JP2003123841A - Polymeric macromolecular compound and manufacturing method of the same, bridged macromolecular compound and manufacturing method of the same, electrolyte component, and nonaqueous electrolyte secondary cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polymeric macromolecular compound, a bridged macromolecular compound obtained from the polymeric macromolecular compound, a new electrolyte component containing the bridged macromolecular compound having high ion conductivity and high ion transference number, and to provide a nonaqueous electrolyte secondary cell with high capacity using the electrolyte component. SOLUTION: A nonaqueous electrolyte secondary cell uses an electrolytic substance containing a polymeric macromolecular compound partially having a structure shown by the formula (1), a bridged macromolecular compound obtained by bridging the polymeric macromolecular compound, and a salt composed of the bridged macromolecular compound and metal ion belonging to the first group and the second group of periodic table, and the nonaqueous electrolyte secondary cell uses the above electrolyte component. In the formula (1), R<1> and R<2> represents alkyl group or aryl group independently. At least either one of R<1> or R<2> contains a polymeric group as a substitutional group. M represents silicon, boron, or metal element. Valence of M is shown by n.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymerizable polymer compound and a method for producing the same, a cross-linked polymer compound and a method for producing the same, an electrolyte composition, and a non-aqueous electrolyte secondary battery, and more specifically to a specific structure. Polymerizable polymer compound having the same and method for producing the same, crosslinked polymer compound obtained from the polymerizable polymer compound and method for producing the same, antistatic agent, battery, and other electrochemical device containing the crosslinked polymer compound The present invention relates to an electrolyte composition suitable as a material for use as well as a high capacity non-aqueous electrolyte secondary battery.

[0002]

2. Description of the Related Art An electrolyte used in 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 non-aqueous secondary battery, transport of lithium ions is a problem. In a battery, generally, a solution system having high ionic conductivity is often used as an electrolyte, but there is a problem that solvent depletion or leakage when incorporated in a battery deteriorates durability of the battery. In addition, since the metal container must be used to seal the solution, the battery mass becomes heavy and it is difficult to give the battery shape a degree of freedom.

In order to overcome the drawbacks of the above solution-based electrolytes,
In recent years, solidification of electrolytes (polymer electrolytes) has been studied. A polymer electrolyte in which a salt is dissolved in a polymer such as polyethylene oxide is expected to solve the problem of a solution-type electrolyte, but has a problem that the ionic conductivity is still insufficient. In order to improve the above-mentioned problems, a polymer ion conductive material combining siloxane and polyether with extremely high molecular mobility is a solid state material.
Ionics, Vol. 15, p. 233 (1985), JP-A-63-170857, and the like. However, when a battery is manufactured using such a polymer material, there is a problem that the performance is not always sufficient.
In particular, polymer electrolytes that have been mainly reported so far generally have a low ion transport number (for example, lithium ion transport number in the case of a lithium secondary battery), which is one of the important properties of the electrolyte. Therefore, for example, in the case of a lithium secondary battery, the charging / discharging current decreases with time, causing a problem such as a decrease in capacity, and in reality, it is difficult to incorporate it into a versatile product.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in the prior art and achieve the following objects. That is, the present invention includes a novel polymerizable polymer compound and a method for producing the same, a crosslinked polymer compound obtained from the polymerizable polymer compound and a method for producing the same, and a high ion conductivity and a high ionic conductivity. It is an object of the present invention to provide a novel electrolyte composition exhibiting an ion transport number, and a high-capacity non-aqueous electrolyte secondary battery using the electrolyte composition.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, the following polymerizable polymer compound and a method for producing the same, and the following high crosslinking amount obtained from the polymerizable polymer compound were obtained. The present invention has been accomplished by discovering a molecular compound, a method for producing the same, an electrolyte composition, and a non-aqueous electrolyte secondary battery.

<1> A polymerizable polymer compound having a structure represented by the following general formula (1) as a partial structure.

[0007]

[Chemical 5]

In the general formula (1), R ¹ and R
^2's each independently represent an alkyl group or an aryl group.
At least one of R ¹ and R ² has a polymerizable group as a substituent. M represents silicon, boron, or a metal element. n represents the valence of M.

<2> The above-mentioned <1 in which M is silicon.
> Is a polymerizable polymer compound.

<3> The polymerizable polymer compound according to <1> or <2>, wherein the polymerizable group is an ethylenically unsaturated group.

<4> The polymerizable polymer compound according to any one of <1> to <3>, wherein the polymerizable group contains a group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group. Is.

<5> The polymerizable group is the polymerizable polymer compound according to any one of <1> to <4>, which is represented by the following general formula (2).

[0013]

[Chemical 6]

In the general formula (2), R ³ represents a hydrogen atom or an alkyl group. -Y- is -O-, -N
(R ⁴⁾ -, or a single bond. R ⁴ represents a hydrogen atom or an alkyl group.

<6> The above-mentioned <1> obtained by reacting a polymer compound having a structure represented by the following general formula (4) as a partial structure with an alcohol compound represented by the following general formula (5). To <5>.

[0016]

[Chemical 7]

In the general formula (4), R ⁵ and R
Each ⁶ independently represents an alkyl group or an aryl group. M
Represents silicon, boron, or a metal element. n represents the valence of M. In the general formula (5), R ¹ and R
² represents an alkyl group or an aryl group having a polymerizable group as a substituent.

<7> A crosslinked polymer compound characterized by being obtained by crosslinking and polymerizing the polymerizable polymer compound according to any one of <1> to <6>.

<8> An electrolyte composition comprising the crosslinked polymer compound according to <7> and a salt of a metal ion belonging to Group 1 or 2 of the periodic table.

<9> A non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode, wherein the non-aqueous secondary battery has the above-mentioned <8>.
A non-aqueous electrolyte secondary battery containing the electrolyte composition described in 1.

<10> A polymer compound having a structure represented by the following general formula (4) as a partial structure is reacted with an alcohol compound represented by the following general formula (5) to react with the following general formula (1 ) A polymerizable polymer compound having a structure represented by the formula (1) as a partial structure is obtained.

