JPH11339557A - Solid polymer electrolyte and nonaqueous electrolyte secondary battery using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance ion conductivity near at a room temperature and improve the film strength and filming property by polymerizing at least a monofunctional styrene derivative monomer and/or a multifunctional monomer with an ion conductive solvent having a salt of metal ion of the group Ia or IIa of the periodic table group dissolved therein to form a polymer matrix. SOLUTION: The monomer to be used is represented by formula I and/or formula II. In formula I, R1 and R2 represent hydrogen atom or an alkyl group, R3 represents hydrogen atom or an alkyl group, alkenyl group, aryl group or the like, and L1 represents an atomic group represented by formulae III-V. In formulae III-V, R7 represents a lower alkylene group, R8 and R9 represent hydrogen atom or a lower alkyl group, (p) represents an integer of 0-30, and (q) and (r) each independently represent an integer of 1-30. In formula II, R5 , R6 and L2 represent the same as R1 , R2 and L1 , respectively, and L3 represents a z-valent connecting group, wherein (z) represents an integer of 2 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic solid electrolyte, and particularly to an organic solid electrolyte suitable as an antistatic agent, a material for batteries and other electrochemical devices, and a non-aqueous electrolyte having high capacity and excellent cycle stability. It relates to a secondary battery.

[0002]

2. Description of the Related Art In order to apply an organic solid electrolyte to an antistatic material or an electrochemical device such as a battery, it must have not only good ionic conductivity but also excellent film forming property. It is also necessary that the storage stability is good and that the material can be easily produced. However, a solid electrolyte satisfying all such required performances has not been developed so far. Polyethylene oxide (hereinafter PE
O) is a salt of a metal ion belonging to various groups Ia or IIa of the periodic table, for example, LiCF ₃ SO ₃ , LiI, LiClO ₄ , Na
I, NaCF ₃ SO ₃ , KCF ₃ SO _3, etc., form a complex that functions as a solid electrolyte and show relatively good ionic conductivity (for example, fast ion transport by P. Vashista et al.).・ Fast Ion Transport in Solid, 131 pages (1979)
And viscoelasticity and flexibility peculiar to polymers, and have good processability and storage stability. However, the ionic conductivity of PEO is highly temperature-dependent, and although it exhibits good ionic conductivity at 60 ° C or higher, the ionic conductivity deteriorates remarkably near room temperature, and it has general versatility such that it can be used in a wide temperature range. It was difficult to incorporate it into a certain product. Therefore,
Various PEO-modified polymers have been proposed to solve the drawbacks of PEO, but their ionic conductivity is still low and it has not been possible to put them to practical use. In recent years, as a method for improving the low ionic conductivity, particularly the ionic conductivity at room temperature, a material in which an organic solvent electrolyte is held in a gel of a polymer compound has been actively studied (for example, R. et al. Koksbang
et al., Solid State Ionics, 69, 320 (1994)). But,
In general, a solid electrolyte combined with an electrolytic solution needs to use a large amount of an organic solvent in order to increase ionic conductivity, and if this is the case, the membrane strength is significantly reduced, and the solid electrolyte cannot function as a solid electrolyte. JP-A-2-229826 and JP-A-8-241734 show a material comprising a block-graft copolymer comprising a polystyrene derivative and a vinyl polymer, which is intended to improve the film strength. However, even with these materials, there is a problem that the film strength and the cycle stability when used in a battery are not sufficient.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel organic solid electrolyte which exhibits high ionic conductivity even at around room temperature, has a sufficient film strength and is excellent in film forming properties, and has a high cycle stability. It is to provide a non-aqueous electrolyte secondary battery excellent in the above.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide at least an ionic conductive material obtained by dissolving at least a monofunctional styrene derivative monomer and / or a polyfunctional monomer and a salt of a metal ion belonging to Group Ia or IIa of the periodic table. This has been achieved by a solid polymer electrolyte characterized by polymerizing a solvent to form a polymer matrix.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention are described below, but the present invention is not limited thereto. Polymerizing at least a monomer represented by the following general formula (1) and / or an ion conductive solvent obtained by dissolving a monomer represented by the following general formula (2) and a salt of a metal ion belonging to Group Ia or IIa of the periodic table; A polymer solid electrolyte characterized by forming a polymer matrix. General formula (1)

[0006]

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In the formula, R ₁ and R ₂ represent a hydrogen atom or an alkyl group. R ₃ is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a —COR ₄ group or —SO ₂ R ₄
R ₄ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. L ₁ is represented by the following general formula (3)
Represents an atomic group represented by (5). General formula (2)

[0008]

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In the formula, R ₅ , R ₆ and L ₂ have the same meanings as R ₁ , R ₂ and L ₁ respectively. L ₃ represents a z-valent linking group. z
Represents an integer of 2 or more. General formula (3)

[0010]

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General formula (4)

[0012]

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General formula (5)

[0014]

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In the formula, R ₇ represents a lower alkylene group. R ₈
And R ₉ represent a hydrogen atom or a lower alkyl group. p represents an integer of 0 to 30, and q and r are each independently an integer of 1 to 30. Item 2. The polymer solid electrolyte according to Item 1, wherein the mixture contains an acrylate monomer. A non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode, wherein the battery contains the polymer solid electrolyte according to item 1 or 2.

Hereinafter, the general formulas (1) to (5) will be described in detail. R ₁ , R ₂ , R ₅ and R ₆ may be the same or different and represent a hydrogen atom or an alkyl group. Preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ₃
Is a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group, an aryl group, an aralkyl group, a -COR ₄ group or -SO ₂
It represents R ₄ group, R ₄ is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and these groups may have a substituent.

Among the groups represented by R ₃ or R ₄ , examples of the substituent of the alkyl group and the alkenyl group include a halogen atom,
Cyano group, sulfo group, hydroxy group, carboxy group, alkyl group, aryl group, aralkyl group, acyloxy group, acylamino group, amino group, sulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, carbamoyl group, sulfamoyl Group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, aryloxysulfonyl group, carbamoylamino group, sulfamoylamino group, carbamoyloxy group, alkoxycarbamoylamino group, aryloxycarbamoyl And an amino group.

