JPH10223044A - Polymer solid electrolyte gel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high ion conductivity and electrochemical stability by containing an acrylic ester type polymer containing a constitutive unit induced from acrylic ester having a specific structure, a nonaqueous solvent composed of carbonic ester and metallic salt of No.1a group of a periodic table. SOLUTION: An acrylic ester type polymer matrix is a copolymer of one kind selected from acrylic ester expressed by a formula I (R<1> and R<2> are H or an alkyl group of C1-4 , R<3> is an alkyl group of C1-4 and (n) is 1 to 100) or a formula II (R<4-9> are H and an alkyl group of C1-4 , and (p, q and r) are 1 to 100), a copolymerizable vinyl monomer, a vinylidene monomer or a vinylen monomer. A nonaqueous solvent is selected from ring carbonic ester or chain carbonic ester, and metallic salt of No.1a group of a periodic table is LiClO4 , LiBF4 or the like, and is preferable to be contained by 2 to 40wt.% to the total weight of gel-like polymer solid electrolyte.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gel polymer solid electrolyte used for primary batteries, secondary batteries, capacitors and the like.

[0002]

BACKGROUND OF THE INVENTION Conventionally, primary batteries, secondary batteries,
Liquid electrolytes have been used for electrochemical devices such as capacitors. However, there is a problem that the liquid electrolyte leaks and lacks long-term reliability.

As a method for solving such a problem, a method using a solid electrolyte is known. When a solid electrolyte is used in the above-described electrochemical element, a highly reliable element without liquid leakage is obtained. In addition to providing the element, the element itself can be reduced in size and weight.

In recent years, various polymer solid electrolytes have been studied as solid electrolytes. Since the polymer solid electrolyte has flexibility, it can be flexibly applied to a volume change occurring in the ion-electron exchange reaction process between the electrode and the polymer solid electrolyte, and has the characteristics of the solid electrolyte as described above. doing.

As such a solid polymer electrolyte, a complex of a polyethylene oxide having a polyether structure and an alkali metal salt such as a lithium salt is known. JP-A-5-25353 mainly discloses a crosslinked resin of a copolymer of a polyoxyalkylene diester compound, a polymethoxyoxyalkylene ester compound, and an oxy compound having a double bond, and an inorganic salt. A solid polymer electrolyte as a constituent is described. JP-A-6-223842 describes a polymer solid electrolyte comprising an organic polymer having a carbonate group as a functional group and a metal salt.

However, since a solid electrolyte generally has lower ionic conductivity than a liquid electrolyte, it has been difficult to obtain primary and secondary batteries having excellent discharge characteristics. Under such circumstances, the emergence of a solid polymer electrolyte that satisfies the requirements of excellent ionic conductivity and excellent electrochemical stability has been desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above prior art, and has as its object to provide a gel polymer solid electrolyte having high ionic conductivity and being chemically stable. The purpose is.

[0008]

SUMMARY OF THE INVENTION The gelled polymer solid electrolyte according to the present invention is (a) derived from at least one acrylate ester selected from acrylate esters represented by the following general formulas (I) and (II). Acrylic ester polymer matrix containing structural units such as

[0009]

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(Wherein R ¹ , R ² and R ² ′ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ represents a carbon atom number. Is 1
And n is an integer of 1 to 100. )

[0011]

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(Wherein, R ^{4 to} R ⁹ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p, q and r are the same or different. And may be an integer of 1 to 100.) (b)
A non-aqueous solvent comprising a carbonate ester;
Group metal salts.

The acrylate polymer matrix is preferably an acrylate homopolymer or copolymer selected from the acrylates represented by the general formulas (I) and (II).

The acrylate polymer matrix comprises an acrylate represented by the general formula (I) or (II) and an acrylate represented by the general formula (I) or (II). It is preferably a copolymer with a copolymerizable vinyl monomer, vinylidene monomer or vinylene monomer.

[0015] The non-aqueous solvent is preferably at least one carbonate selected from cyclic carbonates and chain carbonates. The non-aqueous solvent may be a mixed solvent of a cyclic carbonate and a chain carbonate.

