JP2012209230A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a secondary battery having basic properties as a battery, a high capacity, and excellent charge and discharge cycle characteristics.SOLUTION: A cross-linked polymer electrolyte is obtained by suitably selecting a polyether copolymer obtained by polymerization of specific binary or ternary monomers, a photoreaction initiator and an electrolyte salt compound, preliminary mixing a polyether copolymer in an electrode, covering main surfaces of a negative electrode material and a positive electrode material with a composition for a polymer solid electrolyte principally consisting of the polyether copolymer, the photoreaction initiator and the electrolyte salt compound, and then crosslinking the composition. The cross-linked polymer electrolyte is employed for a secondary battery.

Description

  The present invention relates to a non-aqueous electrolyte secondary battery comprising a negative electrode material, a non-aqueous electrolyte, and a positive electrode material, and more specifically, using a porous material for the negative electrode material and the positive electrode material, The present invention relates to a nonaqueous electrolyte secondary battery having a high capacity and excellent cycle charge / discharge characteristics by impregnating an electrode obtained by mixing a polyether copolymer with a crosslinkable polymer solid electrolyte.

  Conventionally, a non-aqueous electrolyte secondary battery represented by a lithium ion battery has been used in the form of a solution or a paste from the viewpoint of ionic conductivity. However, since there is a risk of equipment damage due to liquid leakage, various safety measures are necessary, which is a barrier to the development of large batteries.

  In contrast, solid electrolytes such as inorganic crystalline substances, inorganic glasses, and organic polymer substances have been proposed. However, although the inorganic electrolyte has high ionic conductivity, it is difficult to increase the size of the battery because the electrolyte is crystalline or amorphous and it is difficult to reduce the volume change due to the positive and negative electrode active materials during charge and discharge. On the other hand, organic polymer materials are generally expected to make progress because they are generally excellent in flexibility, bending workability, and moldability, and the degree of freedom in designing applied devices is increased.

  If the organic polymer solid electrolyte can be combined with a carbon-based negative electrode material having a porous structure conventionally used in lithium ion batteries, a large-sized battery with higher safety can be developed. However, good characteristics have not been reported so far for batteries using the above-described negative electrode material and polymer electrolyte.

For example, Non-Patent Document 1 describes 280 as a report on a combination of a lithium ion conductive polymer (polymer electrolyte) and a carbon-based negative electrode material.
There is a report that a reversible capacity of mAh / g was obtained. However, the ratio of insertion / desorption reaction (Coulomb efficiency) at the first charge / discharge is as low as 25%, and the theoretical capacity of the carbon-based negative electrode material (372
Compared with mAh / g), its reversible capacity was also insufficient.

  On the other hand, as solid organic electrolytes, solid polymer electrolytes have been actively researched based on the discovery of ionic conductivity in homopolymers of ethylene oxide and alkali metal ions.

  As a polymer electrolyte having high ionic conductivity, Patent Document 1 discloses a polymer solid electrolyte membrane composed of a copolymer of ethylene oxide, an oxirane compound having an ethylene oxide unit in the side chain, and an oxirane compound having a reactive functional group. A battery sandwiched between the two is described. However, although the battery operates, sufficient battery performance is not obtained.

  In order to achieve both ionic conductivity and shape stability, a method of crosslinking a polymer has been studied. For example, Patent Document 2 describes a crosslinking by ultraviolet rays using an oligomer having a reactive group to crosslink a polymer. However, the performance as a polymer solid electrolyte deteriorates due to the unreacted reactive group, and when combined with an electrode, the cycle characteristics of the battery may be significantly reduced.

Japanese Patent Laid-Open No. 11-073992 Japanese Patent Laid-Open No. 9-185962

Journal of Power Sources, Vol.52, (1994), PP55-59

  In view of the circumstances as described above, an object of the present invention is to provide a secondary battery having high capacity and excellent cycle charge / discharge characteristics with basic performance as a battery.

As a result of intensive studies to solve the above problems, the present inventors have appropriately selected a polyether copolymer, a photoreaction initiator, and an electrolyte salt compound, and the polyether copolymer is mixed in the electrode in advance. The main surface of the negative electrode and the positive electrode material is covered with a composition for a polymer solid electrolyte mainly composed of a polyether copolymer, a photoreaction initiator, and an electrolyte salt compound, and is crosslinked. The inventors have found that a secondary battery having a high capacity and excellent cycle charge / discharge characteristics can be obtained by employing a molecular electrolyte in the secondary battery, and the present invention has been completed.
In the present specification, the “main surface” means a surface in contact with the solid electrolyte. The “main surface” is generally a plane (surface) having the largest area in the negative electrode material or the positive electrode material.

[式中、Ｒは炭素数１〜１２のアルキル基、または−ＣＨ_２Ｏ（ＣＲ^１Ｒ^２Ｒ^３）である。Ｒ^１、Ｒ^２、Ｒ^３は水素原子または−ＣＨ_２Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^４であり、ｎ及びＲ^４はＲ^１、Ｒ^２、Ｒ^３の間で異なっていても良い。Ｒ^４は炭素数１〜１２のアルキル基であり、ｎは０〜１２の整数である。]
で示される単量体から誘導される繰り返し単位５〜９５モル％、及び
式（２）：

で示される単量体から誘導される繰り返し単位９５〜５モル％、及び
式（３）：

[式中、Ｒ^５はエチレン性不飽和基である。]で示される単量体から誘導される繰り返し単位０〜１０モル％を有する重量平均分子量が５万〜２５０万の範囲内であるポリエーテル共重合体、
及び
（ii）光反応開始剤
（iii）電解質塩化合物
が含まれる高分子固体電解質用組成物からなる架橋体により、負極材料および正極材料の主表面のどちらか一方または両方が覆われている非水電解質二次電池であって、
かつ、該非水電解質二次電池を構成する負極材料及び正極材料のうちの少なくとも一方が、該ポリエーテル共重合体を一成分として含有していることを特徴とする非水電解質二次電池である。
項2.
上記主表面に該高分子固体電解質用組成物を塗布した後、架橋させることにより該架橋体を得ることを特徴とする項１に記載の非水電解質二次電池である。
項3.
電解質塩化合物がリチウム塩化合物であることを特徴とする請求項１〜３のいずかに記載の非水電解質二次電池である。
項4.
高分子固体電解質用組成物に非プロトン性有機溶媒が更に添加されたことを特徴とする請求項１〜３のいずかに記載の非水電解質二次電池である。
項5.
非プロトン性有機溶媒がエーテル類及びエステル類からなる群より選ばれることを特徴とする請求項５に記載の非水電解質二次電池である。
項6.
前記負極材料は、負極活物質と導電助剤と結着剤との混合物からなり、その負極活物質は、リチウム、カーボン、シリコン系化合物、スズ系化合物、アルミニウム系化合物、チタン系化合物のうちの１種、あるいは２種以上の混合物からなることを特徴とする請求項１〜５のいずかに記載の非水電解質二次電池である。
項7.
前記正極材料は、ＡＭＯ_２（Ａはアルカリ金属、Ｍは単一または２種以上の遷移金属からなり、その一部に非遷移金属を含んでもよい）、ＡＭ_２Ｏ_４（Ａはアルカリ金属、Ｍは単一または２種以上の遷移金属からなり、その一部に非遷移金属を含んでもよい）、Ａ_２ＭＯ_３（Ａはアルカリ金属、Ｍは単一または２種以上の遷移金属からなり、その一部に非遷移金属を含んでもよい）、ＡＭＢＯ_４（Ａはアルカリ金属、ＢはＰ、Ｓｉ、またはその混合物、Ｍは単一または２種以上の遷移金属からなり、その一部に非遷移金属を含んでもよい）のいずれかの組成からなることを特徴とする請求項１〜７のいずかに記載の非水電解質二次電池である。
項8.
（Ａ）式（１）：