[0022]

[Chemical 8]

In the general formula (1), R ¹ and R
^2's each independently represent an alkyl group or an aryl group.
At least one of R ¹ and R ² has a polymerizable group as a substituent. M represents silicon, boron, or a metal element. n represents the valence of M. In the general formula (4), R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group. M represents silicon, boron, or a metal element. n represents the valence of M. In the general formula (5), R ¹ and R ² represent an alkyl group or an aryl group having a polymerizable group as a substituent.

<11> A method for producing a crosslinked polymer compound, which comprises crosslinking and polymerizing a polymerizable polymer compound having a structure represented by the following general formula (1) as a partial structure.

[0025]

[Chemical 9]

In the general formula (1), R ¹ and R
^2's each independently represent an alkyl group or an aryl group.
At least one of R ¹ and R ² has a polymerizable group as a substituent. M represents silicon, boron, or a metal element. n represents the valence of M.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Polymerizable polymer compound and method for producing the same, crosslinked polymer compound and method for producing the same, an electrolyte composition containing the crosslinked polymer compound, and a non-aqueous electrolyte secondary battery according to the present invention are described below. explain.

(Polymerizable Polymer Compound and Crosslinked Polymer Compound) The polymerizable polymer compound of the present invention has the following general formula (1):
The cross-linked polymer compound of the present invention is characterized by having a structure represented by the following as a partial structure, and a cross-linking polymerization of a polymerizable polymer compound having a structure represented by the following general formula (1) as a partial structure. It is obtained by. First, the polymerizable polymer compound and the method for producing the same in the present invention will be described.

<Polymerizable polymer compound and method for producing the same>
The polymerizable polymer compound of the present invention is characterized by having a structure represented by the following general formula (1) as a partial structure.

[0030]

[Chemical 10]

In the general formula (1), R ¹ and R
^2's each independently represent an alkyl group or an aryl group.
At least one of R ¹ and R ² has a polymerizable group as a substituent. M represents silicon, boron or a metal element. n represents the valence of M.

In the general formula (1), examples of the metal element represented by M include titanium, aluminum, zirconium, germanium, iron, gallium, magnesium, phosphorus, tin and vanadium. other than this,
The metal elements shown in the raw materials for the sol-gel method described in "Science of the sol-gel method" (Sakuo Sakuo) (published by Agne Shengfu in 1988) can be used.

The M is preferably silicon, boron, titanium or aluminum, and among them, silicon is more preferable.

In the general formula (1), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, such as methyl. Group, ethyl group, propyl group, n-butyl group, t-butyl group and the like are preferable.

In the general formula (1), the aryl group represented by R ¹ is preferably an aryl group having 6 to 24 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, for example, a phenyl group. And naphthyl groups are suitable.

In the general formula (1), R ¹ is preferably an alkyl group.

In the general formula (1), the alkyl group and aryl group represented by R ² have the same meanings as the alkyl group and aryl group represented by R ¹ , and the preferred ranges are also the same.

In the general formula (1), the alkyl group and aryl group represented by R ¹ or R ² may further have a substituent, and specific examples of the substituent are:
The following are preferred. For example, a halogen atom,
Alkyl group, aryl group, heterocyclic group, cyano group, nitro group, alkoxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group,
Acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group,
Arylthio group, heterocyclic thio group, sulfamoyl group,
Preferable examples are alkyl and arylsulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, silyl groups and polymerizable groups.

The halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom.

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

Among the above aryl groups, for example, phenyl group, p-tolyl group, naphthyl group, 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 substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and among them, for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group A group, a 2-benzothiazolyl group, and the like are more preferable.

Among the above alkoxy groups, for example, methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, 2-methoxyethoxy group,
Such as _{-O (CH 2 CH 2 O)} nCH 3 are more preferable.

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 group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-
A methoxyphenylcarbonyloxy group and the like are more preferable.

Among the above carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy group, N, N-
Diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like are more preferable.

Among the above alkoxycarbonyloxy groups, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, t-butoxycarbonyloxy group,
An n-octylcarbonyloxy group and the like are more preferable.

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

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

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

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

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

Among the above aryloxycarbonylamino groups, for example, phenoxycarbonylamino group, p-
A chlorophenoxycarbonylamino group, m-n-octyloxyphenoxycarbonylamino group and the like are more preferable.

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

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

Of the above alkylthio groups, for example, methylthio group, ethylthio group, 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, the number of carbon atoms is 2 to
The substituted or unsubstituted heterocyclic thio group of 30 is preferable, and for example, a 2-benzothiazolylthio group, a 1-phenyltetrazol-5-ylthio group, and the like are more preferable.

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

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

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

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

Of 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 above carbamoyl groups, for example, carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group and the like can be mentioned. 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.

Among the above-mentioned polymerizable groups, for example, vinyl group, acryloyl group, methacryloyl group, styryl group,
A cinnamic acid residue and the like are more preferable.

Among the preferable substituents of the alkyl group and aryl group represented by R ¹ or R ² , the alkoxycarbonyl group and the polymerizable group are more preferable.

In the general formula (1), R ¹ and R ² are more preferably alkyl groups having 1 to 10 carbon atoms,
A linear alkyl group having 2 to 6 carbon atoms and having the above-mentioned polymerizable group as a substituent is particularly preferable.

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

In the general formula (1), at least one of R ¹ and R ² has a polymerizable group as a substituent. The polymerizable group substituting for R ¹ or R ² is preferably an ethylenically unsaturated group, and among them, it is more preferable to include a group selected from the group consisting of an acryloyl group, a methacryloyl group and a styryl group. General formula (2)
The substituent represented by is more preferable.

[0072]

[Chemical 11]

In the general formula (2), R ³ represents a hydrogen atom or an alkyl group. -Y- is -O-, -N
(R ⁴⁾ -, or a single bond. R ⁴ represents a hydrogen atom or an alkyl group.

In the general formula (2), R ³ and R
Each ⁴ independently represents a hydrogen atom or an alkyl group. The alkyl group represented by R ³ and R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms, and may be linear or branched, and examples thereof include a methyl group, an ethyl group, More preferred are propyl group, butyl group, i-propyl group, i-butyl group, pentyl group and the like. As R ³ and R ⁴ ,
A hydrogen atom or a methyl group is preferred.

When there are a plurality of polymerizable groups in R ¹ and R ² of the general formula (1), they may be the same or different.