Examples of the substituent of the aryl group and the aralkyl group represented by R ₃ or R ₄ include an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom). , Hydroxyl, carboxy, sulfo, acylamino (eg, acetamido, benzamide), sulfonamido, carbamoyl, acyloxy, alkoxycarbonyl, acyl, alkoxy (eg, methoxy), aryloxy (eg, phenoxy) , A nitro group, a formyl group, an alkylsulfonyl group and an arylsulfonyl group. Examples of the group that can be substituted for the alkyl group include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an acyloxy group, an acyl group, and a nitro group. May be.

R ₃ or R ₄ is preferably a hydrogen atom, carbon number 1
8 substituents alkyl group which may have a alkenyl or aryl group, examples, hydrogen atom, methyl, ethyl, hexyl, -CH ₂ CF _3, allyl, phenyl and the like.

L ₁ or L ₂ represents a linking group represented by formulas (3) to (5). L ₁ or L ₂ may be substituted at any position on the benzene ring, but is preferably at the ortho or para position with respect to the vinyl group, more preferably at the para position.

R ₇ represents a linear or branched alkylene group having 1 to 6 carbon atoms, preferably a linear or branched alkylene group having 1 to 3 carbon atoms, particularly preferably-
CH ₂ CH ₂ — or —CH ₂ CH (CH ₃ ) —.

R _{8 and} R ₉ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. Preferably it is a hydrogen atom.

P represents an integer of 0 to 30, q or r is an integer of 1 to 30, and p, q and r are preferably 1
To 20, more preferably an integer of 2 to 16.

Z is an integer of 2 or more, preferably 2 to
4 is an integer. L ₃ represents a z-valent linking group. When z = 2, L ₃ is an alkylene group, an arylene group, -O-, -S-,
_{-NH -, - N (CH 3} ) -, or represent these combined linking group. When z = 2, a preferred example of L ₃ is -CH _{2
-, -CH 2 CH 2 -,} - CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, - CH 2 OC
H _2- , -CH ₂ CH ₂ OCH ₂ CH _2- , -CH ₂ CH ₂ NHCH ₂ CH _2- , -CH ₂ CH (C
H ₃ ) OCH ₂ CH (CH ₃ )-

[0025]

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And so on. These groups have 1 to 16 carbon atoms.
Are preferable, and these groups may have a substituent. Examples of the substituent include the substituents described in the R _3.

When z = 3, L ₃ is represented by the following general formula (6). General formula (6)

[0028]

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Where A is

[0030]

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Wherein R ₁₀ is a hydrogen atom or a carbon atom having 1 to
8 is an alkyl group or an alkoxy group. L ₄ , L ₅ and L ₆ may be the same or different, and have the same meaning as L ₃ when z = 2. l, m, and n each independently represent 0 or 1.

When z = ₃ , preferred examples of L ₃ include:

[0033]

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And the like. These groups may have a substituent, and examples of the substituent include the substituents described for R ₃ .

When z = 4, L ₃ is represented by the following general formula (7).

General formula (7)

[0037]

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In the formula, B is

[0039]

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L ₇ , L ₈ , L ₉ , and L ₁₀ may be the same or different and have the same meaning as L ₃ when z = 2. t, u, v, and w are each independently 0 or 1.

When z = 4, a preferred example of L ₃ is:

[0042]

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And so on. The polymer compound used in the present invention may contain a repeating unit derived from another monomer component in addition to the repeating unit derived from the general formula (1) and / or (2). Examples of other monomer components include acrylic acid, α-chloroacrylic acid, α-alkacrylic acid (eg, methacrylic acid), and amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n -Butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl Acrylate, 2-ethoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl carbonate ethyl methacrylate and β-hydroxyethyl Acrylates, vinyl esters (eg, vinyl acetate, vinyl propionate, and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, such as vinyl toluene, divinylbenzene, vinyl acetophenone, and sulfostyrene) , Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2-, 4-vinyl pyridine. Can be

Further, as an example of the copolymer monomer,

[0045]

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The examples are not limited to these. Preferred as other monomer components are
Acrylic acid ester, methacrylic acid ester or acrylonitrile. More preferably, it is an acrylic ester or a methacrylic ester.

The polymer compound used in the present invention contains at least one kind of a repeating unit derived from the general formula (1) or (2). A repeating unit derived from 2) may be contained together.

The repeating unit derived from the general formula (1) is preferably contained in the polymer at 10 mol% or more. More preferably, it is at least 50 mol%.

The content of the repeating unit derived from the general formula (2) is preferably 0.5% to 50% by mole, more preferably 1 to 20% by mole in the polymer compound.

Further, the polymer compound used in the present invention may have at least one kind of a repeating unit derived from the general formula (1) or (2). Examples of the monomer represented by the general formula (1) are shown below, but the invention is not limited thereto.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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Examples of the monomer represented by the general formula (2) are shown below, but it should not be construed that the invention is limited thereto.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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The monomer of the present invention may be a compound of the periodic table Ia or II.
The polymer matrix can be formed by dissolving in a salt of a metal ion belonging to group a and an ion conductive solvent, and polymerizing by heating and / or irradiation.

When a high molecular compound is formed by thermal polymerization of the corresponding monomer, 0.01 to 5 m
It is preferable to add ol% of the polymerization initiator because the polymerization time can be shortened. Examples of the polymerization initiator include azobis compounds, peroxides, hydroperoxides, and redox catalysts such as potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl peroxide, isopropyl percarbonate, and 2,4-dichlorobenzoyl peroxide. Oxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, 2,
2-azobis (2-amidinopropane) hydrochloride and the like. The heating polymerization temperature is preferably from 40 to 150C, more preferably from 50 to 120C. The heating polymerization time is preferably from 1 to 180 minutes, more preferably from 2 to 60 minutes, and particularly preferably from 3 to 20 minutes.

When a polymer matrix is formed by polymerization of the monomer of the present invention by irradiation with radiation, a method of irradiating active light such as ultraviolet light, visible light, electron beam and γ-ray is used. In the case of ultraviolet visible light, the polymerization time can be reduced by adding 0.01 to 5 mol% of a radiation polymerization initiator.