The metal salt of Group Ia of the Periodic Table includes Li
_{ClO 4, LiBF 4, LiPF 6} , LiAsF 6, LiC
F ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃
And at least one lithium salt selected from

The gelled polymer solid electrolyte according to the present invention comprises:
It is preferable to produce the solution by integrally polymerizing a solution containing a metal salt of Group Ia of the periodic table, a nonaqueous solvent composed of a carbonate, and an acrylate represented by the general formula (I) or (II). .

[0018]

DETAILED DESCRIPTION OF THE INVENTION The solid polymer electrolyte according to the present invention will be specifically described below. In this specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It is sometimes used in a sense that also includes coalescence. In this specification, the term "acrylic acid ester" is used to mean not only an ester of acrylic acid but also an ester such as methacrylic acid in which a hydrogen atom of acrylic acid is substituted with an alkyl group.

[Acrylic Ester Polymer Matrix] First, the acrylate polymer matrix used in the present invention will be described.

The acrylate polymer matrix contains a structural unit derived from at least one acrylate selected from acrylates represented by the following general formula (I) or (II). I have.

[0021]

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In the formula, R ¹ , R ² and R ² ′ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. is there.

R ³ represents an alkyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group and a t-butyl group. n is an integer of 1 to 100, preferably 1
Is an integer of 10 to 10.

Specific examples of the acrylate represented by the general formula (I) include:

[0025]

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2-methacryloyloxy-2-methylethylmethyl carbonate, 2 (2-methacryloyloxy-2-methylethoxy) isopropylmethyl carbonate, 2 (2-
(Methacryloyloxy-2-methylethoxy) 2-methylethyl methyl carbonate, 2 (2-methacryloyloxy isopropoxy) 2-methylethyl methyl carbonate,

[0027]

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And the like.

The acrylate represented by the general formula (I) can be prepared, for example, from a compound represented by the following general formula (i) and a compound represented by the following general formula (ii) in the following manner. Can be synthesized.

[0030]

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In the formula, R ¹ , R ² , R ² ′, R ³ and n are the same as defined in the above formula (I). In the above synthesis step, the compound represented by the general formula (ii) is used in an amount of 0.5 to 5 mol based on 1 mol of the compound represented by the general formula (i). In the above reaction, as a catalyst, for example, K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , Na
OCH ₃ or the like can be used. Such a catalyst is 1 × 1 to 1 mol of the compound represented by the general formula (i).
It is used in an amount of 0 ^-5 to 1 × 10 ^-2 mol.

The reaction between the compound represented by the general formula (i) and the compound represented by the general formula (ii) is usually carried out while stirring and removing the alcohol formed under reflux. The reaction temperature is usually 40 to 140 ° C, and the reaction time is usually 2 to 60 hours.

[0033]

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In the formula, R ^{4 to} R ⁹ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group. P, q and r may be the same or different from each other, and are integers of 1 to 100, preferably 1
Is an integer of 10 to 10.

Specific examples of the acrylate represented by the general formula (II) include:

[0036]

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[0037]

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Di (2-methacryloyloxyisopropyl)
Carbonate, di (2-acryloyloxyisopropyl)
Carbonate, di (2 (2-methacryloyloxyisopropoxy) isopropyl) carbonate, di (2 (2-acryloyloxyisopropoxy) isopropyl) carbonate and the like.

The acrylate represented by the general formula (II) can be prepared, for example, from a compound represented by the following general formula (iii) and a compound represented by the following general formula (iv) in the following manner. Can be synthesized.

[0040]

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In the formula, R ^{4 to} R ⁹ , p, q and r are the same as defined in the formula (II). In the above synthesis step, the compound represented by the general formula (iv) is converted to a compound represented by the general formula (ii)
It is used in an amount of 0.3 to 2.0 mol based on 1 mol of the compound represented by i). In the above reaction, as a catalyst, for example, K ₂ CO ₃ , Na ₂ CO ₃ , Li ₂ CO ₃ , Na
OCH ₃ or the like can be used. Such a catalyst is 1 × with respect to 1 mol of the compound represented by the general formula (iii).
It is used in an amount of 10 ^-5 to 1 × 10 ^-2 mol.

The reaction between the compound represented by the general formula (iii) and the compound represented by the general formula (iv) is usually carried out while stirring and removing the alcohol formed under reflux. The reaction temperature is usually 40 to 140 ° C, preferably 40 to 100 ° C.
℃, reaction time is usually 2 to 60 hours.