[式中、Ｒは炭素数１〜１２のアルキル基、または−ＣＨ_２Ｏ（ＣＲ^１Ｒ^２Ｒ^３）である。Ｒ^１、Ｒ^２、Ｒ^３は水素原子または−ＣＨ_２Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^４であり、ｎ及びＲ^４はＲ^１、Ｒ^２、Ｒ^３の間で異なっていても良い。Ｒ^４は炭素数１〜１２のアルキル基であり、ｎは０〜１２の整数である。]
で示される単量体から誘導される繰り返し単位５〜９５モル％、及び
式（２）：

で示される単量体から誘導される繰り返し単位９５〜５モル％、及び
式（３）：

[式中、Ｒ^５はエチレン性不飽和基である。] で示される単量体から誘導される繰り返し単位０〜１０モル％で示される単量体を重合させて得られる重量平均分子量が５万〜２５０万のポリエーテル共重合体を得る工程と、
（Ｂ）該ポリエーテル共重合体を一成分として含有する負極材料および正極材料の少なくともどちらか一つを得る工程と、
（Ｃ）該ポリエーテル共重合体、光反応開始剤及び電解質塩化合物が含まれる高分子固体電解質用組成物を、負極材料及び正極材料の一方または両方における少なくとも１つの主表面に塗布する工程と、
（Ｄ）該高分子固体電解質用組成物を架橋する工程と、
を含む非水電解質二次電池の製造方法である。 The present invention has been completed based on the above findings, and specifically, a lithium polymer battery and a lithium polymer battery using the composition for a polymer solid electrolyte comprising the following components (i) to (iii): A manufacturing method is provided.
Item 1.
(I) Formula (1):

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² , and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² , and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. A polyether copolymer having a weight average molecular weight in the range of 50,000 to 2,500,000 having 0 to 10 mol% of repeating units derived from the monomer represented by
And (ii) a photoreaction initiator, (iii) one or both of the main surfaces of the negative electrode material and the positive electrode material are covered with a cross-linked body comprising a composition for a solid polymer electrolyte containing an electrolyte salt compound. A water electrolyte secondary battery,
And at least one of the negative electrode material and positive electrode material which comprises this non-aqueous electrolyte secondary battery contains this polyether copolymer as one component, It is a non-aqueous electrolyte secondary battery characterized by the above-mentioned. .
Item 2.
Item 2. The nonaqueous electrolyte secondary battery according to Item 1, wherein the crosslinked product is obtained by applying the polymer solid electrolyte composition to the main surface and then crosslinking the composition.
Item 3.
4. The nonaqueous electrolyte secondary battery according to claim 1, wherein the electrolyte salt compound is a lithium salt compound.
Item 4.
The nonaqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein an aprotic organic solvent is further added to the composition for polymer solid electrolyte.
Item 5.
6. The nonaqueous electrolyte secondary battery according to claim 5, wherein the aprotic organic solvent is selected from the group consisting of ethers and esters.
Item 6.
The negative electrode material comprises a mixture of a negative electrode active material, a conductive additive, and a binder, and the negative electrode active material is selected from lithium, carbon, silicon-based compounds, tin-based compounds, aluminum-based compounds, and titanium-based compounds. The nonaqueous electrolyte secondary battery according to any one of claims 1 to 5, comprising one kind or a mixture of two or more kinds.
Item 7.
The positive electrode material is AMO ₂ (A is an alkali metal, M is a single or two or more kinds of transition metals, and a part thereof may include a non-transition metal), AM ₂ O ₄ (A is an alkali metal, M consists of a single or two or more transition metals, part of which may contain a non-transition metal), A ₂ MO ₃ (A is an alkali metal, M is a single or two or more transition metals) , Part of which may contain a non-transition metal), AMBO ₄ (A is an alkali metal, B is P, Si, or a mixture thereof, M is a single or two or more transition metals, The nonaqueous electrolyte secondary battery according to any one of claims 1 to 7, wherein the nonaqueous electrolyte secondary battery has a composition of any one of (which may contain a non-transition metal).
Item 8.
(A) Formula (1):

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² , and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² , and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. A step of obtaining a polyether copolymer having a weight average molecular weight of 50,000 to 2,500,000 obtained by polymerizing a monomer represented by 0 to 10 mol% of a repeating unit derived from
(B) obtaining at least one of a negative electrode material and a positive electrode material containing the polyether copolymer as one component;
(C) applying a composition for a polymer solid electrolyte containing the polyether copolymer, a photoreaction initiator, and an electrolyte salt compound to at least one main surface of one or both of the negative electrode material and the positive electrode material; ,
(D) crosslinking the polymer solid electrolyte composition;
Is a method for producing a non-aqueous electrolyte secondary battery.

  According to the present invention, the crosslinked polymer solid obtained by mixing the polyether copolymer of the present invention inside the electrode, and crosslinking the main surface of the electrode material with the composition for polymer solid electrolyte of the present invention. By covering with an electrolyte, a non-aqueous electrolyte secondary battery having a high capacity and excellent cycle charge / discharge characteristics can be provided.

  Hereinafter, the configuration of the present invention will be described in detail.

The compound of the formula (1) can be easily synthesized by obtaining it from a commercial product or by a general ether synthesis method from epihalohydrin and alcohol. Examples of commercially available compounds include propylene oxide, butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, tertiary butyl glycidyl ether, benzyl glycidyl ether, 1,2-epoxide decane, 1,2 -Epoxy octane, 1,2-epoxyheptane, 2-ethylhexyl glycidyl ether, 1,2-epoxydecane, 1,2-epoxyhexane, glycidyl phenyl ether, 1,2-epoxypentane, glycidyl isopropyl ether, etc. can be used. . Among these commercially available products, propylene oxide, butylene oxide, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, and glycidyl isopropyl ether are preferable, and propylene oxide, butylene oxide, methyl glycidyl ether, and ethyl glycidyl ether are particularly preferable.
In the monomer represented by the formula (1) obtained by synthesis, R is preferably —CH ₂ O (CR ¹ R ² R ³ ), and at least one of R ¹ , R ² , and R ³ is —CH ₂ O. it is preferably _{(CH 2 CH 2 O) n} R 4. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. n is preferably from 2 to 6, and more preferably from 2 to 4.

