Preparation of Electrolyte Composition 5 g of the exemplified compound (Y2-3) as a molten salt and the exemplified compound (S
i-1) A mixture of 16 g and N-lithiotrifluoromethanesulfonimide (LiNTf ₂ ) 7 g was dissolved in an acetonitrile solution (10 ml), and acetonitrile was distilled off under reduced pressure to prepare an electrolyte composition (SiE-1). Furthermore, molten salts, salts of silicon polymers and metal ions,
(SiE-2) to (SiE-16) were obtained in the same manner as (SiE-1) except for the change as shown in Table 2.

[0226]

[Table 2]

(D) Preparation of solid electrolyte The electrolyte composition (SiE-1) 10 prepared in the above (c) was prepared.
g was mixed with 0.5 g of Exemplified Compound d as a nucleophile. This mixture was cast on Teflon (registered trademark).
The casting liquid was heated at 100 ° C under an argon gas atmosphere.
Heating was performed for 4 hours to obtain a solid electrolyte thin film (SPE-1). Further, solid electrolyte thin films (SPE-2) to (SPE-13) having compositions shown in Table 3 were obtained in the same manner as described above.

[0228]

[Table 3]

(E) Evaluation of electrolyte <Measurement of ionic conductivity and transport number> The electrolyte composition and the solid electrolyte prepared in the above (a) to (d) were evaluated for 0.5%.
The impedance was measured between 100,000 and 0.1 Hz at 25 ° C., and the ion conductivity was determined from a Cole-Cole plot. Further, the Li ion transport number was determined by using both the DC polarization measurement and the complex impedance measurement. The results are shown in Tables 2 and 3.

As shown in Tables 2 and 3, the electrolyte composition using the compound of the present invention showed a high Li ion transport number with almost no loss in ionic conductivity, It was confirmed that it was useful as a conductive material.

(F) Production of cylinder type battery <Preparation of positive electrode mixture paste> LiC was used as the positive electrode active material.
The a oO ₂ and 200g of acetylene black 10 g, were mixed in a homogenizer, followed as a binding agent, 2-ethylhexyl acrylate and aqueous dispersion of the copolymer of acrylic acid and acrylonitrile (solid concentration 50 wt%) 8 g, 60 g of a 2% by mass carboxymethylcellulose aqueous solution was added, kneaded and mixed, and 50 g of water was further added, followed by stirring and mixing with a homogenizer to prepare a positive electrode mixture paste.

<Preparation of negative electrode mixture paste> SnGe _0.1 B _0.5 P _0.58 Mg _0.1 K _0.1 O _3.35 was used as the negative electrode active material.
30 g of water and 30 g of a conductive agent (artificial graphite) were mixed with a homogenizer, and 50 g of a 2% by mass aqueous solution of carboxymethylcellulose and 10 g of polyvinylidene fluoride were added and mixed as a binder. The mixture was mixed to produce a negative electrode mixture paste.

<Preparation of Positive and Negative Electrode Sheets> The positive electrode mixture paste prepared above was coated on both sides of a 30 μm-thick aluminum foil current collector with a blade coater in an amount of 40 μm.
It was applied so that the sheet thickness after compression was 0 g / m ² and the thickness after compression was 280 μm. After drying, it was compression-molded with a roller press and cut into a predetermined size to produce a belt-shaped positive electrode sheet. Further, in a dry box (dew point; dry air having a temperature of -50 ° C. or less), dehydration and drying were sufficiently performed by a far-infrared heater to produce a positive electrode sheet. Similarly, paste the negative electrode mixture
m, and 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.

<Preparation of Cylinder Type Battery> According to FIG.
Explain how to make a battery. The positive electrode sheet prepared above,
30 μm thick Tonen Tapyrus Co., Ltd. non-woven fabric TAPYR
US P22FW-OCS, a negative electrode sheet, and a 30 μm thick Tonen Tapyrus Co., Ltd. nonwoven fabric TAPYRU
SP22FW-OCS were sequentially laminated, and this was spirally wound. The wound electrode group 2 was accommodated 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 under reduced pressure at 70 ° C. Thereafter, the upper insulating plate 3 was further inserted. Positive electrode terminal 6, insulating ring, PTC element 63, current interrupter 62,
The stack of the pressure-sensitive valve bodies 61 was caulked via a gasket 5 to produce a cylinder type (cylindrical type) battery D-1. Similarly, batteries D-2 to D-15 using the electrolyte compositions shown in Table 2 were produced. Ten batteries were produced.