The acrylate polymer matrix contains a structural unit derived from at least one acrylate selected from the acrylates represented by formula (I) or (II). .

Examples of such a high molecular polymer matrix include (i) a homopolymer of an acrylate ester represented by the general formula (I) or (II), and (ii) a homopolymer represented by the general formula (I). At least 2 selected from acrylic esters
(Iii) a copolymer of at least two acrylates selected from the acrylates represented by the general formula (II); and (iv) a copolymer of at least two acrylates selected from the acrylates represented by the general formula (II). A copolymer of at least one acrylate selected from acrylates represented by the formula and at least one acrylate selected from the acrylates represented by the general formula (II), )
At least one acrylate selected from the acrylates represented by the general formula (I) or (II), and at least one selected from a vinyl monomer, a vinylidene monomer and a vinylene monomer copolymerizable with the acrylate; And a copolymer with one kind of compound.

The vinyl monomer, vinylidene monomer or vinylene monomer copolymerizable with the acrylate ester includes vinyl ester, vinyl ether,
(Meth) acrylates, allyl ethers, allyl esters, and cyclic olefins are preferred, and specifically,
Ethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, allyl alcohol, vinyl acetate, styrene, α-methylstyrene, vinyl chloride, vinylidene chloride, Vinyl fluoride,
Examples include vinylidene fluoride, acrylonitrile, vinyl cyanoacetate, allylamine, isopropylacrylamide, isobutene, isoprene, vinylene carbonate, and maleic anhydride.

The acrylate polymer matrix has a molecular weight (number average molecular weight) of usually 2 × 10
^It is preferably in the range of ³ to 1 × 10 ⁸ , preferably 1 × 10 ⁴ to 1 × 10 ⁷ .

When the polymer matrix is a copolymer of at least two acrylates selected from the acrylates represented by the general formula (I), or is represented by the general formula (II) When the copolymer is a copolymer of at least two acrylates selected from the acrylates, two or more structural units derived from the acrylate represented by the general formula (I) or (II) Is not particularly limited, but is preferably in the range of 98/2 to 2/98 in molar ratio.

Further, the polymer matrix is composed of at least one acrylate selected from the acrylates represented by the general formula (I) and the acrylate represented by the general formula (II)
In the case of a copolymer with at least one acrylate selected from the acrylates represented by the following formulas, two types derived from the acrylates represented by the general formula (I) or (II) The ratio of the above constituent units is
Although not particularly limited, the molar ratio is desirably in the range of 98/2 to 2/98.

Further, the polymer matrix is formed by copolymerizing an acrylate represented by the above general formula (I) or (II) with a vinyl monomer, a vinylidene monomer or a vinylene monomer copolymerizable with the acrylate. In the case of a polymer, the molar ratio of the structural unit derived from the acrylate represented by the general formula (I) or (II) to the structural unit derived from the vinyl monomer, vinylidene monomer or vinylene monomer is as follows: , Usually 5:95 to 100: 0, preferably 5:95 to 95:
5, more preferably in the range of 10:90 to 90:10.

The molar ratio of the structural unit derived from the acrylate represented by the general formula (I) or (II) to the structural unit derived from the copolymerizable vinyl monomer, vinylidene monomer or vinylene monomer is as follows: It is adjusted within the above range according to the desired physical and chemical properties.

The acrylate polymer matrix as described above can be produced by a conventional method. For example, (i) at least one selected from acrylates represented by the general formula (I) or (II);
i) at least one selected from the acrylates represented by the general formula (I) and at least one acrylate selected from the acrylates represented by the general formula (II);
Or (iii) at least one selected from acrylates represented by the general formula (I) or (II);
It can be easily produced by polymerizing at least one compound selected from a copolymerizable vinyl compound, vinylidene compound or vinylene compound by a radical polymerization method, a photopolymerization method or the like.

The acrylate polymer matrix may contain, for example, 20 units of structural units other than the structural units derived from the general formulas (I) and (II) and the vinyl compound, vinylidene compound or vinylene compound.
It may be contained at a ratio of not more than mol%.