As the radiation polymerization initiator, known radiation polymerization initiators can be used. Examples thereof include carbonyl compounds,
Azobis compounds, peroxides, sulfur compounds, halogen compounds, redox compounds, cationic polymerization initiators such as benzoin, 2-methylbenzoin, trimethylsilylbenzoin, 4-methoxybenzophenone,
Michler's ketone, benzoin methyl ether, acetophenone, anthraquinone, benzyl-2-chlorothioxanthone, 2,2-dimethoxy-2-phenylacetophenone, benzoyl peroxide, azobispropane,
Thiophenol, 2-bromopropane, 1-chloromethylnaphthalene, p-methoxyphenyl-2,4-dichloromethyl-1,3,5-triazine, benzophenone / triethanolamine, 2-stilbene-4,6-trichloro Methyl-1,3,5-triazine, diphenyliodonium tetrafluoroborate and the like can be mentioned.

The following are typical examples of the polymer compound used in the present invention, but the invention is not limited thereto.

[0073]

[Table 1]

[0074]

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Representative examples of the ion conductive solvent used in the present invention include ethylene carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, and the like.
Diethyl carbonate, dipropyl carbonate,

[0076]

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Γ-butyrolactone, γ-valerolactone, γ-capryrolactone, crotlactone, γ-caprolactone, δ-valerolactone,

[0078]

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Dimethoxyethane, dimethylsulfoxide, sulfolane, N, N-dimethylformamide, acetonitrile, nitromethane, N-methylpyrrolidone, tetrahydrofuran, 2-methyltetrahydrofuran, methyltetrahydrofuranfurfuryl ether, 5-methyltetrahydrofuran-2-methanol, Examples thereof include 3-dioxolan, 1,4-dioxane, 4-methyl-1,3-dioxane, 2-methyl-1,3-dioxolan, and the like.

Preferably, ethylene carbonate, propylene carbonate, diethyl carbonate, γ-butyrolactone, acetonitrile, 2-methyltetrahydrofuran, 4-methyl-1,3-dioxane, 2-methyl-
Examples thereof include 1,3-dioxolan and dimethoxyethane. These ion conductive compounds may be used alone or in combination of two or more.

The Group Ia or II of the Periodic Table used in the present invention
As the metal ions belonging to group a, lithium, sodium, and potassium ions are preferable, and typical metal ion salts include LiCF ₃ SO ₃ , LiPF ₆ , LiClO ₄ , LiI, and LiBF.
_{4, LiCF 3 CO 2, LiSCN} , LiN (SO 2 CF 3) 2, NaI, NaCF 3 S
O ₃ , NaClO ₄ , NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KSCN, KPF ₆ ,
KClO ₄ , KAsF _{6 and the} like. More preferably, it is the above-mentioned Li salt. These may be used alone or in combination of two or more.

When the solid polymer electrolyte of the present invention is formed, a solvent which can dissolve both the monomer used in the present invention and the metal ion may be used in combination. Preferred examples of the solvent include solvents having a boiling point of 100 ° C. or lower, such as acetone, methyl ethyl ketone, isopropanol, and ethanol.

The solid polymer electrolyte of the present invention comprises: 1. When used in combination with a polymer network, a lithium salt, and an aprotic organic solvent Polymer network, lithium salt, may be used in combination with aprotic organic solvent and porous membrane,
Each is used for different purposes.

As the porous membrane used in the present invention, a material having high ion permeability, predetermined mechanical strength, insulating microporous material or having a gap is used.

The thickness of the porous film of the present invention is 5 μm or more and 1
It is a microporous film, woven fabric, non-woven fabric, or the like having a size of 00 μm or less, more preferably 10 μm to 80 μm.

The porous membrane of the present invention includes polyethylene, polypropylene, polybutene, polyfluorinated ethylene, polyvinyl chloride and polyacrylonitrile, and preferably contains at least 20% by weight of an ethylene component, particularly preferably 30% or more. Including. Further, those made by mixing and dissolving polyethylene, polypropylene polyethylene and polytetrafluoroethylene are also preferable.

The non-woven fabric or woven fabric has a yarn diameter of 0.1 μm to 5 μm.
μm, polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-
Those comprising a methylbutene copolymer, an ethylene-methylpentene copolymer, polypropylene, and polytetrafluoroethylene fiber are preferred.

The porous membrane of the present invention may contain inorganic fibers such as glass fibers and carbon fibers, and inorganic particles such as silicon dioxide, zeolite, alumina and talc.

The general method for forming the solid polymer electrolyte of the present invention will be described below.

(Formation by Heat Polymerization) A monomer of the present invention and a salt of a metal ion belonging to Group Ia or IIa of the periodic table are dissolved in an ion conductive solvent, and if necessary, a heat polymerization initiator and a boiling point of 100 ° C. or lower are used. A solvent is added to dissolve and cast on a Teflon plate, aluminum foil, or polyethylene terephthalate film, or impregnated in a porous membrane. The casting liquid or the porous film is heated at 40 to 150 ° C. in a nitrogen gas or argon gas atmosphere at a temperature of
Let react for 180 minutes, and if necessary, 50-200 mmHg
Dry under reduced pressure for 30 to 120 minutes.

(Formation by Light Irradiation Polymerization) A monomer of the present invention and a salt of a metal ion belonging to Group Ia or IIa of the periodic table are dissolved in an ion-conductive solvent, and if necessary, a photopolymerization initiator and a boiling point of 100 ° C. or lower are used. And then dissolved and cast on a Teflon plate, aluminum foil, or polyethylene terephthalate film or impregnated in a porous membrane. After the solvent is removed from the casting liquid or the porous film by heating at 20 to 100 ° C. under normal pressure or reduced pressure, an actinic ray such as an ultra-high pressure mercury lamp is irradiated at room temperature in a nitrogen gas or argon gas atmosphere for 1 to 60 minutes. And optionally under reduced pressure of 50 to 200 mmHg for 30 minutes.
Dry for ~ 120 minutes. When a polymer solid electrolyte is formed by polymerization by light irradiation, heating is preferable because the polymerization time can be further reduced. Further, it is preferable to further heat after performing polymerization by light irradiation in order to improve the polymerization rate.