In the general formula (1), the polymerizable group substituting for R ¹ or R ² is particularly preferably a substituent represented by the following general formula (3).

[0077]

[Chemical 12]

In the general formula (3), R ³ has the same meaning as R ³ in the general formula (2) and is preferably a hydrogen atom or a methyl group. l represents an integer of 1 to 10, with 2 to 6 being particularly preferable.

Specific examples of the structure represented by the general formula (1), which is the partial structure of the polymerizable polymer compound of the present invention, are shown below, but the present invention is not limited thereto.

[0080]

[Chemical 13]

[0081]

[Chemical 14]

[0082]

[Chemical 15]

The polymerizable polymer compound of the present invention is obtained by reacting a polymer compound having a structure represented by the following general formula (4) as a partial structure with an alcohol compound represented by the following general formula (5). It is preferable to obtain it. The alcohol compound represented by the following general formula (5) has a polymerizable group.

[0084]

[Chemical 16]

In the general formula (4), R ⁵ and R
Each ⁶ independently represents an alkyl group or an aryl group. M
Represents silicon, boron, or a metal element. n represents the valence of M. The alkyl group represented by R ⁵ and R ⁶ has the same meaning as the alkyl group represented by R ¹ and R ² in the general formula (1), and the aryl group represented by R ⁵ and R ⁶ is
In the general formula (1), it has the same meaning as the aryl group represented by R ¹ and R ² . However, the case where R ⁵ and R ⁶ do not have a polymerizable group as a substituent is also included.

In the general formula (5), R ¹ and R
Each of ^2's independently represents an alkyl group or an aryl group having a polymerizable group as a substituent. For the description of the alkyl group and the aryl group and the polymerizable group as a substituent, refer to R in the general formula (1). It is synonymous with ¹ and R ² .

Specific examples (4-1 to 4-5) of the structure represented by the general formula (4) are shown below, but the invention is not limited thereto.

[0088]

[Chemical 17]

Specific examples (5-1 to 5-7) of the alcohol compound represented by the general formula (5) are shown below, but the invention is not limited thereto.

[0090]

[Chemical 18]

The reaction of the polymer compound containing the structure represented by the general formula (4) as a partial structure with the alcohol compound represented by the general formula (5) may be carried out in the presence or absence of a solvent. You may go in. In the reaction, the reaction temperature is preferably room temperature or higher and lower than the reflux start temperature of the reaction mixture. The reaction time is preferably 30 minutes to 7 days, more preferably 1 hour to 2 days. However, the reaction temperature and the reaction time are not limited to the above ranges in order to adjust the reaction rate or not to decompose the compound. After the reaction, it is preferable from the viewpoint of storage stability that the raw material compound or mainly low-molecular volatile components by-produced in the reaction be distilled off from the reaction mixture as much as possible. It is preferable to remove the volatile component by heating under reduced pressure so that the compound is not decomposed. For example, 50 ℃ / 5
The mass reduction rate of the reaction mixture is 5 at mmHg (667 Pa).
It is preferable to distill off until it becomes 0% or less.
More preferably, it is distilled off until it becomes less than or equal to%.

In the reaction, the addition amount of the alcohol compound represented by the general formula (5) is 1 mass with respect to the polymer compound having the structure represented by the general formula (4) as a partial structure. % To 300% by mass is preferable, and 5
Mass% to 200 mass% is more preferable, and 10 mass% to 1
50% by weight is particularly preferred.

<Crosslinked polymer compound and method for producing the same> The crosslinked polymer compound of the present invention is characterized by being obtained by crosslinking and polymerizing the polymerizable polymer compound. That is, since the polymerizable polymer compound has a polymerizable group, the crosslinked polymer compound of the present invention having a crosslinked structure can be obtained by polymerizing the polymerizable group. In particular,
The polymerizable polymer compound having the structure represented by the general formula (1) as a partial structure has a polymerizable group in at least one of the side chains represented by OR ¹ and OR ² , A polymer is also formed in the side chain by the polymerization of the functional group, and as a result, a crosslinked polymer compound in which the main chain polymer and the side chain polymer are crosslinked is obtained. As the polymer formed in the side chain, there are a mode formed by reaction between polymerizable groups having the same main chain and a mode formed by reaction between polymerizable groups having different main chains. An example of the crosslinked polymer compound of the present invention is shown below as a schematic diagram.

[0094]

[Chemical 19]

Since the cross-linked polymer compound of the present invention has a cross-linking structure and is solidified, it is preferable that it is contained in the electrolyte composition of the present invention described later because it is possible to prevent liquid leakage and volatilization.

As a method for producing the crosslinked polymer compound of the present invention by polymerizing the polymerizable polymer compound, Takayuki Otsu and Masayoshi Kinoshita: Experimental method of polymer synthesis (Kagaku Dojin) and Takayuki Otsu: Lecture Polymerization reaction theory 1 A radical polymerization method which is a general polymer synthesis method described in Radical Polymerization (I) (Chemical Doujin) can be used. There are a thermal polymerization method using a thermal polymerization initiator and a photopolymerization method using a photopolymerization initiator, and the thermal polymerization initiator preferably used in the thermal polymerization method is, for example, 2,2′-azobis (iso Butyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2′-azobis (2-methylpropionate) and other azo initiators, and benzoyl peroxide and other peroxides. An oxide type initiator and the like are included. In the photopolymerization method, the photopolymerization initiator preferably used includes, for example, α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670) and acyloin ether (US Pat. No. 244828). ), An α-hydrocarbon substituted aromatic acyloin compound (described in US Pat. No. 2,722,512), a polynuclear quinone compound (US Pat. Nos. 3,046,127 and 295175).
No. 8, each specification), a combination of triazole imidazole dimer and p-aminophenyl ketone (described in US Pat. No. 3,549,676), acridine and phenazine compounds (JP-A-60-105667,
U.S. Pat. No. 4,212,970). The addition amount of the polymerization initiator is preferably 0.01% by mass or more and 20% by mass or less with respect to the polymerizable polymer compound having the structure represented by the general formula (1) as a partial structure, It is more preferably 1% by mass or more and 10% by mass or less.

