JPH09153354A - Separator film for electrochemical device, and its manufacture and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film having good film strength, excellent workability, a large absorption quantity of an electrolyte, and high ionic conductivity by providing a cross-linking polymer having the oxyalkylene group as the constituting component. SOLUTION: A film provided with a polymer having the oxyalkylene group or having urethane bonding and the oxyalkylene group as the constituting component is obtained for the separator film of an electrochemical device. The film having good film strength, excellent workability, a large absorption quantity of an electrolyte, and high ionic conductivity is obtained. A battery or the electrochemical device such as an electric double-layer capacitor utilizing this film for a separator can be operated at a high capacity and a high current.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a separator for an electrochemical device containing a crosslinked polymer containing an oxyalkylene group as a constituent, a method for producing the same, and uses thereof. More specifically, it relates to a battery and a capacitor having the separator.

[0002]

2. Description of the Related Art Li primary batteries and Li secondary batteries, which are a type of electrochemical device, have recently been rapidly mounted in small portable devices and have been rapidly expanding due to their high energy density. A porous film called a polyolefin non-woven fabric or a polyolefin microporous film is used as a separator, which is important as its constituent element. The function of the separator is to prevent electrical short circuit by electrically separating the positive and negative electrodes.
It is required not to interfere with the movement of ions in the electrolytic solution interposed between the positive and negative electrodes. In addition, if it has the above-mentioned function, it is preferable that it is as thin as possible because the energy density of the entire battery is increased. In order to have these functions, a porous thin film is currently used as a separator. Therefore, film manufacturing and processing costs are high, which is a factor of high cost. In addition, there is a problem in terms of long-term reliability and safety as a battery because it does not have an ability to carry an electrolytic solution and liquid leakage from the battery to the outside of the component or elution of an electrode substance is likely to occur.

Recently, a so-called solid polymer electrolyte, which is a composite of a polyethylene oxide polymer and a Li salt, has been receiving attention. Examples of these polymer solid electrolytes include “British Polymer Journal (Br. Polym. J.),
319, p. 137, 1975 ", describes that a composite of polyethylene oxide and an inorganic alkali metal salt exhibits ionic conductivity. It has also been reported that the comb polymer having oligooxyethylene introduced into the side chain enhances the thermal mobility of the oxyethylene chain which is responsible for the ionic conductivity and improves the ionic conductivity. For example, "Journal of Physical Chemistry (J. Phys. Chem.), Vol. 89, p. 987, 1984"
In "Year", there is described an example in which oligooxyethylene is added to a side chain of polymethacrylic acid and an alkali metal salt is complexed. In addition, "Journal of American Chemical Society (J. Am. Chem. Soc.)
106, 6854, 1984 "describes an example in which a polyphosphazene having an oligooxyethylene side chain is complexed with an alkali metal salt. It is said that the polymer itself forms a complex with a Li salt that is an electrolyte, and ionic conduction can be exhibited by thermal motion of the polymer chain.
Therefore, a hole for passing an electrolytic solution, such as a current separator, is basically unnecessary. However, these materials do not have sufficient material in terms of membrane strength and ionic conductivity, and cannot contain much electrolyte.

On the other hand, there has been proposed a polymer solid electrolyte in which a continuous network of polyethylene oxide is impregnated with an electrolytic solution containing a metal salt and an aprotic solvent (US Pat. No. 4,792,504). These show that the oxyethylene chains can be impregnated with aprotic solvents as well as Li salts, providing a uniform ionic conductor without pores. However, it is difficult to manufacture it into a film having high strength, and it is difficult to absorb the electrolytic solution later, and there is no such idea. Further, due to the structure of the cross-linking agent, no one satisfying the ionic conductivity has been obtained.

Further, in recent years, electric double-layer capacitors in which a carbon material having a large specific surface area, such as activated carbon or carbon black, is used as a polarizable electrode and an ion-conductive solution is interposed therebetween for use as a memory backup power supply or the like have been frequently used. . For example, "Functional Materials, February 1989, p. 33"
Discloses a capacitor using a carbon-based polarizable electrode and an organic electrolyte, "173rd Electrochemical Society Meeting Atlanta Georgia, May, No.
18, 1988 "describes an electric double layer capacitor using a sulfuric acid aqueous solution. Also, JP-A-63-2
No. 44570 discloses Rb ₂ C having high electrical conductivity.
A capacitor using u ₃ I ₃ Cl ₇ as an inorganic solid electrolyte is disclosed.

However, the current electric double layer capacitor using an electrolyte solution is liable to leak to the outside of the capacitor for a long period of time during an abnormal condition such as long-term use or application of high voltage. There is a problem in use and reliability. On the other hand, the electric double layer capacitor using the conventional inorganic ion conductive material has a problem that the decomposition voltage of the ion conductive material is low and the output voltage is low.

Japanese Patent Application Laid-Open No. Hei 4-253771 discloses the use of a polyphosphazene-based polymer as an ion-conductive substance for batteries and electric double-layer capacitors. The use of a conductive material has the advantages that the output voltage is higher than that of an inorganic ion conductive material, that the material can be processed into various shapes, and that sealing is simple.

However, in this case, the ionic conductivity of the solid polymer electrolyte is not sufficient at 10 ^-4 to 10 ^-6 S / cm, and there is a drawback that the extraction current is small.
It is also possible to increase the ionic conductivity by adding a plasticizer to the polymer solid electrolyte, but since it imparts fluidity, it cannot be treated as a complete solid and has poor film strength and film formability. When applied to an electric double layer capacitor or a battery, a short circuit easily occurs, and a sealing problem occurs as in the case of the liquid ion conductive material. On the other hand, when assembling a solid electrolyte together with a polarizable electrode into a capacitor, there is a problem that it is difficult to uniformly compound a carbon material having a large specific surface area because the solids are mixed with each other.

The solid polymer electrolyte layer in an electrochemical device such as a battery or a capacitor is responsible only for ion migration, and the thinner the device, the smaller the volume of the whole device,
The energy density of batteries, capacitors, etc. can be increased. If the polymer solid electrolyte layer is made thin, the electric resistance of the battery and the capacitor can be reduced, and the extraction current,
The charging current can be increased and the power density of the battery can be improved. Further, corrosion of ions, particularly alkali metal ions, hardly occurs, and the cycle life is improved. Therefore,
There has been a demand for a high polymer solid electrolyte film having high ionic conductivity, which has a film strength as good as possible and can be made thin.

Further, when the polymer solid electrolyte is arranged between the electrodes of an electrochemical device such as a battery or an electric double layer capacitor, a constant plate frame-like spacer is arranged between both electrodes facing each other, and the distance between the electrodes is increased. Although it is possible to keep constant, it is not easy to process the electrolyte or spacer or manufacture the device.For example, in the case of a thin device or a wound type device, the solid electrolyte occupies the part other than the spacer between the electrodes. Depending on the type of layer, there is a problem with the dimensional stability of its thickness, and it is difficult to keep the thickness (that is, the distance between electrodes) precisely at a constant distance, or because of problems with mechanical strength, Variation in the distance between the electrodes in the device occurs,
Therefore, a short circuit is likely to occur, or there is a problem in the stability of the device characteristics.

[0011]

The present invention is easy to process, has a uniform film thickness, can contain a large amount of electrolyte or electrolytic solution, has good film strength, and has an ionic conductivity after inclusion of the electrolyte or electrolytic solution. High, safe, excellent in reliability, a polymer solid electrolyte polymer having good ion conductivity even at room temperature or lower temperature as a constituent component, a film for a separator of a novel electrochemical device, a separator and It is an object to provide a method for producing them. It is another object of the present invention to provide an electrochemical device which does not leak and combines the ion conductive separator film or separator of the present invention and a polymer solid electrolyte, and a method for producing the same. Further, the present invention aims to provide a battery and a method for manufacturing the same, which is easy to be thinned by using the separator film or the separator, can operate at high capacity and high current, and has excellent reliability. To do. It is another object of the present invention to provide a secondary battery having a separator having the separator film and having good cycleability, and a method for producing the secondary battery. Further, the present invention, using the ion-conductive separator film or separator of the present invention, a high output voltage, a large extraction current, workability, an electric double layer capacitor excellent in reliability and a manufacturing method thereof. The purpose is to provide.

[0012]

Means for Solving the Problems The present inventors have conducted extensive studies in view of the above problems and found that a film containing a crosslinked polymer containing an oxyalkylene group as a constituent component is extremely suitable as a target separator. Has reached the present invention. Further, as a crosslinked polymer containing an oxyalkylene group, particularly, by using a polymer obtained from a polymerizable compound having a urethane bond and containing an oxyalkylene group as a constituent component, the film strength is good, It has been found that a separator film and a separator having excellent properties and having a large content of an electrolyte or an electrolytic solution can be obtained.

Further, by combining the polymer and the support, a separator film and a separator having good film strength and uniform film thickness can be obtained. By using such a film or a separator, It has been found that the problems of the film for separator, the separator and the electrochemical device in terms of mechanical strength or stability of properties can be solved. It was also found that an excellent electrochemical device without leakage can be obtained by using this separator. For example, they have found that by using this separator in a battery, a battery in which problems such as long-term reliability and safety are improved can be manufactured.
Furthermore, the inventors of the present invention can produce an electric double layer capacitor having a high output voltage, a large extraction current, and excellent workability and reliability by using the separator of the present invention. It has been found that a multilayer capacitor can be manufactured.

That is, the present invention has achieved the above object by developing the following. [1] A film for a separator of an electrochemical device, which comprises a crosslinked polymer having an oxyalkylene group as a constituent component. [2] A film for a separator of an electrochemical device, which comprises a crosslinked polymer having a urethane bond and an oxyalkylene group as a constituent component.

[3] The polymer has the general formula (1) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) In the above, R ¹ represents hydrogen or an alkyl group, and R ² represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0
And when y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However,
The values of R ¹ , R ² and x, y, z in a plurality of units represented by the above general formula (1) in the same molecule are independent of each other and need not be the same. [1] A polymer of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above and / or a copolymer containing the compound as a copolymerization component [1]
Alternatively, a film for a separator of the electrochemical device according to [2].

The polymer [4] has the general formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n- (2 [In the formula, R ¹ represents hydrogen or an alkyl group, and R ³ is-.
(CH _{2) 2} - or -CH (CH ₃₎ CH ₂ - represents, n represents an integer of 1 or more. x, y, and z are the same as those in the general formula (1)], which is a polymer of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the formula (1) and / or a copolymer containing the compound as a copolymerization component. A film for a separator of the electrochemical device according to the above [1] or [2].

[5] The separator film for an electrochemical device according to the above [1] to [4], which contains an electrolyte and / or a solvent. [6] At least one kind of electrolyte is an alkali metal salt, 4
The film for a separator of an electrochemical device according to the above [5], which is a quaternary ammonium salt or a quaternary phosphonium salt. [7] The film for a separator of an electrochemical device according to the above [5], wherein the solvent is a carbonate compound. [8] The film for a separator of an electrochemical device according to the above [1] to [7], wherein the support is composite. [9] The film for a separator of an electrochemical device according to the above [1] to [7], which is a composite of a porous support.

[10] The support has a thickness of 0.01 μm to 100 μm.
The film for a separator of an electrochemical device according to the above [8] or [9], which is a granular support having a size of m. [11] The separator film for an electrochemical device according to the above [8] or [9], wherein the support is an aggregate of primary particles, and the size of the aggregate is 0.01 μm to 100 μm. . [12] The film for separator of an electrochemical device according to the above [10] or [11], wherein the support has a BET specific surface area of 10 m ² / g or more. [13] A separator for an electrochemical device, comprising the film according to the above [8] to [12]. [14] Thickness of 1 μm to 110 μm, which is obtained by combining supports having a uniform size in the range of 1 μm to 100 μm.
[13] The separator according to the above [13], which has a uniform thickness in the range. [15] The separator according to the above [13] or [14], wherein the total content of the solvent and the electrolyte is 100 to 1000% of the total weight of the separator.

[16] General formula (1) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) (symbol in the formula Is the same as the above [3].) At least one of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above, or at least one selected from the group consisting of an electrolyte, a solvent and another polymerizable compound. A method for producing a separator film for an electrochemical device, which comprises arranging a mixture to which a substance is added on a support and polymerizing the acryloyl-based or methacryloyl-based compound.

[17] General formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n- (2) (formula The symbol is the same as the above [4].) Selected from at least one of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above, or a group consisting of an electrolyte, a solvent and another polymerizable compound. A method for producing a film for a separator of an electrochemical device, which comprises arranging a mixture to which at least one kind is added on a support and polymerizing the acryloyl-based or methacryloyl-based compound.

[18] General formula (1) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) (symbol in the formula Is the same as the above [3].) At least one of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above, or at least one selected from the group consisting of an electrolyte, a solvent and another polymerizable compound. A method for producing a composite film for a separator of an electrochemical device, which comprises polymerizing the acryloyl-based or methacryloyl-based compound after impregnating a porous support with the mixture to which the compound is added.

[19] A mixture of at least one acryloyl or methacryloyl compound having a structure containing a unit represented by the general formula (1) and a granular support, or at least one of the above compounds, a granular support,
And a mixture containing at least one selected from an electrolyte, a solvent and another polymerizable compound is placed on another support, and the acryloyl-based or methacryloyl-based compound is polymerized. Film manufacturing method. [20] A mixture of at least one acryloyl-based or methacryloyl-based compound having a structure containing the unit represented by the general formula (1) and a granular support, or at least one of the compounds, a granular support, and an electrolyte and a solvent. And a mixture containing at least one selected from other polymerizable compounds is placed on an electrode, and the acryloyl-based or methacryloyl-based compound is polymerized, and a method for producing a separator for an electrochemical device.

[21] General formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n- (2) (formula The symbol is the same as the above [4].) Selected from at least one of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above, or a group consisting of an electrolyte, a solvent and another polymerizable compound. A method for producing a composite film for a separator of an electrochemical device, which comprises polymerizing the acryloyl-based or methacryloyl-based compound after impregnating a porous support with a mixture to which at least one kind is added.

[22] A mixture of at least one acryloyl or methacryloyl compound having a structure containing a unit represented by the general formula (2) and a granular support, or at least one of the above compounds, a granular support,
And a mixture containing at least one selected from an electrolyte, a solvent and another polymerizable compound is placed on another support, and the acryloyl-based or methacryloyl-based compound is polymerized. Film manufacturing method. [23] A mixture of at least one of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the general formula (2) and a granular support, or at least one of the compounds, a granular support, and an electrolyte and a solvent. And a mixture containing at least one selected from other polymerizable compounds is placed on an electrode, and the acryloyl-based or methacryloyl-based compound is polymerized, and a method for producing a separator for an electrochemical device.

[24] A battery using the film described in [1] to [12] as a separator. [25] The battery according to the above [24], wherein the negative electrode of the battery comprises an electrode containing lithium, a lithium alloy, or a substance capable of inserting and extracting lithium ions.

[26] In the method for producing a battery, a positive electrode, a separator made of the film described in the above [1] to [12] and a negative electrode are laminated in any order as a structure for battery construction, and the positive electrode and the negative electrode are interposed between the positive electrode and the negative electrode. A step of forming a positive electrode / separator / negative electrode laminate by sandwiching and holding separators, and a general formula (1) or a general formula (2) CH ₂ = C (R ¹ ) CO [O _{(CH 2) x (CH (} CH 3)) y] z NHCOO- R 2 - (1) (. symbols in the formula are as defined above _{[3]) CH 2 = C} (R 1) CO [O (CH _{2) x (CH (CH 3} )) y] z NHCOO (R 3 O) n - acryloyl (2) (the symbols in the formula have a structure containing a unit represented by the same) and the [4]. Or at least one and less methacryloyl compound A method for manufacturing a battery, which comprises a step of filling a polymerizable monomer-containing material containing one kind of electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material.

[27] In the method for producing a battery, a positive electrode in which at least one of the positive electrode and the negative electrode is preliminarily laminated with a separator made of the film described in the above [1] to [12].
A positive electrode / separator / wherein a separator is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure using the separator laminate and / or the negative electrode / separator laminate.
A method for producing a battery, comprising: a step of forming a negative electrode laminate; and a step of filling a liquid material containing at least one electrolyte as an essential constituent in a battery constituent structure having such a constitution.

[28] In the method for producing a battery, a positive electrode in which at least one of the positive electrode and the negative electrode is preliminarily laminated with a separator comprising the film described in the above [1] to [12].
A positive electrode / separator / wherein a separator is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure using the separator laminate and / or the negative electrode / separator laminate.
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH _{3)) y] z NHCOO- R} 2 -. (1) ( as defined above [3] symbols in the ^{_{formula) CH 2 = C (R 1}} ) CO [O (CH 2) x (CH (CH 3) ^{_{) y] z NHCOO (R 3}} O) n - (2) ( at least one and at least the symbols in the formula acryloyl or methacryloyl compound having a structure containing a unit represented by the same) and the [4]. A method for producing a battery, comprising: a step of filling a polymerizable monomer-containing material containing one kind of electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material.

[29] In the method for producing a battery, a positive electrode / porous support laminate and / or a negative electrode / porous support laminate in which a porous support is laminated on at least one of a positive electrode and a negative electrode are used, A step of forming a positive electrode / porous support / negative electrode laminate in which a porous support is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure, and the general formula ( 1) or general formula _{(2) CH 2 = C (} R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO- R 2 - (1) ( symbols in the formula above [ . 3] and the ^{_{same) CH 2 = C (R 1}} ) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO (R 3 O) n - (2) ( the symbols in the formula the Same as [4].) Acryloyl-based or methacryloyl having a structure containing a unit represented by [1] to [12], characterized by including a step of filling a polymerizable monomer-containing material containing at least one type of ill compound and an electrolyte of at least one type as an essential constituent and a step of polymerizing the polymerizable monomer-containing material. ]
A method for producing a battery having a separator comprising the film as described.

[30] In the method for manufacturing a battery, at least one of the positive electrode and the negative electrode is previously prepared by the general formula (1) or the general formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH _{(CH 3)) y] z} NHCOO- R 2 -. (1) ( same as the symbols in the formula _{[3]) CH 2 = C} (R 1) CO [O (CH 2) x (CH (CH _{3)) y] z NHCOO (} R 3 O) n - (2) ( at least one of the symbols in the formula acryloyl or methacryloyl compound having a structure containing a unit represented by the same) and the [4]. A step of impregnating and / or coating a polymerizable monomer-containing material containing as an essential constituent, a positive electrode, a negative electrode, and a positive electrode as a battery constituent structure using a separator composed of the film described in [1] to [12] above. A separator is stacked between the negative electrodes A step of forming a sandwiched positive electrode / separator / negative electrode laminate,
And a method for producing a battery, comprising a step of polymerizing the polymerizable monomer-containing material.

[31] The polymerizable monomer-containing material is represented by the general formula (1) or the general formula (2): CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z ^{NHCOO- R 2 - (1) (} . the symbols in the formula as defined above _{[3]) CH 2 = C} (R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO ( R ³ O) _n − (2) (the symbols in the formula are the same as those in the above [4]) and at least one acryloyl or methacryloyl compound having a structure containing a unit is essential and at least one electrolyte is essential. The method for producing a battery according to the above [30], which is a polymerizable monomer-containing material contained as a component.