  The compound of the formula (2) is a basic chemical product, and a commercially available product can be easily obtained.

In the compound of formula (3), R ⁵ is a substituent containing an ethylenically unsaturated group. Examples of the monomer component containing an ethylenically unsaturated group include allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpinyl glycidyl ether, cyclohexenyl methyl glycidyl ether, p-vinylbenzyl glycidyl ether, allyl phenyl glycidyl ether, vinyl Glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1,2-epoxy-5,9-cyclododecandiene, 3,4 -Epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl cinnamate, glycidyl crotonic acid, glycidyl-4-hexenoate are used. Preferred are allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate.

[式中、Ｒは炭素数１〜１２のアルキル基、または−ＣＨ_２Ｏ（ＣＲ^１Ｒ^２Ｒ^３）である。Ｒ^１、Ｒ²、Ｒ³は水素原子または−ＣＨ_２Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^４であり、ｎ及びＲ⁴はＲ^１、Ｒ²、Ｒ³の間で異なっていても良い。Ｒ^４は炭素数１〜１２のアルキル基であり、ｎは０〜１２の整数である。]及び
（Ｂ）：式（２）の単量体から誘導された繰り返し単位、

及び必要なら（Ｃ）：式（３）の単量体から誘導された繰り返し単位、

[式中、Ｒ^５はエチレン性不飽和基である。]
から構成される。 The copolymer of the present invention comprises (A): a repeating unit derived from the monomer of formula (1),

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. And (B): a repeating unit derived from the monomer of formula (2),

And if necessary (C): a repeating unit derived from the monomer of formula (3),

[Wherein R ⁵ represents an ethylenically unsaturated group. ]
Consists of

  Here, each of the repeating units (A) and (C) may be derived from two or more monomers.

The polyether copolymer of the present invention can be synthesized as follows. Coordination anion initiator such as catalyst system mainly composed of organic aluminum, catalyst system mainly composed of organic zinc, organotin-phosphate ester condensate catalyst system as a ring-opening polymerization catalyst, or potassium containing K ⁺ as a counter ion By using an anionic initiator such as alkoxide, diphenylmethyl potassium, potassium hydroxide, and the like, each of the monomers is reacted in the presence or absence of a solvent at a reaction temperature of 10 to 120 ° C. with stirring to obtain a polyether copolymer. can get. From the viewpoint of the degree of polymerization or the properties of the resulting copolymer, a coordination anion initiator is preferred, and an organotin-phosphate ester condensate catalyst system is particularly preferred because of ease of handling.

In the polyether copolymer of the present invention, the molar ratio of the repeating unit (A), the repeating unit (B), and the repeating unit (C) is (A) 5 to 95 mol%, (B) 95 to 5 mol%. And (C) 0 to 10 mol% is suitable, preferably (A) 10 to 95 mol%, (B) 90 to 5 mol%, and (C) 0 to 7 mol%, more preferably (A). ) 15-95 mol%, (B) 85-5 mol%, and (C) 0-5 mol%. When the repeating unit (C) exceeds 10 mol%, the hardness increases and the ionic conductivity decreases. If the repeating unit (B) exceeds 95 mol%, the glass transition temperature rises and the oxyethylene chain crystallizes, resulting in a marked deterioration in the ionic conductivity of the solid electrolyte. In general, it is known that ion conductivity is improved by reducing the crystallinity of polyethylene oxide, but the polyether copolymer of the present invention is remarkably superior in this respect.
In particular, with respect to the polyether copolymer in the case where it is contained in at least one of the negative electrode material and the positive electrode material, which is a characteristic part of the present invention, the repeating unit (A), the repeating unit (B) and the repeating unit (C) The molar ratio may be (A) 5 to 95 mol%, (B) 95 to 5 mol%, and (C) 0 to 10 mol%, preferably 10 to 95 mol% of repeating units (A), repeating A binary polyether copolymer composed of 90 to 5 mol% of the unit (B) is more desirable. A small amount of electrolyte salt compound may be used together with the polyether copolymer.

  The molecular weight of the polyether copolymer of the present invention is within the range of 50,000 to 2,500,000, preferably 100,000 to 1,800,000 in order to obtain good processability, mechanical strength, and flexibility. Is suitable. For copolymers having a weight average molecular weight of less than 50,000, it is necessary to increase the crosslink density in order to increase the shape stability, so that only a plastic form can be obtained, there is almost no elongation, and the ionic conductivity is low. . When the copolymer having a weight average molecular weight of more than 2.5 million is extremely poor in processability and difficult to handle, the polymer solid electrolyte solution in which the polyether copolymer is dissolved has a high viscosity and is applied to the electrode surface. The electrode cannot be sufficiently impregnated.

  The polyether copolymer before cross-linking of the present invention may be a copolymer type of either a block copolymer or a random copolymer. Random copolymers are preferred because they have a greater effect of lowering the crystallinity of polyethylene oxide.

  The crosslinked polymer solid electrolyte of the present invention comprises a polyether copolymer and a photoinitiator, and constitutes a polymer solid electrolyte by coexisting an electrolyte salt compound in the polymer solid electrolyte composition. It is a crosslinked product crosslinked by irradiating with active energy rays such as ultraviolet rays in the presence or absence of a solvent.

  As the active energy beam used for crosslinking by light, ultraviolet rays, electron beams and the like can be used. Ultraviolet light is preferred.

  Examples of the photoreaction initiator that can be used in the present invention include alkylphenone series, benzophenone series, acylphosphine oxide series, titanocenes, triazines, bisimidazoles, and oxime esters. Preferably, an alkylphenone-based, benzophenone-based, or acylphosphine oxide-based photoinitiator is used. It is free to use two or more of the aforementioned compounds in combination as a photoreaction initiator.

  Specific examples of the alkylphenone photoinitiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1- Phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- [4- [4 -(2-hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2-methyl-propan-1-one and the like. 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one are preferred.

  Specific examples of the benzophenone photoinitiator include benzophenone, 2-chlorobenzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, methyl-2-benzoylbenzoate, and the like. Can be mentioned. Benzophenone, 4,4′-bis (diethylamino) benzophenone, and 4,4′-bis (dimethylamino) benzophenone are preferred.

  Specific examples of the acylphosphine oxide photoreaction polymerization initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. It is done. Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferred.

  The amount of the photoinitiator used for the crosslinking reaction is preferably in the range of 0.01 to 6.0 parts by weight, more preferably 0.1 to 4.0 parts by weight with respect to 100 parts by weight of the polyether copolymer. It is.

In the present invention, a crosslinking aid may be used in combination with a photoreaction initiator. Crosslinking aid is usually polyfunctional compound - a _{(e.g., CH 2 = CH-, CH 2} = CH-CH 2, CF 2 = CF- at least two containing compound). Specific examples of the crosslinking aid include triallyl cyanurate, triallyl isocyanurate, triacryl formal, triallyl trimellitate, N, N′-m-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate Amides, triallyl phosphate, hexafluorotriallyl isocyanurate, N-methyltetrafluorodiallyl isocyanurate and the like.