(Formation by Electron Beam Irradiation) A monomer of the present invention and a salt of a metal ion belonging to Group Ia or IIa of the Periodic Table are dissolved in an ion-conductive solvent, and
The solution is dissolved by adding a solvent at a temperature of not more than ℃ and cast on a Teflon plate, an aluminum foil or a polyethylene terephthalate film or impregnated in a porous film. After the solvent is removed from the casting liquid or the porous film by heating at 20 to 100 ° C. under normal pressure or reduced pressure, an electron beam is irradiated with 2 to 15 Mrad at room temperature in a nitrogen gas or argon gas atmosphere.

When the polymer matrix of the present invention is used as a secondary battery, the positive electrode active material may be a transition metal oxide capable of reversibly inserting and releasing lithium ions, but a lithium-containing transition metal oxide is particularly preferable. Preferred lithium-containing transition metal oxide cathode active materials used in the present invention include lithium-containing Ti, V, Cr, Mn, F
An oxide containing e, Co, Ni, Cu, Mo, and W is mentioned. 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, B
i, Si, P, B, etc. may be mixed. The mixing amount is preferably 0 to 30 mol% based on the transition metal.

More preferable lithium-containing transition metal oxide positive electrode active materials used in the present invention include lithium compounds / transition metal compounds (where transition metals are Ti, V,
It is preferable to mix and synthesize such that the total molar ratio of Cr, Mn, Fe, Co, Ni, Mo, and W) is 0.3 to 2.2.

Particularly preferred lithium-containing transition metal oxide cathode active materials used in the present invention include lithium compounds / transition metal compounds (where transition metals are V, Cr,
At least one selected from Mn, Fe, Co, Ni)
It is preferable to mix and synthesize so that the total molar ratio of the above is 0.3 to 2.2.

A particularly preferred lithium-containing transition metal oxide positive electrode active material used in the present invention is Li _g M ³ O ₂ (M ³ is C
one or more selected from o, Ni, Fe, and Mn;
Material containing 1.2) or ^{_{Li h M 4 2 O 4 (}} M 4 is Mn,,
h = 0 to 2) having a spinel structure, and M ³ and M ⁴ may be Al, Ga, I
n, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc. may be mixed. The mixing amount is 0 to 30 with respect to the transition metal.
mol% is preferred.

The most preferred lithium-containing transition metal oxide positive electrode active materials used in the present invention include Li _g CoO ₂ , Li
_g NiO ₂ , Li _g MnO ₂ , Li _g Co _j Ni _1-j O ₂ , Li _h Mn ₂ O ₄ (where g = 0.02 to 1.2, j = 0.1 to 0.9) No. Here, the above-mentioned g value is a value before the start of charging and discharging, and increases or 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. The firing temperature used in the present invention may be a temperature at which a part of the mixed compound used in the present invention decomposes and melts.
50-2000 ° C is preferred, and especially 350-1500 ° C
Is preferred. In firing, it is preferable to calcine at 250 to 900 ° C. The firing time is preferably from 1 to 72 hours, more preferably from 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 ° C. to 900 ° C.

The firing gas atmosphere is not particularly limited, and may be an oxidizing atmosphere or a reducing atmosphere. For example, in air, or gas with oxygen concentration adjusted to any ratio,
Alternatively, hydrogen, carbon monoxide, nitrogen, argon, helium, krypton, xenon, carbon dioxide and the like can be mentioned.

The average particle size of the positive electrode active material used in 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 preferably 0.01 to 50 m ² / g by the BET method. In addition, the positive electrode active material 5
The pH of the supernatant when g is dissolved in 100 ml of distilled water is preferably 7 or more and 12 or less.

To obtain a predetermined particle size, a well-known pulverizer or classifier is used. For example, a mortar, a ball mill, a vibrating ball mill, a vibrating mill, a satellite ball mill, a planetary ball mill, a swirling air jet mill, a sieve, and the like are used. The positive electrode active material obtained by firing may be used after being washed with water, an acidic aqueous solution, an alkaline aqueous solution, or an organic solvent.

One of the negative electrode active materials used in the present invention is:
It is a carbonaceous material that can store and release lithium. The carbonaceous material is a material substantially composed of carbon. For example,
Carbonaceous materials obtained by firing artificial pitches such as petroleum pitch, natural graphite, vapor-grown graphite, and various synthetic resins such as PAN-based resins and furfuryl alcohol resins can be given.
Furthermore, various carbon fibers such as PAN-based carbon fiber, cellulose-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, dehydrated PVA-based carbon fiber, lignin carbon fiber, glassy carbon fiber, activated carbon fiber, etc. Spherical particles, graphite whiskers, flat graphite, and the like can also be used. These carbonaceous materials can be classified into non-graphitizable carbon materials and graphite-based carbon materials according to the degree of graphitization. Further, carbonaceous materials are disclosed in JP-A-62-22066 and JP-A-2-6856.
No., the surface spacing and density described in 3-45473,
It preferably has a crystallite size. 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.

Another negative electrode active material used in the present invention is an oxide and / or a chalcogenide.

In particular, amorphous oxides and / or chalcogenides are preferred. The term “amorphous” as used herein refers to a substance having a broad scattering band having an apex in a region of 20 ° to 40 ° in 2θ value by X-ray diffraction using CuKα ray, and having a crystalline diffraction line. You may. Preferably 40 at 2θ value
The strongest intensity of the crystalline diffraction lines found at not less than 70 ° or less is 100 times or less the intensity of the diffraction line at the apex of the broad scattering band seen at not less than 20 ° and not more than 40 ° in 2θ value. It is preferably 5 times or less, and particularly preferably has no crystalline diffraction line.

In the present invention, among them, an amorphous oxide of a metalloid element and / or a chalcogenide are preferable, and an element of Group 13 (IIIB) to Group 15 (VB) of the periodic table, A
An oxide or chalcogenide consisting of 1, Ga, Si, Sn, Ge, Pb, Sb, and Bi alone or in combination of two or more thereof is selected.