[Gel-like Polymer Solid Electrolyte] The gel-like polymer solid electrolyte according to the present invention comprises the above-mentioned acrylate polymer matrix, a non-aqueous solvent comprising a carbonate ester, and a periodic table Ia. Group metal salts. Such a gelled polymer solid electrolyte may be composed of a non-aqueous solvent composed of an acrylate-based polymer matrix, a carbonate, and a metal salt of Group Ia of the periodic table. May contain other components.

Examples of the metal salt of Group Ia of the periodic table include Li
Br, LiI, LiSCN, LiClO ₄ , LiBF ₄ ,
LiAsF ₆ , LiPF ₆ , LiCF ₃ SO ₃ , LiAlC
l ₄ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ) ₃ , N
aBr, NaSCN, NaClO ₄ , KSCN, KCl
O _{4 and the} like. Among these metal salts, L
iClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , Li
CF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ S
O ₂ ) ₃ is preferably used. These metal salts can be used alone or in combination of two or more.

As the non-aqueous solvent, a carbonate ester is used. In particular, at least one carbonate ester selected from a cyclic carbonate and a chain carbonate is preferably used.

Examples of the cyclic carbonate include a carbonate represented by the following general formula (III).

[0057]

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Here, R ¹⁰ and R ¹¹ may be the same or different and represent a hydrogen atom, a linear, branched or cyclic alkyl group. Preferred examples of the linear alkyl group include a linear alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the branched alkyl group include a branched alkyl group having 1 to 4 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Examples of the cyclic alkyl group include a cyclopropyl group and a cyclobutyl group. As the cyclic carbonate, not only the 5-membered ring compound represented by the above formula (III) but also 6-membered ring compound can be used.
It may be a membered ring compound.

Specific examples of such carbonates include ethylene carbonate, propylene carbonate,
Examples thereof include 1,3-propylene carbonate, 1,3-butylene carbonate, 2,4-pentylene carbonate, and 1,3-pentylene carbonate.

Of these cyclic carbonates, ethylene carbonate, propylene carbonate or a mixture thereof is preferred.

Examples of the chain carbonate include a carbonate represented by the following general formula (IV).

[0062]

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In the formula (IV), R ¹² and R ¹³ may be the same or different and represent a linear, branched or cyclic alkyl group, and particularly preferably a straight-chain alkyl group having 1 to 4 carbon atoms. Or a branched alkyl group or a cyclic alkyl group having 3 to 6 carbon atoms.

As such a chain carbonate ester,
Specific examples include dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, dibutyl carbonate, diisopropyl carbonate, and methyl ethyl carbonate.

Of these chain esters, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate are preferably used.

Such chain carbonates may be used as a mixture of two or more. Particularly, a symmetric chain carbonate having the same R ¹² and R ^{13 and} an asymmetric chain carbonate having different R ¹² and R ^13. A solvent mixed with a chain carbonate is preferred. When the symmetric chain carbonate and the asymmetric chain carbonate are mixed, the volume of the symmetric chain carbonate: the volume of the asymmetric chain carbonate is 20:80 to 95: 5, preferably 30. : 70 to 90:10.

In the present invention, a mixed solvent of a cyclic carbonate and a chain carbonate is preferably used as the non-aqueous solvent. The mixing ratio of the cyclic carbonate and the chain carbonate is (volume of the cyclic carbonate: volume of the chain carbonate) in a range of 10:90 to 90:10, preferably 20:80 to 80:20. Is desirable.

In the gelled polymer solid electrolyte according to the present invention, the ratio of the total weight of the carbonate ester to the total weight of the acrylate polymer (total weight of the carbonate ester: total weight of the acrylate polymer) is as follows. 40: 60-90: 10,
Preferably, the ratio is 60:40 to 85:15. Further, in the gelled polymer solid electrolyte according to the present invention, although a carbonate ester is contained as an essential component as a non-aqueous solvent, other solvents such as methyl ethyl ketone, γ-butyrolactone, dimethylformamide and the like according to the present invention. A small amount may be contained so as not to impair the physical properties of the gelled polymer solid electrolyte.

In the gelled polymer solid electrolyte according to the present invention, the metal salt of Group Ia of the periodic table contains 1 to 50% by weight, preferably 2 to 50% by weight, based on the total weight of the gelled polymer solid electrolyte.
It is preferably contained in the range of 40% by weight.