For the crosslinking reaction, a xenon lamp, a mercury lamp, a high-pressure mercury lamp, and a metal halide lamp can be used in the case of using ultraviolet rays. For example, the electrolyte is irradiated with a wavelength of 365 nm and a light amount of 1 to 50 mW / cm ² for 0.1 to 30 minutes. Can be done.

  The electrolyte salt compound that can be used in the present invention is preferably compatible with a mixture comprising a polyether copolymer or a crosslinked product of the copolymer and, if necessary, an aprotic organic solvent. Here, “compatible” means a state where the electrolyte salt does not precipitate due to crystallization.

In the present invention, the following electrolyte salt compounds are preferably used. That is, a cation selected from a metal cation, an ammonium ion, an amidinium ion, and a guanidinium ion, a chlorine ion, a bromine ion, an iodine ion, a perchlorate ion, a thiocyanate ion, a tetrafluoroborate ion, Nitrate ion, AsF ₆ ⁻ , PF ₆ ⁻ , stearyl sulfonate ion, octyl sulfonate ion, dodecylbenzene sulfonate ion, naphthalene sulfonate ion, dodecyl naphthalene sulfonate ion, 7,7,8,8-tetracyano-p- Quinodimethane ion, X ₁ SO ₃ ⁻ , [(X ₁ SO ₂
) (X ₂ SO ₂ ) N] ⁻ , [(X ₁ SO ₂ ) (X ₂ SO ₂ ) (X ₃ SO ₂ ) C] ⁻ , and [(X ₁ SO ₂ ) (X ₂ SO ₂ ) YC] A compound comprising an anion selected from-. _{However, X 1, X 2, X} 3, and Y is an electron withdrawing group. Preferably, X ₁ , X ₂ and X ₃ are each independently a C 1-6 perfluoroalkyl group or a C 6-18 perfluoroaryl group, Y is a nitro group, a nitroso group, A carbonyl group, a carboxyl group or a cyano group; X ₁ , X ₂ and X ₃ may be the same or different.

  As the metal cation, a cation of a transition metal can be used. Preferably, a metal cation selected from Mn, Fe, Co, Ni, Cu, Zn, and Ag metal is used. In addition, preferable results can be obtained by using a metal cation selected from Li, Na, K, Rb, Cs, Mg, Ca, and Ba metals. It is free to use two or more kinds of the aforementioned compounds in combination as the electrolyte salt compound. In the Li ion battery, an Li salt compound is preferably used as the electrolyte salt compound.

  In the present invention, the amount of the electrolyte salt compound used is preferably 0.0001 to 5, more preferably 0.001 to 5 in terms of the number of moles of the electrolyte salt compound / the total number of moles of ether oxygen atoms in the polyether copolymer. A range of 0.5 is good.

  In the present invention, an aprotic organic solvent may be added as a plasticizer, for example. When an aprotic organic solvent is mixed in the polymer solid electrolyte, the crystallization of the polymer is suppressed, the glass transition temperature is lowered, and many amorphous phases are formed even at a low temperature, so that the ionic conductivity is improved. The aprotic organic solvent is suitable for obtaining a high-performance battery having a low internal resistance by combining with the solid polymer electrolyte that can be used in the present invention. The polymer solid electrolyte of the present invention may be gelled by combining with an aprotic organic solvent. Here, the gel is a polymer swollen by a solvent.

As the aprotic organic solvent, aprotic ethers and esters are preferable. Specifically, propylene carbonate, γ-butyrolactone, butylene carbonate,
Vinyl carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl monoglyme, methyl diglyme, methyl triglyme, methyl tetraglyme, ethyl monoglyme, ethyl diglyme, ethyl triglyme, ethyl methyl monoglyme, butyl Diglyme, 3-methyl-2-oxazolidone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 4,4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, etc. Among them, propylene carbonate, γ-butyrolactone, butylene carbonate,
Vinyl carbonate, ethylene carbonate, methyl triglyme, methyl tetraglyme, ethyl triglyme, and ethyl methyl monoglyme are preferred. A mixture of two or more of these may be used.

  There is no particular limitation on the method of mixing the electrolyte salt compound and the necessary aprotic organic solvent into the polyether copolymer, but the polyether copolymer is long in the solution containing the electrolyte salt compound and the necessary aprotic organic solvent. Method of soaking by impregnation for a period of time, method of mechanically mixing electrolyte salt compound and necessary aprotic organic solvent into polyether copolymer, dissolving polyether copolymer and electrolyte salt compound in aprotic organic solvent Or a method in which the polyether copolymer is once dissolved in another solvent and then mixed with an aprotic organic solvent. Other polar solvents such as tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, etc. used alone or in combination are used as other solvents in the case of producing using other solvents. It is done. Other solvents can be removed before, during or after cross-linking the polyether copolymer.

  The negative electrode material is, for example, a metal electrode substrate as an electrode material substrate, a negative electrode active material on the metal electrode substrate, and exchange of good ions with the electrolyte layer, and the conductive auxiliary agent and the negative electrode active material are fixed to the metal substrate It is made up of a binder. In this case, for example, copper is used for the metal electrode substrate, but the metal electrode substrate is not limited to this, and may be nickel, stainless steel, gold, platinum, titanium, or the like.

  The negative electrode active material used in the present invention is a carbon material (natural graphite, artificial graphite, amorphous carbon, etc.) having a structure (porous structure) capable of occluding and releasing alkali metal ions such as lithium ions, lithium, or the like. It is a powder made of a metal such as lithium, an aluminum compound, a tin compound, a silicon compound, or a titanium compound that can occlude and release alkali metal ions such as ions. The particle diameter is preferably from 10 nm to 100 μm, more preferably from 20 nm to 20 μm. Moreover, you may use as a mixed active material of a metal and a carbon material. Note that a negative electrode active material having a porosity of about 70% is used.

  The positive electrode material is, for example, a metal electrode substrate as an electrode material substrate, a positive electrode active material on the metal electrode substrate, and a good ion exchange with the electrolyte layer, and the conductive auxiliary agent and the positive electrode active material are fixed to the metal substrate. It is made up of a binder. For example, aluminum is used for the metal electrode substrate, but is not limited thereto, and may be nickel, stainless steel, gold, platinum, titanium, or the like.

The positive electrode active material used in the present invention is an alkali metal-containing composite oxide powder having a composition of any one of AMO ₂ , AM ₂ O ₄ , A ₂ MO ₃ , and AMBO ₄ . Here, A in the formula is an alkali metal, and Li is preferably used. M is mainly made of a transition metal and contains at least one of Co, Mn, Ni, Cr, Fe, and Ti. M is composed of a transition metal, but besides the transition metal, Al, Ga, Ge, Sn, Pb, Sb, Bi, Si, P, B, or the like may be added. B contains at least one of P and Si. More specifically, AMO ₂ (A is an alkali metal, M is composed of at least one transition metal, and a part thereof may include a non-transition metal), AM ₂ O ₄ (A is an alkali metal, and M is at least A ₂ MO ₃ (A may be an alkali metal, M may be at least one transition metal, and a part thereof may include a non-transition metal) Good), AMBO ₄ (A is an alkali metal, B is P, Si, or a mixture thereof, M is composed of at least one transition metal, and a part thereof may include a non-transition metal). The particle diameter of the positive electrode active material is preferably 50 μm or less, more preferably 20 μm or less. These active materials have an electromotive force of 3 V (vs. Li / Li +) or more.