[32] An electric double layer capacitor using the film described in [1] to [12] as a separator. [33] In the method for producing an electric double layer capacitor, two polarizable electrodes and a separator made of the film according to the above [1] to [12] are laminated in arbitrary order as a capacitor-constituting structure. A step of forming an electrode / separator / electrode laminate by laminating and sandwiching a separator between polarizable electrodes, and filling a liquid substance containing at least one electrolyte as an essential component in a capacitor structure structure having such a configuration. A method of manufacturing an electric double layer capacitor, comprising:

[34] In the method for producing an electric double layer capacitor, two polarizable electrodes and a separator made of the film described in [1] to [12] above are laminated in any order as a structure for constructing a capacitor. A step of forming an electrode / separator / electrode laminate by sandwiching and sandwiching a separator between two polarizable electrodes, and a general formula (1) or a general formula (2) CH ₂ ^{= C (R 1) CO [} O (CH 2) x (CH (CH 3)) y] z NHCOO- R 2 - (1) (. symbols in the formula are as defined above [3]) CH ₂ = C ^{(R 1) CO [O (} CH 2) x (CH (CH 3)) y] z NHCOO (R 3 O) n - (2) ( symbols in the formula are as defined above [4].) expressed in Acryloyl-based or polymer having a structure containing A method for producing an electric double layer capacitor, comprising a step of filling a polymerizable monomer-containing material containing at least one kind of tacryloyl compound and at least one electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material. .

[35] In the method for producing an electric double layer capacitor, two polarizable electrodes and a porous support are laminated in arbitrary order as a capacitor structure structure to form a capacitor structure structure.
An electrode in which the support is laminated and sandwiched between a number of polarizable electrodes /
The step of forming the porous support / electrode laminate, and the general formula (1) or the general formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _{x (CH (CH 3)) y} ] z NHCOO- R 2 - (1) (. the symbols in the formula [3] the ^{_{same) CH 2 = C (R 1}} ) CO [O (CH 2) x (CH ( _{CH 3)) y] z NHCOO} (R 3 O) n - (2) ( at least acryloyl or methacryloyl compound symbols in the formula have a structure containing a unit represented by the same) and the [4]. From the film according to the above [1] to [12], which comprises a step of filling a polymerizable monomer-containing material containing one and at least one electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material. With a separator Method for manufacturing air double layer capacitor.

[36] In the method for manufacturing an electric double layer capacitor, at least one of the two polarizable electrodes is previously provided with
Formula (1) or general formula _{(2) CH 2 = C (} R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO- R 2 - (1) ( symbols in the formula same as the above _{[3]) CH 2 = C} (R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO (R 3 O) n -. (2) ( in the formula The symbol is the same as the above [4].) A step of impregnating and / or coating a polymerizable monomer-containing material containing at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above Two polarizable electrodes and the above [1] to [1
2] a step of forming an electrode / separator / electrode laminate in which a separator is laminated and sandwiched between two polarizable electrodes as a structure for constructing an electric double layer capacitor, using the separator composed of the film described in 2) above; A method for producing an electric double layer capacitor, comprising a step of polymerizing a substance containing a hydrophilic monomer.

[37] The polymerizable monomer-containing material is represented by the general formula (1) or the general formula (2): CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z ^{NHCOO- R 2 - (1) (} . the symbols in the formula as defined above _{[3]) CH 2 = C} (R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO ( R ³ O) _n − (2) (the symbols in the formula are the same as those in the above [4]) and at least one acryloyl or methacryloyl compound having a structure containing a unit is essential and at least one electrolyte is essential. The method for producing an electric double layer capacitor according to the above [36], which is a polymerizable monomer-containing substance contained as a component.

The present invention will be described in detail below, but in the description of the present specification, the expression "oxyalkylene" also includes oligooxyalkylene and polyoxyalkylene containing at least one oxyalkylene group. The expression “Li battery” also includes a Li ion battery.

The polymer as a constituent component of the separator film of the present invention is a crosslinked polymer having an oxyalkylene structure. Among them, a crosslinked polymer having a urethane bond and an oxyalkylene group is preferable because it is easy to process and has good film strength, and further, the above general formula (1) or (2)
In particular, a polymer of a polymerizable compound having a structure containing a unit (hereinafter, a polymerizable compound having the structure may be simply referred to as a monomer) has good film strength and is easy to form a film. preferable. A compound having a structure containing a unit represented by the general formula (1) or (2) is represented by CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH
₃ )) _y ] _z NCO and oligoalkylene glycol or oligoalkylene glycol and polyhydric alcohol can be obtained by reaction with polyhydric alcohol (in the formula, R ¹ , x, y and z are each a general formula). Same as formula (1).).

As a concrete method, the monomer having one ethylenically unsaturated group is, for example, a methacryloyl isocyanate compound (hereinafter abbreviated as MI) or an acryloyl isocyanate compound (hereinafter abbreviated as AI). It can be easily obtained by reacting a monoalkyl oligoalkylene glycol with a molar ratio of 1: 1. The monomer having two ethylenically unsaturated groups can be easily obtained by reacting MIs and / or AIs with oligoalkylene glycol at a molar ratio of 2: 1. Further, as the monomer having three ethylenically unsaturated groups, for example, MIs and / or AIs are reacted with a triol obtained by addition-polymerizing an alkylene oxide to a trihydric alcohol such as glycerin at a molar ratio of 3: 1. It can be easily obtained.

The monomer having four ethylenically unsaturated groups is, for example, MIs and / or AIs, and tetraol obtained by addition-polymerizing an alkylene oxide with a tetrahydric alcohol such as pentaerythritol in a ratio of 4: 1. It can be easily obtained by reacting in a molar ratio. Further, a monomer having five ethylenically unsaturated groups is, for example, MI
And / or AIs are easily obtained by reacting α-D-glucopyranose with an addition-polymerized alkylene oxide pentaol at a molar ratio of 5: 1. The monomer having six ethylenically unsaturated groups is obtained by reacting, for example, MIs and / or AIs with hexaol obtained by addition-polymerizing alkylene oxide with mannitol or sorbitol at a molar ratio of 6: 1. Can be easily obtained.

Similarly, as the polymerizable compound used for producing the polymer which is a constituent component of the separator film of the present invention, a compound having a structure containing a unit represented by the general formula (1) or (2) is used. Preference is given to using. The unit represented by the general formula (1) or (2) is 1
A polymer obtained by polymerizing only a compound containing only one compound has no cross-linking structure and lacks sufficient film strength. Therefore, when a thin film is used, there is a high risk of electrical short circuit. The compound containing only one unit represented by (2) should not be used alone. Therefore, for example, it is necessary to form a crosslinked structure by copolymerizing with a polymerizable compound having two or more units represented by the general formula (1) or (2) that is crosslinkable or another crosslinkable polymerizable compound. There is. In that case, the ratio of the compound containing only one unit represented by the general formula (1) or (2) to the total amount of polymerizable compounds is 0.5 to 99.5% by weight, and 1 to 80. A range of 5% by weight is preferable, and a range of 5 to 60% by weight is particularly preferable. However, when a compound having two or more units represented by the general formula (1) or (2) is contained as a copolymerization component, a compound containing only one unit may be omitted. Therefore, the ratio of the compound containing only one unit to the total amount of the polymerizable compounds can be expressed as 0 to 99.5% by weight. In the production of the separator film of the present invention, it is essential to use a crosslinkable polymerizable compound for polymerization or copolymerization. When the crosslinkable polymerizable compound to be used is a polymerizable compound having two or more units represented by the general formula (1) or (2) which are crosslinkable, the ratio thereof in the total amount of polymerizable compounds is 0.5. -100% by weight is preferable, 30-100% by weight is more preferable, and 50-100% by weight is particularly preferable. When the crosslinkable polymerizable compound used is a polymerizable compound other than the polymerizable compound having two or more crosslinkable units represented by the general formula (1) or (2), the total amount of the polymerizable compounds. As a ratio to 0.5 to 1
00% by weight is preferable, 0.5 to 80% by weight is more preferable, and 0.5 to 50% by weight is particularly preferable. Considering the thin film strength of the separator, the number of units represented by the general formula (1) or (2) contained in one molecule of the monomer is considered as the monomer of the polymer used as a constituent component of the separator film of the present invention. It is particularly preferred to include three or more monomers. Further, among the compounds having the structure containing the unit represented by the general formula (1), the compound having the structure containing the unit represented by the general formula (2) is the oxyalkylene content in the obtained polymer. Is more preferable and the film strength when formed into a thin film is large, so that the contained amount of the electrolytic solution or the electrolyte is large, which is particularly preferable.

The polymer preferable as a constituent component of the separator film of the present invention is obtained by polymerizing at least one compound having a structure containing a unit represented by the general formula (1) and / or the general formula (2), or It is obtained by polymerizing the compound as a copolymerization component. The polymer used for the separator film of the present invention belongs to the category even if it is a homopolymer of a compound having a structure containing a unit represented by the general formula (1) and / or the general formula (2). It may be a copolymer of two or more kinds, or a copolymer of at least one kind of the compound and another polymerizable compound.

As the other polymerizable compound used for copolymerization with the polymerizable compound (monomer) having a structure containing the unit represented by the general formula (1) and / or the general formula (2), There is no particular limitation as long as it is a compound that can be copolymerized with a compound having a structure containing a unit represented by (1) or (2), and a known monofunctional polymerizable compound or polyfunctional polymerizable compound can be used depending on the purpose. It can be appropriately selected and used accordingly. For example, copolymerizable monofunctional polymerizable compounds include acrylic (or methacrylic) esters having an oxyalkylene chain such as methacrylic acid ω-methyl oligooxyethyl ester, acrylic acid such as methyl methacrylate or n-butyl acrylate. (Or methacrylic acid) alkyl ester, acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, acryloylmorpholine, methacryloylmorpholine, or N, N-dimethylaminopropylacryl (or methacryl) amide Acrylic (or methacryl) amide compounds, styrene compounds such as styrene or α-methylstyrene, N-vinylamido such as N-vinylacetamide or N-vinylformamide Examples thereof include alkyl compounds such as a vinyl compound and ethyl vinyl ether. Of these, preferred are urethane acrylate (or methacrylate) having an oxyalkylene chain, acrylic (or methacrylic) ester having an oxyalkylene chain,
Alternatively, it is an acryl (or methacryl) amide compound.

Examples of the copolymerizable crosslinkable polyfunctional polymerizable compound include, for example, polyalkylene glycols having a molecular weight of 10,000 or less (for example, oligoethylene oxide, polyethylene oxide, oligopropylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer and the like). ) Diacrylate or dimethacrylate, linear, branched or cyclic alkylene glycol having 2 to 20 carbon atoms (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,4
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,7-heptanediol, 1,
8-octanediol, 1,9-nonanediol, 1,
10-decanediol, cyclohexane-1,4-diol) diacrylate or dimethacrylate, for example, a straight chain having three or more OH groups such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, glucose and mannitol, A polyfunctional acrylate or methacrylate compound in which two or more OH groups of a branched or cyclic polyhydric alcohol are replaced with an acryloyloxy group or a methacryloyloxy group (for example, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate ( TMPTM), pentaerythritol triacrylate (PETA), pentaerythritol trimethacrylate (PETM), dipentaerythritol hexaacrylate (DP A), dipentaerythritol hexamethacrylate (DPHM), etc.), a polyhydric alcohol having two or more OH groups replaced with acryloyloxy-oligo (or poly) ethyleneoxy (or propyleneoxy) groups and having a molecular weight of 20,000 or less. Functional acrylate compound, wherein two or more OH groups of the polyhydric alcohol have methacryloyloxy-oligo (or poly)
Aromatic urethane acrylate (or methacrylate) such as a polyfunctional methacrylate compound having a molecular weight of 20,000 or less substituted with an ethyleneoxy (or propyleneoxy) group, and a reaction product of tolylene diisocyanate and a hydroxyalkyl acrylate (or methacrylate) (for example, hydroxyethyl acrylate). ) Compounds, aliphatic diisocyanates such as hexamethylene diisocyanate and hydroxyalkyl acrylates (or methacrylates) (eg hydroxyethyl methacrylate)
Aliphatic urethane acrylate (or methacrylate) compounds such as reaction products with divinyl compounds such as divinylbenzene, divinyl ether, divinyl sulfone,
Examples thereof include diallyl compounds such as diallyl phthalate and diallyl carbonate.

Of these polyfunctional polymerizable compounds, the polymerizable functional group is an acryloyl group or an acryloyl group from the viewpoint of ion conductivity, strength, shapeability, etc. of the film for a separator of the present invention or the film used in the present invention. Those having a methacryloyl group and having a plurality of oxyalkylene structural units are preferable, and those having a urethane bond are particularly preferable.

In the production of the separator film of the present invention or the electrochemical device using the same, polymerization or copolymerization of a polymerizable compound (monomer) having a structure containing the unit represented by the general formula (1) or (2) is carried out. For the polymerization, a general method utilizing the polymerizability of the acryloyl group or methacryloyl group in the monomer can be adopted. That is, these monomers alone, or a mixture of these monomers and the other copolymerizable polymerizable compounds described above, is added to a radical polymerization catalyst such as azobisisobutyronitrile and benzoyl peroxide, a protic acid such as CF ₃ COOH or BF. ₃ or cationic polymerization catalyst such as a Lewis acid such as AlCl ₃ or butyl lithium, using an anionic polymerization catalyst such as sodium naphthalene, and lithium alkoxide radical polymerization, can be cationic polymerization or anionic polymerization. Further, the total content of the polymerizable compound having a structure containing the unit represented by the general formula (1) or (2) and the urethane acrylate (or methacrylate) having an oxyalkylene chain as one kind of the other polymerizable compounds. When the amount is more than 20% by weight based on the total weight of the polymerizable compound, the polymerization can be carried out by raising the temperature to 70 ° C. or higher under conditions close to oxygen-free conditions.

The polymer used in the separator film of the present invention is a polymer obtained from at least one polymerizable compound having a structure containing the unit represented by the general formula (1) or (2), and / or Alternatively, it may be a mixture or composite of a copolymer containing the compound as a copolymerization component and another polymer. For example, a polymer obtained from at least one polymerizable compound having a structure containing a unit represented by the general formula (1) or (2) and / or a copolymer containing the compound as a copolymerization component, and polyethylene. , Polypropylene, polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide copolymer, polyacrylonitrile, polybutadiene,
Electrochemically used as separator component of electrochemical device such as polymethacrylic (or acrylic) acid ester, polystyrene, polyphosphazenes, polysiloxane, polyvinylidene fluoride, polyvinylidene chloride, polyvinyl ethyl ether, or polymer such as polysilane. It is a stable polymer, and if it is a polymer that does not impair the function of the resulting separator and does not adversely affect the operation or performance of the electrochemical device such as ionic conductivity, any polymer such as thermoplastic resin or thermosetting resin can be used. You may use the mixture or composite with a coalescence in the film for separators of this invention.

In the case of a copolymer, the amount of the structural unit derived from the polymerizable compound having a structure containing the unit represented by the general formula (1) or (2) contained in the copolymer is
Depending on the type of other copolymerization component, polymer mixture, or composite component, if a urethane acrylate (or methacrylate) having an oxyalkylene chain as another polymerizable compound is not contained as a copolymerization component, it may be used in a battery or an electric battery. Considering the ionic conductivity and the membrane strength when used in an electrochemical device such as a multilayer capacitor, it is preferably 20% by weight or more, more preferably 50% by weight or more, based on the total amount of this copolymer.
When another urethane acrylate (or methacrylate) having an oxyalkylene chain is contained as a copolymerization component, the above general formula (1) or (2)
Although sufficient ionic conductivity and membrane strength can be obtained even if the content of the structural unit derived from the polymerizable compound having a structure containing the unit is reduced, it must be at least 0.5% by weight or more. It is preferably 2% by weight or more, and particularly preferably 5% by weight or more.

The amount of the copolymer having a polymerizable compound having a structure containing the unit represented by the general formula (1) or (2) as a copolymerization component is the total amount of the polymer used in the separator film. It is desirable to be 50% by weight or more. When the structural unit derived from the polymerizable compound having a structure containing the unit represented by the general formula (1) or (2) is within the specified amount range, the film strength of the polymer can be sufficiently expressed, Also, the ionic conductivity is large when used as a battery. The number of oxygen atoms contained in the oxyalkylene chain derived from the unit represented by the general formula (1) or (2) in the repeating monomer unit of the polymer used for the separator film of the present invention is 1 to 10
The range of 00 is preferable, the range of 2 to 500 is more preferable, and the range of 5 to 150 is particularly preferable. The molecular weight of the polymerizable compound having a structure containing the unit represented by the general formula (1) or (2) of the present invention is about 150 to 6000.
The range of 0 is preferable, the range of about 180 to 30,000 is more preferable, and the range of about 270 to 9000 is particularly preferable. Among these, the compound having a high molecular weight may have limited use depending on the purpose because of its high viscosity or solid and low crosslink density in the resulting polymer. When used in combination with these compounds, the problems can be solved and the compounds can be preferably used.

The monomer in the (co) polymer used in the separator film of the present invention has (a) x of 0 in the unit represented by the general formula (1) or (2).
Or 1, y is 0 or 1, z is 0 or 1 (where x =
In the case of 0 and z = 0 when y = 0, the corresponding isocyanate compound CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH
₃ )) _y ] _z NCO. This compound has high reactivity and can be easily reacted with various oxyalkylene compounds. In addition, the monomer obtained after the reaction is liquid and has a low viscosity, and there is an advantage that the reaction in a solvent system is easy.

On the other hand, in the monomer which is an essential component in the (co) polymer used in the separator film of the present invention, (b) x = 2-5, y = 0, z = 1-10, (c)
x = 1-5, y = 1-5 (random or alternating arrangement),
z = 1 to 10, or (d) x = 0, y = 1 to 5, z =
The monomer of 1 to 10 has low polymerizability, and therefore has good storage stability and good handleability as a monomer. Especially in the cases of (c) and (d), the presence of a large number of side chain methyl groups lowers the dielectric constant. It is a polymer that is not advantageous and is a very advantageous polymer for some applications. Therefore, by utilizing the characteristics of these monomers, by combining suitable monomers, or by combining with other polymerizable compounds or other polymers, a separator film suitable for use can be obtained.

In the case of producing the separator film of the present invention, the solvent, electrolyte or other polymerizable compound used in the electrolytic solution of the battery is added to the monomer in advance and polymerized to obtain the separator film of the present invention. It is also possible to preliminarily contain a solvent or an electrolyte therein, which is one of the preferred embodiments of the present invention. By doing this,
It is not always necessary to post-impregnate the electrolytic solution after the battery is assembled as it is currently done, which is advantageous in simplifying the battery assembling process and improving the yield. Any solvent and electrolyte can be used as long as they are solvents and electrolytes that can be used in the electrolytic solution used in the battery. Examples of such a solvent include oligoethers such as triethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, or diethyl carbonate, aromatic nitriles such as benzonitrile or tolunitrile, Examples thereof include nitrogen-containing solvents such as dimethylformamide, N-methylpyrrolidone or N-vinylpyrrolidone, sulfur-containing solvents such as dimethyl sulfoxide or sulfolane, and phosphoric acid esters. Of these, oligoethers or carbonates are preferable, and carbonates are particularly preferable.