If the content of the metal salt of Group Ia in the periodic table is out of the above range, problems such as a decrease in ionic conductivity, a decrease in viscosity and elasticity of the polymer, and a decrease in tensile strength are caused. May occur.

Such a gelled polymer solid electrolyte can be produced as follows. In general, a gel polymer solid electrolyte is used in the form of a film. Therefore, a solution containing a metal salt of Group Ia of the periodic table, a nonaqueous solvent, and a monomer of the general formula (I) or (II) is used. Is preferably produced by integrally polymerizing

Specifically, the following method is employed. One or more compounds such as the following (1) to (4) are dissolved in a carbonate solvent in the presence of a Group Ia metal salt, and the resulting solution is flowed on a flat substrate. A method of solidifying or coating, and polymerizing and curing together with ultraviolet rays, irradiation of radiation, or heat.

(1) At least one compound selected from the acrylates represented by formula (I) or (II). (2) at least one selected from the acrylates represented by the general formula (I) and at least one selected from the acrylates represented by the general formula (II) and a vinyl monomer, a vinylidene monomer or a vinylene monomer One compound.

(3) At least one compound selected from the acrylates represented by the general formula (I) and at least one compound selected from a vinyl monomer, a vinylidene monomer or a vinylene monomer.

(4) At least one compound selected from the acrylates represented by the general formula (II) and at least one compound selected from a vinyl monomer, a vinylidene monomer and a vinylene monomer.

In the present method, a photosensitizer can be used when polymerizing by irradiating ultraviolet rays. Examples of such a photosensitizer include benzophenone, acetophenone, and 2,2-dimethoxy-2-. Phenylacetophenone can be exemplified.

In the case of performing polymerization by heat, a thermal polymerization initiator can be used. Examples of such a thermal polymerization initiator include peroxides such as benzoyl peroxide and peroxydicarbonate; Azo compounds such as' -azobisisobutyronitrile and the like can be used alone or in combination.

One or more compounds shown in the above (1) to (4) are dissolved in a mixed solvent of a carbonate ester and another organic solvent in the presence of a Group Ia metal salt and a polymerization initiator. Then, the obtained solution is flowed or applied onto a flat substrate, and the solution is heated to polymerize and cure. In this case, after the solution is spread on a flat substrate, an organic solvent other than the carbonate may be evaporated. Examples of the solvent used here include methyl ethyl ketone, γ-butyrolactone, dimethylformamide and the like.

The gel polymer solid electrolyte according to the present invention comprises:
It has high ionic conductivity and is electrochemically stable. Such a gelled polymer solid electrolyte can be used for, for example, primary batteries, secondary batteries, capacitors, electrochemical devices such as electrochromic display devices, and medical actuators.

Further, the gelled polymer solid electrolyte according to the present invention can be used as a substitute for an organic electrolyte for a lithium ion battery. Furthermore, it can be used as a binder used for dispersing and fixing the powdered electrode material on the current collector.

When such a gelled polymer solid electrolyte is used in a battery, the battery can be manufactured by forming the gelled polymer solid electrolyte into a film shape and sandwiching it between a positive electrode and a negative electrode. .

In a battery manufacturing process having a step of forming a three-layer structure of a positive electrode, a separator and a negative electrode and then impregnating with an electrolytic solution, an acrylic acid ester monomer and a metal salt of Group Ia of the periodic table are used instead of the electrolytic solution. And a solution consisting of a non-aqueous solvent, and then cured.
Process modifications can be minimized.

[0083]

As described above, the gel polymer solid electrolyte according to the present invention has a high ionic conductivity and a high electrochemical conductivity because it contains an acrylate polymer as a polymer matrix and contains a specific non-aqueous solvent. Stable, for example, primary batteries,
It can be used for secondary cells, capacitors, electrochemical devices such as electrochromic displays, medical actuators, and the like.