(Electrolyte Composition) Here, the electrolyte composition of the present invention will be described. The electrolyte composition of the present invention is
It is characterized by containing the crosslinked polymer compound and a salt of a metal ion belonging to Group 1 (Ia) or Group 2 (IIa) of the periodic table.

The electrolyte composition of the present invention comprises a reaction of a compound having the structure represented by the general formula (4) as a partial structure with an alcohol compound represented by the general formula (5), and a cross-linking polymerization reaction. In the Periodic Table 1 (Ia)
It may be prepared in the presence of a salt of a metal ion belonging to Group 2 or Group 2 (IIa), or may be prepared by adding the salt of the metal ion to the reaction product (crosslinked polymer compound) later. You may.

In the electrolyte composition of the present invention, a solvent can be used preferably up to the same mass as the crosslinked polymer compound, but it is more preferable not to use a solvent from the viewpoint of storage stability. The electrolyte composition of the present invention is a method of dissolving by heating, or a method of permeating onto the electrode under reduced pressure if necessary, permeating onto the electrode using a low boiling point solvent (methanol, acetonitrile, methylene chloride, etc.), After that, the solvent can be removed by heating and the like, and the like, and the like can be incorporated into the battery.

The solvent used in the electrolyte composition of the present invention has a low viscosity to improve ionic mobility, or a high dielectric constant to improve effective carrier concentration.
A compound capable of exhibiting excellent ionic conductivity is preferable. Examples of such a solvent include carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, dioxane, ether compounds such as diethyl ether, ethylene glycol dialkyl ether, and the like.
Chain ethers such as propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc. Alcohols, polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, etc., acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, nitrile compounds such as benzonitrile, carboxylic acid esters, phosphoric acid esters , Phosphonate ester, etc. , Dimethyl sulfoxide, aprotic polar substances such as sulfolane, and the like preferably. Among them, carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, nitrile compounds such as acetonitrile, glutalodinitrile, methoxyacetonitrile, propionitrile and benzonitrile, and esters are particularly preferable. preferable. These may be used alone or in combination of two or more.

As a preferable property of the solvent, a boiling point at atmospheric pressure (1 atm) is preferably 200 ° C. or higher, and 250 ° C., from the viewpoint of durability improvement due to volatility resistance.
The above is more preferable, and it is further preferable that the temperature is 270 ° C. or more.

Periodic table contained in the electrolyte composition of the present invention
Metal ions belonging to Group 1 (Ia) or Group 2 (IIa)
As the lithium, sodium and potassium ions
LiCF is preferably a typical metal ion salt.
₃SO₃, LiPF₆, LiClO_Four, LiI, LiB
F_Four, LiCF₃CO₂, LiSCN, LiN (SO₂CF
₃)₂, NaI, NaCF₃SO₃, NaClO_Four, NaB
F_Four, NaAsF₆, KCF ₃SO₃, KSCN, KP
F₆, KClO_Four, KAsF₆And so on. The money
Among the preferred specific examples of the salt of the genus ion, the Li salt is
More preferable.

The metal ion salts 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 preferably 3% by mass to 300% by mass, and further 5% by mass to 20% by mass with respect to the crosslinked polymer compound.
0 mass% is more preferable.

The electrolyte composition of the present invention is as described above.
A crosslinked polymer compound obtained by polymerizing and crosslinking a polymerizable group in the polymerizable polymer compound to solidify is used. From the viewpoint of preventing liquid leakage and volatilization, it is preferable to use after solidifying.

The electrolyte composition of the present invention can be used for a chemical reaction, a reaction solvent for metal plating, a CCD (charge coupled device) camera,
It can be used for various batteries, photoelectric conversion elements and the like, and is preferably used for a non-aqueous electrolyte secondary battery, particularly a lithium secondary battery.

(Nonaqueous Electrolyte Secondary Battery) Here, the nonaqueous electrolyte secondary battery of the present invention will be described. The non-aqueous electrolyte secondary battery of the present invention is a non-aqueous secondary battery including a positive electrode and a negative electrode, and is characterized by containing the electrolyte composition. <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. It is preferable to use an oxide. In the present invention, the lithium-containing transition metal oxide preferably used as the positive electrode active material is lithium-containing Ti, V, Cr, Mn, Fe, Co, Ni, Cu, M.
Suitable examples include oxides containing o and W. Alkali metals other than lithium (elements of Group 1 (Ia) and Group 2 (IIa) 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 the transition metal.
30 mol% is preferable.

Among the lithium-containing transition metal oxides preferably used as the positive electrode active material, a lithium compound / transition metal compound (transition metal here means Ti, V, C).
It means at least one selected from r, Mn, Fe, Co, Ni, Mo, and W. ) Total molar ratio is 0.3
It is more preferable that the compound is prepared by mixing so as to be 2.2.

Further, among the lithium compounds / transition metal compounds, Li _g M ³ O ₂ (M ³ is Co, Ni, Fe,
And one or more elements selected from Mn. g is
It represents 0 to 1.2. ) -Containing material, or Li _h M ⁴ ₂ O
(M ⁴ represents Mn. H represents 0 to 2) and a material having a spinel structure is particularly preferable. Examples of M ³ and M ⁴ include Al, Ga, In, in addition to transition metals.
Ge, Sn, Pb, Sb, Bi, Si, P, B and the like may be mixed. The mixing amount is 0 to 30 mo with respect to the transition metal
1% is preferred.

Material containing Li _g M ³ O ₂ , Li _h M ⁴ ₂ O
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.
Represents 2. j represents 0.1 to 0.9. h represents 0 to 2. ) Is particularly preferable. Here, the g value and the h value are
It is a value before the start of charging / discharging and is a value that increases or decreases due to charging / discharging.

The positive electrode active material can be synthesized by a method of mixing and firing a lithium compound and a transition metal compound or a solution reaction, but a firing method is particularly preferable. In the firing method used in the present invention, the firing temperature may be a temperature at which a part of the mixed compound is decomposed and melted, and for example, 250 to 2000 ° C. is preferable, and 35
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 raw material may be mixed in either a dry method or a wet method. Also, after firing, 20
You may anneal at 0-900 degreeC.