For example, Ga ₂ O ₃ , SiO, GeO, S
nO, SnO ₂ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb
₂ O ₄ , Pb ₃ O ₄ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂
O ₅ , Bi ₂ O ₃ , Bi ₂ O ₄ , SnSiO ₃ , Ge
S, SnS, SnS ₂ , PbS, PbS ₂ , Sb ₂ S
₃ , Sb ₂ S ₅ , SnSiS _{3 and the} like are preferable. Also,
These are complex oxides with lithium oxide, for example, Li
₂ SnO ₂ may be used.

In the negative electrode material of the present invention, Sn, Si,
Amorphous oxide is more preferable that the center of Ge, among them the general formula (6) SNM in ¹ _d M ² _e O _f (wherein, M ¹ is, Al, B, P, Ge from at least one or more selected The element, M ² , represents at least one or more elements selected from Group 1 (IA), Group 2 (IIA), Group 3 (IIIA), and halogen elements of the periodic table. A number not less than 2 and e is 0.01
0.2 <d + e <2, where f is 1 or more and 6 or less
It is preferably an amorphous oxide represented by the following numbers:

Examples of the amorphous oxide mainly composed of Sn include the following compounds, but the present invention is not limited to these compounds. C-1 SnSiO ₃ C-2 Sn0.8A l0.2B 0.3P 0.2S i
0.5O 3.6 C-3 SnAl0.4B 0.5C s0.1P 0.5O
3.65 C-4 SnAl0.4B 0.5M g0.1P 0.5O
3.7 C-5 SnAl0.4B 0.4B a0.08P 0.4O
3.28 C-6 SnAl0.4B 0.5B a0.08M g0.
08P 0.3O 3.26 C-7 SnAl0.1B 0.2C a0.1P 0.1S
i0.5O 3.1 C-8 SnAl0.2B 0.4S i0.4O 2.7 C-9 SnAl0.2B 0.1M g0.1P 0.1S
i0.5O 2.6 C-10 SnAl0.3B 0.4P 0.2S i0.5O
3.55 C-11 SnAl0.3B 0.4P 0.5S i0.5O
4.3 C-12 SnAl0.1B 0.1P 0.3S i0.6O
3.25 C-13 SnAl0.1B 0.1B a0.2P 0.1S
i0.6O 2.95 C-14 SnAl0.1B 0.1C a0.2P 0.1S
i0.6O 2.95 C-15 SnAl0.4B 0.2M g0.1S i0.6
O 3.2 C-16 SnAl0.1B 0.3P 0.1S i0.5O
3.05 C-17 SnB0.1K 0.5P 0.1S iO3.65 C-18 SnB0.5F 0.1M g0.1P 0.5O
3.05 As the amorphous oxide and / or chalcogenite of the present invention, any of a firing method and a solution method can be employed, but the firing method is more preferable. In the firing method, it is preferable that oxides, chalcogenites or compounds of the corresponding elements are mixed well and then fired to obtain an amorphous oxide and / or chalcogenite.

The sintering temperature is 500 ° C. or more and 1500 ° C.
The firing time is preferably 1 hour or more and 100 hours or less.

The temperature may be cooled in a firing furnace, or may be taken out of the firing furnace and put into, for example, water for cooling. Also ceramic processing (Gihodo Publishing 19
87) Gun method described on page 217, Hammer-Anv
An ultra-quenching method such as an il method, a slap method, a gas atomizing method, a plasma spray method, a centrifugal quenching method, and a melt drag method can also be used. Alternatively, cooling may be performed using a single roller method or a twin roller method described in page 172 of the New Glass Handbook (Maruzen 1991). 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 calcination gas atmosphere is preferably an atmosphere having an oxygen content of 5% by volume or less, and more preferably an inert gas atmosphere. Examples of the inert gas include nitrogen, argon, helium, krypton, xenon, and the like. The most preferred inert gas is pure argon.

The average particle size of the negative electrode material used in the present invention is preferably 0.1 to 60 μm. In order 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 used. At the time of pulverization, wet pulverization in the presence of water or an organic solvent such as methanol can also be performed as 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 calcining can be calculated by inductively coupled plasma (ICP) emission spectroscopy as a measuring method, and by a weight difference between powder before and after calcining as a simple method.

Examples of the negative electrode material which can be used in combination with the amorphous oxide negative electrode material mainly comprising Sn, Si, and Ge of the present invention include carbon materials capable of inserting and extracting lithium ions or lithium metal, lithium, and lithium. Examples include lithium alloys and metals that can be alloyed with lithium.

The electrode mixture of the present invention includes, in addition to the conductive agent, the binder and the filler, a polymer network containing the structural unit of the general formula (1), a lithium salt, and an aprotic organic solvent. Is added.

The conductive agent may be any electronic conductive material that does not cause a chemical change in the constructed 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 (JP-A-59-20,971).
It can be included as a seed or a mixture thereof.
A combination of graphite and acetylene black is particularly preferred. The addition amount is preferably 1 to 50% by weight, particularly 2 to 30% by weight.
% By weight is preferred. For carbon and graphite, 2 to 15% by weight is particularly preferred.

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.
Preferred binders include starch, carboxymethyl cellulose, cellulose, diacetyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium alginate, polyacrylic acid, sodium polyacrylate, polyvinyl phenol, polyvinyl methyl ether, polyvinyl alcohol, polyvinyl pyrrolidone Water-soluble polymers such as polyacrylonitrile, polyacrylamide, polyhydroxy (meth) acrylate, styrene-maleic acid copolymer, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, Vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyethylene, polypropylene, (Meth) acrylate copolymers containing (meth) acrylates such as ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, polyvinyl acetal resin, methyl methacrylate, and 2-ethylhexyl acrylate; )
Acrylate-acrylonitrile copolymer, polyvinyl ester copolymer containing vinyl ester such as vinyl acetate, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polybutadiene, neoprene rubber, fluorine rubber, polyethylene oxide, polyester Emulsions (latex) or suspensions of polyurethane resins, polyether polyurethane resins, polycarbonate polyurethane resins, polyester resins, phenol resins, epoxy resins, and the like can be given. In particular, polyacrylate latex, carboxymethylcellulose, polytetrafluoroethylene, and polyvinylidene fluoride are exemplified. These binders can be used alone or in combination. If the amount of the binder is small, the holding power and cohesive strength of the electrode mixture are weak. If it is too large, the electrode volume increases and the capacity per unit volume or unit weight of the electrode decreases. For these reasons, the amount of the binder added is preferably 1 to 30% by weight, particularly preferably 2 to 10% by weight.

