JP2002260441A - Polymeric solid electrolyte and method of making the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polymeric solid electrolyte that has high ion conductivity even at room temperature and has excellent film formability, flexibility and mechanical strength. SOLUTION: It is characterized in that this polymeric solid electrolyte contains a polymeric compound composed of a ring-opening polymer of an acrylate backbone-having oxetane compound of the following general formula (1), wherein a is 10-400, m1 is each independently 1-6, n1 is each independently 1<=n1<=20, and R1 and R2 is each independently an alkyl group which may be branched containing 1-12 carbon atoms or hydrogen atom, and electrolytic salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ion-conductive solid polymer electrolyte and a method for producing the same. More specifically, the present invention is a polymer solid electrolyte comprising a ring-opened polymer of an oxetane compound, which contains an alkali metal ion-based ion-conductive carrier such as lithium ion, and has a high ion conductivity. Having, and film-forming properties,
The present invention relates to a polymer solid electrolyte having excellent flexibility and mechanical strength. The polymer solid electrolyte of the present invention can be used as an electrolyte for a primary battery, a secondary battery, an electrochromic display element, a capacitor, and the like.

[0002]

2. Description of the Related Art Liquid electrolytes have been used as electrolytes for primary batteries, secondary batteries, electrochromic display elements, capacitors and the like. However, the liquid electrolyte has a problem of long-term reliability since the liquid electrolyte easily leaks to the outside of the component, elution of the electrode material, and the like. On the other hand, when the primary battery, the secondary battery, and the like are formed using a solid electrolyte, there is no problem such as the liquid leakage, and the safety and reliability of the battery are improved. Also, because it can be made thinner,
This has the advantage that the battery can be thinned and laminated, and the components can be reduced in size and weight. For this reason, solid electrolytes have attracted attention as materials for batteries and other electrochemical devices,
The research and development is being actively conducted.

[0003] Incidentally, it is generally desired that a solid electrolyte has high ionic conductivity and is excellent in film-forming property, flexibility and mechanical strength.

Conventionally, solid electrolyte materials are broadly divided into two types: those made of inorganic materials and those made of organic materials. Of these, solid electrolytes made of inorganic materials have relatively high ionic conductivity, but have poor mechanical strength due to being crystalline, and are often difficult to form and form into an arbitrary shape, and are generally high. Due to the price, there is a practical problem.

On the other hand, a polymer solid electrolyte using a polymer substance (polymer) can be formed into a thin film having flexibility, and a formed thin film is excellent in flexibility inherent in polymers. The thin film made of the polymer solid electrolyte has many advantages as compared with the solid electrolyte made of the inorganic material, because the thin film can be provided with the same mechanical properties. For this reason, a solid polymer electrolyte using a polymer substance (polymer) has been continuously developed as a solid electrolyte material for a high energy density battery such as a lithium secondary battery.

As such a solid polymer electrolyte, solid electrolytes using various polymers have been proposed. For example, a large number of solid electrolyte compositions comprising a combination of polymers such as polyethylene oxide, polypropylene oxide, polyethylene imine, polyepichlorohydrin, and polyethylene succinate and inorganic ionic salts such as Li and Na, and a large number of batteries using such compositions. It has been proposed (for example, JP-A-55-98480).

[0007]

However, these compositions do not have sufficient ionic conductivity, have higher ionic conductivity, and are excellent in film formability, flexibility and mechanical strength. There is a need for an electrolyte.

[0008]

Means for Solving the Problems As a result of repeated studies on oxetane derivatives, the present inventors have found that a polymer compound comprising a ring-opened polymer of a specific oxetane compound has high ionic conductivity, The present invention has been found to be a novel polymer solid electrolyte having excellent properties, flexibility and mechanical strength, and has led to the present invention.