Preferred examples of the positive electrode active material include Li _x CoO ₂ , Li _x NiO ₂ ,
Li _x MnO ₂ , Li _x CrO ₂ , Li _x FeO ₂ ,
Li _x Co _a Mn _1-a O ₂ , Li _x Co _a Ni _1-a O ₂ ,
Li _x Co _a Cr _1-a O ₂ , Li _x Co _a Fe _1-a O ₂ ,
Li _x Co _a Ti _1-a O ₂ , Li _x Mn _a Ni _1-a O ₂ ,
Li _x Mn _a Cr _1-a O ₂ , Li _x Mn _a Fe _1-a O ₂ ,
Li _x Mn _a Ti _1-a O ₂ , Li _x Ni _a Cr _1-a O ₂ ,
Li _x Ni _a Fe _1-a O ₂ , Li _x Ni _a Ti _1-a O ₂ ,
Li _x Cr _a Fe _1-a O ₂ , Li _x Cr _a Ti _1-a O ₂ ,
Li _x Fe _a Ti _1-a O ₂ , Li _x Co _b Mn _c Ni _1-bc O ₂ ,
Li _x Cr _b Mn _c Ni _1-bc O ₂ , Li _x Fe _b Mn _c Ni _1-bc O ₂ ,
Li _x Ti _b Mn _c Ni _1-bc O ₂ , Li _x Mn ₂ O ₄ ,
Li _x Mn _d Co _2-d O ₄ , Li _x Mn _d Ni _2-d O ₄ ,
Li _x Mn _d Cr _2-d O ₄ , Li _x Mn _d Fe _2-d O ₄ ,
Li _x Mn _d Ti _2-d O ₄ , Li _y MnO ₃ ,
Li _y Mn _e Co _1-e O ₃ , Li _y Mn _e Ni _1-e O ₃ ,
Li _y Mn _e Fe _1-e O ₃ , Li _y Mn _e Ti _1-e O ₃ ,
Li _x CoPO ₄ , Li _x MnPO ₄ , Li _x NiPO ₄ ,
Li _x FePO ₄ , Li _x Co _f Mn _1-f PO ₄ ,
Li _x Co _f Ni _1-f PO ₄ , Li _x Co _f Fe _1-f PO ₄ ,
Li _x Mn _f Ni _1-f PO ₄ , Li _x Mn _f Fe _1-f PO ₄ ,
Li _x Ni _f Fe _1-f PO ₄ , Li _y CoSiO ₄ ,
Li _y MnSiO ₄ , Li _y NiSiO ₄ , Li _y FeSiO ₄ ,
Li _y Co _g Mn _1-g SiO ₄ , Li _y Co _g Ni _1-g SiO ₄ ,
Li _y Co _g Fe _1-g SiO ₄ , Li _y Mn _g Ni _1-g SiO ₄ ,
Li _y Mn _g Fe _1-g SiO ₄ , Li _y Ni _g Fe _1-g SiO ₄ ,
Li _y CoP _h Si _1-h O ₄ , Li _y MnP _h Si _1-h O ₄ ,
Li _y NiP _h Si _1-h O ₄ , Li _y FeP _h Si _1-h O ₄ ,
Li _y Co _g Mn _1-g P _h Si _1-h O ₄ ,
Li _y Co _g Ni _1-g P _h Si _1-h O ₄ ,
Li _y Co _g Fe _1-g P _h Si _1-h O ₄ ,
Li _y Mn _g Ni _1-g P _h Si _1-h O ₄ ,
Li _y Mn _g Fe _1-g P _h Si _1-h O ₄ ,
Examples thereof include lithium-containing composite oxides such as Li _y Ni _g Fe _1-g P _h Si _1-h O ₄ . (Where x = 0.01 to 1.2,
y = 0.01-2.2, a = 0.01-0.99, b = 0.01-0.98, c = 0.01-0.98, but b + c = 0.02-0 .99, d = 1.49 to 1.99,
e = 0.01-0.99, f = 0.01-0.99, g = 0.01-0.99, h = 0.01-0.99. )

Among the preferable positive electrode active materials, more preferable positive electrode active materials include, specifically, Li _x CoO ₂ ,
Li _x NiO ₂ , Li _x MnO ₂ , Li _x CrO ₂ ,
Li _x Co _a Ni _1-a O ₂ , Li _x Mn _a Ni _1-a O ₂ ,
Li _x Co _b Mn _c Ni _1-bc O ₂ , Li _x Mn ₂ O ₄ ,
Li _y MnO ₃ , Li _y Mn _e Fe _1-e O ₃ ,
Li _y Mn _e Ti _1-e O ₃ , Li _x CoPO ₄ ,
Li _x MnPO ₄ , Li _x NiPO ₄ , Li _x FePO ₄ ,
Li _x Mn _f Fe _1-f PO ₄ , can be mentioned. (Where x = 0.01 to 1.2,
y = 0.01-2.2, a = 0.01-0.99, b = 0.01-0.98, c = 0.01-0.98, but b + c = 0.02-0 .99, d = 1.49 to 1.99,
e = 0.01-0.99, f = 0.01-0.99. In addition, the value of said x, y increases / decreases with charging / discharging. )

In order to produce an electrode material containing the polyether copolymer of the present invention, the polyether copolymer is mixed with a negative active material powder or a positive active material using an ordinary stirring device such as a mixer or a planetary stirring device. It may be mixed with a substance powder or the like to make a paste. In this case, the polyether copolymer is preferably mixed with a solvent such as acetonitrile in advance and adjusted to an appropriate viscosity.
The addition amount of the polyether copolymer to the electrode material may be 0.5 to 20 wt%, preferably 1 to 15 wt%, with respect to the negative electrode active material powder or the positive electrode active material powder.

  Formation of a paste made of a polyether copolymer, a negative electrode active material powder, a positive electrode active material powder, and the like on a metal electrode substrate is performed by a doctor blade method, a silk screen method, or the like.

  For example, in the doctor blade method, a polyether copolymer, a negative electrode active material powder, a positive electrode active material powder, and the like are dispersed in an organic solvent such as n-methylpyrrolidone and applied to a metal electrode substrate. Uniform to an appropriate thickness with a blade having a width. After the application of the active material, the electrode is dried, for example, in a vacuum state at 80 ° C. to remove excess organic solvent. An electrode material is manufactured by press-molding the dried electrode with a pressing device.