In the firing method, the firing gas atmosphere is not particularly limited, and either an oxidizing atmosphere or a reducing atmosphere can be used. Examples thereof include air, a gas whose oxygen concentration is adjusted to an arbitrary ratio, hydrogen, carbon monoxide, nitrogen, argon, helium, krypton, xenon, carbon dioxide, and the like.

The average particle size of the positive electrode active material used in the non-aqueous electrolyte secondary battery of the present invention 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.

A well-known crusher or classifier is used to make the positive electrode active material have a predetermined particle size. For example, mortar, ball mill, vibrating ball mill, vibrating mill,
A satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve, etc. are used. The 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 non-aqueous 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 consisting essentially of carbon. Examples thereof include petroleum pitch, natural graphite, artificial graphite such as vapor-grown graphite, and carbonaceous materials obtained by firing various synthetic resins such as PAN resin and furfuryl alcohol resin. Furthermore, PAN-based carbon fibers, cellulose-based carbon fibers, pitch-based carbon fibers, vapor-grown carbon fibers, dehydrated PV
A-based carbon fiber, lignin carbon fiber, glassy carbon fiber,
Other examples include various carbon fibers such as activated carbon fibers, mesophase microspheres, graphite whiskers, and flat graphite.

These carbonaceous materials can be classified into non-graphitizable carbon materials and graphitic carbon materials depending on the degree of graphitization. The carbonaceous material preferably has the interplanar spacing, density, and crystallite size described in JP-A-62-122066, JP-A-2-6856, and JP-A-3-45473. The carbonaceous material does not have 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, etc. may be used. You can also

In the non-aqueous electrolyte secondary battery of the present invention, another negative electrode active material used is preferably an oxide and / or chalcogenide.

Of these, amorphous oxides and / or chalcogenides are particularly preferable. Amorphous here means
X-ray diffractometry using CuKα rays, 2θ value of 20 ° to 4
It means one having a broad scattering band having an apex in the region of 0 °, and may have a crystalline diffraction line. The strongest intensity of the crystalline diffraction lines observed in the 2θ value of 40 ° or more and 70 ° or less is 100 of the diffraction line intensity at the apex of the broad scattering band observed in the 2θ value of 20 ° or more and 40 ° or less.
It is preferably not more than twice, more preferably not more than 5 times, and particularly preferably not having a crystalline diffraction line.

Among the above amorphous oxides and / or chalcogenides, amorphous oxides of metalloid elements and / or chalcogenides are more preferable, and the periodic table 13 (III)
B) to 15 (VB) group elements, Al, Ga, Si, S
Particularly preferred are n, Ge, Pb, Sb and Bi alone or an oxide composed of a combination of two or more thereof, and chalcogenide.

The preferred amorphous oxide and / or calcium
As the cogenide, for example, Ga ₂O₃, SiO, Ge
O, SnO, SnO₂, PbO, PbO₂, Pb₂O₃, P
b₂O_Four, Pb₃O_Four, Sb₂O₃, Sb₂O_Four, Sb₂O_Five, B
i₂O₃, Bi₂O_Four, SnSiO₃, GeS, SnS, S
nS₂, PbS, PbS₂, Sb₂S₃, Sb₂S_Five, SnS
iS₃Are preferred. In addition, these are lithium oxide
Complex oxide with, for example, Li₂SnO₂Even
Yes.

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

[0121] general formula _{^{(6) SnM 1 d M 2}} e O f

In the general formula (6), M ¹ is A
Represents at least one element selected from l, B, P and Ge. M ² represents at least one element selected from Group 1 (Ia) group elements, Group 2 (IIa) group elements, Group 3 (IIIa) group elements, 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 relationship of 0.2 <d + e <2. f represents a number of 1 or more and 6 or less. It is preferably an amorphous oxide represented by.

Specific examples (C-1 to 18) of the amorphous oxide containing Sn as a main component are shown below, but the present invention is not limited thereto.

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

As the method for synthesizing the amorphous oxide and / or chalcogenite of the present invention, either a calcination method or a solution method can be adopted, but the calcination method is more preferable. In the firing method, oxides of corresponding elements,
It is preferable that the amorphous oxide and / or chalcogenite is obtained by calcining well after mixing the chalcogenite or the compound.

The firing temperature in the firing method is 5
The temperature is preferably 00 ° C. or higher and 1500 ° C. or lower, and the firing time is preferably 1 hour or longer and 100 hours or shorter.

In the firing method, the temperature may be lowered in the firing furnace after firing, or may be taken out of the firing furnace and put in water for cooling. In addition, ceramic processing (Gihodo Publishing 1987), page 217, gun method, Hammer-Anvil method, slap method,
Gas atomization method, plasma spray method, centrifugal quenching method,
An ultraquenching method such as the melt drag method can also be used. New Glass Handbook (Maruzen 1991)
You may cool using the single roller method and the twin roller method as described on page 172. In the case of a material that melts during firing, the fired product may be continuously taken out while supplying the raw material 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. Preferable examples of the inert gas include nitrogen, argon, helium, krypton, and xenon. Among them, pure argon is particularly preferable.

In the non-aqueous electrolyte secondary battery of the present invention, the average particle size of the negative electrode active material used is 0.1 to 0.1.
60 μm is preferable. A well-known crusher or classifier is used to obtain a predetermined particle size. For example, a mortar, a ball mill, a sand mill, a vibrating ball mill, a satellite ball mill, a planetary ball mill, a swirling airflow type jet mill, a sieve and the like are preferably used. At the time of pulverization, wet pulverization in which water or an organic solvent such as methanol is allowed to coexist can be performed as necessary. In order to obtain the desired particle size, it is preferable to carry out classification. The classification method is not particularly limited, and a sieve, an air classifier, or the like can be used as necessary. Classification can be carried out both dry and wet.

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

Examples of the negative electrode active material that 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 carbon materials capable of inserting and extracting lithium ions or lithium metal, Lithium, lithium alloy,
A metal that can be alloyed with lithium is preferable.

<Electrode Mixture> As the electrode mixture of the present invention,
In addition to the conductive agent, the binder, the filler, and the like, a polymer network having the structure represented by the general formula (6) as a repeating unit, a lithium salt, an aprotic organic solvent, and the like are added.