That is, the present invention relates to an oxetane compound having an acrylate skeleton represented by the following general formula (1) (wherein, in the formula (1), a and b each independently represent 1
0 to 600, and m1 and m2 are each independently 1
And n1 and n2 are each independently 1 ≦ n1
≦ 20, ₁ ≦ n2 ≦ 20, and R ₁ and R ₂ are each independently an alkyl group having 1 to 12 carbon atoms or a hydrogen atom which may be branched. R ₃ and R ₄ are independently an alkyl group having 1 to 12 carbon atoms which may be branched. The present invention relates to a solid polymer electrolyte characterized by containing a polymer compound comprising a ring-opening polymer of (1) and an electrolyte salt.

[0010]

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In the present invention, an oxetane compound represented by the following general formula (2) or (3) (wherein m3 and m4 in formulas (2) and (3) each independently represent N3 and n4 are each independently 1 ≦ n3 ≦ 20, 1 ≦ n4 ≦ 20, and R _{5 to} R ₈ are each independently a carbon atom of 1 which may be branched. To 12), a polymer solid electrolyte having more excellent mechanical strength can be obtained.

[0012]

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[0013]

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Further, the present invention relates to an oxetane compound having an acrylate skeleton represented by the following general formula (1) (wherein, in the formula (1), a and b each independently represent 10 to 6)
00, m1 and m2 are each independently 1 to 6, and n1 and n2 are each independently 1 ≦ n1 ≦ 2
0 and 1 ≦ n2 ≦ 20, and R ₁ and R ₂ are each independently an alkyl group having 1 to 12 carbon atoms or a hydrogen atom which may be branched. R ₃ and R ₄ are independently an alkyl group having 1 to 12 carbon atoms which may be branched. ) In the presence of a catalyst.

[0015]

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In the present invention, the oxetane compound represented by the general formula (1) further contains at least one of the oxetane compounds represented by the general formulas (2) and (3) to open the ring. By polymerizing, a solid polymer electrolyte having excellent mechanical strength can be produced.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below.
I do. Electrolyte salt contained in solid polymer electrolyte of the present invention
As used in conventional solid polymer electrolytes
Can be used. For example, LiBr, LiC
1, LiI, LiSCN, LiBF_Four, LiAsF₆, L
iCLO_Four, CH_ThreeCOOLi, CF_ThreeCOOLi, Li
CF_ThreeSO_Three, LiPF₆, LiN (CF_ThreeSO_Two) _Two, Li
C (CF_ThreeSO_Two)_Three, LiN (C_TwoF_FiveSO_Two)_Two, LiP
F_Three(CF_Three)_Three, LiPF_Three(C_TwoF_Five)_Three, LiPF_Four(C
_TwoF_Five)_Two, LiPF_Three(Iso-C_ThreeF₇)_Three, LiPF
_Five(Iso-C_ThreeF₇) Etc. can be used
it can. In this case, use a single species as the electrolyte salt
Or a plurality of salts may be used simultaneously.

Further, as the electrolyte salt, a salt of the above-mentioned anion of the lithium salt and a salt of an alkali metal other than lithium, for example, potassium, sodium or the like can be used in combination. In the solid polymer electrolyte of the present invention, the constituent ratio of the oxetane compound having an acrylate skeleton and the electrolyte salt is such that the molar ratio of the electrolyte salt to the ether chain [-O-] ([electrolyte salt] / [ether chain]) is: 0.01-0.
9 is preferable.

As the oxetane compound used in the solid polymer electrolyte of the present invention, a compound represented by the aforementioned general formula (1) having units in which m1 and n1 are specified can be used alone. An oxetane compound having a plurality of types of units can be used alone or as a mixture. Further, m2, m3, n2 represented by the general formulas (2) and (3),
Compounds having a unit in which n3 is specified can be used alone or as a mixture, and compounds having a plurality of types of units can be used alone or as a mixture.

In the method for producing a solid polymer electrolyte of the present invention, examples of the catalyst used include the above-mentioned electrolyte salts and / or cationic initiators. As a catalyst, L
iBF ₄ , LiAsF ₆ , LiPF ₆ , LiN (CF ₃ SO
_When at least one electrolyte salt selected from ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) _{2 and the} like is used, it can be used also as an electrolyte salt contained in a solid polymer electrolyte,
Since the electrolyte salt can be uniformly dispersed in the obtained polymer compound, a polymer compound having excellent ionic conductivity and stable characteristics can be provided, which is preferable.