As the electrolyte, LiCF ₃ SO ₃ or LiN is used.
(CF ₃ SO ₂ ) ₂ , LiPF ₆ , LiClO ₄ , Li
I, LiBF ₄ , LiSCN, LiAsF ₆ , NaCF
₃ SO ₃ , NaPF ₆ , NaClO ₄ , NaI, NaB
Alkali metal salts such as F ₄ , NaAsF ₆ , KCF ₃ SO ₃ , KPF ₆ , or KI, quaternary ammonium salts such as (CH ₃ ) ₄ NBF ₄ , or quaternary phosphonium salts such as (CH ₃ ) ₄ PBF _4. Etc.

The separator film according to the present invention is particularly preferably a thin film because of its intended use. To obtain such a thin film, the monomer-containing material is polymerized after being formed into a film-like shape. Alternatively, pressure molding polymerization is one of the particularly preferred embodiments.

That is, at least one polymerizable compound (monomer) having a structure containing a unit represented by the above-mentioned general formula (1) or (2) and, if necessary, an alkali metal salt, a quaternary ammonium salt, a quaternary salt. Mixing with at least one electrolyte such as a phosphonium salt, and optionally other polymerizable compounds and / or plasticizers and / or
Alternatively, in the presence or absence of the catalyst, the polymerizable monomer-containing material to which a solvent is added and mixed is extruded, calendered, pressed or the like after being formed into a film-like shape or during forming, for example, by heating. And / or irradiation with electromagnetic waves such as visible light and ultraviolet rays to polymerize them to form a film-like polymer expands the degree of freedom in terms of processing, which is a great advantage in application.

When a solvent is used, the type of monomer,
Depending on the presence or absence of other polymerizable compounds, and the presence or absence of a polymerization catalyst, any solvent may be used as long as it does not inhibit the polymerization, for example, tetrahydrofuran, acetonitrile,
Toluene, dimethyl carbonate, ethanol, or a mixture of two or more of these may be used. The temperature for the polymerization depends on the kind of the monomer and the presence or absence of other polymerizable compounds, but it may be any temperature at which the polymerization occurs, and it is usually carried out in the range of 0 ° C to 200 ° C. In the case of polymerizing by irradiation with electromagnetic waves, it depends on the kind of the monomer and the presence or absence of other polymerizable compounds, but for example, an initiator such as benzyl methyl ketal, benzophenone or the like is used, and ultraviolet light or γ rays of several mW or more is used. Etc. can be irradiated to polymerize.

The separator of the present invention may be a composite film with another support. By doing so, the strength of the film can be further increased, or the film thickness can be accurately controlled. Depending on the type and amount of the composite support, the ionic conductivity after absorption of the electrolytic solution may be deteriorated and the stability may be deteriorated. Therefore, it is necessary to select a suitable one.
In addition, when the composite film is compounded so that the pores capable of containing the electrolytic solution or the ionic species are appropriately present, the electrolytic solution absorbing liquid fills the pores with the electrolytic solution or the ionic species, The electrolytic solution or the ionic species is dispersed and held in the film, and the ionic conductivity and the ionic mobility can be increased without impairing the strength of the film and the separator. As the composite support, it is possible to use a plate, a grid, a sintered body, a granular shape, a film-like shape or the like according to the purpose. In particular, the porous support is used in terms of ionic conductivity and the like. It is more preferably used in the film and separator of the present invention. Further, when the support is used when the separator used in the electrochemical device is desired to be a thin film, for example, in order to reduce the ratio of the separator amount occupied in the electrochemical device as much as possible, the support is in a film form or uniform. Granules of various sizes are particularly preferable. In such a case, a composite film or separator having excellent flexibility and flexibility and good thickness accuracy can be obtained by combining a film-like or granular support, and by using this, performance and stability can be improved. It can be a good electrochemical device.

Examples of the membranous support include porous polyolefin sheets such as polypropylene non-woven fabric and reticulated polyolefin sheet such as polyethylene net, polyolefin micro-porous film such as Celgard (trade name of Celanese Co.) and nylon non-woven fabric. Examples of the non-conductive film-like support or ion-conductive film-like support are mentioned above, and among them, the porous polyolefin sheet is particularly preferable from the viewpoint of stability and the like.

The shape and size of the pores of the membrane-like support are not particularly limited as long as they can be impregnated or filled with the polymerizable monomer-containing material and / or the electrolyte-containing liquid. To give an example of the shape of the pores, the lattice or mesh space of the lattice-like or mesh-like support, or the shape when it is usually expressed as porous, for example, at least the support formed on the surface or inside of the support, Examples of the space include a concave shape, a bag shape, or a tunnel shape that communicates with the outside world of the body. Among the membrane-like support having pores of such size and shape, the strength of the separator film to be formed, as long as the function as a separator film such as processability is not impaired, and also of a separator containing an electrolyte. As long as the ionic conductivity is suitable for the purpose of use, it is better that the size of the pores is larger. If it is expressed by the size of the sieve, 500 mesh (AST
Those larger than M) are particularly preferable, and those having 300 mesh or more are even more preferable.

The porosity of the membranous support is from 10 to 90.
%, But it is preferable that the porosity be as large as possible as long as the strength allows, and the preferable porosity range is 20 to 90%. The range of porosity is particularly preferably in the range of 30 to 80%.

The compounding method is not particularly limited. For example, at least one polymerizable compound (monomer) having a structure containing a unit represented by the general formula (1) or (2), or at least one of them For example, a method of polymerizing such a monomer after impregnating a mixture obtained by adding an electrolyte and / or a solvent, and optionally other polymerizable compound into a membranous membrane-like support can be uniformly compounded, and the film thickness can be controlled. It is simple and particularly preferable.

Examples of the granular support include polystyrene / divinylbenzene copolymer gel, various non-conductive polymers such as polyethylene and polypropylene, or ion conductive polymer fillers, and ion-conductive materials such as α-, β- or γ-alumina and silica. Examples of the filler include conductive or non-conductive ceramic fillers. From the viewpoint of increasing the strength of the composite film, increasing the amount of electrolyte retained, etc., the support is porous or a structure such as secondary particles in which primary particles are aggregated, fibrous, reticulated or three-dimensional reticulated structure. Those having an aggregate structure having pores inside are particularly preferable. Specific examples of the support having such a structure include silica particles such as Aerosil (trade name, manufactured by Nippon Aerosil Co., Ltd.), alumina particles, various fibers, and aggregate structures thereof. Alumina particles are particularly preferable in terms of stability and easiness of compounding.

As a typical example of the electrochemical device of the present invention,
There are batteries and electric double layer capacitors, but when the battery of the present invention is produced using the separator film of the present invention, the electrolyte is pre-impregnated and used by impregnating an appropriate amount of electrolytic solution in advance during film production. It may be used after impregnating an electrolyte with an appropriate amount of electrolyte after the film is produced, and the film of the present invention is difficult for the electrolyte to seep out of the film, resulting in ion conduction as a film. The degree is also good. Furthermore, by combining such an ion conductive separator of the present invention with a positive electrode and a negative electrode which are compounded with a polymer solid electrolyte, there is no leakage, the reliability is high, and the shape of the solid Li secondary battery is flexible. You can get a battery.

A composite obtained by using a homogeneous support having a size as large as possible, such as a rod-shaped material or a spherical material (collectively referred to as a granular material in the present invention) used as a spacer in a liquid crystal display device as a support. Since the thickness accuracy of the separator composed of the film and the composite film can be increased, a homogeneous support having such a size is extremely preferably used in the film for separator and the separator of the present invention. It is needless to say that it is preferable to use a film-like or net-like support such as a non-woven fabric as a support as the support in order to obtain a composite film or separator having a uniform thickness and high thickness accuracy. However, by using such a granular material having an appropriate size, for example, a spherical, oval, cubical, rectangular parallelepiped, cylindrical or rod-shaped, or yarn-shaped support, strength and flexibility can be reduced in a smaller amount. It is possible to obtain a homogeneous film or separator excellent in flexibility and ion conductivity.

The thickness of the film or separator in the thickness direction of the film or separator in which the continuous layer is formed in the composite film or separator in the direction parallel to the film or separator surface is not more than the thickness of the film or separator. Any material may be used, and it may be appropriately selected and determined according to the purpose. Further, the size of the support (the above-mentioned particulate matter) other than the film-like or net-like form, which does not form a continuous layer, can be mixed with the polymerizable monomer-containing material and / or the electrolyte-containing liquid, and the obtained composite film or separator There is no particular limitation as long as the strength, processability, shape and other functions of the separator are not impaired, and the ion conductivity of the separator containing the electrolyte is suitable for the intended purpose. For example, when the target to be used is a thin film or a separator, the size is 0.01 μm to 10 μm.
It is preferably 0 μm, and 0.01 μm to 30 μm
Is more preferable. In the present invention, the "size" of the support means the size of the support existing in the composite film or separator in the direction perpendicular to the film or separator surface, that is, in the thickness direction of the film or separator. The above-mentioned granular material which is a support having a shape forming a discontinuous layer, for example, in the case of a spherical "size" is a particle diameter, a cylinder,
In the case of a rod or a prism, it is the height (cross-sectional diameter) when the longitudinal direction is placed horizontally, and in the case of a hexahedron, a polyhedron, or a yarn ball, it is the maximum height. For example, in the case of a columnar granular material (usually also called a fiber spacer) obtained by cutting a non-alkali glass having a diameter of 9 μm to a length of 50 μm, the height is 9 μm.

As a homogeneous support granular material having a composite size for increasing the thickness accuracy of the composite film and the separator composed of the composite film, the electrochemical characteristics, stability, safety, etc. of the target electrochemical device can be used. Any material such as an organic material or an inorganic material may be used as long as it does not adversely affect the surface. For example, a granular material used as a spacer in a liquid crystal display device is an example of a suitable support, and more specifically Examples thereof include inorganic particles such as silica, alumina and alkali-free glass, and organic particles such as melamine resin, urea resin, acrylic resin, polystyrene / divinylbenzene copolymer gel, polyethylene and polypropylene. Among such particles,
Spherical and cylindrical or rod-shaped materials are particularly preferable for uniform dispersion in the solid electrolyte layer between the electrodes.

According to the present invention, a separator of an electrochemical device having a uniform thickness in the range of 1 μm to 110 μm can be obtained. The term “homogeneous thickness” as used herein means a thickness of 1 μm to
It is a specific value within the range of 110 μm, and the variation is within ± 10%. For example, when the film thickness is 10 μm, the variation in film thickness is within ± 1.0 μm.

In the present invention, the thickness is 1 μm to 110 μm.
As the granular support used in combination to obtain a separator for an electrochemical device having a uniform thickness in the range of m, a support having a uniform size in the range of 1 μm to 100 μm is used. Here, for "homogeneous size",
The "size" is as described above, and the "homogeneous" means that the size (for example, the particle size in the case of a spherical shape) of the granular support has the following variations. That is, the size is 1 μm to 10
It is a specific value within the range of 0 μm, and its variation is ±
It is within 10%, for example, the size is 10 μm
In the case of the granular support (1), it means that the variation is within ± 1.0 μm. In the present invention, the thickness is 1 μm to 110
As a granular support used in combination to obtain a separator for an electrochemical device having a uniform thickness in the range of μm, the size may be in the range of 1 μm to 100 μm and its variation may be in the above range. However, it is more preferable that the variation is within ± 7%.

The separator of the electrochemical device of the present invention preferably has a thickness in the range of 1 μm to 110 μm in view of the characteristics of the electrochemical device, and more preferably in the range of 1 μm to 50 μm. In the case of a device such as a double-layer capacitor, the range of 1 μm to 30 μm is particularly preferable.

In the present invention, when it is intended to increase the ionic conductivity and ionic mobility by increasing the amount of the electrolyte or ionic species retained in the composite film in which the granular support is composited, the granular film used is used. The specific surface area of the support is preferably as large as possible, and the value measured by the BET method is preferably 10 m ² / g or more, and more preferably 50 m ² / g or more in order to improve the ion conductivity and the ion mobility.

Examples of the negative electrode active material used in the battery of the present invention include alkali metals, alkali metal alloys, and
By using a material with a low redox potential that uses an alkali metal ion as a carrier, such as a carbon material, a high voltage,
It is preferable because a high capacity battery can be obtained. Therefore, an alkali metal salt is required as an electrolyte in the case of using such a negative electrode and using it in a battery using an alkali metal ion as a carrier.

The types of the alkali metal salts include, for example, LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ and L.
iPF ₆ , LiClO ₄ , LiI, LiBF ₄ , Li
SCN, LiAsF ₆ , NaCF ₃ SO ₃ , NaPF
₆ , NaClO ₄ , NaI, NaBF ₄ , NaAsF
₆ , KCF ₃ SO ₃ , KPF ₆ , KI and the like can be mentioned. Among them, the use of lithium or a lithium alloy as the alkali metal is the most preferable because it has a high voltage, a high capacity, and can be formed into a thin film. In the case of a carbon material negative electrode, not only alkali metal ions but also quaternary ammonium salts, quaternary phosphonium salts, transition metal salts, and various protonic acids can be used.

In the structure of the battery of the present invention, an electrode active material (negative electrode active material) having a low oxidation-reduction potential which uses an alkali metal ion such as an alkali metal, an alkali metal alloy, a carbon material or a conductive polymer as a carrier for the negative electrode. The use of is preferable because a high voltage and high capacity battery can be obtained. Among such electrode active materials, lithium metal or lithium alloys such as lithium / aluminum alloy, lithium / lead alloy, and lithium / antimony alloy are particularly preferable because they have the lowest redox potential. Also, the carbon material is Li
Occlusion of ions is particularly preferred in that it has a low oxidation-reduction potential and is stable and safe. Examples of the carbon material capable of occluding and releasing Li ions include natural graphite, artificial graphite, pyrolytic carbon synthesized by a vapor phase method and its graphitized product, petroleum coke, coal coke, pitch-based carbon, polyacene, C ₆₀ , C _{70, and the} like. Fullerenes and the like can be mentioned.

In the structure of the battery of the present invention, by using an electrode active material (positive electrode active material) having a high redox potential such as a metal oxide, a metal sulfide, a conductive polymer or a carbon material for the positive electrode, This is preferable because a battery having a high voltage and a high capacity can be obtained. Among such electrode active materials, the packing density is high, and the volume capacity density is high.
Metal sulfides such as titanium sulfide and vanadium sulfide are preferable, and manganese oxide, nickel oxide, cobalt oxide and the like are particularly preferable in terms of high capacity and high voltage.

The method for producing the metal oxide or the metal sulfide in this case is not particularly limited, and examples thereof include "electrochemistry, second method".
Volume 2, page 574, 1954 ”, manufactured by a general electrolytic method or heating method. In addition, when these are used in a lithium battery as an electrode active material, for example, Li _x CoO ₂ or Li is used at the time of manufacturing the battery.
_It is preferable to use the Li element in the form of _x MnO ₂ or the like inserted (composite) into a metal oxide or a metal sulfide.
The method of inserting the Li element in this way is not particularly limited,
For example, a method of electrochemically inserting Li ions, or L as described in US Pat. No. 4,357,215.
It can be carried out by mixing a salt such as i ₂ CO ₃ and a metal oxide and heating the mixture.

In addition, in terms of flexibility and easy thinning,
A conductive polymer is preferable as the positive electrode active material. Examples of the conductive polymer include polyaniline, polyacetylene and its derivatives, polyparaphenylene and its derivatives, polypyrrolylene and its derivatives, polythienylene and its derivatives, polypyridinediyl and its derivatives, polyisothianaphthenylene and its derivatives, and polyfurylene. And derivatives thereof, polyselenophene and derivatives thereof, polyparaphenylene vinylene, polythienylene vinylene, polyfurylene vinylene, polynaphthenylene vinylene, polyselenophene vinylene, polyarylene vinylene such as polypyridinediyl vinylene, and derivatives thereof. Is mentioned.
Among them, a polymer of an aniline derivative soluble in an organic solvent is particularly preferable. The conductive polymer used as an electrode active material in these batteries or electrodes is manufactured according to a chemical or electrochemical method described later or other known methods.

Examples of the carbon material include natural graphite, artificial graphite, vapor grown graphite, petroleum coke, coal coke, fluorinated graphite, pitch carbon and polyacene. Further, as the carbon material used as the electrode active material in the battery or the electrode of the present invention, a commercially available carbon material can be used, or it is manufactured according to a known method.

When an organic solvent-soluble aniline polymer is used as the positive electrode active material in the electrode or battery of the present invention, the molding can be performed by solution coating, which is particularly advantageous. It is extremely advantageous. Examples of the aniline-based polymer include polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-
Anisidine, poly-m-anisidine, polyxylidines, poly-2,5-dimethoxyaniline, poly-2,6
-Dimethoxyaniline, poly-2,5-diethoxyaniline, poly-2,6-diethoxyaniline, poly-o-
Examples thereof include ethoxyaniline, poly-m-ethoxyaniline and copolymers thereof, but the invention is not particularly limited thereto, and any polymer having a repeating unit derived from an aniline derivative may be used. In addition, the introduction amount of the side chain in the organic solvent-soluble aniline-based polymer is more convenient in terms of solubility as the amount is larger, but as the introduction amount increases, the capacity per weight as the positive electrode decreases. A surface appears. Therefore, preferred aniline-based polymers include, for example, polyaniline, poly-o-toluidine, poly-m-toluidine, poly-o-anisidine, poly-m-anisidine, and polyxylidines.

The polymerization method of the aniline polymer used in the present invention is not particularly limited, but generally, for example, "Journal of Chemical Society, Chemical Communication, page 1784 (1
987) "and the like, aniline, o-
Examples thereof include a method of electrochemically or chemically oxidizing and oxidizing an aniline derivative such as anisidine.

The electrochemical oxidative polymerization is carried out by anodic oxidation, and the current density is about 0.01 to 50 mA / cm ² , and the electrolysis voltage is 0.1 to 30 V. Any method can be used.
The pH of the electrolytic solution is not particularly limited, but preferably p
H is 3 or less, particularly preferably 2 or less. Specific examples of the acid used for pH adjustment include HCl, HBF ₄ , CF ₃
Strong acids such as COOH, H ₂ SO ₄ , HNO ₃ , and paratoluenesulfonic acid can be mentioned, but the acid is not particularly limited thereto. In the case of chemical oxidative polymerization, for example, the aniline derivative can be oxidatively polymerized in an acidic solution with an oxidizing agent such as peroxide or persulfate. As the acid used in this case, the same acid as that used in the electrochemical oxidative polymerization can be used, but the acid is not limited thereto.

The molecular weight of the aniline polymer used in the present invention obtained by such a method is not particularly limited, but it is usually preferably 2000 or more. The aniline-based polymer obtained by such a method is generally obtained in a state where the anion in the polymerization solution is contained as a dopant, which is disadvantageous in terms of solubility and capacity per weight. Therefore, by, for example, a film forming method, dedoping these anions before forming the electrode,
The reduced form is preferred. The dedoping method is not particularly limited, but a method of treating with a base such as aqueous ammonia or sodium hydroxide is generally used. The reduction method is not particularly limited, and general chemical or electrochemical reduction may be performed. For example, regarding the chemical reduction method, the aniline-based polymer treated with a base in a hydrazine or phenylhydrazine solution can be easily reduced by immersion or stirring at room temperature.

The dedoped or reduced aniline polymer thus obtained is soluble in various organic solvents, and in solution, it can be dissolved in the above-mentioned general formula (1) and / or (2).
Can be mixed with a polymerizable monomer-containing material containing at least one kind of a polymerizable compound having a unit represented by various support materials such as an electrode by the coating method and the like. Forming a thin film on the top,
Alternatively, the electrode can be manufactured by molding into another shape.