Any material may be used as the conductive agent as long as it is an electron conductive material that does not cause a chemical change in the constructed secondary battery. Usually, natural graphite (scaly graphite, flake graphite, earthy graphite, etc.), artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber and metal powder (copper, nickel, aluminum, silver (JP-A-63-
148,554)), metal fibers, polyphenylene derivatives (described in JP-A-59-20971), or the like, and one or a mixture thereof. Among them, the combined use of graphite and acetylene black is particularly preferable. The amount of the conductive agent added is preferably 1 to 50% by mass, and 2 to 30% by mass.
Is more preferable. In the case of carbon or graphite, 2 to 15 mass% is particularly preferable.

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, and among them, for example, starch, carboxymethyl cellulose, cellulose, diacetyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium alginate. , Polyacrylic acid, sodium polyacrylate, polyvinylphenol, polyvinylmethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer and other water-soluble polymers, polyvinyl Chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylide (Meth) acryl such as fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, 2-ethylhexyl acrylate (Meth) acrylic acid ester copolymer containing acid ester, (meth) acrylic acid ester-acrylonitrile copolymer, polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene-butadiene copolymer, acrylonitrile -Butadiene copolymer, polybutadiene, neoprene rubber, fluororubber, polyethylene oxide, polyester polyurethane resin, polyether polyurethane resin, polycarbonate 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 binder may be used alone or in combination of two or more. When the amount of the binder added is small, the holding power and cohesive force of the electrode mixture become weak. If it is too large, the electrode volume increases and the capacity per unit volume or unit mass of the electrode decreases. For this reason, the addition amount of the binder is preferably 1 to 30% by mass, more preferably 2 to 10% by mass.

As the filler, any fibrous material that does not cause a chemical change in the secondary battery of the present invention can be used. Generally, olefin polymers such as polypropylene and polyethylene, fibers such as 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 for ensuring safety. The separator used together to ensure safety is required to have the function of blocking the following gaps at 80 ° C or higher to increase resistance and cut off the current, and when the blocking temperature is 90 ° C or higher and 180 ° C or lower. Preferably there is.

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

The separator may be a single material such as polyethylene or polypropylene, or may be a composite material of two or more kinds. A laminate of two or more kinds of microporous films having different pore diameters, porosities, pore blocking temperatures and the like is preferable.

<Collector> As the positive and negative electrode collectors, electron conductors that do not chemically change in the non-aqueous electrolyte secondary battery of the present invention are used. The positive electrode current collector is preferably aluminum, stainless steel, nickel, titanium, or the like, as well as aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, or silver.
Among them, aluminum and aluminum alloys are more preferable.

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

As the shape of the current collector, a film sheet is usually used, but a net, a punch, a lath body, a porous body, a foamed body, a molded body of fibers, etc. may also be used. You can The thickness of the current collector is not particularly limited, but is preferably 1 to 500 μm. Also,
It is also preferable that the surface of the current collector be roughened by surface treatment.

<Preparation of Non-Aqueous Electrolyte Secondary Battery> Here,
The production of the non-aqueous electrolyte secondary battery of the present invention will be described.
The shape of the non-aqueous electrolyte secondary battery of the present invention is a sheet,
It can be applied to any shape such as corner or cylinder. 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 a 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 and a squeeze method are suitable. Can be mentioned. Among them, the blade method, the knife method and the extrusion method are preferable. In addition, the application is 0.1 to
It is preferably carried out at a speed of 100 m / min. At this time, a good surface condition of the coating layer can be obtained by selecting the above-mentioned coating method according to the solution physical properties and drying properties of the mixture. The coating may be carried out one by one or simultaneously on both sides.

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

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

The positive and negative electrode sheets produced by the above method are superposed on each other via a separator, and then directly processed into a sheet-like battery or folded and then inserted into a square can, and the can and the sheet are electrically connected. After being electrically connected, an electrolyte is injected and a prismatic battery is formed using a sealing plate. In addition, positive and negative electrode sheets are stacked and wound with a separator in between and then inserted into a cylindrical can, after electrically connecting the can and the sheet, an electrolyte is injected, and a cylinder battery is sealed using a sealing plate. Form. At this time, the 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 safety valve, as a measure against the rise in internal pressure of the battery can, a method of making a cut in the battery can, a method of cracking a gasket, a method of cracking a sealing plate, or a method of cutting with a lead plate can be used. Further, the charger may be provided with a protection circuit incorporating measures against overcharge or overdischarge, or may be connected independently.

As a measure against overcharge, it is possible to provide a method of interrupting the current by increasing the internal pressure of the battery. At this time, a compound that increases the internal pressure can be included in the mixture or the electrolyte. Examples of the compound used for increasing the internal pressure include Li ₂ CO ₃ , LiHCO ₃ , Na ₂ C
Examples thereof include carbonates such as O ₃ , NaHCO ₃ , CaCO ₃ , and MgCO ₃ .

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

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

The use of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited. For example, when it is mounted in an electronic device,
Notebook computer, pen input computer, mobile computer, electronic 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 and so on. Other consumer products such as automobiles, electric vehicles, motors, lighting equipment, toys,
Game devices, road conditioners, watches, strobes, cameras, medical devices (pacemakers, hearing aids, shoulder massagers, etc.), etc. Furthermore, it can be used for various military purposes and for space. It can also be combined with a solar cell.

[0153]

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

Example 1 (a) Synthesis of Polymerizable Polymer Compound A compound having a structure represented by the general formula (4) as a partial structure and an alcohol compound represented by the general formula (5). By the reaction of, a polymerizable polymer compound having the structure represented by the general formula (1) as a partial structure was synthesized by the following method.

<Synthesis of Compound Having Structure (4-1) as Partial Structure> Tetramethoxysilane 30.4
g and 9.0 g of oxalic acid were mixed and reacted with heating under reflux for 10 hours. After the reaction, 150 ℃ / 5mmHg (667P
After distilling off the volatile components in a), a compound having a structure represented by (4-1) as a partial structure (hereinafter, referred to as "compound (4-
1) ”. 12 g of a colorless liquid substance) was obtained.