As the filler, any fibrous material that does not cause a chemical change in the constructed battery can be used. Usually, fibers such as olefin-based polymers such as polypropylene and polyethylene, glass, and carbon are used. Although the amount of the filler is not particularly limited,
~ 30% by weight is preferred.

The solid polymer electrolyte of the present invention can be used in combination with a separator to ensure safety. The separator used at 80 ° C to ensure safety
As described above, it is necessary to have a function of closing the above gap to increase the resistance and cut off the current, and it is preferable that the closing temperature is 90 ° C. or more and 180 ° C. or less.

The shape of the pores of the separator is usually circular or elliptical, and the size is 0.05 μm to 30 μm.
1 μm 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
% To 90%, preferably 35% to 80%.

These separators are made of polyethylene,
It may be a single material such as polypropylene or a composite material of two or more. In particular, those obtained by laminating two or more kinds of microporous films having different pore diameters, porosity, and pore closing temperatures are particularly preferable.

As the current collector for the positive and negative electrodes, an electron conductor that does not cause a chemical change in the constructed battery is used.

As the current collector of the positive electrode, in addition to aluminum, stainless steel, nickel, titanium, and the like, those obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium, or silver are preferable, and aluminum is particularly preferable. , Aluminum alloy.

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

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 can also be used. . The thickness is not particularly limited, but is 1 to 500
μm. It is also desirable that the surface of the current collector be made uneven by surface treatment.

The shape of the battery can be applied to any sheet, corner, cylinder and the like. The mixture of the positive electrode active material and the negative electrode material is applied (coated) on the current collector, dried and compressed,
Mainly used.

Examples of the coating method include a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion method, a curtain method, a gravure method, a bar method, a dip method and a squeeze method. Among them, a blade method, a knife method and an extrusion method are preferred. The coating is preferably performed at a speed of 0.1 to 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 coating may be performed on one side at a time or on both sides simultaneously.

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

The method for drying and dehydrating the electrode sheet coating material is as follows.
Hot air, vacuum, infrared rays, far-infrared rays, electron beams and low-humidity air can be used alone or in combination. The drying temperature is preferably in the range of 80 to 350 ° C, particularly 100 to 350 ° C.
A range of 250 ° C. is preferred. The water content is 20
It is preferably at most 00 ppm, and more preferably at most 500 ppm 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, but is 0.2 to 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 room temperature to
200 ° C. is preferred. The ratio of the negative electrode sheet width to the positive electrode sheet is preferably 0.9 to 1.1, and more preferably 0.95 to 1.0.
Is particularly preferred. The content ratio between the positive electrode active material and the negative electrode material is
It depends on the compound type and the mixture formulation.

[0130] After the positive and negative electrode sheets are overlapped with a separator interposed therebetween, the sheet is directly processed into a sheet battery or folded and inserted into a rectangular can, and the can and the sheet are electrically connected. The liquid is injected, and a prismatic battery is formed using a sealing plate. After the positive and negative electrode sheets are overlapped and wound via a separator, they are inserted into a cylindrical can, and after the can and the sheet are electrically connected, an electrolyte is injected and the cylinder battery is sealed using a sealing plate. Form. 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, fuses,
A bimetal, a PTC element, or the like is used.

In addition to the 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, the internal pressure of the battery increases.
To interrupt the current. This
At the same time, the compound or electrolyte contains a compound that increases the internal pressure.
I can do it. Compound used to increase internal pressure
An example of a product is Li_TwoCO _Three , LiHCO_Three , Na_Two
CO_Three , NaHCO_Three , CaCO_Three , MgCO_Three Such as
Carbonates and the like.

For the can or 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 used.

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

The use of the non-aqueous secondary battery of the present invention is not particularly limited. For example, when the non-aqueous secondary battery is mounted on an electronic device, it is used in a notebook personal computer, pen input personal computer, mobile personal computer, electronic book player, mobile phone, cordless phone handset. ,
Pager, handy terminal, mobile fax,
Portable copy, portable printer, headphone stereo,
Video movies, LCD TVs, handy cleaners,
Portable CD, mini disk, electric shaver, transceiver, electronic organizer, calculator, memory card, portable tape recorder, radio, backup power supply, memory card, and the like. Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game machines, road conditioners, watches, strobes, cameras, medical equipment (pacemakers, hearing aids, shoulder fir machines, etc.). Furthermore, it can be used for various military purposes and space applications. Further, it can be combined with a solar cell.

[0136]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the invention. Compound P-1 16.5 parts by weight Example 1 The present invention, LiPF ₆ 11 parts by weight, benzoyl peroxide 1.1 parts by weight of ethylene carbonate: propylene carbonate = 1: 1 (by weight)
71.4 parts by weight were mixed to obtain a homogeneous solution. This solution was cast on Teflon. The casting liquid was heated at 80 ° C. for 10 minutes in an argon gas atmosphere to obtain a polymer solid electrolyte thin film (SPE-1). Further, thin films (SPE-2) to (SPE-2) having compositions as shown in Table 2 in the same manner as described above.
−11). As a comparative example, a similar thin film made of the compound (compound D) described in Example 1 of JP-A-2-29826 was prepared. With respect to the thin film thus obtained, a sample composed of lithium / thin film / lithium was prepared.
The impedance was measured at 10,000 to 0.1 Hz, and the ionic conductivity was determined from the Cole-Cole plot. The film forming property was determined by the following method. The thin film was cut into a rectangle having a width of 1 cm and a length of 5 cm, a tensile test was performed in the major axis direction at 25 ° C., and the load when the thin film was cut was measured. Table 2 shows the evaluation results.