The solvent in which the aniline-based polymer is dissolved depends on the kind of the substituent on the benzene ring, and is not particularly limited. Pyrrolidones such as N-methylpyrrolidone, amides such as dimethylformamide, and m- Examples include polar solvents such as cresol and dimethylpropyleneurea.

Next, an example of the method for manufacturing the battery of the present invention will be described in detail. The battery manufacturing method of the present invention includes a positive electrode as a battery structure structure, and [1] to [1] above.
2] A step of forming a positive electrode / separator / negative electrode laminate by laminating a separator and a negative electrode made of the film described above in any order to sandwich the separator between the positive electrode and the negative electrode to form a positive electrode / separator / negative electrode laminate. A polymerizable monomer-containing substance containing at least one acryloyl-based or methacryloyl-based compound having a structure containing the unit represented by the general formula (1) or the general formula (2) and at least one electrolyte as essential constituents in the body. There is a method for manufacturing a battery, which includes a step of satisfying the condition and a step of polymerizing the polymerizable monomer-containing material.

Further, as a method of manufacturing the battery of the present invention,
At least one of the positive electrode and the negative electrode is previously provided with the above [1] to [1.
[2] A positive electrode / separator in which a separator is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure, using a positive electrode / separator laminate and / or a negative electrode / separator laminate in which a separator made of the film described in 2] above is laminated. / A method for producing a battery, including a step of forming a negative electrode laminate, and a step of filling a liquid material containing at least one electrolyte as an essential component in a battery constituent structure having such a constitution. .

As another method for manufacturing the battery of the present invention, the above [1] to
Using the positive electrode / separator laminate and / or the negative electrode / separator laminate in which the separator comprising the film described in [12] is laminated, a positive electrode in which a separator is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure / A step of forming a separator / negative electrode laminate, and an acryloyl-based or methacryloyl-based compound having a structure including the unit represented by the general formula (1) or the general formula (2) in the battery structure having such a structure. A method for producing a battery is characterized by including a step of filling a polymerizable monomer-containing material containing at least one kind and at least one electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material.

Furthermore, as another method for producing the battery of the present invention, a positive electrode / porous support laminate in which a porous support is laminated on at least one of a positive electrode and a negative electrode and / or a negative electrode / porous support A step of forming a positive electrode / porous support / negative electrode laminate in which a porous support is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure using the laminate, and a battery structure having such a configuration In the structure, the general formula (1)
Alternatively, a step of filling a polymerizable monomer-containing material containing at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the general formula (2) and at least one electrolyte as essential constituents, and containing a polymerizable monomer A method for producing a battery having a separator made of the film according to the above [1] to [12], which comprises a step of polymerizing a product.

Further, as another method for producing the battery of the present invention, an acryloyl system having a structure containing a unit represented by the general formula (1) or the general formula (2) in at least one of the positive electrode and the negative electrode in advance. Alternatively, a step of impregnating and / or coating a polymerizable monomer-containing material containing at least one kind of methacryloyl compound or further at least one kind of electrolyte as an essential constituent component, from the positive electrode, the negative electrode and the film described in [1] to [12] above. Positive electrode / separator / wherein a separator is laminated and sandwiched between a positive electrode and a negative electrode as a structure for battery construction using
A method for producing a battery is characterized by including a step of forming a negative electrode laminate and a step of polymerizing the polymerizable monomer-containing material.

In the above-mentioned method for producing a battery of the present invention, "filling the structure for battery structure having such a structure ..." Means that the polymerizable monomer-containing material or the liquid is contained inside the structure. To fill the space into which the substance can substantially infiltrate them as much as possible and to coat the surface of the structure with the polymerizable monomer-containing material or the liquid substance, that is, inside the structure and / or It is not limited to impregnating and / or coating the surface with the polymerizable monomer-containing material or the liquid material, and the battery structure structure may be other structure for battery structure, for example, a cylindrical battery, a coin battery, Configure the outer surface of a battery, such as a sheet-type battery, or such outer surface that is present when placed within the structure to be configured, such as in a cylinder for a cylindrical battery configuration ( Should) also encompass satisfies the polymerizable monomer-containing material or as much as possible the liquid material in the space between the structure and the battery-constituting structure.

The positive electrode, the negative electrode, or the separator of the present invention used in the method for producing a battery of the present invention is not particularly limited to those prepared by being formed on a support.
Since it is more preferable to use a sheet or film type for battery production, it is preferable that the positive electrode, the negative electrode or the separator of the present invention is formed in a sheet shape or a film shape on a support made of a different material. The separator of the present invention is a support other than a current collector and an electrode forming a part of the battery structure, for example, an organic polymer support such as polyethylene terephthalate and polytetrafluoroethylene, an inorganic support such as glass. Formed on a body and then processed into a desired shape and then separated from the support for use, or separated from the support and processed into a desired shape for use in manufacturing the battery of the present invention You can

Alternatively, the separator of the present invention is manufactured by manufacturing the battery of the present invention by forming an electrode forming a part of the battery constituting structure as a support, and forming it on the electrode, and processing it into a desired shape if necessary. Can also be used for. Similarly, the electrode used in the production of the battery of the present invention is formed on a support other than the current collector and the electrode forming a part of the battery structure,
It can be processed into a desired shape before or after being separated from the support and used in the production of the battery of the present invention, or an electrode on a support such as a current collector which forms a part of the structure for constructing a battery. Without separating from the support,
If necessary, it can be processed into a desired shape and used for producing the battery of the present invention.

The positive electrode or the negative electrode used in the various methods for producing the battery of the present invention is a positive electrode / current collector laminate or negative electrode in which the current collector used in the construction of the battery is previously laminated with the positive electrode or the negative electrode. / A current collector laminate may be used, and it is more preferable to use such a laminate in the manufacturing process. Further, at least one of the positive electrode, the negative electrode, the porous support, and the separator used in the method for producing a battery of the present invention has an acryloyl-based structure having a unit previously represented by the general formula (1) or (2). Alternatively, a polymerizable monomer-containing material containing at least one of a methacryloyl-based polymerizable compound (monomer) as an essential constituent or a polymerizable monomer-containing material containing the monomer and at least one electrolyte as an essential constituent is impregnated and / or It may be coated. Thus, by using at least one of the electrode, the porous support or the separator coated with the polymerizable monomer-containing material and then used in the production of the battery, the adhesion between the positive electrode, the separator and the negative electrode in the produced battery is improved. improves. In the case where the positive electrode, the negative electrode or the separator before impregnation / coating has pores, or the porous support is preliminarily impregnated with the polymerizable monomer-containing material as described above, Monomers and / or electrolytes can be present even in the pores.

From these facts, the polymerizable monomer-containing substance was previously impregnated in the electrode, the porous support or the separator /
By coating and forming a structure for battery construction, and then polymerizing, the adhesion between the constituent elements of the positive electrode / separator / negative electrode or the current collector / positive electrode / separator / negative electrode / current collector becomes extremely good, This is one of the extremely preferable methods because it is possible to improve the capacity density, current density, cycle characteristics, etc. of the manufactured battery. In the above-described method for producing a battery according to the present invention, when the structure for battery construction is impregnated with and / or coated with the polymerizable monomer-containing material, the polymerizable monomer-containing material is added in the following formula to the general formula (1 ) And / or (2) a polymer obtained from at least one kind of a polymerizable compound having a unit and / or the same polymerization method as described above in the case of obtaining a copolymer having the compound as a copolymerization component. Polymerization by a method, for example, by heating and / or electromagnetic wave irradiation, or after the polymerization, if necessary, the unsealed portion of the battery-constituting structure is made of an insulating material such as a polyolefin resin or an epoxy resin. A battery in which the electrode and the electrolyte are in good contact with each other can be obtained through steps such as sealing with a resin.

The constituent material of the outer surface of the battery or the support may be a metal such as stainless steel (SUS), a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass. The material is not particularly limited to those made of these materials, and the shape may be any shape such as a tubular shape, a box shape, a sheet shape and the like.

The current collector is not particularly limited as long as it is a material that is electronically conductive and electrochemically stable, but it is preferable to use a material having a large specific surface area as much as possible. For example, various metals such as stainless steel, aluminum and copper and their sintered bodies, electron conductive polymers, carbon sheets, graphite materials and the like can be mentioned. When forming a laminate using a porous support, it is possible to use, as the porous support, the porous support shown in the separator of the present invention composed of a composite film with the porous support. .

FIG. 1 shows a schematic cross-sectional view of an example of a thin film solid secondary battery as an example of the battery manufactured in this way. In the figure, 1 is a positive electrode, 2 is a separator of the present invention, 3 is a negative electrode, 4 is a current collector, and 5 is an insulating resin sealant (cured product). In the case of manufacturing a wound type battery, the positive electrode and the negative electrode are laminated and wound in advance by interposing the separator film of the present invention, or the positive electrode / separator / negative electrode are laminated simultaneously with the winding. By forming a laminate, inserting the laminate into a cylindrical battery structure structure, and then further injecting an electrolyte solution, or in addition to the electrolyte solution, a unit represented by the general formula (1) or (2) is added. A method of injecting and polymerizing the polymerizable monomer-containing material in which the polymerizable compound or the plasticizer is mixed is also possible.

When a battery is formed by using the separator made of the film of the present invention, an arbitrary outer edge portion of the surface of at least one of the positive electrode and the negative electrode facing the separator (the end portion of the electrode on the surface). The positive electrode / separator / negative electrode laminate structure is configured by disposing a spacer such as an insulating protective plate, a protective frame or a protective ring having a surface area of 40% or less, preferably 10% or less of the surface area on the (part). You may. By adopting such a configuration, the battery of the present invention can achieve proper and uniform distance between the positive electrode and the negative electrode, or short circuit or deterioration of battery performance due to mechanical stress concentration on the outer edge of the electrode which may occur during assembly. It can be prevented and the reliability of the battery is improved.
Therefore, this structure is one of the preferred embodiments in the battery and the method for manufacturing the battery of the present invention. The spacer used is not particularly limited as long as it is an insulating material, and may be an organic or inorganic material, but from the aspects of battery stability and operating characteristics, it is made of polyimide, polyolefin such as polyethylene, polypropylene, etc. Polymer materials of are preferred. 2 and 3 are schematic cross-sectional views of an example of a thin film solid secondary battery as an example of the battery manufactured in this manner. 2 or 3, 1 is a positive electrode, 2 is a separator of the present invention, 3 is a negative electrode, 4 is a current collector, 5 is an insulating resin sealant (cured product), 6 is a protective frame (spacer), 7 Is a separator.

In the method for producing the battery of the present invention, at least one of the positive electrode and the negative electrode is impregnated and / or coated with the above-mentioned polymerizable monomer-containing material in advance, and the separator film of the present invention is used as the separator. An insulating spacer is arranged on at least one of the outer edges of the surface facing the separator, and (current collector /)
A positive electrode (for example, with a spacer) / separator / (negative electrode with a spacer) / (collector) laminate is formed, one end of the laminate is left, and the remaining end is sealed with an insulating resin,
In some cases, a method of producing a battery by further injecting a polymerizable monomer-containing material or an electrolyte-containing liquid and then polymerizing the polymerizable monomer-containing material, and then sealing the unsealed end portion with an insulating resin is particularly preferable. It is mentioned as one of the preferred embodiments.

As another method for producing the battery of the present invention, the monomer, the electrolyte used in the electrolytic solution of the battery, the solvent, A mixture of another polymerizable compound and / or a granular support serving as a spacer is injected, and the positive electrode /
The mixture / negative electrode laminate is polymerized by the same method as described above while applying an appropriate pressure from the outside to the above [1] to
A method for producing a battery having a separator composed of the film described in [12] can be mentioned. In this method, the inter-electrode distance of the obtained battery can be controlled to a desired distance by previously disposing the frame-shaped spacer or the film-shaped support having a desired thickness between the positive electrode and the negative electrode. It is desirable, but not limited to the case where the granular support is used for controlling the distance between the electrodes and the mixture is used by including the granular support, as described above using the mixture including the granular support. The method of manufacturing a battery by using the above method is one of the extremely preferable methods.

Next, the electric double layer capacitor of the present invention will be described. In the electric double layer capacitor of the present invention,
By using the separator of the present invention, an electric double layer capacitor having a high output voltage, a large extraction current, or excellent workability and reliability, particularly an all-solid-state electric double layer capacitor is provided. A schematic sectional view of an example of the electric double layer capacitor of the present invention is shown in FIG. In this example, a thin cell having a size of 1 cm × 1 cm and a thickness of about 0.5 mm, 9 is a current collector, and a pair of polarizable electrodes 8 are arranged inside the current collector, and a main electrode is provided between them. The inventive separator 10 is arranged. Reference numeral 11 is an insulating resin sealant (cured product), and 12 is a lead wire.

The current collector 9 is not particularly limited as long as it is a material having electronic conductivity and electrochemical stability, but it is preferable to use a material having a large specific surface area as much as possible. For example, stainless steel, various metals and their sintered bodies, electron conductive polymers, carbon sheets, graphite materials and the like can be mentioned. The polarizable electrode 8 may be an electrode made of a polarizable material such as a carbon material normally used in electric double layer capacitors, and such a carbon material is combined with a polymer similar to the constituent component of the separator of the present invention. Those are preferable. The carbon material as the polarizable material is not particularly limited as long as it has a large specific surface area. For example, carbon blacks such as furnace black, thermal black (including acetylene black), channel black,
Examples thereof include activated carbon such as coconut charcoal, natural graphite, artificial graphite, so-called pyrolytic carbon produced by a vapor phase method and its graphitized product, polyacene and fullerenes such as C ₆₀ and C ₇₀ .

The type of the electrolyte used for the composite in the case of the electric double layer capacitor of the present invention is not particularly limited, and a compound containing an ion to be used as a charge carrier may be used, but a polymer solid electrolyte to be formed. Alternatively, it is desirable to contain ions that have a large dissociation constant in the electrolytic solution and that easily form a polarizable electrode and an electric double layer. Examples of such compounds include (CH ₃ ) ₄ NBF ₄ and (CH ₃ C
H ₂ ) ₄ NClO _{4 and} other quaternary ammonium salts, AgCl
Transition metal salts such as O _4, quaternary phosphonium salts such as (CH ₃ ) ₄ PBF ₄ , LiCF ₃ SO ₃ , LiPF ₆ , LiC
lO ₄ , LiI, LiBF ₄ , LiSCN, LiAsF
₆ , NaCF ₃ SO ₃ , NaPF ₆ , NaClO ₄ , N
aI, NaBF ₄ , NaAsF ₆ , KCF ₃ SO ₃ , K
Examples thereof include alkali metal salts such as PF ₆ and KI, organic acids and salts thereof such as paratoluenesulfonic acid, and inorganic acids such as hydrochloric acid and sulfuric acid. Among these, a quaternary ammonium salt, a quaternary phosphonium salt, and an alkali metal salt are preferable from the viewpoints of high output voltage and large dissociation constant. Among the quaternary ammonium salts, (CH ₃ CH ₂ ) (CH ₃ CH ₂ CH
Such as ₂ CH _{2) 3} NBF _4, which is a substituent on the nitrogen of the ammonium ion are different, preferably in that solubility or dissociation constant of a polymer solid electrolyte or electrolytic solution is large is formed .

Next, an example of a method for manufacturing the electric double layer capacitor of the present invention will be described. In the method for manufacturing an electric double layer capacitor of the present invention, two polarizable electrodes and a separator made of the film described in [1] to [12] above are laminated in arbitrary order as a capacitor structure structure to form two sheets. A step of forming an electrode / separator / electrode laminate by laminating and sandwiching a separator between polarizable electrodes, and filling a liquid substance containing at least one electrolyte as an essential component in a capacitor structure structure having such a configuration. An electric double layer capacitor manufacturing method is characterized by including steps.

In the method for manufacturing an electric double layer capacitor of the present invention, two polarizable electrodes and a separator made of the film described in the above [1] to [12] are laminated in any order as a capacitor constituting structure. And forming a electrode / separator / electrode laminate by sandwiching and sandwiching a separator between two polarizable electrodes, and the general formula (1)
Alternatively, a step of filling a polymerizable monomer-containing material containing at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the general formula (2) and at least one electrolyte as essential constituents, and containing a polymerizable monomer A method for producing an electric double layer capacitor is characterized by including a step of polymerizing a substance.

Furthermore, in the method of manufacturing an electric double layer capacitor of the present invention, the capacitor structure structure is 2
Laminating a polarizable electrode and a porous support respectively in any order and sandwiching the support between two polarizable electrodes to form an electrode / porous support / electrode laminate,
At least one electrolyte and at least one electrolyte of an acryloyl-based or methacryloyl-based compound having a structure including the unit represented by the general formula (1) or the general formula (2) in a capacitor structure having such a configuration is an essential constituent component. Of an electric double layer capacitor having a separator made of the film according to the above [1] to [12], characterized in that it has a step of filling the polymerizable monomer content contained therein and a step of polymerizing the polymerizable monomer content. There is a method.

Furthermore, in the method for manufacturing an electric double layer capacitor of the present invention, a structure including a unit represented by the general formula (1) or general formula (2) in advance in at least one of the two polarizable electrodes. A step of impregnating and / or coating a polymerizable monomer-containing material containing at least one kind of an acryloyl-based or methacryloyl-based compound or further containing at least one electrolyte as an essential constituent, two polarizable electrodes and the above [1] to A step of forming an electrode / separator / electrode laminate in which a separator is laminated and sandwiched between two polarizable electrodes as a structure for constructing an electric double layer capacitor, using the separator comprising the film according to [12]; and A method for producing an electric double layer capacitor, comprising a step of polymerizing a polymerizable monomer-containing material And the like.

In the above-described method for manufacturing a capacitor of the present invention, "in the capacitor structure structure having such a structure ...
"... fill the object" means inside the structure,
To fill the polymerizable monomer-containing material or the liquid material in a space into which the liquid material can substantially infiltrate as much as possible and to coat the surface of the structure with the polymerizable monomer-containing material or the liquid material, That is, the inside and / or the surface of the structure is not limited to impregnating and / or coating the polymerizable monomer-containing material or the liquid material, and the structure for forming a capacitor may be a structure for another structure for forming a capacitor, The outer surface of a capacitor such as a cylindrical capacitor, a coin-type capacitor, or a sheet-type capacitor, which constitutes the outer surface of the capacitor, or which is present in the structure to be constructed, for example, in the cylinder for forming the cylindrical capacitor, constitutes such outer surface. The polymerizable monomer-containing substance or the Also it encompasses satisfying Jo product as possible.

In the method of manufacturing the capacitor of the present invention,
The polarizable electrode used, or the separator of the present invention, is not particularly limited to those formed by forming it on a support, but it is more preferable to use it as a sheet or film type for the production of a capacitor, and therefore, it is preferable. An electrode or the separator of the present invention is formed in a sheet shape or a film shape on supports made of different materials. The separator of the present invention is a support other than the current collector and the electrode forming a part of the structure for capacitor construction,
For example, polyethylene terephthalate, organic polymer-based support such as polytetrafluoroethylene, formed on an inorganic support such as glass, then processed into a desired shape and then used by separating from the support, After being separated from the support, it can be processed into a desired shape and used for manufacturing the capacitor of the present invention.