The cylindrical batteries D-16 to D-25 were produced in the same manner as the production of the cylinder batteries D-2 to D-15 except that graphite powder was used as the negative electrode active material.

(G) Evaluation of Battery Characteristics The battery prepared by the above method was repeatedly charged and discharged 10 times under the conditions of 0.2 C, a final charge voltage of 4.1 V, and a final discharge voltage of 2.7 V. The discharge capacity was determined. This was examined for 10 batteries of the same prescription,
The average was taken as the capacity of the battery. Thus, the 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. In addition, 0.5C of each battery (charge end voltage 4.1 V, discharge end voltage 2.
7V), the discharge capacity at the 100th cycle was determined, and the ratio to the discharge capacity at the 10th cycle was calculated and represented as the cycle capacity. Table 4 shows the respective values.

[0237]

[Table 4]

From the results shown in Table 4, it was revealed that when the electrolyte composition of the present invention was used as an electrolyte in a battery, the capacity was not reduced and the cyclability was improved. It was also confirmed that the cycle stabilizing effect was greater when using an amorphous composite oxide than when using a carbon material for the negative electrode. On the other hand, it was clarified that the conventional electrolyte composition was inferior in capacity reduction and cycleability.

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 2) (a) Production of sheet type battery <Production of positive electrode sheet 1> LiCoO 2 was used as a positive electrode active material.
₂ parts by mass, 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 a slurry obtained by kneading with 100 parts by mass of acrylonitrile as a medium, A 20 μm aluminum foil is applied by using an extrusion type applicator, and after drying and compression molding by a calender press, an aluminum lead plate is welded to the end and a thickness of 9 μm.
5 μm, 54 mm wide × 49 mm long positive electrode sheet (CA
-1) was prepared.

<Preparation 2 of Positive Electrode Sheet> 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 1 was added.
Slurry obtained by kneading 00 parts by mass as a medium,
An aluminum foil having a thickness of 20 μm is applied using an extrusion coating machine, and after drying, compression-molded by a calender press machine, an aluminum lead plate is welded to the end, and a thickness of 114 μm and a width of 54 mm × length A positive electrode sheet (CA-2) having a length of 49 mm was produced.

<Preparation 3 of Positive Electrode Sheet> 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 acrylonitrile 1 was added.
Slurry obtained by kneading 00 parts by mass as a medium,
An aluminum foil having a thickness of 20 μm is applied using an extrusion coating machine, dried and then compression-molded by a calender press. Then, an aluminum lead plate is welded to the end, and a thickness of 75 μm and a width of 54 mm × length. A positive electrode sheet (CA-3) having a length of 49 mm was prepared.

[0243] SnSiO ₃ to 43 parts by weight as a negative electrode active material <Preparation 1 of the negative electrode sheet> were mixed at a ratio of acetylene black 2 parts by weight as a conductive agent and graphite 2 parts by mass, further 3 parts by mass of polyacrylonitrile as binder The mixture was kneaded with 100 parts by mass of N-methylpyrrolidone 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. The negative electrode mixture slurry is applied as a lower layer and the auxiliary layer slurry as an upper layer on a copper foil having a thickness of 10 μm using an extrusion coating machine, dried, and then compression-molded by a calender press to obtain a thickness of 46 μm.
m, a negative electrode sheet having a width of 55 mm and 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. A 35 μm-thick lithium foil (purity 99.8%) cut into 4 mm × 55 mm was attached to the entire surface of the heat-treated negative electrode sheet at 10 mm intervals perpendicular to the sheet length direction (AN-1).

<Preparation 2 of Negative Electrode Sheet> In Preparation 1 of the negative electrode sheet, SnSiO ₃ was changed to Sn _0.8 Al _0.2 B _0.3 P
_{0.2 Si 0.5 O 3.6, SnAl 0.4} B 0.5 Cs 0.1 P 0.5 O
Except for _3.65 , in the same manner, a width of 55 mm with a lithium foil with a nickel lead plate welded to the end
Negative electrode sheets (AN-2) and (AN-3) with a length of 50 mm
Was prepared.