<Synthesis of Polymerizable Polymer Compound Having Structure Represented by (1-1) as Partial Structure> 10 g of compound (4-1) obtained by the above synthesis and the general formula (5) Exemplary Compound (5-1) of Alcohol Compound that is Generated
0 g was mixed, heated at 60 ° C. and reacted for 2 hours. After the reaction, the volatile component was distilled off at 50 ° C./5 mmHg (667 Pa), and then a colorless liquid product (Si-1) 1 of a polymerizable polymer compound having a structure represented by (1-1) as a partial structure.
0.3 g was obtained. The glass transition temperature (Tg) of the polymerizable polymer compound (Si-1) was about -70 ° C.

In the synthesis of the polymerizable polymer compound (Si-1), a compound having the structure represented by the general formula (4) as a partial structure and an alcohol compound represented by the general formula (5) are prepared. In the same manner as in the synthesis of (Si-1), except for the changes shown in Table 1 below, (Si-
2) to (Si-5) were synthesized. These were all liquids. Moreover, the compound (Si-6) having the structure represented by (4-1) as a partial structure was prepared as a comparative compound.

[0158]

[Table 1]

(B) Preparation of Solid Electrolyte Polymerizable polymer compound (Si-1) synthesized in (a) above
~ (Si-5) is used to prepare an electrolyte composition having a composition ratio shown in Table 2 below, and the composition is cast on Teflon (R), and the casting solution is treated under the conditions shown in Table 2 below. Polymerization is performed, and solid electrolyte membrane (SPE-1) ~
(SPE-7) was obtained. In addition, (Si
-6), and an electrolyte composition (RE-
Using 1) and (RE-2), comparative solid electrolyte membranes (SPE-8) to (SPE-11) were obtained.

[0160]

[Table 2]

[0161]

[Chemical 20]

(C) Evaluation of Solid Electrolyte Membrane <Measurement of Ionic Conductivity and Transport Number> The solid electrolyte membrane prepared in (b) above was sandwiched between two lithium electrodes using 0.5 mm polypropylene as a spacer, The Li ion transport number was measured. The results are shown in Table 2 above.

As shown in Table 2, the electrolyte composition (solid electrolyte membrane) using the crosslinked polymer compound of the present invention showed higher ionic conductivity and higher Li ion transport number than those of Comparative Examples. It was confirmed to be useful as a lithium ion conductive material.

(Example 2) (a) Preparation of sheet type battery <Preparation 1 of positive electrode sheet> LiCoO 2 was used as a positive electrode active material.
43 parts by mass of ₂ , ₂ parts by mass of scaly graphite, 2 parts by mass of acetylene black, and 3 parts by mass of polyacrylonitrile as a binder, and kneaded with 100 parts by mass of acrylonitrile as a medium to obtain a slurry having a thickness of 20 μm. The aluminum foil is coated with an extrusion type coating machine, dried, and compression-molded by a calendar press machine. Then, an aluminum lead plate is welded to the end of the aluminum foil to obtain a thickness of 95 μm, a width of 54 mm and a length of 54 mm. A 49 mm-thick positive electrode sheet (CA-1) was produced.

<Production of Positive Electrode Sheet 2> As a positive electrode active material, 43 parts by mass of LiMn ₂ O ₄ , ₂ parts by mass of flake graphite,
2 parts by mass of acetylene black and 3 parts by mass of polyacrylonitrile as a binder were added to give 1 part of acrylonitrile.
100 parts by mass was kneaded as a medium, and the obtained slurry was applied to an aluminum foil having a thickness of 20 μm by using an extrusion type coating machine, dried, and compression-molded by a calender press machine. Welded lead plate made of 114mm thick, 54mm wide x 49mm long
The positive electrode sheet (CA-2) of was produced.

<Preparation of Positive Electrode Sheet 3> As a positive electrode active material, 43 parts by mass of LiNiO ₂ , ₂ parts by mass of flake graphite,
2 parts by mass of acetylene black and 3 parts by mass of polyacrylonitrile as a binder were added to give 1 part of acrylonitrile.
100 parts by mass was kneaded as a medium, and the obtained slurry was applied to an aluminum foil having a thickness of 20 μm by using an extrusion type coating machine, dried, and compression-molded by a calender press machine. A lead plate made of aluminum was welded to produce a positive electrode sheet (CA-3) having a thickness of 75 μm, a width of 54 mm and a length of 49 mm.

<Preparation 1 of Negative Electrode Sheet> 43 parts by mass of SnSiO ₃ was used as a negative electrode active material, and 2 parts by mass of acetylene black and 2 parts by mass of graphite were mixed as a conductive agent.
Add polyacrylonitrile as a binder and add 3
In addition to 100 parts by mass of N-methylpyrrolidone as a medium, kneading was performed 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. With the negative electrode mixture slurry as the lower layer and the auxiliary layer slurry as the upper layer, the thickness is 10 μm.
It was applied to the copper foil of the above using an extrusion type coating machine,
After drying, it is compression molded with a calender press to a thickness of 46.
A negative electrode sheet of μm, width 55 mm × length 50 mm was produced. After a nickel lead plate was welded 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 lower. The heat treatment was performed using a far infrared heater. Lithium foil with a thickness of 35 μm (purity 99.8%) cut into 4 mm × 55 mm on the entire surface of the negative electrode sheet after heat treatment.
Was attached at a 10 mm interval at right angles to the length direction of the sheet to prepare a negative electrode sheet (AN-1).

<Preparation 2 of Negative Electrode Sheet> In Preparation 1 of the negative electrode sheet, SnSiO ₃ was replaced with 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
A negative electrode sheet (AN-2) having a width of 55 mm and a length of 50 mm, in which a lithium foil having a nickel lead plate welded to the end portion thereof was attached in the same manner as in the production of the negative electrode sheet except that the negative electrode sheet was changed to _3.65. (AN-3) was produced.

<Preparation 3 of Negative Electrode Sheet> As a negative electrode active material, a mesophase pitch carbon material (Petka) was used.
2 parts by weight of acetylene black and 2 parts by weight of graphite as a conductive agent are mixed and added, 3 parts by weight of polyacrylonitrile as a binder is further added, and 100 parts by weight of N-methylpyrrolidone is kneaded as a medium to prepare a negative electrode. A mixture slurry was obtained. The negative electrode mixture slurry is formed to a thickness of 10 μm.
m of copper foil was applied by using an extrusion type coating machine, dried and compression-molded by a calender press to prepare a negative electrode sheet having a thickness of 46 μm, a width of 55 mm and a length of 50 mm. After a nickel lead plate was welded 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 lower. The heat treatment was performed using a far infrared heater to obtain a negative electrode sheet (AN-4).