Alternatively, the separator of the present invention is manufactured by forming an electrode forming a part of the structure for constructing a capacitor as a support on the separator and processing it into a desired shape if necessary. Can also be used for. Similarly, the polarizable electrode used for manufacturing the capacitor of the present invention is formed on a support other than the current collector and the electrode forming a part of the structure for constructing the capacitor, and before or after separation from the support. It can be processed into a desired shape and used in the production of the capacitor of the present invention, or it is separated from the support by forming an electrode on a support that forms a part of the structure for constructing the capacitor, for example, a current collector. Without performing, it can be processed into a desired shape as needed and used for manufacturing the capacitor of the present invention.

The polarizable electrode used in the various methods of manufacturing the capacitor of the present invention may be an electrode / collector laminate in which the collector used for the constitution of the capacitor is laminated in advance on the electrode. Good, it is more preferable to use such a laminate in the manufacturing process. Further, at least one of the polarizable electrode, the porous support, and the separator used in the method for producing a capacitor of the present invention has an acryloyl system having a structure containing a unit represented by the general formula (1) or (2) in advance. Alternatively, a polymerizable monomer-containing material containing at least one methacryloyl compound (monomer) as an essential constituent or a polymerizable monomer-containing material containing the monomer and at least one electrolyte as an essential constituent impregnated and / or coated. May be As described above, by coating at least one of the electrode, the porous support and the separator with the polymerizable monomer-containing material and then used in the production of the capacitor, the adhesion between the electrode-separator in the produced capacitor is improved. . Further, in the case where pores exist in the electrode or separator before impregnation / coating, or the porous support is preliminarily impregnated with the polymerizable monomer-containing material in this manner, pores in the electrode or separator are The monomer and / or electrolyte can be present up to.

From the above, the polymerizable monomer-containing material was previously impregnated in the electrode, the porous support or the separator.
By coating and forming a structure for constructing a capacitor and then polymerizing, the adhesion between each component of electrode / separator / electrode or collector / electrode / separator / electrode / collector becomes extremely good, This is one of the most preferable methods because it is possible to improve the capacitance density, current density, cycle characteristics, etc. of the produced capacitor. In the method for producing a capacitor according to the present invention described above, when the structure for constructing a capacitor is impregnated and / or coated with the polymerizable monomer-containing material, the polymerizable monomer-containing material is added in the following formula to the general formula (1 ) And / or (2) a polymer obtained from at least one kind of a polymerizable compound having a unit and / or the same polymerization method as described above in the case of obtaining a copolymer having the compound as a copolymerization component. Polymerization by a method, for example, polymerization by heating and / or electromagnetic wave irradiation, or further, after polymerization, the unsealed portion of the structure for constructing the capacitor may be an insulating resin such as a polyolefin resin or an epoxy resin. By sealing with, a capacitor in which the electrode and the electrolyte are in good contact can be obtained.

When a capacitor is formed by using the separator made of the film of the present invention, an arbitrary outer edge portion of the surface of at least one of the polarizable electrodes facing the separator (the end portion of the electrode on the surface). The electrode / separator / electrode laminate structure is constituted by disposing a spacer such as an insulating protective plate, a protective frame or a protective ring having a surface area of 40% or less, preferably 10% or less of the surface area of the electrode / separator / electrode laminate. You may. By adopting such a configuration, the capacitor of the present invention can properly and homogenize the distance between the polarizable electrodes of the two sheets, or a short circuit or a capacitor due to mechanical stress concentration on the outer edge of the electrode which may occur during assembly. Performance deterioration can be prevented and the reliability of the capacitor is improved. Therefore, such a configuration is one of the preferable embodiments in the method for manufacturing a thin electric double layer capacitor.

For example, as a method for manufacturing a thin all-solid-state electric double layer capacitor such as a sheet type among the electric double layer capacitors of the present invention, at least one of the two polarizable electrodes contains the polymerizable monomer in advance. The separator film of the present invention is used as a separator, and an insulating spacer is disposed on any outer edge portion of the surface facing the separator of at least one of the two electrodes. Electric body /) electrode (with spacer)
/ Separator / electrode (may have spacer) (/
Current collector) forming a laminate, leaving one end of the laminate and sealing the remaining end with an insulating resin, and in some cases further pouring a polymerizable monomer-containing liquid or electrolyte-containing liquid before polymerization One of the preferred embodiments is a method of polymerizing a polymerizable monomer-containing material and then sealing an unsealed end portion with an insulating resin to manufacture a capacitor. The spacer used is not particularly limited as long as it is an insulating material, and may be an organic or inorganic material, but from the viewpoint of stability and operating characteristics of the capacitor, it is made of polyimide, polyolefin such as polyethylene, polypropylene, etc. Polymer materials of are preferred.

As another method of manufacturing the electric double layer capacitor of the present invention, the monomer, the electrolyte, the solvent, the electrolyte, the solvent, and the like are provided between the two electrodes in the capacitor constituting structure in which the two polarizable electrodes are temporarily arranged. Polymerization is carried out in the same manner as above while injecting a mixture in which another polymerizable compound and / or a granular support serving as a spacer is mixed and applying an appropriate pressure from the outside to the laminated surface of the electrode / the mixture / electrode laminate. Then, a method for producing an electric double layer capacitor having a separator made of the film according to the above [1] to [12] can be mentioned. In this method, it is possible to control the distance between electrodes of the obtained capacitor to a desired distance by previously disposing the frame-shaped spacer or the film-shaped support having a desired thickness between the two electrodes. However, this is not the case when the particulate support is used for controlling the distance between the electrodes so as to include the particulate support in the mixture. The method of manufacturing an electric double layer capacitor in this manner is one of the extremely preferable methods.

A polarizable material such as a carbon material and at least one polymerizable compound having a unit represented by the general formula (1) and / or (2), which are preferably used in the electric double layer capacitor of the present invention, are obtained. In the case of producing a polarizable electrode containing a polymer and / or a copolymer containing the compound as a copolymerization component, first, for example, a unit having a unit represented by the general formula (1) and / or (2) is included. At least one kind of the polymerizable compound (monomer) is added to the polarizable material by further adding another polymerizable compound and / or a plasticizer as the case may be. In that case, the ratio of the components to be mixed is determined to be more appropriate for the intended capacitor. The polymerizable compound / polarizable material mixture thus obtained is formed into a film on a support, for example, a current collector, and then has a unit represented by the general formula (1) and / or (2). Polymerization is carried out in the same manner as in the case of obtaining a polymer obtained from at least one polymerizable compound and / or a copolymer having the compound as a copolymerization component, for example, by heating and / or electromagnetic wave irradiation. Thus, a polarizable electrode is manufactured. According to this law,
It is possible to manufacture a composite membrane electrode that is in good contact with the current collector, and
In particular, thin film electrodes can be obtained.

According to the above-mentioned production method of the present invention, for example,
The separator of the present invention is laminated and sandwiched between the two polarizable electrodes thus produced to form an electrode / separator / electrode laminate, and then the monomer and the electrolyte are mixed in the laminate, Depending on the case, after further impregnating the polymerizable monomer-containing material prepared by adding and mixing other polymerizable compound and / or plasticizer, polymerization is carried out by the same method as described above, or further, after polymerization, if necessary. Accordingly, by sealing the unsealed portion of the capacitor structure structure with an insulating resin such as polyolefin resin or epoxy resin, an electric double layer capacitor in which the electrodes and the electrolyte are in good contact can be obtained. When preparing such a monomer mixture, the ratio of each component to be mixed should be appropriate for the intended condenser. The constituent material of the outer surface of the capacitor or the support may be a metal such as SUS, a resin such as polypropylene or polyimide, or a ceramic material such as conductive or insulating glass, but especially from these materials. The shape is not limited to the above, and the shape may be any shape such as a tubular shape, a box shape, and a sheet shape.

As the shape of the electric double layer capacitor, in addition to the sheet type as shown in FIG. 4, a spacer having a constant thickness is provided at the end portion between the polarizable electrodes, and a separator film having the same thickness is sandwiched therebetween. In addition, a coin-shaped or sheet-shaped laminate of a polarizable electrode and the separator of the present invention is rolled into a cylindrical shape, put into a cylindrical tubular capacitor-constituting structure, and manufactured by sealing. It may be a cylindrical type or the like. In the case of manufacturing a wound-type capacitor, the polarizable electrodes are laminated to each other via a separator sheet prepared in advance, and then laminated or wound, or simultaneously laminated and laminated to form an electrode / separator / electrode. It is also possible to use a method in which a laminated body is formed, and after the laminated body is inserted into a cylindrical structure for forming a capacitor, the polymerizable monomer-containing material is further injected to polymerize.

[0118]

The function of the separator film of the electrochemical device of the present invention is that it has both a function as a separator having no electronic conductivity and a function as a polymer solid electrolyte having excellent ionic conductivity. As mentioned above, it is easy to form a film from the monomer that is the raw material,
A crosslinkable polymer having an oxyalkylene group or a crosslinked polymer having an oxyalkylene group bonded to a urethane bond, which can be combined, is a constituent component, and is easy to process.
It is homogeneous, has a high ability to absorb electrolytes or retain electrolytes, has good membrane strength, and is low cost and highly reliable. Further, by combining the separator film of the electrochemical device of the present invention and the polymer solid electrolyte, the separator of the electrochemical device of the present invention has an excellent liquid absorbing ability, and a battery or capacitor having no leakage can be obtained. To be

The battery of the present invention comprises a separator comprising an ion conductive polymer or copolymer of a polymerizable compound having a structure containing the unit represented by the general formula (1) or (2) as a constituent. By using it, it is easy to process such as thinning, there is no fear of short circuit even with thin film, the current for extraction is large, and the reliability is high. In particular, it can be an all-solid-state battery. Further, the battery of the present invention, in which the negative electrode comprises an electrode containing an active material such as lithium or a lithium alloy or a carbon material capable of inserting and extracting lithium ions, is a separator containing the ion conductive polymer or copolymer as a constituent component. By using, the thin film can be easily processed, the short circuit does not occur even in the thin film, the extraction current is large, and the reliability is high. In particular, the solid-state battery can be obtained.

A polymer obtained by using the film for a separator of the present invention as a separator, the positive electrode of which is obtained from at least one polymerizable compound having a unit represented by the general formula (1) and / or (2), And / or an electrode containing a copolymer containing the compound as a copolymerization component and an organic solvent-soluble aniline polymer or other conductive polymer, a metal oxide, a metal sulfide, or an active material such as a carbon material, The battery of the present invention, which is characterized by using a polymer solid electrolyte having the polymer or copolymer as a component as an electrolyte, is easy to process such as thin film formation,
Even with a thin film, there is no danger of short-circuiting, the current is large, the capacity is high, and the battery is highly reliable. In particular, an all-solid-state battery can be obtained.

According to the battery manufacturing method of the present invention,
It is possible to manufacture batteries of various shapes, in particular, it is easy to make the battery thin, and it is possible to manufacture batteries with high capacity, high current operation, or excellent cycleability and excellent reliability, In particular, all-solid-state batteries can be manufactured.

The electric double layer capacitor of the present invention is a highly reliable electric double layer capacitor that has no short circuit even in a thin film, has a large output voltage and a large extraction current, and can be an all-solid-state electric double layer capacitor. . In particular, according to the electric double layer capacitor and the method of manufacturing the same of the present invention,
Good contact between the polarizable electrode and the ion conductive separator or electrolyte or electrolytic solution, no short circuit even in thin film, large output voltage and extraction current, and a highly reliable electric double layer capacitor are provided. In particular, the use of the polymer solid electrolyte and the separator of the present invention provides an all-solid-state electric double layer capacitor.

In particular, in addition to forming an electrode / separator / electrode laminate (which may include a current collector or a spacer as described above) using the separator of the present invention having the above characteristics, the polymerization Of the present invention, which comprises a step of filling the laminate (battery or structure for constructing an electric double layer capacitor) with a polymerizable monomer content and polymerizing the polymerizable monomer content. The manufacturing method of (1) has an advantage that a battery or an electric double layer capacitor excellent in the above-mentioned characteristics can be manufactured.

[0124]

The present invention will be described more specifically with reference to representative examples. Needless to say, these are merely examples for description and the present invention is not limited to these. It should be noted that, in the following examples, a portion expressed as "placement" is not limited to spatially showing a vertical relationship, and the placed one and the placed one are arranged in contact with each other. It may be in a state. Further, each step in the production of the battery, capacitor or its structural structure of the following examples, unless otherwise specified, was carried out in an argon atmosphere glove box, the present invention is not limited thereto. The film of the present invention,
The present invention can be carried out even under other atmospheres that do not hinder the production of batteries or capacitors.

[Example 1]

Embedded image <Synthesis of Compound 3> 57.7 g of Compound 1 (KOH value 34.0 m
g / g, m / n = 4) and 3.89 g of compound 2 (methacryloyl isocyanate) were dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and then 0.44 g of dibutyltin dilaurate was added. Then, a colorless viscous liquid was obtained by reacting at 25 ° C. for about 15 hours. Part ¹ H-NM
From the results of R, IR and elemental analysis, compound 1 and compound 2 are 1
It was found that the reaction was carried out with respect to 3 (molar ratio), the isocyanate group of the compound 2 disappeared, a urethane bond was formed, and the compound 3 was formed. Under argon atmosphere, 1.50 g of compound 3 was added to 0.01 g of 2-hydroxy-2-
Methyl-1-phenyl-propan-1-one (trade name Darocure 1173: manufactured by Ciba Geigy) was added and mixed well. 10 cm of this mixture (containing polymerizable monomer)
After coating on a square polyethylene terephthalate film (PET film), a mercury lamp was irradiated for 10 minutes, and a transparent self-supporting film having a thickness of about 20 μm containing a polymer of compound 3 as a constituent component was obtained on the PET film. It was This film is used as an electrolyte (1.5 mol / l LiBF ₄ / E
When immersed in C (ethylene carbonate) + DEC (diethyl carbonate) (weight ratio 1: 1) for about 1 hour, this film absorbed about 2.5 times (weight) of the electrolytic solution. The ionic conductivity of the film after absorbing the liquid at 25 ° C. was measured by the impedance method to be 1 × 10 ⁻³ S / cm.
Met. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

Example 2 1.50 g of compound 3, 1.5 g of diethyl carbonate (DEC), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ and 0.02 g of Darocur 1173 in an argon atmosphere. The mixture was mixed well to obtain a polymerizable monomer-containing material. This polymerizable monomer-containing material was applied onto a 10 cm square PET film in an argon atmosphere, and then irradiated with a mercury lamp for 10 minutes.
A transparent self-supporting film having a thickness of about 50 μm and having a polymer of compound 3 impregnated with an electrolytic solution on the film as a constituent component was obtained. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 2 × 10 ⁻³ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

[Example 3]

Embedded image <Synthesis of Compound 6> 38.5 g of Compound 4 (KOH value 22.7 m
g / g, m / n = 5), 2.42 g of compound 5 (methacryloyloxyethyl isocyanate) was dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and then 0.29 g of dibutyltin dilaurate was added. Then, at 25 ℃, about 1
A colorless viscous liquid was obtained by reacting for 5 hours.
From the results of ¹ H-NMR, IR and elemental analysis, Compound 4 and Compound 5 reacted at a ratio of 1: 2 (molar ratio).
It was found that the isocyanate group of 1 disappeared, a urethane bond was formed, and Compound 6 was formed. 0.01 g of Darocur in 1.50 g of compound 6 under argon atmosphere
1173 was added and mixed well. After coating this mixture (polymerizable monomer-containing material) on a 10 cm square PET film,
Irradiation with a mercury lamp for 10 minutes revealed that the thickness of the compound 6 polymer as a constituent component was about 20 μm on the PET film.
A transparent free-standing film of m 2 was obtained. An electrolyte solution (1.5 mol / l of LiBF ₄ / EC (ethylene carbonate) + DEC (diethyl carbonate) (weight ratio 1:
When immersed in 1)) for about 1 hour, this film absorbed about 3.0 times (by weight) the electrolytic solution. The ionic conductivity of the film after absorbing the liquid at 25 ° C. was measured by an impedance method and found to be 1.2 × 10 ⁻³ S / cm. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

Example 4 LiBF ₄ used in Example 2
Instead of using 0.40 g of NaCF ₃ SO ₃ , a transparent self-supporting film having a thickness of about 50 μm and containing a polymer of compound 3 impregnated with an electrolyte as a constituent component was obtained in the same manner as in Example 2. . The ionic conductivity of this film measured at 25 ° C. by an impedance method was 2 × 10 ⁻³ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

[Embodiment 5] <Synthesis of Compound 8> 55 g of Compound 7 (average molecular weight Mn = 55
0), 11.1 g of compound 2 was dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and then 0.66 g of dibutyltin dilaurate was added. Then, a colorless viscous liquid was obtained by reacting at 25 ° C. for about 15 hours. Part ¹ H-NM
From the results of R, IR and elemental analysis, compound 7 and compound 2 are 1
It was found that the reaction was carried out with respect to 1 (molar ratio), the isocyanate group of the compound 2 disappeared, a urethane bond was formed, and the compound 8 was formed. 0.01 g of Darocur 11 was added to a mixture of 1.00 g of Compound 3 synthesized in Example 1 and 0.5 g of Compound 8 synthesized above under an argon atmosphere.
73 was added and mixed well. This mixture (polymerizable monomer-containing material) was applied on a PET film of 10 cm square and then irradiated with a mercury lamp for 10 minutes to find that the thickness of the PET film including the copolymer of compound 3 and compound 8 as a constituent component was increased. A transparent self-supporting film of about 20 μm was obtained. This film is treated with electrolyte (1.5 mol / l LiBF ₄ / EC (ethylene carbonate) + DEC (diethyl carbonate)
(Weight ratio 1: 1)), the film absorbed about 2.5 times (weight) electrolyte solution.
The ion conductivity at 25 ° C. of the film after the liquid absorption was measured by the impedance method and found to be 1.5 × 10 ⁻³ S / cm. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

Example 6 1.00 g of compound 3, 0.5 g of compound 8 and 1.5 g of diethyl carbonate (DEC), 1.
5g ethylene carbonate (EC), 0.30g LiBF
₄ and 0.02 g of Darocur 1173 were mixed well in an argon atmosphere to obtain a polymerizable monomer-containing substance. This polymerizable monomer-containing material was applied onto a 10 cm square PET film in an argon atmosphere and then irradiated with a mercury lamp for 10 minutes to form a copolymer of compound 3 and compound 8 impregnated with an electrolytic solution on the PET film. The component thickness is about 5
A 0 μm transparent free-standing film was obtained. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 3 × 10 ⁻³ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

[Embodiment 7]

Embedded image <Synthesis of Compound 10> 57.7 g of Compound 9 (KOH value 68.
0 mg / g, m / n = 6), 10.86 g of compound 5 was dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and then 0.44 g
Of dibutyltin dilaurate was added. Then 25
A colorless viscous liquid was obtained by reacting at 15 ° C. for about 15 hours. From the results of ¹ H-NMR, IR and elemental analysis, Compound 9 and Compound 5 reacted at a ratio of 1: 6 (molar ratio), and
It was found that the isocyanate group of Compound 5 disappeared, a urethane bond was formed, and Compound 10 was formed. Under an argon atmosphere, 0.01 g of Darocur 1173 was added to 1.50 g of Compound 10 and mixed well. After coating this mixture (polymerizable monomer-containing material) on a 10 cm square PET film, it was irradiated with a mercury lamp for 10 minutes.
A transparent self-supporting film having a thickness of about 20 μm and containing the polymer of Compound 10 as a constituent component was obtained on the PET film.
This film is used as an electrolyte (1.5 mol / l LiBF ₄ / EC
When immersed in (ethylene carbonate) + DEC (diethyl carbonate) (weight ratio 1: 1) for about 1 hour, this film absorbed about 3.0 times (weight) electrolyte. The ionic conductivity of the film after absorbing the liquid at 25 ° C. was measured by the impedance method to be 1 × 10 ⁻³ S / cm.
Met. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