[0084]

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

[0085]

Example 1 2-methacryloyloxyethyl methyl carbonate (the following formula
(V)), 50% by weight of 2-methacryloyloxyethyl methyl carbonate and 5% of propylene carbonate
0% by weight, a mixture of a Group Ia metal salt (LiN (C
A solution obtained by adding 2 mol% of F ₃ SO ₂ ) ₂ ) to the carbonate unit and 1 mol% of perloyl IPP50 (manufactured by NOF Corporation) to the acrylate monomer was made uniform, and the mixture was mixed with a glass plate. The solid was heated and cured at 70 ° C. for 30 minutes on a hot plate in an inert gas atmosphere to produce a gel polymer solid electrolyte having a thickness of about 1 mm.

[0086]

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The gel polymer solid electrolyte was punched into a disk having a diameter of 10 mm, sandwiched between electrodes provided on a conductivity measurement holder, and controlled at 25 ° C. by a Peltier device to obtain an impedance analyzer (HP4).
285A) and complex impedance measurement (measurement voltage 10m
V) was performed, and the ionic conductivity was measured analytically.

Table 1 shows the results.

[0089]

Example 2 In Example 1, the molar ratio of 2-methacryloyloxyethyl methyl carbonate and 2 (2-methacryloyloxyethoxy) ethyl methyl carbonate (the following formula (VI)) was 5: 5 as the acrylate. The gel polymer electrolyte was measured in the same manner as in Example 1 except that the acrylate monomer mixed as described above was used.

[0090]

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The ionic conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0092]

Example 3 In Example 1, di (2-methacryloyloxyethyl) carbonate (the following formula (VI) was used instead of the mixture of 50% by weight of 2-methacryloyloxyethyl methyl carbonate and 50% by weight of propylene carbonate.
I)) A gel polymer solid electrolyte was produced in the same manner as in Example 1 except that a mixture of 30% by weight and 70% by weight of propylene carbonate was used.

[0093]

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The ionic conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0095]

Example 4 In Example 3, the group Ia metal salt (L
A gel polymer solid electrolyte was produced in the same manner as in Example 3 except that iN (CF ₃ SO ₂ ) ₂ ) was replaced with LiPF ₆ .

The obtained gelled polymer solid electrolyte was measured for ionic conductivity in the same manner as in Example 1. Table 1 shows the results.

[0097]

Example 5 As an acrylate monomer, di (2-
Methacryloyloxyethyl) carbonate,
Di (2-methacryloyloxyethyl) carbonate 2
2.2 parts by weight, 66.5 parts by weight of propylene carbonate,
A liquid obtained by mixing 11.3 parts by weight of a metal salt of Group Ia (LiPF ₆ ) and adding 2 mol% of benzophenone to the polymerizable double bond of the acrylate monomer to obtain a uniform solution was placed on a glass plate. Cast, and in an inert gas atmosphere, an ultraviolet irradiation apparatus (Ushio Electric Co., Ltd .: UIS-2510)
2, using an optical fiber unit: SF-101Q)
Ultraviolet rays were irradiated from a position 7 cm above the substrate for 30 minutes to cure, thereby producing a gel polymer solid electrolyte having a thickness of about 0.5 mm.

The ionic conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0099]

Example 6 Using di (methacryloyltetra (oxyethylene)) carbonate (formula (VIII)) as an acrylate monomer, 33.3 parts by weight of di (methacryloyltetra (oxyethylene)) carbonate was used.
66.7 parts by weight of an electrolyte obtained by dissolving LiPF ₆ at a concentration of 1 mol / liter in a solvent in which ethylene carbonate and propylene carbonate are mixed at a weight ratio of 1: 1 are mixed,
Further, a liquid obtained by adding 2 mol% of perloyl IPP-50 to the polymerizable double bond of the acrylate monomer and making the solution uniform was cast on a glass plate and placed on an inert gas atmosphere at 70 ° C. on a hot plate. For 30 minutes to produce a gelled polymer solid electrolyte having a thickness of about 0.5 mm.

[0100]

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The ionic conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0102]

Example 7 As an acrylate monomer, di (2-
Using acryloyloxypropyl) carbonate (provided that the propyl group is a branched propyl group, the following formula (IX)), 25.0 parts by weight of di (2-acryloyloxyisopropyl) carbonate, ethylene carbonate and propylene carbonate are used. Li in a solvent mixed at a weight ratio of 1: 1
Electrolyte solution in which PF ₆ is dissolved at a concentration of 1 mol / liter75.
0 parts by weight, and 2 mol% of perloyl IPP-50 was added to the polymerizable double bond of the acrylate monomer, and the mixture was cast on a glass plate. 70 ° C on hot plate in atmosphere
For 30 minutes to produce a gelled polymer solid electrolyte having a thickness of about 0.5 mm.