Thereafter, a polymer solid electrolyte is applied to the main surface of the electrode material using, for example, a doctor blade method, a dip method, a transfer method, a printing method, or the like. The polymer solid electrolyte is mixed with a solvent such as acetonitrile according to its viscosity, adjusted to an appropriate viscosity, applied, and allowed to stand as needed, the electrode is impregnated with the polymer solid electrolyte, and this is heated. You may dry dry. The viscosity of the polymer solid electrolyte or polymer solid electrolyte solution during coating is 10 to 50000
mPa · s is preferable, and 100 to 20000 mPa · s is more preferable. In addition, the thickness of the coating layer (polymer solid electrolyte) after drying the solvent is preferably 400 μm or less, and more preferably 200 μm or less.

  A non-aqueous electrolyte secondary battery is assembled by applying a polymer solid electrolyte and superimposing a negative electrode and a positive electrode subjected to necessary crosslinking. Since the applied polymer solid electrolyte has sufficient mechanical strength, there is no need to introduce a polymer solid electrolyte membrane between the electrode materials, the process is simple, and the manufacturing cost can be reduced.

  When evaluating the characteristics of only the negative electrode material or the positive electrode material, the reversibility of the electrode material can be evaluated by using a lithium sheet for the counter electrode.

[式中、Ｒは炭素数１〜１２のアルキル基、または−ＣＨ_２Ｏ（ＣＲ^１Ｒ^２Ｒ^３）である。Ｒ^１、Ｒ^２、Ｒ^３は水素原子または−ＣＨ_２Ｏ（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^４であり、ｎ及びＲ^４はＲ^１、Ｒ^２、Ｒ^３の間で異なっていても良い。Ｒ^４は炭素数１〜１２のアルキル基であり、ｎは０〜１２の整数である。]
で示される単量体から誘導される繰り返し単位５〜９５モル％、及び
式（２）：

で示される単量体から誘導される繰り返し単位９５〜５モル％、及び
式（３）：

[式中、Ｒ^５はエチレン性不飽和基である。] で示される単量体から誘導される繰り返し単位０〜１０モル％で示される単量体を重合させて得られる重量平均分子量が５万〜２５０万のポリエーテル共重合体を製造する工程と、
（Ｂ）該ポリエーテル共重合体を一成分として含有する負極材料および正極材料の少なくともどちらか一つを製造する工程と、
（Ｃ）該ポリエーテル共重合体、光反応開始剤及び電解質塩化合物が含まれる高分子固体電解質用組成物を、負極材料及び正極材料の一方または両方における少なくとも１つの主表面に塗布する工程と、
（Ｄ）該高分子固体電解質用組成物を架橋する工程と、
を含む非水電解質二次電池の製造方法である。 As a method for producing the nonaqueous electrolyte secondary battery of the present invention,
(A) Formula (1):

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² , and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² , and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. A step of producing a polyether copolymer having a weight average molecular weight of 50,000 to 2.5 million obtained by polymerizing a monomer represented by 0 to 10 mol% of a repeating unit derived from the monomer represented by ,
(B) a step of producing at least one of a negative electrode material and a positive electrode material containing the polyether copolymer as one component;
(C) applying a composition for a polymer solid electrolyte containing the polyether copolymer, a photoreaction initiator, and an electrolyte salt compound to at least one main surface of one or both of the negative electrode material and the positive electrode material; ,
(D) crosslinking the polymer solid electrolyte composition;
Is a method for producing a non-aqueous electrolyte secondary battery.

In the polymerization step (A), the monomers represented by the above formula (1), formula (2) and formula (3) are polymerized to obtain a polyether copolymer. Coordination anion initiator such as catalyst system mainly composed of organic aluminum, catalyst system mainly composed of organic zinc, organotin-phosphate ester condensate catalyst system as a ring-opening polymerization catalyst, or potassium containing K ⁺ as a counter ion By using an anionic initiator such as alkoxide, diphenylmethyl potassium, potassium hydroxide, and the like, each of the monomers is reacted in the presence or absence of a solvent at a reaction temperature of 10 to 120 ° C. with stirring to obtain a polyether copolymer. can get. From the viewpoint of the degree of polymerization or the properties of the resulting copolymer, a coordination anion initiator is preferred, and an organotin-phosphate ester condensate catalyst system is particularly preferred because of ease of handling. The polyether copolymer previously mixed in the electrode is a monomer copolymer represented by the above formulas (1) and (2), and the polyether copolymer applied on the electrode is the above formula (1). Copolymerization of monomers represented by the formulas (2) and (3) is used.

  In the step (B) of mixing the polyether copolymer inside the electrode, the polyether copolymer is mixed in the negative electrode active material powder, the positive electrode active material powder, etc., and a uniform slurry is prepared using a normal stirring device. obtain.

  In the coating step (C), a polyether copolymer, a photoreaction initiator, and an electrolyte salt compound are mixed to obtain a composition for a polymer solid electrolyte, and the obtained composition for a polymer solid electrolyte is obtained. It is applied to at least one main surface of one or both of the negative electrode material and the positive electrode material.

  The polymer solid electrolyte composition is applied to one main surface of one of the negative electrode material and the positive electrode material, and at least one component of the polymer solid electrolyte composition is applied to one main surface of the other of the negative electrode material or the positive electrode material ( However, you may apply | coat except a photoinitiator). For example, a composition for a solid polymer electrolyte may be applied to the negative electrode material, and only the copolymer, only the electrolyte salt compound, or a combination of the copolymer and the electrolyte salt compound may be applied to the positive electrode material. A combination of a copolymer and an electrolyte salt compound may be applied.

In the crosslinking step (C), the applied polymer solid electrolyte composition is crosslinked to form a polymer solid electrolyte layer on the electrode material. Crosslinking can be performed by irradiating active energy rays in the presence or absence of an aprotic organic solvent. Specific examples of the active energy rays are electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays.
After the polymer solid electrolyte is formed by the crosslinking step (C), a nonaqueous electrolyte secondary battery having a configuration of negative electrode material / polymer solid electrolyte / positive electrode material is obtained.

  In the present invention, the battery may be manufactured by applying a polymer solid electrolyte film to the electrode material. The polymer solid electrolyte film is produced by manufacturing a polymer solid electrolyte composition, applying the polymer solid electrolyte composition to, for example, a release sheet, cross-linking the release sheet, and peeling the release sheet from the release sheet. be able to.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples described below as long as the gist of the invention is not exceeded.

  In this example, the following experiment was performed in order to compare Coulomb efficiency, reversible capacity, and cycle performance in a nonaqueous electrolyte secondary battery including a negative electrode material, a nonaqueous electrolyte, and a positive electrode material.

EXAMPLES Specific modes for carrying out the present invention will be described below with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

[Synthesis Example (Production of Polyether Copolymer Catalyst)]
In a three-necked flask equipped with a stirrer, thermometer and distillation apparatus, 10 g of tributyltin chloride and 35 g of tributyl phosphate are added and heated at 250 ° C. for 20 minutes with stirring under a nitrogen stream to distill off the distillate. As a product, a solid condensate was obtained. It used as a polymerization catalyst in the following polymerization examples.