[Embodiment 8]

Embedded image <Synthesis of Compound 12> 57.7 g of Compound 11 (KOH value 6
8.0 mg / g), 7.78 g of compound 2 was dissolved in 100 ml of well-purified THF in a nitrogen atmosphere, and then 0.44 g of dibutyltin dilaurate was added. Then, at 25 ° C, about 15
A colorless viscous liquid was obtained by reacting for a time. From the results of ¹ H-NMR, IR and elemental analysis, Compound 11 and Compound 2 reacted at a ratio of 1: 5 (molar ratio), and Compound 2
It was found that the isocyanate group of 1 disappeared, a urethane bond was formed, and Compound 12 was formed. 1.50
g of compound 12 and 1.5 g of diethyl carbonate (DE
C), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ and 0.02 g of Darocur 1173 were thoroughly mixed in an argon atmosphere to obtain a polymerizable monomer-containing substance.
This polymerizable monomer-containing material was treated with an argon atmosphere at 10c.
After coating on a m-square PET film, it was irradiated with a mercury lamp for 10 minutes, and the compound 12 polymer in which the electrolytic solution was impregnated on the PET film was used as a constituent component, and the thickness was about 50 μm.
A transparent free-standing film of m 2 was obtained. 2 of this film
When the ionic conductivity at 5 ° C. was measured by the impedance method, it was 1 × 10 ⁻³ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

Example 9 LiBF ₄ used in Example 2
In the same manner as in Example 2 except that 0.50 g of tetraethylammonium tetrafluoroborate (TEAB) was used, and a polymer of compound 3 containing an electrolytic solution was used as a constituent component and a thickness of about 50 μm. A transparent free-standing film was obtained. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 3 × 10 ⁻³ S / cm.
In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

[Example 10] LiBF used in Example 2
A transparent self-supporting film having a thickness of about 50 μm and containing a polymer of compound 3 containing an electrolytic solution as a constituent component was prepared in the same manner as in Example 2 except that 0.35 g of LiPF ₆ was used instead of _4. Obtained. The ionic conductivity of this film measured at 25 ° C. by an impedance method was 2 × 10 ⁻³ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

Example 11 1.50 g under argon atmosphere
0.01 g of Darocur 1173 was added to a mixture of the compound 3 of Example 1 and 0.2 g of N, N-dimethylacrylamide and mixed well. This mixture (polymerizable monomer-containing material) was applied on a 10 cm square PET film and then irradiated with a mercury lamp for 10 minutes. As a result, Compound 3 / N, N- was formed on the PET film.
A transparent self-supporting film having a thickness of about 20 μm and containing the dimethylacrylamide copolymer as a constituent was obtained. This film is treated with electrolyte (1.5 mol / l LiBF ₄ / EC (ethylene carbonate) + DEC (diethyl carbonate)
(Weight ratio 1: 1)), the film absorbed about 3.3 times (weight) of the electrolytic solution.
The ionic conductivity of the film after liquid absorption at 25 ° C. was measured by an impedance method and found to be 1.5 × 10 ⁻³ S / cm. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

[Example 12] 1.50 g under an argon atmosphere
Compound 3 and 0.2 g of polyethylene oxide PEO-
0.01 g of Darocur 1173 was added to the mixture of No. 1 (Sumitomo Seika Co., Ltd.) and mixed well. This mixture (polymerizable monomer-containing material) was applied on a 10 cm square PET film and then irradiated with a mercury lamp for 10 minutes, whereby Compound 3 polymer / polyethylene oxide P was applied on the PET film.
A transparent self-supporting film having a thickness of about 20 μm was obtained, which was composed of the EO-1 mixture. An electrolyte solution (1.5 mol / l of LiBF ₄ / EC (ethylene carbonate) + DEC (diethyl carbonate) (weight ratio 1:
When immersed in 1)) for about 1 hour, this film absorbed about 2.8 times (weight) electrolyte solution. The ion conductivity at 25 ° C. of the film after the liquid absorption was measured by the impedance method and found to be 0.8 × 10 ⁻³ S / cm. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

Example 13 0.50 g of compound 3, 1.00 g
Compound 8 from 1.5 g of diethyl carbonate (DE
C), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ and 0.02 g of Darocur 1173 were thoroughly mixed in an argon atmosphere to obtain a polymerizable monomer-containing substance.
This polymerizable monomer-containing material was treated with an argon atmosphere at 10c.
After impregnating and coating a polypropylene microporous film (Hexist, Duraguard 2500; porosity about 30%) of m square and thickness of about 25 μm, it was irradiated with a mercury lamp for 10 minutes. A composite film (thickness: 30 μm) with Duraguard containing the / Compound 8 copolymer as a constituent component was obtained. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 5 × 10 ⁻⁴ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

Example 14 1.50 g of compound 3, 1.5 g of diethyl carbonate (DEC), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ and 0.02 g of Darocur 1173 are mixed in an argon atmosphere. By mixing, a polymerizable monomer-containing material was obtained. After impregnating and coating this polymerizable monomer-containing material on a polypropylene non-woven fabric (porosity: about 60%) of 10 cm square and a thickness of about 50 μm in an argon atmosphere,
Irradiation with a mercury lamp for 10 minutes gave a composite film (thickness: 50 μm) with a polypropylene non-woven fabric containing a polymer of compound 3 impregnated with an electrolytic solution as a constituent.
When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 8 × 10 ⁻⁴ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

Example 15 1.50 g of compound 3, 1.5 g
Diethyl carbonate (DEC), 1.5 g ethylene carbonate (EC), 0.30 g LiBF ₄ and 0.02 g
Darocure 1173 of 1. was thoroughly mixed in an argon atmosphere to obtain a polymerizable monomer-containing substance. This polymerizable monomer-containing material was treated in an argon atmosphere in a 10 cm square and had a thickness of about 50 μ.
m polyethylene net (250 mesh) was impregnated and coated with a mercury lamp for 10 minutes, and a composite film with a polyethylene net containing a polymer of compound 3 impregnated with an electrolytic solution as a constituent (thickness: about 50 μm) )was gotten. When the ionic conductivity of this film at 25 ° C. was measured by the impedance method, it was 1.2 × 10 ⁻³ S / cm. In the following examples, when the film was used as a separator, the film was cut into a desired size and used.

Example 16 1.50 g under argon atmosphere
Compound 3 of 0.01 g of 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name Irgacure 651
: Ciba Geigy) was added and mixed well. This mixture (polymerizable monomer-containing material) was applied on a 10 cm square PET film and then irradiated with a mercury lamp for 10 minutes. As a result, a polymer of compound 3 was contained as a constituent on the PET film, and the thickness was about 20 μm. A transparent free-standing film was obtained. Electrolyte this film: 1.5 mol / l LiBF ₄ / E
When immersed in C (ethylene carbonate) + DEC (diethyl carbonate) (weight ratio 1/1) for about 1 hour, this film absorbed about 2.5 times (by weight) electrolyte solution. The ionic conductivity of the film after absorbing the liquid at 25 ° C. was measured by the impedance method to be 1 × 10 ⁻³ S / cm.
Met. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

Example 17 1.50 g of compound 3 and 1.5 g
Of diethyl carbonate (DEC), ethylene carbonate (EC) (1.5 g), 0.30 g of LiBF ₄ and 0.02 g of Irgacure 651 were mixed well in an argon atmosphere.
A polymerizable monomer-containing material was obtained. This polymerizable monomer-containing material was applied on a 10 cm square PET film in an argon atmosphere and then irradiated with a mercury lamp for 10 minutes.
It was obtained as a transparent self-supporting film having a thickness of about 50 μm and having a compound 3 polymer impregnated with an electrolytic solution on a T film as a constituent. The ionic conductivity of this film at 25 ° C was measured by the impedance method to be 2 × 10 ^-3 S / cm.
Met. In the following examples, when this film was used as a separator, the film after absorbing the liquid was cut into a desired size and used.

Example 18 Production of Lithium Cobaltate Positive Electrode 11 g of Li ₂ CO ₃ and 24 g of Co ₃ O ₄ were mixed well,
After heating at 800 ° C. for 24 hours in an oxygen atmosphere, pulverization was performed to obtain a LiCoO ₂ powder. This LiCoO ₂ powder was mixed with acetylene black and polyvinylidene fluoride at a weight ratio of 8: 1: 1, and 5 times by weight of N-methylpyrrolidone was added to the mixture to obtain a gel composition. About 50 μm thick stainless steel SUS316 foil (1
2mm x 12mm) 1mm width on the inside 10mm x 10m
m Polyimide molding spacer frame (thickness 200μ
m) and place this composition in the spacer frame for about 20 minutes.
It was applied and molded to a thickness of 0 μm. Further, by heating and vacuum drying at about 100 ° C. for 24 hours, a lithium cobalt oxide positive electrode (80 mg) adhered to the SUS foil was obtained. Example 1
Before using in 9, remove the spacer frame and stack the positive electrode / current collector (positive electrode 10 mm × 10 mm, current collector 12 mm ×
12 mm).

Example 19 Production of Li Secondary Battery A lithium foil having a thickness of 75 μm was cut into 10 mm × 10 mm (5.3 mg) in an argon atmosphere glove box.
50 μm thick SUS316 foil (12 mm x 12 mm)
A 10 mm × 10 mm square portion leaving 1 mm square on the outer edge of the surface was pressure-bonded to form a lithium (negative electrode) / current collector laminate (negative electrode 10 mm × 10 mm, current collector 12 mm × 12 mm). The separator film after absorbing the electrolyte solution prepared in 1 was cut into a size of 10 mm × 10 mm, and the separator was placed on a lithium foil to form a collector / negative electrode / separator laminate, and further on the separator surface,
An electrolyte solution (1.5 mol / l of LiBF ₄ / EC + DEC) was added to the lithium cobalt oxide positive electrode / current collector laminate prepared in Example 18.
The positive electrode surface of the impregnated (weight ratio 1: 1)) was placed to prepare a current collector / positive electrode / separator / negative electrode / current collector laminate. The end of this laminate was sealed with an epoxy resin to obtain a lithium / cobalt oxide-based solid secondary battery. FIG. 1 shows a cross-sectional view of the obtained battery. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.5 mA,
The maximum discharge capacity was 7.3 mAh, and the cycle life was 100 times until the capacity was reduced to 50%.

[Example 20] Production of graphite negative electrode MCMB graphite (manufactured by Osaka Gas Co., Ltd.), vapor grown graphite fiber (manufactured by Showa Denko KK: average fiber diameter, 0.3 µm, average fiber length, 2.0 µm, (2700 ° C. heat-treated product) and polyvinylidene fluoride in a weight ratio of 8.6: 0.4: 1.0 was added with 10 times the weight of N-methylpyrrolidone to obtain a gel composition. SU as in Example 18
On a S316 foil (12 mm × 12 mm, thickness about 50 μm), a polyimide molding spacer frame (thickness 250 μm) having a width of 1 mm and an inner dimension of 10 mm × 10 mm is arranged, and the composition is about 250 μm in the spacer frame. It was applied and molded to the thickness of. Further, by heating and vacuum drying at about 100 ° C. for 24 hours, a graphite negative electrode (30 mg) adhered to the SUS316 foil was obtained. Prior to use in Example 21, the spacer frame was removed and the negative electrode / current collector laminate (negative electrode 10 mm x 1
0 mm, current collector 12 mm × 12 mm).

Example 21 Production of Li-Ion Secondary Battery Instead of the lithium / current collector laminate, the graphite negative electrode / current collector laminate produced in Example 20 was replaced with an electrolyte solution (1.5 mol / l LiB).
A graphite / lithium cobalt oxide based solid Li-ion secondary battery was obtained in the same manner as in Example 19 except that the impregnated F ₄ / EC + DEC (weight ratio 1: 1) was used. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2V and a current of 0.5mA, the maximum discharge capacity was 7.3mAh and the capacity was 50%.
The cycle life until it decreased to 250 was 250 times.

Example 22 Production of solid Li secondary battery 0.50 g of compound 3, 1.00 g of compound 8, 1.5 g of diethyl carbonate (DEC), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ And 0.01 g of azobisisobutyronitrile (AIBN) were thoroughly mixed in an argon atmosphere to obtain a polymerizable monomer-containing material. In an argon atmosphere glove box, a 75 μm thick lithium foil was cut into 10 mm × 10 mm (5.3 mg) and the thickness was 50 μm.
m of SUS316 foil (12 mm x 12 mm), and a lithium (negative electrode) / current collector laminate (negative electrode 10 mm x)
10 mm, current collector 12 mm × 12 mm), and thin the polymerizable monomer-containing material (thickness 1 to 1) on the lithium foil.
2 μm), and then the separator film prepared in Example 1 after absorbing the electrolyte solution was cut into a size of 10 mm × 10 mm, and the separator was placed on a lithium foil coated with a monomer-containing material to collect a current. / Negative electrode / separator laminate, and the positive electrode surface of the lithium cobalt oxide positive electrode / current collector laminate produced in the same manner as in Example 18 by impregnating and coating the polymerizable monomer-containing material on the separator surface. It was placed and a current collector / positive electrode / separator / negative electrode / current collector laminate was prepared. This laminate is 3 at 80 ℃
After heating for 0 minutes to polymerize the polymerizable monomer-containing material, the end of the laminate was sealed with an epoxy resin to obtain a lithium / cobalt acid solid lithium secondary battery. This battery, operating voltage
When charge and discharge were repeated at 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 7.3 mAh, and the cycle life until the capacity decreased to 50% was 200 times.

Example 23 Production of Solid Li Secondary Battery Except that the lithium foil was not coated with the polymerizable monomer-containing material, the surface of the separator facing the lithium foil was lightly coated with the polymerizable monomer-containing material. A lithium / lithium cobaltate solid Li secondary battery was obtained in the same manner as in Example 22. This battery, operating voltage 2.0 ~ 4.2V, current
Repeated charging and discharging at 0.1mA, the maximum discharge capacity is 7.3m.
At Ah, the cycle life until the capacity is reduced to 50% is 2
It was 50 times.

Example 24 Production of Solid Li-Ion Secondary Battery Graphite negative electrode / current collector laminate produced in the same manner as in Example 20 instead of the lithium / current collector laminate coated with the polymerizable monomer-containing material. A graphite / lithium cobalt oxide-based solid Li-ion secondary battery was obtained in the same manner as in Example 22 except that the product obtained by impregnating and coating the polymerizable monomer-containing material prepared in the same manner as in Example 22 was used. . This battery, operating voltage
When charge and discharge were repeated at 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 7.3 mAh, and the cycle life until the capacity decreased to 50% was 380 times.

[Example 25] Production of solid Li-ion secondary battery The same as Example 23 except that the compound 3 polymer / polypropylene non-woven fabric composite film impregnated with the electrolytic solution produced in Example 14 was used as a separator. Thus, a graphite / lithium cobalt oxide-based solid Li-ion secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 6.8 mAh and the capacity was 50
The cycle life was 410 times before it was reduced to%.

[Example 26] Production of solid Li-ion secondary battery Graphite / cobalt was produced in the same manner as in Example 25 except that the compound 6 polymer film impregnated with the electrolytic solution produced in Example 3 was used as the separator. A lithium oxide solid Li-ion secondary battery was obtained. This battery, operating voltage 2.0 ~ 4.2V,
When charging and discharging were repeated at a current of 0.1 mA, the maximum discharge capacity was
At 6.6 mAh, the cycle life was 350 cycles until the capacity decreased to 50%.

Example 27 Production of Solid Li-Ion Secondary Battery Same as Example 25 except that the compound 3 / compound 8 copolymer film impregnated with the electrolytic solution produced in Example 5 was used as a separator. A graphite / lithium cobaltate solid Li-ion secondary battery was obtained. This battery, operating voltage
When charge and discharge were repeated at 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 7.3 mAh, and the cycle life until the capacity decreased to 50% was 300 times.

[Example 28] Production of solid Li-ion secondary battery Example 25 except that the compound 3 / N, N-dimethylacrylamide copolymer film impregnated with the electrolytic solution produced in Example 11 was used as a separator. A graphite / lithium cobalt oxide-based solid Li-ion secondary battery was obtained in the same manner as in. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 7.0 mAh, and the cycle life until the capacity decreased to 50% was 280 times.

Example 29 Production of Solid Li-Ion Secondary Battery Graphite negative electrode / current collector laminate (negative electrode 10 m, produced in the same manner as in Example 20 in an argon atmosphere glove box).
m × 10 mm, current collector 12 mm × 12 mm), the separator film cut into 10 mm × 10 mm of the separator film after absorbing the electrolytic solution prepared in Example 1 was placed on the surface of the negative electrode / separator / negative electrode / current collector. A body laminate,
Furthermore, a lithium cobalt oxide positive electrode / current collector laminate (12 manufactured in the same manner as in Example 18) was formed on the separator surface.
(mm × 12 mm) was placed to obtain a collector / positive electrode / separator / negative electrode / collector laminate. Then, only one end of the laminate was left and the remaining end was sealed with an epoxy resin. Then, the polymerizable monomer-containing material produced in the same manner as in Example 22 was evacuated from the unsealed end (up to 50 mm).
Hg) for 2 minutes and heated at 80 ° C. for 30 minutes to polymerize the polymerizable monomer-containing material, and then seal the unsealed end with an epoxy resin to obtain graphite / cobalt oxide-based solid Li.
An ion secondary battery was obtained. This battery, operating voltage 2.0 ~ 4.
When charge and discharge were repeated at 2 V and a current of 0.1 mA, the maximum discharge capacity was 7.0 mAh, and the cycle life until the capacity decreased to 50% was 400 times.

Example 30 Production of Solid Li-Ion Secondary Battery Graphite negative electrode / current collector laminate (negative electrode 10 m, produced in the same manner as in Example 20 in an argon atmosphere glove box).
m × 10 mm, current collector 12 mm × 12 mm), a polypropylene non-woven fabric (MU3005 made by Nippon Vilene) (10 mm × 10 mm) with a thickness of about 50 μm was placed on the negative electrode surface, and the non-woven fabric surface was further subjected to the same procedure as Example 18 The lithium cobalt oxide positive electrode / current collector laminate (positive electrode 10 mm × 10 mm, current collector 12 mm × 12 mm) manufactured as described above is placed, and the current collector / positive electrode / porous support / negative electrode / current collector laminate is placed. It was created. Only one end of this laminate was left and the remaining end was sealed with an epoxy resin. Then, the polymerizable monomer-containing material produced in the same manner as in Example 22 was injected from the unsealed end portion under reduced pressure (up to 50 mmHg) over 2 minutes, and heated at 80 ° C. for 30 minutes to contain the polymerizable monomer. After polymerizing the product, the unsealed end was sealed with an epoxy resin to obtain a graphite / cobalt oxide-based solid Li-ion secondary battery. This battery, operating voltage 2.0 ~ 4.2 V, current 0.1 mA
Repeated charging and discharging at, the maximum discharge capacity 6.3 mAh
And the cycle life until the capacity is reduced to 50% is 42
It was 0 times.