[0137]

[Table 2]

[0138]

Embedded image

Example 2 (Preparation of positive electrode mixture paste) LiCoO ₂ was used as a positive electrode active material.
Was mixed with 200 parts by weight of acetylene black and 10 g of acetylene black using a homogenizer, and 8 g of an aqueous dispersion (solid content concentration: 50% by weight) of a copolymer of 2-ethylhexyl acrylate, acrylic acid, and acrylonitrile was subsequently used as a binder.
6% by weight carboxymethylcellulose aqueous solution
0 g was added, kneaded and mixed, 50 g of water was further added, and the mixture was stirred and mixed with a homogenizer to prepare a positive electrode mixture paste.

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

(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 by a roller press and cut into a predetermined size to prepare a belt-shaped positive electrode sheet.
Further, in a dry box (dew point; dry air having a temperature of -50 ° C. or lower), dehydration and drying were sufficiently performed with a far-infrared heater to prepare a positive electrode sheet. Similarly, paste the negative electrode mixture paste to 20 μm
And the thickness of the sheet after compression is 90 g / m ² and the thickness of the compressed sheet is 90 in the same manner as in the preparation of the positive electrode sheet.
A negative electrode sheet having a thickness of μm was prepared.

[0142] Compound P-1 16.5 parts by weight (of creating polymer solid electrolyte) present invention, LiPF ₆ 11 parts by weight, benzoyl peroxide 1.1 parts by weight of ethylene carbonate: propylene carbonate = 1: 1 (by weight) 71.4 wt The parts were mixed to form a homogeneous solution. This solution was applied through a 30 μm-thick nonwoven fabric TAPYRUS P22FW-OCS manufactured by Tonen Tapils Co., Ltd., and then heated at 80 ° C. for 10 minutes to prepare a 50 μm-thick polymer solid electrolyte thin film (SPE-20). . Instead of P-1, P-2,4,5,8,9,12,15,16,17 and Compound D were used and the polymer solid electrolyte thin films (SPE-21) to (SPE- 30)
It was created.

(Preparation of Cylinder Battery) A method of preparing a battery will be described with reference to FIG. The positive electrode sheet, the polymer solid electrolyte thin film, the negative electrode sheet, and the polymer solid electrolyte thin film (SPE-20) prepared above were sequentially laminated and spirally wound. The wound electrode group (2) was housed in a nickel-plated iron bottomed cylindrical battery can (1) also serving as a negative electrode terminal, and an upper insulating plate (3) was further inserted. A stack of a positive electrode terminal (6), an insulating ring, a PTC element (63), a current interrupter (62), and a pressure-sensitive valve element (61) is caulked via a gasket (5) to form a cylindrical battery D-1. Created. Similarly, solid polymer electrolytes (SPE-21) to (SPE-3)
Batteries D-2 to D-11 using the above (0) were prepared. Ten batteries were prepared for each.

Example 3 A cylindrical battery was prepared in the same manner as in Example 2 except that graphite powder was used as a negative electrode material. The polymer solid electrolyte thin film was prepared using SPE-20, 21, 23, 25, 26, 28, and 30 batteries.
~ D-18.

(Evaluation of Battery Characteristics) For the battery prepared by the above method, the current density was 4.8 mA / cm ² , and the charging end voltage was 4.
The charge and discharge were repeated 10 times under the conditions of 1 V and a discharge end voltage of 2.7 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 was obtained, and this value was divided by the capacity of the battery of the battery number 1 to obtain the relative capacity. Further, the discharge capacity at the 300th cycle of each battery was determined, and the ratio to the discharge capacity at the 10th cycle was calculated and represented as the cycle capacity. Table 2 shows the respective values.

[0146]

[Table 3]

From the above results, it can be seen that when the compound of the present invention is used as a solid electrolyte, the capacity is not reduced and the cyclability is improved. It can also be seen that the cycle stabilizing effect is greater when an amorphous composite oxide is used than when a carbon material is used for the negative electrode. On the other hand, it has also been found that the copolymer composition described in JP-A-2-29826 is inferior in capacity reduction and cycleability.

The same results were obtained when the positive electrode active material was LiNiO ₂ or LiMnO ₂ .

Example 4 (Preparation of Positive Electrode Sheet 1) LiCoO ₂ was used as a positive electrode active material.
3 parts by weight, flake graphite 2 parts by weight, acetylene black 2
Parts by weight, and 3 parts by weight of polyacrylonitrile as a binder were further added, and a slurry obtained by kneading with 100 parts by weight of acrylonitrile as a medium was applied to an aluminum foil having a thickness of 20 μm using an extrusion coating machine.
After drying and compression molding with a calender press machine, an aluminum lead plate was welded to the end, and a thickness of 95 μm,
A positive electrode sheet (CA-1) having a width of 54 mm and a length of 49 mm was prepared.

(Preparation of positive electrode sheet 2) As a positive electrode active material, 43 parts by weight of LiMn ₂ O ₄ , 2 parts by weight of flaky graphite, 2 parts by weight of acetylene black, and 3 parts by weight of polyacrylonitrile as a binder were added. A slurry obtained by kneading 100 parts by weight of acrylonitrile as a medium is applied to an aluminum foil having a thickness of 20 μm by using an extrusion type applicator, and after being dried and compression-molded by a calender press, an aluminum-made end is formed. Was welded to produce a positive electrode sheet having a thickness of 114 μm, a width of 54 mm and a length of 49 mm (CA-2).

(Preparation 3 of Positive Electrode Sheet) As a positive electrode active material, 43 parts by weight of LiNiO ₂ , ₂ parts by weight of flake graphite,
2 parts by weight of acetylene black and 3 parts by weight of polyacrylonitrile as a binder were added, and acrylonitrile 1 was added.
The slurry obtained by kneading the mixture with 00 parts by weight as a medium was applied to an aluminum foil having a thickness of 20 μm using an extrusion coating machine, dried, compression-molded by a calender press, and an aluminum The lead plate was welded to produce a positive electrode sheet having a thickness of 75 μm, a width of 54 mm and a length of 49 mm (CA-3).