The monomer equivalent composition of the polyether copolymer was determined by ¹ H NMR spectrum.
For measuring the molecular weight of the polyether copolymer, gel permeation chromatography (GPC) measurement was performed, and the weight average molecular weight was calculated in terms of standard polystyrene. GPC measurement was performed at 60 ° C. using RID-6A manufactured by Shimadzu Corporation, Showdex KD-807, KD-806, KD-806M and KD-803 columns manufactured by Showa Denko KK, and DMF as a solvent. .

１６７ｇ、および溶媒としてｎ−ヘキサン１０００ｇを仕込み、化合物（ａ）の重合率をガスクロマトグラフィーで追跡しながら、エチレンオキシド１４０ｇを逐次添加した。このときの重合温度は２０℃とし、１０時間反応を行った。重合反応はメタノールを１ｍＬ加え反応を停止した。デカンテーションによりポリマーを取り出した後、常圧下４０℃で２４時間、更に減圧下４５℃で１０時間乾燥してポリマー２７０ｇを得た。得られたポリエーテル共重合体の重量平均分子量及びモノマー換算組成分析結果を表１に示す。 [Polymerization Example 1]
The inside of a glass four-necked flask having an internal volume of 3 L was purged with nitrogen, and 1 g of the condensate shown in the synthesis example of the catalyst as a polymerization catalyst and a glycidyl ether compound (a) adjusted to a water content of 10 ppm or less:

167 g and 1000 g of n-hexane as a solvent were charged, and 140 g of ethylene oxide was successively added while monitoring the polymerization rate of the compound (a) by gas chromatography. The polymerization temperature at this time was 20 ° C., and the reaction was carried out for 10 hours. The polymerization reaction was stopped by adding 1 mL of methanol. The polymer was taken out by decantation and then dried at 40 ° C. under normal pressure for 24 hours and further at 45 ° C. for 10 hours under reduced pressure to obtain 270 g of polymer. Table 1 shows the weight average molecular weight and monomer conversion composition analysis results of the obtained polyether copolymer.

[Polymerization Example 2]
The same operation as in Polymerization Example 1 was carried out except that 95 g of glycidyl ether compound (a) and 210 g of ethylene oxide were used for polymerization.

[Polymerization Example 3]
The same operation was performed except that 200 g of glycidyl ether compound (a), 110 g of ethylene oxide, and 0.2 g of n-butanol were charged and polymerized in the preparation of polymerization example 1.

[Polymerization Example 4]
The same operation was carried out except that 160 g of glycidyl ether compound (a), 18 g of allyl glycidyl ether, and 130 g of ethylene oxide were polymerized in the preparation of polymerization example 1.

[Polymerization Example 5]
The same operation was performed except that 70 g of glycidyl ether compound (a), 25 g of allyl glycidyl ether, and 210 g of ethylene oxide were polymerized in the preparation of polymerization example 1.

[Polymerization Example 6]
The same operation as in Polymerization Example 1 was performed except that 170 g of glycidyl ether compound (a), 25 g of allyl glycidyl ether, 110 g of ethylene oxide, and 0.2 g of n-butanol were polymerized.

Example 1 Production of Battery Constructed of Anode Material / Polymer Solid Electrolyte / Cathode Material A graphite powder (porous structure material) having an average particle size of 12 μm was used as the anode active material. With respect to 10.0 g of this negative electrode active material, 0.6 g of the polyether copolymer obtained in Polymerization Example 1, 0.23 g of bis (trifluoromethanesulfonyl) imide lithium, 6 g of a solution dissolved in 10 g of acetonitrile as a solvent, After adding 0.25 g of carbon fiber (VGCF) synthesized at 2000 ° C. or more as an auxiliary agent, 0.91 g of polyvinylidene fluoride as a binder, and stirring for 1 hour using a stainless ball mill with n-methylpyrrolidone as a solvent, This was coated on a copper current collector using a 50 μm gap bar coater, dried at 80 ° C. in a vacuum state for 12 hours or more, and then roll-pressed to obtain a negative electrode sheet containing a polyether copolymer.
Further, 1.0 g of the polyether copolymer obtained in Polymerization Example 1, 0.005 g of the photoreaction initiator benzophenone, 0.05 g of the crosslinking assistant N, N′-m-phenylenebismaleimide, and a molar ratio (electrolyte salt compound) Of bis (trifluoromethanesulfonyl) imide lithium in 10 ml of acetonitrile so that the total number of moles of ether oxygen atoms in the copolymer is 0.05, 500 μm on the above negative electrode sheet. After applying using a bar coater in the gap, heating to 80 ° C. as it is, and thoroughly impregnating the polymer electrolyte composition in the negative electrode sheet and drying it, the surface of the electrolyte was covered with a laminate film. ) GS Yuasa made of a high-pressure mercury lamp (30mW / cm ²⁾ of crosslinking by irradiation for 30 seconds, is integrated polyelectrolyte to the anode sheet Was negative electrode / electrolyte sheet was prepared.
As the positive electrode active material, LiCo _1/3 Mn _1/3 Ni _1/3 O ₂ having an average particle diameter of 20 μm or less was used. To 10.0 g of this positive electrode active material, 0.7 g of the polyether copolymer obtained in Polymerization Example 1, 0.15 g of lithium borofluoride, 6 g of a solution dissolved in 10 g of acetonitrile as a solvent, acetylene as a conductive auxiliary agent After adding 0.6 g of spherical carbon microparticles produced by thermal decomposition of, 0.84 g of polyvinylidene fluoride as a binder, and stirring for 1 hour using a stainless ball mill with n-methylpyrrolidone as a solvent, on the aluminum current collector The sample was applied using a bar coater with a gap of 100 μm, dried at 80 ° C. in a vacuum state for 12 hours or more, and then roll-pressed to obtain a positive electrode sheet containing a polyether copolymer.
Further, 1.0 g of the polyether copolymer obtained in Polymerization Example 1, 0.005 g of the photoreaction initiator benzophenone, 0.05 g of the crosslinking assistant N, N′-m-phenylenebismaleimide, and a molar ratio (electrolyte salt compound) Of lithium borofluoride in 10 ml of acetonitrile so that the total number of moles of ether oxygen atoms in the copolymer is 0.05, a bar coater with a gap of 500 μm is placed on the positive electrode sheet. And then heated to 80 ° C. as it is, impregnated with the polymer electrolyte composition in the positive electrode sheet and dried, and then the high pressure mercury lamp (30 mW / cm ^{2) with the} electrolyte surface covered with a laminate film. ) Was irradiated for 30 seconds to produce a positive electrode / electrolyte sheet in which a polymer electrolyte was integrated on the positive electrode sheet.
The negative electrode / electrolyte sheet and the positive electrode / electrolyte sheet were bonded together in a glove box substituted with argon gas to assemble a test 2032 type coin battery. The electrochemical characteristics are a charge / discharge device manufactured by Hokuto Denko Co., Ltd., with 4.2 V upper limit and 2.5 V lower limit under test conditions (C / 8) where predetermined charge and discharge can be performed in 8 hours. The positive electrode and negative electrode were evaluated by applying a constant current. The test temperature was 60 ° C. environment. The test results are shown in Table 2.