Example 31 Production of Solid Li-Ion Secondary Battery Graphite negative electrode / current collector laminate (negative electrode 10 m, produced in the same manner as in Example 20 in an argon atmosphere glove box).
The outer edge portion of 1 mm square on the surface of the negative electrode (m × 10 mm, current collector 12 mm × 12 mm) was covered with a polyimide film spacer of 5 μm. Next, the separator film prepared in Example 1 after absorbing the electrolytic solution was 10 mm × 10
The separator cut out into mm was placed so as to cover the spacer on the graphite negative electrode surface to obtain a current collector / negative electrode / spacer / separator laminate. On the surface of the separator side, a lithium cobalt oxide positive electrode / current collector laminate (positive electrode 10 mm × 10 mm, manufactured in the same manner as in Example 18).
The positive electrode surface of the current collector (12 mm × 12 mm) was placed to prepare a current collector / negative electrode / spacer / separator / positive electrode / current collector laminate. Then, only one end of the laminate was left and the remaining end was sealed with an epoxy resin. Then, the polymerizable monomer-containing material produced in the same manner as in Example 22 was injected from the unsealed end portion under reduced pressure (up to 50 mmHg) over 2 minutes, and heated at 80 ° C. for 30 minutes to contain the polymerizable monomer. After polymerizing the object, seal the unsealed end with epoxy resin,
A graphite / cobalt oxide-based solid Li-ion secondary battery was obtained.
A sectional view of the obtained battery is shown in FIG. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 6.7 mAh and the cycle life until the capacity decreased to 50% was 430 times.

Example 32 Production of Solid Li-Ion Secondary Battery Graphite negative electrode / collector laminate (negative electrode 10 m produced in the same manner as in Example 20 in an argon atmosphere glove box).
m × 10 mm, current collector 12 mm × 12 mm), and 1 mm square on the edge of the negative electrode surface was covered with a 50 μm polyimide film spacer. Next, a film for separator (thickness 50 μm) after absorbing the electrolytic solution prepared in Example 2
A separator cut into a size of 8 mm × 8 mm was placed in the spacer on the negative electrode surface of the graphite. Further, on the film and the spacer, a lithium cobalt oxide positive electrode / current collector laminate (positive electrode 10 mm × 1) manufactured in the same manner as in Example 18.
The positive electrode surface (0 mm, current collector 12 mm × 12 mm) was placed to prepare a current collector / negative electrode / spacer / separator / positive electrode / current collector laminate. Then, only one end of the laminate was left and the remaining end was sealed with an epoxy resin. Then, Example 2
The polymerizable monomer-containing material produced in the same manner as in 2 was injected from the unsealed end portion under reduced pressure (up to 50 mmHg) over 2 minutes and heated at 80 ° C. for 30 minutes to polymerize the polymerizable monomer-containing material. Then, the unsealed end was sealed with an epoxy resin to obtain a graphite / cobalt oxide-based solid Li-ion secondary battery shown in FIG. Operate the battery with an operating voltage of 2.0 to 4.2.
When charging and discharging were repeated at V and a current of 0.1 mA, the maximum discharge capacity was 5.9 mAh, and the cycle life until the capacity decreased to 50% was 480 times.

[Example 33] Production of lithium cobalt oxide positive electrode / separator laminate Performed on the positive electrode surface of the lithium cobalt oxide positive electrode / collector laminate produced in the same manner as in Example 18 in an argon atmosphere glove box. The polymerizable monomer-containing material prepared in Example 16 was applied in a thickness of 10 μm, and a film containing a polymer of compound 3 as a constituent was formed on the positive electrode surface by irradiating a mercury lamp for 10 minutes,
A current collector / lithium cobalt oxide positive electrode / separator laminate was prepared.

Example 34 Manufacture of Graphite Negative Electrode / Separator Film Laminate Example 16 was prepared on the negative electrode surface of the graphite negative electrode / collector laminate manufactured in the same manner as in Example 20 in an argon atmosphere glove box. A polymerizable monomer-containing material prepared in the same manner was applied to a thickness of 10 μm, and a mercury lamp was irradiated for 10 minutes to form a film containing a polymer of compound 3 as a constituent on the negative electrode surface as a separator. An electric body / graphite negative electrode / separator laminate was prepared.

Example 35 Production of Solid Li-Ion Secondary Battery Graphite negative electrode / collector laminate (negative electrode 10 m produced in the same manner as in Example 20 in an argon atmosphere glove box).
m × 10 mm, current collector 12 mm × 12 mm), the separator film after absorbing the electrolytic solution prepared in Example 1 cut into 10 mm × 10 mm separator was placed on the negative electrode surface to collect current / negative electrode / As a separator laminate,
On the surface of the separator side, the separator side surface of the current collector / lithium cobalt oxide positive electrode / separator laminate (positive electrode / separator 10 mm × 10 mm) produced in Example 33 was placed, and the current collector / negative electrode / separator / positive electrode was placed. / A current collector laminate. After that, only one end of the laminate was left and the remaining end was sealed with an epoxy resin. Then, the polymerizable monomer-containing material produced in the same manner as in Example 22 was evacuated from the unsealed end (up to 50 mmH).
g), the mixture is injected over 2 minutes, heated at 80 ° C. for 30 minutes to polymerize the polymerizable monomer-containing material, and then the unsealed end is sealed with an epoxy resin, and the graphite / cobalt oxide-based solid Li ion secondary I got a battery. Operate the battery with an operating voltage of 2.0 to 4.2.
When charging and discharging were repeated at V and a current of 0.1 mA, the maximum discharge capacity was 6.5 mAh, and the cycle life until the capacity decreased to 50% was 410 times.

Example 36 Production of Solid Li Ion Secondary Battery Current collector / graphite negative electrode / separator laminate (negative electrode / negative electrode / produced in Example 34) in an argon atmosphere glove box.
Separator 10mm × 10mm, Current collector 12mm × 1
2 mm) on the surface of the separator, the film for separator after absorbing the electrolytic solution prepared in Example 1 was 10 mm × 10
The separator cut out in mm was placed to form a current collector / negative electrode / separator laminate, and a current collector / lithium cobalt oxide positive electrode (positive electrode 10 mm × 10 mm) manufactured in the same manner as in Example 18 on the surface of the separator side. , Current collector 12
(mm × 12 mm) of the positive electrode surface was placed to obtain a current collector / negative electrode / separator / positive electrode / current collector laminate. After that, only one end of the laminate was left and the remaining end was sealed with an epoxy resin. Then, the polymerizable monomer-containing material produced in the same manner as in Example 22 was injected from the unsealed end portion under reduced pressure (up to 50 mmHg) over 2 minutes, and heated at 80 ° C. for 30 minutes to contain the polymerizable monomer. After polymerizing the product, the unsealed end was sealed with an epoxy resin to obtain a graphite / cobalt oxide-based solid Li-ion secondary battery. When this battery was repeatedly charged and discharged with an operating voltage of 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 6.5 mAh and the cycle life until the capacity decreased to 50% was 425 times.

Example 37 Production of Solid Li Ion Secondary Battery Current collector / graphite negative electrode / separator laminate (negative electrode / separator 10 mm × 10 mm, produced in the same manner as in Example 34) in an argon atmosphere glove box. Current collector 1
10 mm of the separator film after absorbing the electrolytic solution prepared in Example 1 on the surface of the separator (2 mm × 12 mm)
A separator cut out into m × 10 mm was placed to form a collector / negative electrode / separator laminate, and a current collector / lithium cobalt oxide positive electrode / separator manufactured in the same manner as in Example 33 on the surface of the separator side. Laminate (positive electrode / separator 10 mm x 10 mm, current collector 12 mm x
The side surface of the separator (12 mm) was placed to prepare a current collector / negative electrode / separator / positive electrode / current collector laminate. afterwards,
Only one end of the laminate was left and the remaining end was sealed with epoxy resin. Then, the polymerizable monomer-containing material produced in Example 22 was evacuated from the unsealed end (to about 5
At 0 mmHg) for 2 minutes and heated at 80 ° C. for 30 minutes to polymerize the polymerizable monomer-containing material, and then seal the unsealed end with an epoxy resin to obtain a graphite / cobalt oxide-based solid Li ion secondary I got a battery. This battery has an operating voltage of 2.
When charging and discharging were repeated at 0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 6.0 mAh and the cycle life until the capacity decreased to 50% was 435 times.

Example 38 Production of Activated Carbon Electrode Palm by weight activated carbon to polyvinylidene fluoride weight ratio: 9.
A 10-fold weight of N-methylpyrrolidone was added to the mixture of 0: 1.0 to obtain a gel composition. S
1mm wide on US316 foil (12mm x 12mm),
A molding spacer frame (thickness: 150 μm) made of polyimide having an inner dimension of 10 mm × 10 mm was placed, and the composition was applied in a thickness of about 150 μm in the spacer frame. Further, by vacuum drying at about 100 ° C. for 10 hours, an activated carbon electrode (14 mg) adhered to the SUS foil current collector was obtained. Prior to use in Example 39, remove spacer frame and remove SUS
The foil was cut into the same size as the activated carbon electrode (10 mm × 10 mm) to obtain an activated carbon electrode / collector laminate. A plurality of laminates were prepared in the same manner.

Example 39 Production of Solid Electric Double Layer Capacitor 0.50 g of compound 3, 1.00 g of compound 8, 1.5 g of diethyl carbonate (DEC), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ And 0.01 g of AIBN were thoroughly mixed in an argon atmosphere to obtain a polymerizable monomer-containing material. In an argon atmosphere glove box, two current collector / activated carbon electrode laminates (14 m
g) (10 mm × 10 mm), two electrode / current collector laminates in which the above polymerizable monomer-containing material was impregnated and coated were prepared. Next, the separator film prepared in Example 1 after absorbing the electrolytic solution was cut into a size of 10 mm × 10 mm, and the separator was placed on the electrode-side surface of one electrode / collector stack to collect the collector / electrode. / Separator laminate and the other electrode on the separator side surface /
Place the side surface of the electrode of the current collector laminate to prepare a current collector / electrode / separator / electrode / current collector laminate at 100 ° C.
After heating for 1 hour, seal the edge of the laminate with epoxy resin,
A solid electric double layer capacitor as shown in FIG. 4 was manufactured. When this capacitor was charged and discharged with an operating voltage of 0 to 2.0 V and a current of 0.1 mA, the maximum capacity was 480
It was mF. In addition, even if charging and discharging were repeated 50 times under these conditions, the capacity hardly changed.

Example 40 Production of Solid Electric Double Layer Capacitor In the same manner as in Example 39 except that the compound 3 polymer / polyethylene net composite film impregnated with the electrolytic solution produced in Example 15 was used as the separator, A solid-state electric double layer capacitor as shown in FIG. 4 was manufactured. When this capacitor was charged and discharged at an operating voltage of 0 to 2.0 V and a current of 0.1 mA, the maximum capacity was 450 mF. In addition, even if charging and discharging were repeated 50 times under these conditions, the capacity hardly changed.

Example 41 1.50 g of compound 3, 1.5 g of diethyl carbonate (DEC), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ and 0.02 g of Irgacure 651 were added in an argon atmosphere. By mixing, a polymerizable monomer-containing material was obtained. Aluminum oxide C (manufactured by Nippon Aerosil Co., Ltd., specific surface area about 10
0 m ^{2 /} g) 0.24 g was added and well stirred to give a milky white solution. After coating this milky white polymerizable monomer-containing material on a 10 cm square PET film under an argon atmosphere,
By irradiating with a mercury lamp for 10 minutes, a compound 3 polymer / aluminum oxide composite film in which an electrolytic solution was impregnated on a PET film was obtained as a cloudy self-supporting film having a thickness of about 30 μm. 25 ° C, -20 ° C of this film
The ionic conductivities were measured by the impedance method to be 3.0 × 10 ⁻³ and 1.0 × 10 ⁻³ S / cm, respectively, and the conductivity was higher than that in the case where no granular support was added. Improved.

Example 42 Example 42 was repeated except that the same amount of silica fine particles (Aerosil RX200: Nippon Aerosil Co., Ltd., specific surface area: about 140 m ² / g) was used instead of the aluminum oxide C used in Example 41. In the same manner as in Example 41, a transparent self-supporting film having a film thickness of the compound 3 polymer / silica composite film of about 30 μm was obtained. 2 of this film
The ionic conductivities at 5 ° C. and −20 ° C. were measured by the impedance method to be 3.5 × 10 ⁻³ and 1.2, respectively.
It was x10 ^-3 S / cm, and the conductivity was improved as compared with the case where no granular support was added.

Example 43 1.50 g of compound 3, 1.5 g of diethyl carbonate (DEC), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ and 0.02 g of Irgacure 651 were added in an argon atmosphere. By mixing, a polymerizable monomer-containing material was obtained. Polymer beads for liquid crystal spacers (trade name: Micropearl SP-213 manufactured by Sekisui Fine Chemical Co., Ltd .: particle diameter 13.00 ± 0.
10 μm) 0.05 g was added and well stirred to obtain a polymer bead-containing polymerizable monomer-containing material. This polymerizable monomer-containing material was applied onto a PET film under an argon atmosphere and then polymerized by irradiation with a mercury lamp for 10 minutes to polymerize the compound 3 polymer / polymer beads SP-213 in which the electrolytic solution was impregnated on the PET film. Composite film thickness 1
Obtained as a transparent free-standing film of 5 μm ± 2 μm. The ionic conductivities of this film at 25 ° C. and −20 ° C. were measured by the impedance method to be 2.5 × 1.
It was 0 ⁻³ , 0.8 × 10 ⁻³ S / cm.

Example 44 A rod-shaped alumina for liquid crystal spacer (Alfitt FT-20 manufactured by Showa Denko KK: diameter 20 ± 0.5 μm, average length about 30 μm) was used in the same amount instead of the polymer beads. In the same manner as in Example 43, an electrolytic solution-impregnated compound 3 polymer / alumina composite film was obtained as a transparent self-supporting film having a thickness of 23 μm ± 3 μm. When the ionic conductivities of this film at 25 ° C. and −20 ° C. were measured by the impedance method, they were 2.2 × 10 ⁻³ and 0.6 × 10 ⁻³ S / cm, respectively.

Example 45 Production of Solid Li-Ion Secondary Battery Same as Example 24 except that the compound 3 polymer / aluminum oxide composite film impregnated with the electrolytic solution produced in Example 41 was used as a separator. A graphite / lithium cobaltate solid Li-ion secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.1 mA, the maximum discharge capacity was 7.3 mAh and the capacity was 5
The cycle life until it decreased to 0% was 450 times.

[Example 46] Production of Li-ion secondary battery The same procedure as in Example 21 was repeated except that the compound 3 polymer / aluminum oxide composite film impregnated with the electrolytic solution produced in Example 41 was used as a separator. A graphite / lithium cobalt oxide-based Li-ion secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.5 mA, the maximum discharge capacity was 7.3 mAh and the capacity was 50%.
The cycle life before it decreased to 330 was 330 times.

[Example 47] Production of Li-ion secondary battery The same procedure as in Example 21 was repeated except that the compound 3 polymer / polymer bead composite film impregnated with the electrolytic solution produced in Example 43 was used as a separator. A graphite / lithium cobalt oxide-based Li-ion secondary battery was obtained. When this battery was repeatedly charged and discharged at an operating voltage of 2.0 to 4.2 V and a current of 0.5 mA, the maximum discharge capacity was 7.3 mAh, and the cycle life until the capacity decreased to 50% was 380 times.

Example 48 Production of Li-Ion Secondary Battery In a argon atmosphere glove box, a graphite negative electrode (10 mm × 10 mm) produced in the same manner as in Example 20 was mixed with an electrolytic solution (1.5 mol / l LiBF ₄ /). EC + DEC (weight ratio 1: 1)) and impregnated with about 1 part of the polymer bead-containing polymerizable monomer content prepared in Example 43.
It was applied to a thickness of 5 μm using a coater. Then, by irradiating with a mercury lamp for 10 minutes to polymerize, a compound 3 polymer / polymer bead composite film impregnated with the electrolytic solution was formed on the graphite negative electrode as a transparent film of about 15 μm. Further, a lithium cobalt oxide positive electrode (10 mm × 10 mm) produced in the same manner as in Example 18 was placed on the compound 3 polymer / polymer bead composite film, and an electrolytic solution (1.5 mo was added).
1 / l LiBF ₄ / EC + DEC (weight ratio 1: 1)) impregnated together, the electrode ends were sealed with epoxy resin, and the graphite / lithium cobaltate-based lithium ion secondary battery shown in FIG. Got This battery is operated at an operating voltage of 2.0
When charging and discharging were repeated at up to 4.2 V and a current of 0.5 mA, the maximum discharge capacity was 7.3 mAh, and the cycle life until the capacity decreased to 50% was 430 times.

Example 49 Production of Li-Ion Secondary Battery Graphite was prepared in the same manner as in Example 21 except that the compound 3 polymer / alumina composite film impregnated with the electrolytic solution produced in Example 44 was used as the separator. A lithium ion cobalt-based Li-ion secondary battery was obtained. This battery, operating voltage
When charge and discharge were repeated at 2.0 to 4.2 V and a current of 0.5 mA, the maximum discharge capacity was 7.0 mAh, and the cycle life until the capacity decreased to 50% was 360 times.

Example 50 Production of Li-Ion Secondary Battery In a argon atmosphere glove box, a graphite negative electrode (10 mm × 10 mm) produced in the same manner as in Example 20 was mixed with an electrolytic solution (1.5 mol / l LiBF ₄ /). EC + DEC (weight ratio 1: 1)), and further the alumina-containing polymerizable monomer content prepared in Example 44 was further added thereto in an amount of about 20 μm.
Was applied using a coater. Then, the compound 3 polymer / alumina composite film impregnated with the electrolytic solution is approximately 23 μm by irradiating with a mercury lamp for 10 minutes to polymerize.
m transparent film was formed on the graphite negative electrode. Furthermore, Example 1 was formed on the compound 3 polymer / alumina composite film.
A lithium cobalt oxide positive electrode (10
mm × 10 mm) with electrolyte (1.5 mol / l LiBF ₄ /
Those impregnated with EC + DEC (weight ratio 1: 1) were attached to each other, and the ends of the electrodes were sealed with an epoxy resin to obtain a graphite / lithium cobalt oxide-based lithium ion secondary battery shown in FIG. This battery, operating voltage 2.0 ~ 4.2V, current 0.5mA
When the battery was repeatedly charged and discharged at a maximum discharge capacity of 7.1 mAh
And the cycle life until the capacity decreases to 50% is 41
It was 0 times.