[0103]

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(One of R ¹⁴ and R ¹⁵ is a methyl group and the other is a hydrogen atom. Also, one of R ¹⁶ and R ¹⁷ is a methyl group,
The other is a hydrogen atom. The ionic conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0105]

Example 8 The procedure of Example 7 was repeated, except that di (2-acryloyloxyisopropyl) carbonate was replaced with di (acryloyltetra (oxyethylene)) carbonate (formula (X)). A gel polymer solid electrolyte was produced.

[0106]

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The obtained gelled polymer solid electrolyte was measured for ionic conductivity in the same manner as in Example 1. Table 1 shows the results.

[0108]

Example 9 In Example 6, instead of di (methacryloyltetra (oxyethylene)) carbonate, di (2-methacryloyloxyethyl) carbonate and di (methacryloyltetra (oxyethylene)) carbonate were used in a weight ratio of 3%. A gel polymer solid electrolyte was produced in the same manner as in Example 6, except that the mixture mixed at 1: 1 was used.

The obtained gelled polymer solid electrolyte was measured for ionic conductivity in the same manner as in Example 1. Table 1 shows the results.

[0110]

Example 10 In Example 1, 2-methacryloyloxyethyl methyl carbonate and di-2-methacryloyloxyethyl carbonate were replaced with a mixture of 50% by weight of 2-methacryloyloxyethyl methyl carbonate and 50% by weight of propylene carbonate. Molar ratio = 1:
30% by weight of acrylate monomer mixed in 9
A gel polymer solid electrolyte was produced in the same manner as in Example 1 except that a mixture of propylene carbonate and 70% by weight of propylene carbonate was used.

The gelled solid polymer electrolyte was measured for ionic conductivity in the same manner as in Example 1. Table 1 shows the results.

[0112]

Example 11 In Example 3, the weight ratio of di (2-methacryloyloxyethyl) carbonate to methoxydiethylene glycol methacrylate (the following formula (XI)) was changed to 1: 1 instead of di (2-methacryloyloxyethyl) carbonate. A gel polymer solid electrolyte was produced in the same manner as in Example 3 except that the above procedure was repeated.

[0113]

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The gelled solid polymer electrolyte was measured for ionic conductivity in the same manner as in Example 1. Table 1 shows the results.

[0115]

EXAMPLE 12 In Example 3, a mixture of 50% by weight of di-2-methacryloyloxyethyl carbonate and 50% by weight of acrylonitrile was used in place of 2-methacryloyloxyethyl methyl carbonate, and a metal salt of Group Ia (LiN A gel polymer solid electrolyte was produced in the same manner as in Example 3 except that (CF ₃ SO ₂ ) ₂ ) was changed to LiPF ₆ .

The gelled solid polymer electrolyte was measured for ionic conductivity in the same manner as in Example 1. Table 1 shows the results.

[0117]

Example 13 In Example 5, di (2-methacryloyloxyethyl) was used as the acrylate monomer.
45.5 parts by weight of carbonate, NK ester M-40G
A mixture of 45.5 parts by weight of the following formula (XII), manufactured by Shin-Nakamura Chemical Co., Ltd. and 9.0 parts by weight of NK ester TMPT (lower formula (XIII), manufactured by Shin-Nakamura Chemical Co., Ltd.) A gel polymer solid electrolyte was produced in the same manner as in Example 5 except that the solid electrolyte was used.

[0118]

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The ionic conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0120]

Example 14 In Example 3, a solvent in which propylene carbonate and dimethyl carbonate were mixed at a ratio of 1: 1 (weight ratio) was used instead of propylene carbonate.
Group Ia metal salt (LiN (CF ₃ SO ₂ ) ₂ ) is converted to LiPF ₆
A gel polymer electrolyte was produced in the same manner as in Example 3 except that the above-mentioned was used.