<Production of Sheet Type Battery> The negative electrode sheet and the positive electrode sheet were dehydrated and dried at 230 ° C. for 30 minutes in dry air having a dew point of −40 ° C. or less. In a dry atmosphere, a dehydrated and dried positive electrode sheet (CA-1) 11 having a width of 54 mm and a length of 49 mm, a solid electrolyte 12 having a width of 60 mm, a length of 60 mm and a thickness of 30 μm, a width of 55 mm and a length of 50 mm
Of the dehydrated and dried negative electrode sheet (AN-1) 13 are laminated in this order, and the outer edges of the laminated film of polyethylene (50 μm) -polyethylene terephthalate (50 μm) are used, and the four edges are heat-sealed in a vacuum and sealed. Then, a sheet type battery (SB-1) was produced. Similarly, sheet type batteries (SB-2) to (SB-
19) was produced.

[0171]

[Table 3]

(B) Evaluation of battery performance For the sheet type battery prepared in (a) above, 0.2
Charging and discharging were repeated 10 times under the conditions of C, end-of-charge voltage 4.2V, and end-of-discharge voltage 2.6V, and the discharge capacity at the 10th cycle was determined. This was examined for 10 batteries of the same formulation, and the average was taken as the capacity of the battery. In this way, the capacity of each battery is calculated, and this value is SB-2 ...
5, 11-14 are SB-1, SB-15 is SB-6
So SB-16 is SB-7, SB-17 is SB-8.
So SB-18 is SB-9, SB-19 is SB-10.
The relative capacitance between the same electrode compositions was obtained by dividing by. The respective values are shown in Table 3 above.

From the results of Table 3 above, when the electrolyte composition of the present invention was used as the electrolyte of the battery, as compared with Comparative Example,
It was confirmed that the battery capacity would increase.

[0174]

INDUSTRIAL APPLICABILITY According to the present invention, a novel polymerizable polymer compound and a method for producing the same, a crosslinked polymer compound obtained from the polymerizable polymer compound and a method for producing the same, and a high ion containing the crosslinked polymer compound are obtained. It is possible to provide a novel electrolyte composition exhibiting conductivity and a high ion transport number, and a high-capacity non-aqueous electrolyte secondary battery using the electrolyte composition.

[Brief description of drawings]

FIG. 1 shows a conceptual diagram of a sheet type battery manufactured in an example.

[Explanation of symbols]

11 Positive electrode sheet 12 Solid electrolyte 13 Negative electrode sheet 14 Positive terminal 15 Negative electrode terminal

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J027 AC07 AC09 AF04 AF05 BA01                 4J030 CB02 CB03 CB13 CC04 CC05                       CC06 CC15 CC17 CC21 CC23                       CC30 CF02 CG01 CG19                 4J035 CA06U CA061 CA13M CA152                       CA182 CA262 FB01 LB20                 5G301 CA16 CA17 CA30 CD01                 5H029 AJ02 AJ06 AK03 AL02 AL03                       AL04 AL06 AL07 AL12 AM03                       AM04 AM05 AM07 AM16 CJ11                       HJ02

Claims (10)

[Claims] 1. A polymerizable polymer compound having a structure represented by the following general formula (1) as a partial structure. [Chemical 1] In the general formula (1), R ¹ and R ² each independently represent an alkyl group or an aryl group. At least one of R ¹ and R ² has a polymerizable group as a substituent.
M represents silicon, boron, or a metal element. n is M
Represents the valence of. 2. The polymerizable polymer compound according to claim 1, wherein M is silicon. 3. The polymerizable polymer compound according to claim 1, wherein the polymerizable group is an ethylenically unsaturated group. 4. The polymerizable polymer compound according to claim 1, wherein the polymerizable group contains a group selected from the group consisting of an acryloyl group, a methacryloyl group, and a styryl group. 5. A polymer compound having a structure represented by the following general formula (4) as a partial structure and an alcohol compound represented by the following general formula (5) are reacted with each other. The polymerizable polymer compound according to any one of 1. [Chemical 2] In the general formula (4), R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group. M represents silicon, boron, or a metal element. n represents the valence of M. In the general formula (5), R ¹ and R ² represent an alkyl group or an aryl group having a polymerizable group as a substituent. 6. A cross-linked polymer compound obtained by cross-linking and polymerizing the polymerizable polymer compound according to any one of claims 1 to 5. 7. A crosslinked polymer compound according to claim 6,
An electrolyte composition comprising a salt of a metal ion belonging to Group 1 or 2 of the periodic table. 8. A non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode, wherein the non-aqueous secondary battery contains the electrolyte composition according to claim 7. Next battery. 9. A polymer compound having a structure represented by the following general formula (4) as a partial structure and an alcohol compound represented by the following general formula (5) are reacted to give a compound represented by the following general formula (1). A method for producing a polymerizable polymer compound, comprising obtaining a polymerizable polymer compound having a structure represented by as a partial structure. [Chemical 3] In the general formula (1), R ¹ and R ² each independently represent an alkyl group or an aryl group. At least one of R ¹ and R ² has a polymerizable group as a substituent.
M represents silicon, boron, or a metal element. n is M
Represents the valence of. In the general formula (4), R ⁵ and R ⁶
Each independently represents an alkyl group or an aryl group. M
Represents silicon, boron, or a metal element. n represents the valence of M. In the general formula (5), R ¹ and R
² represents an alkyl group or an aryl group having a polymerizable group as a substituent. 10. A method for producing a crosslinked polymer compound, which comprises crosslink-polymerizing a polymerizable polymer compound having a structure represented by the following general formula (1) as a partial structure. [Chemical 4] In the general formula (1), R ¹ and R ² each independently represent an alkyl group or an aryl group. At least one of R ¹ and R ² has a polymerizable group as a substituent.
M represents silicon, boron, or a metal element. n is M
Represents the valence of.