[Example 2] Production of battery composed of negative electrode material / polymer solid electrolyte / positive electrode material The same procedure was used except that the polyether copolymer obtained in Polymerization Example 4 of Example 1 was used as the polymer electrolyte. A coin battery was prepared and the electrochemical characteristics of the positive electrode and the negative electrode were evaluated. The test results are shown in Table 2.

[Comparative Example 1] Production of Battery Constructed with Anode Material / Polymer Solid Electrolyte (Uncrosslinked) / Cathode Material In the polymer electrolyte composition for overcoating the cathode and anode of Example 1, a photoreaction initiator and crosslinking aid A coin battery was prepared in the same manner as in Example 1 except that a positive electrode / electrolyte sheet and a negative electrode / electrolyte sheet prepared without adding an agent and without irradiating a high-pressure mercury lamp were used. Characteristics were evaluated. The test results are shown in Table 2.

[Comparative Example 2] Preparation of Battery Constructed with Anode Material / Polymer Solid Electrolyte / Cathode Material In the polymer electrolyte composition for overcoating the cathode and anode of Example 2, a photoreaction initiator and a crosslinking aid were added. In addition, a coin battery was prepared in the same manner as in Example 1 except that the positive electrode / electrolyte sheet and the negative electrode / electrolyte sheet prepared without irradiation with a high-pressure mercury lamp were used, and the electrochemical characteristics of the positive electrode and the negative electrode were evaluated. . The test results are shown in Table 2.

[Comparative Example 3] Preparation of Battery Constructed of Anode Material / Polymer Solid Electrolyte / Cathode Material In the polymer electrolyte composition for overcoating the electrode of Example 1, the polyether copolymer obtained in Polymerization Example 2 was used. A coin battery was prepared in the same manner except that it was used, and the electrochemical characteristics of the positive electrode and the negative electrode were evaluated. The test results are shown in Table 2.

[Comparative Example 4] Preparation of Battery Constructed of Anode Material / Polymer Solid Electrolyte / Cathode Material In the polymer electrolyte composition for overcoating the electrode of Example 1, the polyether copolymer obtained in Polymerization Example 3 was used. A coin battery was prepared in the same manner except that it was used, and the electrochemical characteristics of the positive electrode and the negative electrode were evaluated. The test results are shown in Table 2.

[Comparative Example 5] Preparation of Battery Constructed of Anode Material / Polymer Solid Electrolyte / Cathode Material In the polymer electrolyte composition for overcoating the electrode of Example 2, the polyether copolymer obtained in Polymerization Example 5 was used. A coin battery was prepared in the same manner except that it was used, and the electrochemical characteristics of the positive electrode and the negative electrode were evaluated. The test results are shown in Table 2.

[Comparative Example 6] Preparation of Battery Constructed of Anode Material / Polymer Solid Electrolyte / Cathode Material In the polymer electrolyte composition for overcoating the electrode of Example 2, the polyether copolymer obtained in Polymerization Example 6 was used. A coin battery was prepared in the same manner except that it was used, and the electrochemical characteristics of the positive electrode and the negative electrode were evaluated. The test results are shown in Table 2.

  Since the nonaqueous electrolyte secondary battery of the present invention has a high capacity and excellent cycle charge / discharge characteristics, it can be used as a stationary battery and a load leveling battery.

Claims (8)

(I) Formula (1):

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² , and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² , and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3):

[Wherein R ⁵ represents an ethylenically unsaturated group. A polyether copolymer having a weight average molecular weight in the range of 50,000 to 2,500,000 having 0 to 10 mol% of repeating units derived from the monomer represented by
And (ii) a photoreaction initiator, (iii) one or both of the main surfaces of the negative electrode material and the positive electrode material are covered with a cross-linked body comprising a composition for a solid polymer electrolyte containing an electrolyte salt compound. A water electrolyte secondary battery,
And at least one of the negative electrode material and positive electrode material which comprise this nonaqueous electrolyte secondary battery contains this polyether copolymer as one component, The nonaqueous electrolyte secondary battery characterized by the above-mentioned.   Item 2. The nonaqueous electrolyte secondary battery according to Item 1, wherein the crosslinked product is obtained by applying the composition for a polymer solid electrolyte to the main surface and then crosslinking the composition.   The nonaqueous electrolyte secondary battery according to claim 1, wherein the electrolyte salt compound is a lithium salt compound.   The non-aqueous electrolyte secondary battery according to any one of claims 1 to 3, wherein an aprotic organic solvent is further added to the polymer solid electrolyte composition.   6. The nonaqueous electrolyte secondary battery according to claim 5, wherein the aprotic organic solvent is selected from the group consisting of ethers and esters.   The negative electrode material comprises a mixture of a negative electrode active material, a conductive additive and a binder, and the negative electrode active material is selected from lithium, carbon, silicon-based compounds, tin-based compounds, aluminum-based compounds, and titanium-based compounds. The nonaqueous electrolyte secondary battery according to any one of claims 1 to 5, comprising one kind or a mixture of two or more kinds. The positive electrode material is AMO ₂ (A is an alkali metal, M is a single or two or more kinds of transition metals, and a part thereof may include a non-transition metal), AM ₂ O ₄ (A is an alkali metal, M consists of a single or two or more transition metals, part of which may contain a non-transition metal), A ₂ MO ₃ (A is an alkali metal, M is a single or two or more transition metals) , Part of which may contain a non-transition metal), AMBO ₄ (A is an alkali metal, B is P, Si, or a mixture thereof, M is a single or two or more transition metals, The nonaqueous electrolyte secondary battery according to any one of claims 1 to 7, wherein the nonaqueous electrolyte secondary battery has a composition of any one of (which may contain a non-transition metal). (A) Formula (1):

[Wherein, R represents an alkyl group having 1 to 12 carbon atoms, or —CH ₂ O (CR ¹ R ² R ³ ). R ¹ , R ² , and R ³ are hydrogen atoms or —CH ₂ O (CH ₂ CH ₂ O) _n R ⁴ , and n and R ⁴ may be different among R ¹ , R ² , and R ^3. . R ⁴ is an alkyl group having 1 to 12 carbon atoms, and n is an integer of 0 to 12. ]
5 to 95 mol% of repeating units derived from the monomer represented by formula (2):

And 95 to 5 mol% of repeating units derived from the monomer represented by formula (3)

[Wherein R ⁵ represents an ethylenically unsaturated group. A step of obtaining a polyether copolymer having a weight average molecular weight of 50,000 to 2,500,000 obtained by polymerizing a monomer represented by 0 to 10 mol% of a repeating unit derived from
(B) obtaining at least one of a negative electrode material and a positive electrode material containing the polyether copolymer as one component;
(C) applying a composition for a polymer solid electrolyte containing the polyether copolymer, a photoreaction initiator, and an electrolyte salt compound to at least one main surface of one or both of the negative electrode material and the positive electrode material; ,
(D) crosslinking the polymer solid electrolyte composition;
The manufacturing method of the nonaqueous electrolyte secondary battery containing this.