The ionic conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0122]

EXAMPLE 15 In Example 3, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate were used in place of propylene carbonate in a ratio of 2: 2: 1.
A gelled polymer solid electrolyte was produced in the same manner as in Example 3 except that the Group Ia metal salt (LiN (CF ₃ SO ₂ ) ₂ ) was replaced with LiPF ₆ using a solvent mixed at (weight ratio). did.

The ion conductivity of the obtained gelled polymer solid electrolyte was measured in the same manner as in Example 1. Table 1 shows the results.

[0124]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/00 C08K 3/00 C08L 33/14 C08L 33/14 H01G 9/028 H01M 6/18 E H01M 6/18 6/22 C 6/22 10/40 B 10/40 H01G 9/02 331G

Claims (13)

[Claims] 1. An acrylate polymer containing a structural unit derived from at least one acrylate selected from acrylates represented by the following general formula (I) or (II): Matrix and (Wherein, R ¹ , R ² and R ² ′ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ has 1 to 4 carbon atoms. 4 represents an alkyl group, and n is an integer of 1 to 100.) (Wherein, R ^{4 to} R ⁹ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and p, q and r may be the same or different from each other. It is preferably an integer of 1 to 100.) (b) A gelled polymer solid electrolyte comprising: a nonaqueous solvent composed of a carbonate ester; and (c) a metal salt of Group Ia of the periodic table. 2. The acrylate polymer matrix is a acrylate homopolymer or copolymer selected from the acrylates represented by the general formulas (I) and (II). The gelled polymer solid electrolyte according to claim 1, wherein 3. The acrylate polymer matrix according to claim 1, wherein the acrylate polymer matrix comprises an acrylate ester represented by the general formula (I) or (II) and an acrylate ester represented by the general formula (I) or (II). 2. The gel polymer solid electrolyte according to claim 1, which is a copolymer with a copolymerizable vinyl monomer, vinylidene monomer or vinylene monomer. 4. The gel according to claim 3, wherein said vinyl monomer, vinylidene monomer or vinylene monomer is a vinyl ester, vinyl ether, (meth) acrylate, allyl ether, allyl ester or cyclic olefin. Polymer solid electrolyte. 5. The gel polymer solid according to claim 1, wherein the non-aqueous solvent is at least one carbonate selected from cyclic carbonates and chain carbonates. Electrolytes. 6. The cyclic carbonate is ethylene carbonate, propylene carbonate or a mixture thereof, and the chain carbonate is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate or a mixture thereof. The gel polymer solid electrolyte according to claim 5, wherein 7. The non-aqueous solvent is a mixed solvent of a cyclic carbonate and a chain carbonate.
Or a gel polymer solid electrolyte according to item 6. 8. The volume ratio of the cyclic carbonate to the chain carbonate (cyclic carbonate: chain carbonate) is 1
The ratio is 0:90 to 90:10.
8. The gelled polymer solid electrolyte according to any one of items 1 to 7. 9. The gel polymer solid according to claim 5, wherein the chain carbonate is a mixture of a symmetric chain carbonate and an asymmetric chain carbonate. Electrolytes. 10. The volume ratio of the symmetric chain carbonate to the asymmetric chain carbonate (symmetric chain carbonate: asymmetric chain carbonate) is 20:80 to 95: 5. The gel polymer solid electrolyte according to claim 9, wherein 11. The ratio of the total weight of the non-aqueous solvent to the total weight of the acrylate-based polymer is (total weight of non-aqueous solvent: total weight of the acrylate-based polymer) of 40:60 to 9
The gel polymer solid electrolyte according to any one of claims 1 to 10, wherein the ratio is 0:10. 12. The metal salt of Group Ia of the Periodic Table is LiCl
O ₄ , LiBF ₄ , LiPF ₆ , LiAsF ₆ , LiCF _{3
SO 3, LiN (CF 3 SO} 2) 2, LiC (CF 3 SO 2) according to claim 1 to 11 is one or more lithium salts selected from ₃
8. The gelled polymer solid electrolyte according to any one of the above. 13. A solution comprising a metal salt of Group Ia of the Periodic Table, a non-aqueous solvent comprising a carbonate, and a monomer of the general formula (I) or (II), being integrally polymerized. A method for producing a gelled polymer solid electrolyte according to any one of claims 1 to 12.