<Preparation of Negative Electrode Sheet 3> A mesoface pitch-based carbon material (Petka) was used as a negative electrode active material.
Parts by mass, 2 parts by mass of acetylene black and 2 parts by mass of graphite are mixed as a conductive agent, and 3 parts by mass of polyacrylonitrile is further added as a binder, and 100 parts by mass of N-methylpyrrolidone is kneaded with a medium to form a negative electrode. A mixture slurry was obtained. The negative electrode mixture slurry was prepared to have a thickness of 10 μm.
m of copper foil was applied using an extrusion coating machine, dried and then compression-molded by 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, 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. (AN-4).

<Production of Sheet Type Battery> The production of a sheet type battery will be described with reference to FIG. Each of the negative electrode sheet and the positive electrode sheet was placed in dry air having a dew point of -40 ° C or less.
It was dehydrated and dried at 0 ° C. for 30 minutes. In a dry atmosphere, width 54
mm x 49 mm length dehydrated and dried positive electrode sheet (CA-
1) 21, a solid electrolyte composition film 22 cut into a width of 60 mm × length of 60 mm, and a width of 55 mm × length of 50 m
m of dehydrated and dried negative electrode sheets (AN-1) 23 were laminated in this order. Then, polyethylene (50 μm)
Using an exterior material made of a laminated film of polyethylene terephthalate (50 μm), the four edges were heat-sealed under vacuum and sealed to produce a sheet-type battery (SB-1).
In the same manner as in the production of the sheet type battery (SB-1), the sheet type batteries (SB-2) to
(SB-16) was produced.

[0247]

[Table 5]

(D) Evaluation of battery performance The sheet-type battery produced by the above method was evaluated for 0.2 C,
The charge and discharge were repeated 10 times under the conditions of a charge end voltage of 4.2 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. Thus, the capacity of each battery is obtained, and this value is referred to as SB-2 to SB-5.
11 is SB-1 and SB-12 is SB
-6, SB-13 for SB-13, and SB-14 for SB-13
Is SB-8 for SB-15 and SB-9 for SB-15
Then, SB-16 was divided by SB-10 to obtain a relative capacity between the same electrode compositions. Further, 0.5C of each battery (final charge voltage 4.2V, final discharge voltage 2.
6V), the discharge capacity at the 300th cycle was determined, and the ratio to the discharge capacity at the 10th cycle was calculated and represented as the cycle capacity. Table 6 shows the respective values.

[0249]

[Table 6]

(E) Evaluation of Liquid Leakage The package material on one side of the sheet-type battery produced by the above method was peeled off, and a pressure of 200 g / cm ² was applied from above to visually evaluate whether or not the liquid was exuded. did. No liquid leakage was observed in any of the batteries.

From the above results, it has been clarified that the sheet type secondary battery containing the electrolyte composition of the present invention has improved cycleability despite no decrease in battery capacity. In addition, it was confirmed that a liquid leakage failure hardly occurred.

[0252]

According to the present invention, there is provided a novel electrolyte composition which exhibits high ionic conductivity and ion transport number, has low fluidity, or has no fluidity, and further has a high battery capacity and a high capacity. It is possible to provide a non-aqueous electrolyte secondary battery that is not deteriorated and has excellent cycle stability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a cylinder battery manufactured in an example.

FIG. 2 is a conceptual diagram of a sheet-type battery manufactured in an example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Battery can also serve as a negative electrode 2 Winding 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 electrode sheet 22 Solid electrolyte 23 Negative electrode Sheet 24 Positive terminal 25 Negative terminal

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01B 1/06 H01B 1/06 A 1/12 1/12 Z F term (Reference) 4J002 CP011 CP051 CP201 CP211 DD087 DE197 DG037 DG047 DH007 DK007 EN136 ER006 EU026 EU046 EU116 EU236 EW016 GQ00 5G301 CA30 CD01 5H029 AJ03 AJ05 AK03 AL02 AL03 AL04 AL06 AL07 AM02 AM03 AM05 AM06 AM07 AM09 AM16 BJ02 BJ04 BJ12 EJ14 EJ01 DJ09 EJ09 DJ09

Claims (15)