(Preparation of Negative Electrode Sheet 1) 43 parts by weight of SnSiO ₃ as a negative electrode active material, 2 parts by weight of acetylene black and 2 parts by weight of graphite as a conductive agent, and ₃ parts by weight of polyacrylonitrile as a binder were mixed. Was added and kneaded with 100 parts by weight of N-methylpyrrolidone as a medium to obtain a negative electrode mixture slurry. Next, 45 parts by weight of α-alumina, 7 parts by weight of graphite, 3 parts by weight of polyacrylonitrile, and 100 parts by weight 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 nickel lead plate 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 of negative electrode sheet 2) Preparation of negative electrode sheet
At 1, SnSiO_ThreeTo Sn_0.8 Al_0.2B_0.3P_0.2
Si _0.5O_3.6, SnAl_0.4B_0.5Cs_0.1P_0.5O
_3.65In the same way except that
55mm width x length with a lithium foil with a welded plate
50mm negative electrode sheets (AN-2) and (AN-3) are made
did.

(Preparation of Negative Electrode Sheet 3) 43 parts by weight of a mesoface pitch-based carbon material (Petoka) as a negative electrode active material, and 2 parts by weight of acetylene black and 2 parts by weight of graphite as conductive agents were mixed and further combined. 3 parts by weight of polyacrylonitrile was added as a binder, and kneaded with 100 parts by weight of N-methylpyrrolidone as a medium to obtain a negative electrode mixture slurry. The negative electrode mixture slurry was applied to a 10-μm-thick copper foil using an extrusion coating machine, dried and then 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 welding a lead plate made of nickel to the end of the negative electrode sheet, the dew point
Heat treatment was performed at 230 ° C. for 1 hour in dry air of 40 ° C. or less. The heat treatment was performed using a far infrared heater. (AN
-4).

(Preparation of Polymer Solid Electrolyte) A polymer solid electrolyte was prepared in the same manner as in Example 2.

(Preparation of Sheet Battery) Each of the negative electrode sheet and the positive electrode sheet was placed in a dry air having a dew point of −40 ° C. or less in dry air.
Dehydrated and dried at 30 ° C for 30 minutes. 54mm width in dry atmosphere
× Dehydrated and dried positive electrode sheet with a length of 49 mm (CA-1)
(11), polymer solid electrolyte thin film (SPE-20) cut into a width of 60 mm x length of 60 mm (SPE-20) (12), a dehydrated and dried negative electrode sheet (AN-1) of width 55 mm x length 50 mm (13)
Then, using a packaging material consisting of a laminated film of polyethylene (50 μm) -polyethylene terephthalate (50 μm), heat-sealing the four edges under vacuum and sealing to create a sheet-type battery (SB-1) did. Similarly, sheet batteries SB-2 to SB-16 having the configuration shown in Table 4 were prepared.

[0157]

[Table 4]

(Evaluation of Battery Performance) The sheet type battery prepared by the above method was repeatedly charged and discharged 10 times under the conditions of a current density of 2.3 mA / cm ² , a charge end voltage of 4.2 V, and a discharge end voltage of 2.6 V. The discharge capacity at the tenth cycle was determined.
This was examined for 10 batteries of the same prescription, and the average was taken as the capacity of the battery. In this way, the capacity of each battery is obtained, and this value is referred to as SB-1 for SB-2 to 5,11 and SB-12 for SB-12.
-6, SB-13 is SB-7, SB-14 is SB-8, SB-15 is SB-9
Then, SB-16 was divided by SB-10 to obtain the relative capacity between the same electrode compositions. Further, the discharge capacity at the 300th cycle of each battery was determined, and the ratio to the discharge capacity at the 10th cycle was calculated and represented as the cycle capacity. Table 5 shows the values.

[0159]

[Table 5]

From the above results, it can be seen that when the compound of the present invention was used as a solid electrolyte, the capacity was not reduced and the cycleability was improved.

[0161]

EFFECTS OF THE INVENTION From the compound of the present invention, a solid electrolyte having excellent film-forming properties and high ion conductivity can be obtained, and a non-aqueous electrolyte secondary solution capable of improving cycle stability without losing capacity. A battery was obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view of a cylinder type battery used in Examples.

FIG. 2 shows a conceptual diagram of a sheet-type battery used in Examples.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Battery can also serve as a negative electrode 2 Wound electrode group 3 Upper insulating plate 4 Positive electrode lead 5 Gasket 6 Battery lid also serving as a positive electrode terminal 11 Positive sheet 12 Polymer solid electrolyte 13 Negative sheet 14 Positive terminal 15 Negative terminal 61 Pressure sensitive valve body 62 Current cutoff element (switch) 63 PTC element

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 299/02 C08F 299/02 C08K 3/00 C08K 3/00 C08L 25/18 C08L 25/18 55/00 55/00 H01M 10/40 H01M 10/40 B Z

Claims (3)

[Claims] An ionic conductivity obtained by dissolving at least a monomer represented by the following general formula (1) and / or a salt of a metal ion belonging to the group Ia or IIa of the periodic table. A polymer solid electrolyte characterized by forming a polymer matrix by polymerizing a solvent. General formula (1) In the formula, R ₁ and R ₂ represent a hydrogen atom or an alkyl group. R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a —CO—R ₄ group or a —SO ₂ —R ₄ group, and R ₄ represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group Represents L ₁ is represented by the following general formulas (3) to (5)
Represents an atomic group represented by General formula (2) In the formula, R ₅ , R ₆ and L ₂ have the same meanings as R ₁ , R ₂ and L ₁ , respectively. L ₃ represents a z-valent linking group. z represents an integer of 2 or more. General formula (3) General formula (4) General formula (5) In the formula, R ₇ represents a lower alkylene group. R ₈ and R ₉ are
Represents a hydrogen atom or an alkyl group. p represents an integer of 0 to 30, and q and r are each independently an integer of 1 to 30. 2. The solid polymer electrolyte according to claim 1, wherein the mixture contains an acrylate monomer. 3. A non-aqueous electrolyte secondary battery comprising a positive electrode and a negative electrode, wherein the polymer solid electrolyte according to claim 1 is contained in the battery.