Example 51 Production of Li-ion Secondary Battery 1.50 g of Compound 3, 1.5 g of diethyl carbonate (DE
C), 1.5 g of ethylene carbonate (EC), 0.30 g of LiBF ₄ and 0.05 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (Perloyl TCP:
Nippon Oil & Fat Co., Ltd. product name) was mixed well in an argon atmosphere to obtain a polymerizable monomer-containing material. Polymer beads for liquid crystal spacers (Sekisui Fine Chemical Co., Ltd.) as a granular support in this polymerizable monomer-containing material under an argon atmosphere.
Product name Micropearl SP-213: Particle size 13.00
± 0.10 μm) 0.05 g was added and well stirred to obtain a polymer bead-containing polymerizable monomer-containing material. A graphite negative electrode (20 mm × 20 mm) manufactured in the same manner as in Example 20 was charged with an electrolytic solution (1.5
mol / l LiBF ₄ / EC + DEC (weight ratio 1: 1))
And a polyimide film frame having a width of 1 mm (thickness: about 20 μm) was arranged on the four sides at the ends, and a lithium cobalt oxide positive electrode (20 mm × 20 mm) manufactured in the same manner as in Example 18 was further provided with an electrolytic solution. (1.5 mol / l LiB
Those impregnated with F ₄ / EC + DEC (weight ratio 1: 1) were bonded together. Then, the polymer bead-containing polymerizable monomer-containing material is injected into the gap between the positive electrode and the negative electrode,
Polymerization was performed by heating at 0 ° C. for 30 minutes to prepare a graphite negative electrode / electrolyte-impregnated compound 3 polymer / polymer bead composite film / lithium cobalt oxide positive electrode laminated battery. The end of the battery was sealed with an epoxy resin to obtain the graphite / lithium cobalt oxide-based lithium ion secondary battery shown in FIG. This battery, operating voltage
When charging and discharging were repeated at 2.0 to 4.2 V and a current of ² mA (0.5 mA / cm ² ), the maximum discharge capacity was 28 mAh, and the cycle life until the capacity decreased to 50% was 320 times.

Example 52 Production of Solid-state Electric Double Layer Capacitor The procedure of Example 39 was repeated except that the compound 3 polymer / aluminum oxide composite film impregnated with the electrolytic solution produced in Example 41 was used as a separator. A solid state electric double layer capacitor was manufactured. When this capacitor was charged and discharged at an operating voltage of 0 to 2.0 V and a current of 0.1 mA, the maximum capacity was 480 mF. Under these conditions, the charge / discharge was 5
Even if it was repeated 0 times, there was almost no change in the capacity.

[0177]

EFFECT OF THE INVENTION The film for a separator of the present invention has good film strength by using a cross-linked polymer containing an oxyalkylene group or a cross-linked polymer containing an oxyalkylene group bonded by a urethane bond as a constituent component. , Excellent workability, large amount of electrolyte absorption, as a result,
It has the feature of high ionic conductivity. Further, the separator film of the present invention can be efficiently manufactured by the method for manufacturing a separator film of the present invention, and particularly, a film for thin film separator having excellent ion strength and high ion conductivity can be manufactured.

Electrochemical devices such as batteries and electric double layer capacitors using the separator film of the present invention as a separator have the advantage that they can operate at high capacity and high current because the separator has the above characteristics. . In particular, using the separator film of the present invention as a separator, further batteries and capacitors using a polymer solid electrolyte can be stably used for a long period without risk of liquid leakage because the ion conductive material is solid,
Further, by using this separator and the solid polymer electrolyte, thin batteries and capacitors can be manufactured.

The battery and the method for producing the same of the present invention provide an all-solid-state battery which can operate with high capacity and high current, has a long cycle life, and is excellent in safety and reliability. It can be used as a main power supply for portable equipment, a power supply for electric products such as backup power supply, a large power supply for electric vehicles, and load leveling. Further, by using the separator of the present invention having the above characteristics, it is possible to make the battery into a thin film, and there is no problem in strength or long-term use even if the film is made thin, such as an identification card. There is an advantage that a battery having a shape-free property such as a paper battery or a flexible battery can be obtained.

Furthermore, the electric double layer capacitor and the method of manufacturing the same according to the present invention make it possible to manufacture an all-solid-state electric double layer capacitor, which is higher in voltage and capacity than the conventional all-solid-state capacitor. There is provided an electric double layer capacitor which can be operated at a high current, has good cycleability, and is excellent in safety and reliability, and can be an all-solid-state electric double layer capacitor having such characteristics. Therefore, the capacitor of the present invention can be used not only as a backup power source but also as a power source for various electric products when used together with a small battery. Further, by using the separator of the present invention having the above-mentioned characteristics, it has excellent workability such as thinning of a capacitor, and can be expected to be used in applications other than the conventional solid-state electric double layer capacitors.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a battery manufactured in this example.

FIG. 2 is a schematic cross-sectional view of a battery manufactured in this example.

FIG. 3 is a schematic cross-sectional view of a battery manufactured in this example.

FIG. 4 is a schematic cross-sectional view of an electric double layer capacitor manufactured in this example.

[Explanation of symbols]

 1 Positive Electrode 2 Separator 3 Negative Electrode 4 Current Collector 5 Insulating Resin Sealant (Cured Product) 6 Protective Frame (Spacer) 7 Separator 8 Polarizable Electrode 9 Current Collector 10 Separator 11 Insulating Resin Sealant (Cured Product) 12 lead wire

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location H01G 9/02 H01M 6/16 Z H01M 6/16 10/40 Z 10/40 H01G 9/00 301C

Claims (37)

[Claims] 1. A film for a separator of an electrochemical device, which comprises a crosslinked polymer having an oxyalkylene group as a constituent component. 2. A film for a separator of an electrochemical device, which comprises a crosslinked polymer having a urethane bond and an oxyalkylene group as a constituent component. 3. The polymer has the general formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) [in the formula , R ¹ represents hydrogen or an alkyl group, and R ² represents a divalent organic group containing an oxyalkylene group. The organic group may have any of a linear, branched or cyclic structure, and may contain one or more elements other than carbon, hydrogen and oxygen. x and y each represent 0 or an integer of 1 to 5, and z represents a numerical value of 0 or 1 to 10. Where x = 0
And when y = 0, z = 0. (CH ₂ ) and (CH (CH ₃ )) may be arranged irregularly. However,
The values of R ¹ , R ² and x, y, z in a plurality of units represented by the above general formula (1) in the same molecule are independent of each other and need not be the same. ] The electrochemistry according to claim 1 or 2, which is a polymer of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by and a copolymer containing the compound as a copolymerization component. Film for separator of equipment. 4. The polymer has the general formula (2): CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n − (2) [In the formula, R ¹ represents hydrogen or an alkyl group, and R ³ represents-.
(CH _{2) 2} - or -CH (CH ₃₎ CH ₂ - represents, n represents an integer of 1 or more. x, y and z are the same as those in the general formula (1)], which is a polymer of an acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the formula (1) and / or a copolymer containing the compound as a copolymerization component. A film for a separator of an electrochemical device according to claim 1 or 2. 5. The separator film for an electrochemical device according to claim 1, which contains an electrolyte and / or a solvent. 6. The separator film for an electrochemical device according to claim 5, wherein at least one of the electrolytes is an alkali metal salt, a quaternary ammonium salt, or a quaternary phosphonium salt. 7. The separator film for an electrochemical device according to claim 5, wherein the solvent is a carbonate compound. 8. The film for a separator of an electrochemical device according to claim 1, wherein the support is composite. 9. The film for a separator of an electrochemical device according to claim 1, wherein the porous support is compounded. 10. The film for separator of an electrochemical device according to claim 8 or 9, wherein the support is a granular support having a size of 0.01 μm to 100 μm. 11. The support is an aggregate of primary particles,
The film for separator of an electrochemical device according to claim 8 or 9, wherein the size of the aggregate is 0.01 to 100 µm. 12. The BET specific surface area of the support is 10 m ^2.
/ G or more, It is characterized by the above-mentioned.
A film for a separator of the described electrochemical device. 13. A separator for an electrochemical device, comprising the film according to claim 8. 14. A thickness of 1 μm to 1 obtained by compounding a support having a uniform size in the range of 1 μm to 100 μm.
The separator according to claim 13, having a uniform thickness in the range of 10 μm. 15. The separator according to claim 13, wherein the total content of the solvent and the electrolyte is 100 to 1000% of the total weight of the separator. 16. General formula (1) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) (wherein the symbol is The same as in claim 3.) At least one acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the following), or an electrolyte,
A mixture to which at least one selected from the group consisting of a solvent and other polymerizable compounds is added, is placed on a support, and a separator of an electrochemical device characterized by polymerizing the acryloyl-based or methacryloyl-based compound. Film manufacturing method. 17. General formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n − (2) (wherein Symbol is the same as in claim 4.) At least one acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above, or an electrolyte,
A mixture to which at least one selected from the group consisting of a solvent and other polymerizable compounds is added, is placed on a support, and a separator of an electrochemical device characterized by polymerizing the acryloyl-based or methacryloyl-based compound. Film manufacturing method. 18. General formula (1) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) (wherein the symbol is The same as in claim 3.) At least one acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the following), or an electrolyte,
A mixture obtained by adding at least one selected from the group consisting of a solvent and another polymerizable compound, impregnating the porous support, and then polymerizing the acryloyl-based or methacryloyl-based compound. A method for producing a composite film for a separator. 19. General formula (1) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) (wherein the symbol is The same as in claim 3), and a mixture of at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit and a granular support,
Alternatively, a mixture containing at least one of the above compounds, a granular support, and at least one selected from an electrolyte, a solvent and another polymerizable compound is placed on another support, and the acryloyl-based or methacryloyl-based compound is polymerized. A method for producing a film for a separator of an electrochemical device, comprising: 20. General formula (1) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO-R ^2- (1) (wherein the symbol is The same as in claim 3), and a mixture of at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit and a granular support,
Alternatively, a mixture containing at least one of the above compounds, a granular support, and an electrolyte, a solvent, and at least one selected from other polymerizable compounds is disposed on the electrode, and the acryloyl-based or methacryloyl-based compound is polymerized. A method of manufacturing a separator of an electrochemical device, which is characterized. 21. General formula (2) CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n − (2) (wherein Symbol is the same as in claim 4.) At least one acryloyl-based or methacryloyl-based compound having a structure containing a unit represented by the above, or an electrolyte,
A mixture obtained by adding at least one selected from the group consisting of a solvent and another polymerizable compound, impregnating the porous support, and then polymerizing the acryloyl-based or methacryloyl-based compound. A method for producing a composite film for a separator. 22. General formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n − (2) (wherein The symbol is the same as in claim 4.) A mixture of at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit and a granular support,
Alternatively, a mixture containing at least one of the above compounds, a granular support, and at least one selected from an electrolyte, a solvent and another polymerizable compound is placed on another support, and the acryloyl-based or methacryloyl-based compound is polymerized. A method for producing a film for a separator of an electrochemical device, comprising: 23. General formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO (R ³ O) _n − (2) (wherein The symbol is the same as in claim 4.) A mixture of at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit and a granular support,
Alternatively, a mixture containing at least one of the above compounds, a granular support, and an electrolyte, a solvent, and at least one selected from other polymerizable compounds is disposed on the electrode, and the acryloyl-based or methacryloyl-based compound is polymerized. A method of manufacturing a separator of an electrochemical device, which is characterized. 24. A battery using the film according to any one of claims 1 to 12 as a separator. 25. The battery according to claim 24, wherein the negative electrode of the battery comprises an electrode containing lithium, a lithium alloy, or a substance capable of inserting and extracting lithium ions. 26. In a method for manufacturing a battery, a positive electrode, a separator made of the film according to any one of claims 1 to 12 and a negative electrode are laminated in any order as a structure for battery construction, and a separator is laminated and sandwiched between the positive electrode and the negative electrode. The step of forming a positive electrode / separator / negative electrode laminate, and the general formula (1) or the general formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _{x (CH (CH 3))} y] z NHCOO- R 2 - (1) (. the symbols in the formula the same as claim _{3) CH 2 = C (R} 1) CO [O (CH 2) x (CH _{(CH 3)) y] z} NHCOO (R 3 O) n - (2) ( at least in the symbols in the formula acryloyl or methacryloyl compound having a structure containing a unit represented by the same) as claimed in claim 4. One and at least one electrolysis Method for producing a battery, characterized by comprising the step of polymerizing a process and a polymerizable monomer-containing material satisfying the polymerizable monomer-containing material containing as essential constituents. 27. In a method for producing a battery, using a positive electrode / separator laminate and / or a negative electrode / separator laminate in which at least one of a positive electrode and a negative electrode is preliminarily laminated with a separator comprising the film according to claim 1. A step of forming a positive electrode / separator / negative electrode laminate in which a separator is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure, and at least one electrolyte is an essential component in the battery structure structure having such a structure. A method of manufacturing a battery, comprising a step of filling a liquid material contained as. 28. In a method for producing a battery, using a positive electrode / separator laminate and / or a negative electrode / separator laminate in which at least one of a positive electrode and a negative electrode is preliminarily laminated with a separator comprising the film according to claim 1. A step of forming a positive electrode / separator / negative electrode laminate in which a separator is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure, and the general formula (1) or the general formula in the battery structure structure having such a structure. _{(2) CH 2 = C (} R 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO- R 2 - (1) ( symbols in the formula are the same as claim 3.) ^{_{CH 2 = C (R 1)}} CO [O (CH 2) x (CH (CH 3)) y] z NHCOO (R 3 O) n - (2) ( symbols in the formula are the same as defined in claim 4.) Has a structure including a unit represented by A method for producing a battery, comprising a step of filling a polymerizable monomer content containing at least one of acryloyl-based or methacryloyl-based compound and at least one electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material. . 29. A battery manufacturing method, wherein a positive electrode having a porous support laminated on at least one of a positive electrode and a negative electrode.
Positive electrode / porous support / wherein a porous support is laminated and sandwiched between a positive electrode and a negative electrode as a battery structure structure by using the porous support laminate and / or the negative electrode / porous support laminate
CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH _{3)) y] z NHCOO- R} 2 -. (1) ( symbols in the formula are the same as claim _{3) CH 2 = C (R} 1) CO [O (CH 2) x (CH (CH 3)) ^{_{y] z NHCOO (R 3 O}} ) n - (2) ( symbols in the formula are the same as defined in claim 4.) of at least one and at least one acryloyl or methacryloyl compound having a structure containing a unit represented by 13. A method for producing a battery having a separator comprising a film according to claim 1, which has a step of filling a polymerizable monomer-containing material containing an electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material. . 30. A method for producing a battery, advance to at least one of the positive and negative electrodes, the general formula (1) or general formula _{(2) CH 2 = C (} R 1) CO [O (CH 2) x (CH ( _{CH 3)) y] z NHCOO-} R 2 -. (1) ( the symbols in the formula the same as claim _{3) CH 2 = C (R} 1) CO [O (CH 2) x (CH (CH 3) ^{_{) y] z NHCOO (R 3}} O) n - (2) ( essential constituent at least one of the symbols in the formula acryloyl or methacryloyl compound having a structure containing a unit represented by the same) as claimed in claim 4. The step of impregnating and / or coating the polymerizable monomer-containing material contained as a component, the positive electrode, the negative electrode, and the separator comprising the film according to claims 1 to 12 as a structure for battery construction. Positive sandwiched / Forming a separator / negative electrode laminate, and method for producing a battery, characterized by comprising the step of polymerizing the polymerizable monomer-containing material. 31. The polymerizable monomer-containing material is represented by the general formula (1) or the general formula (2): CH ₂ ═C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO ^{- R 2 - (1) (} . the symbols in the formula the same as claim _{3) CH 2 = C (R} 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO (R 3 O) _n- (2) (the symbols in the formula are the same as those in claim 4) and at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit and at least one electrolyte are contained as essential constituents. The method for producing a battery according to claim 30, which is a polymerizable monomer-containing material. 32. An electric double layer capacitor comprising the film according to claim 1 as a separator. 33. A method for manufacturing an electric double layer capacitor, wherein two polarizable electrodes and a separator made of the film according to any one of claims 1 to 12 are laminated in any order as a structure for constructing a capacitor, and two separators are formed. Electrode / separator / with a separator sandwiched between polar electrodes
A method of manufacturing an electric double layer capacitor, comprising: a step of forming an electrode laminate; and a step of filling a liquid material containing at least one electrolyte as an essential constituent in a capacitor constituting structure having such a constitution. 34. A method of manufacturing an electric double layer capacitor, wherein two polarizable electrodes and a separator made of the film according to any one of claims 1 to 12 are laminated in arbitrary order as a structure for constructing a capacitor, and two separators are formed. Electrode / separator / with a separator sandwiched between polar electrodes
The step of forming an electrode laminate, and the general formula (1) or the general formula (2) CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH _{3 ^{)) y] z NHCOO- R 2}} -. (1) ( symbols in the formula are the same as claim _{3) CH 2 = C (R} 1) CO [O (CH 2) x (CH (CH 3)) y ^{_{] z NHCOO (R 3 O)}} n - (2) at least one and at least one electrolyte (the symbols in the formula the same as defined in claim 4.) acryloyl or methacryloyl compound having a structure containing a unit represented by A method for producing an electric double layer capacitor, comprising: a step of filling a polymerizable monomer-containing material containing as an essential constituent and a step of polymerizing the polymerizable monomer-containing material. 35. In a method for manufacturing an electric double layer capacitor, two polarizable electrodes and a porous support are laminated in arbitrary order as a structure for forming a capacitor, and the support is provided between the two polarizable electrodes. A step of forming an electrode / porous support / electrode laminate in which the body is laminated and sandwiched, and a general formula (1) or a general formula (2) CH ₂ = C (R ¹ ) _{CO [O (CH 2) x} (CH (CH 3)) y] z NHCOO- R 2 - (1) (. symbols in the formula are the same as claim _{3) CH 2 = C (R} 1) CO [O _{(CH 2) x (CH (} CH 3)) y] z NHCOO (R 3 O) n - (2) acryloyl (the symbols in the formula the same as defined in claim 4.) having a structure containing a unit represented by At least one and at least one of the methacrylic or methacryloyl compounds An electric double layer capacitor having a separator made of the film according to any one of claims 1 to 12, which has a step of filling a polymerizable monomer-containing material containing an electrolyte as an essential constituent and a step of polymerizing the polymerizable monomer-containing material. Manufacturing method. 36. In the method for manufacturing an electric double layer capacitor, at least one of the two polarizable electrodes is previously represented by the general formula (1) or the general formula (2) CH ₂ = C (R ¹ ) CO [O (CH _{2) x (CH (CH 3} )) y] z NHCOO- R 2 -. (1) ( the symbols in the formula the same as claim _{3) CH 2 = C (R} 1) CO [O (CH 2) x _{(CH (CH 3)) y} ] z NHCOO (R 3 O) n - (2) acryloyl or methacryloyl compounds (symbols in the formula the same as defined in claim 4.) having a structure containing a unit represented by Step of impregnating and / or coating a polymerizable monomer-containing material containing at least one of the above-mentioned as an essential constituent component, an electric double layer capacitor structure using two polarizable electrodes and a separator composed of the film according to claim 1-12. 2 as structure for Method for producing an electric double layer capacitor characterized in that a separator having a step of forming an electrode / separator / electrode laminate laminated sandwich, and the step of polymerizing the polymerizable monomer-containing material between the polarizable electrodes. 37. The polymerizable monomer-containing material is represented by the general formula (1) or the general formula (2): CH ₂ = C (R ¹ ) CO [O (CH ₂ ) _x (CH (CH ₃ )) _y ] _z NHCOO ^{- R 2 - (1) (} . the symbols in the formula the same as claim _{3) CH 2 = C (R} 1) CO [O (CH 2) x (CH (CH 3)) y] z NHCOO (R 3 O) _n- (2) (the symbols in the formula are the same as those in claim 4) and at least one acryloyl-based or methacryloyl-based compound having a structure containing a unit and at least one electrolyte are contained as essential constituents. 37. The method for producing an electric double layer capacitor according to claim 36, wherein the electric double layer capacitor is a polymerizable monomer-containing substance.