[Claims] 1. An electrolyte composition comprising a molten salt, a silicon polymer, and a salt of a metal ion belonging to Group 1 or 2 of the periodic table. 2. The electrolyte composition according to claim 1, wherein the molten salt is represented by any of the following general formulas (1), (2), and (3). Embedded image In the general formula (1), Q is 5 together with a nitrogen atom.
Represents an atomic group capable of forming a six-membered or six-membered aromatic cation. L ¹¹ and L ^{12 each} represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted alkyleneoxy group or a divalent linking group composed of a repetition thereof, a substituted or unsubstituted alkenyleneoxy group, or It represents a divalent linking group formed by repeating the above, or a divalent linking group formed by combining a plurality of these. R ¹¹
Represents a hydrogen atom or a substituent. R ¹² represents a hydrogen atom or a substituent. n1 is 0, or represents the maximum integer less than or equal to the number of the substitutable (L ¹² -R ¹²⁾ on Q 1 or more. X ^-
Represents an anion. When n1 is 2 or more, (L ¹² −
R ¹² ) may be the same or different, and two or more of R ¹¹ and R ¹² may be linked to each other to form a ring structure. In the general formula (2), L ²¹ , L ²² , L ²³ and L ²⁴ have the same meaning as L ¹¹ in the general formula (1).
R ²¹ , R ²² , R ²³ and R ²⁴ represent a hydrogen atom or a substituent. Two or more of R ²¹ , R ²² , R ²³ and R ²⁴ may be linked to each other to form a ring structure. A represents a nitrogen atom or a phosphorus atom. In the general formula (3), L
³¹ ~L ³⁶ has the same meaning as L ¹¹ in the formula (1). R ^{31 to} R ³⁶ represent a hydrogen atom or a substituent. R ³¹ ~
Two or more of R ³⁶ may be linked to each other to form a ring structure. 3. The method according to claim 1, wherein Q in the general formula (1) is an atomic group composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom and a sulfur atom. Item 3. The electrolyte composition according to item 2. 4. The electrolyte composition according to claim 2, wherein the 5-membered or 6-membered aromatic cation formed by Q in the general formula (1) together with the nitrogen atom is an imidazolium cation or a pyridinium cation. object. 5. The electrolyte composition according to claim 1, wherein the silicon polymer has a structure represented by the following general formula (6) as a repeating unit. Embedded image In the general formula (6), R ¹ and R ² represents an alkyl group, an alkoxy group, an aryl group, or an aryloxy group. X represents an oxygen atom, a nitrogen atom, an alkylene group, a phenylene group, a silicon atom, a metal atom, or an atomic group consisting of a combination thereof. 6. The electrolyte composition according to claim 5, wherein the silicon polymer having a structure represented by the general formula (6) as a repeating unit has a structure represented by the following general formula (7) as a repeating unit. . Embedded image In the general formula (7), R ³ represents an alkyl group, an alkoxy group, an aryl group, or an aryloxy group.
R ⁴ represents an alkyl group or an aryl group. 7. The electrolyte composition according to claim 6, wherein R ³ in the general formula (7) is an alkoxy group. 8. R ³ and OR ⁴ in the general formula (7)
The electrolyte composition according to claim 6, wherein at least one of the above has an alkoxycarbonyl group as a substituent. 9. A product obtained by reacting a compound represented by the following general formula (8) with a carboxylic acid having a hydroxyl group, wherein a silicon polymer having a structure represented by the general formula (7) as a repeating unit is used. The electrolyte composition according to any one of claims 6 to 8, wherein Embedded image In the general formula (8), R ³ represents the general formula (7)
Has the same meaning as R ^{3 in} R ⁵ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. 10. The electrolyte composition according to claim 9, wherein the carboxylic acid having a hydroxyl group is a compound represented by the following general formula (9). Embedded image In the general formula (9), R ⁶ and R ⁷ represents a hydrogen atom or an alkyl group. a represents an integer of 1 to 5. b
Represents an integer of 0 to 30. 11. A silicon polymer having a structure represented by the general formula (7) as a repeating unit reacts a silicon polymer having a structure represented by the following general formula (10) as a repeating unit with an alcohol compound. The electrolyte composition according to any one of claims 6 to 8, which is a product obtained by the above method. Embedded image In the general formula (10), R ⁸ has the same meaning as R ³ in the general formula (7). R ⁹ represents an alkoxy group. 12. The electrolyte composition according to claim 11, wherein the alcohol compound has an alkoxycarbonyl group as a substituent. 13. The electrolyte composition according to claim 12, wherein the alcohol compound is represented by the following general formula (11). Embedded image In the general formula (11), R ¹⁰ represents the same substituent as R ⁵ in the general formula (8). 14. The electrolyte composition according to claim 6, which is reacted with a compound having at least two or more nucleophilic groups in a molecule. 15. 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 14. Non-aqueous electrolyte secondary battery.