In the method for producing a solid polymer electrolyte of the present invention, at least one cation initiator such as a quaternary ammonium salt, a phosphonium salt, a sulfonium salt, a diazonium salt and an iodonium salt may be used as another catalyst. Species can be mentioned. Specific examples of the cationic initiator include quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, and tetrabutylammonium hydrogen sulfate; ethyltriphenylphosphonium antimony hexafluoride, tetrabutylphosphonium hexafluoride Phosphonium salts such as antimony bromide; triphenylsulfonium boron tetrafluoride, adekaopton SP-150 (manufactured by Asahi Denka Kogyo KK, counter ion: P
F ₆ ), Adeka Opton SP-170 (manufactured by Asahi Denka Kogyo KK, counter ion: SbF ₆ ), Adeka Opton CP-66
(Made by Asahi Denka Kogyo KK, counter ion: SbF ₆ ), Adeka Opton CP-77 (made by Asahi Denka Kogyo KK, counter ion: Sb
F _6), San-Aid SI-60L (Sanshin Chemical Industry Co., Ltd.,
Sulfonium salts such as SbF ₆ ); benzenediazonium chloride, benzenediazonium bromide, AMERICURE manufactured by American Can (counterion: BF)
₄ ) ULTRASET (counter ion: Asahi Denka Kogyo Co., Ltd.)
Diazonium salts such as BF ₄ and PF ₆ ); toluenediazonium iodide, diphenyliodonium arsenic hexafluoride, di-4-chlorophenyliodonium arsenic hexafluoride, UVE series manufactured by General Electric, Minnesota
Mining and Manufacturing F
C series, UV-9310C manufactured by Toshiba Silicone Co., Ltd.
(Counter ion: SbF ₆ ), Photoin by Rhone Poulin
and iodonium salts such as itiator 2074 (counter ion: (C ₆ F ₅ ) ₄ B).

Further, LiBr, LiCl, LiI, and LiSC are used together with at least one of the above-mentioned cationic initiators.
N, LiBF ₄ , LiAsF ₆ , LiClO ₄ , CH ₃ CO
OLi, CF ₃ COOLi, LiCF ₃ SO ₃ , LiP
F ₆ , LiN (CF ₃ SO ₂ ) ₂ , LiC (CF ₃ S
O ₂ ) ₃ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiPF ₃ (CF ₃ )
₃ , LiPF ₃ (C ₂ F ₅ ) ₃ , LiPF ₄ (C ₂ F ₅ ) ₂ , L
iPF ₃ (iso-C ₃ F ₇ ) ₃ , LiPF ₅ (iso-C ₃
At least one of electrolyte salts such as F ₇ ) may be used in combination.

The oxetane compound is mixed with the cation initiator and the electrolyte salt and heated or irradiated with light to thereby effect ring-opening polymerization to obtain the solid polymer electrolyte of the present invention. When ring-opening polymerization is carried out by heating, it is usually preferable to carry out in the presence of an organic solvent. When ring-opening polymerization is performed by irradiation with light such as ultraviolet rays or electron beams, it is preferable to remove the organic solvent in advance.

In the method for producing a solid polymer electrolyte according to the present invention, the organic solvents usually used include tetrahydrofuran, ethyl acetate, acetone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, dimethyl carbonate, diethyl carbonate, methyl ethyl Carbonate, methyl propyl carbonate, methyl isopropyl carbonate, methyl butyl carbonate, dipropyl carbonate, dibutyl carbonate, at least one of polar solvents such as acetonitrile is preferred, but other than those which do not significantly inhibit the ring-opening reaction of oxetane, Can be used alone or as a mixture with the polar solvent. Other organic solvents include, for example, ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl vinylene carbonate, cyclic carbonates such as vinyl ethylene carbonate, lactones such as γ-butyrolactone, 1,2-dimethoxyethane, 1,2-dimethoxyethane, and the like. Ethers such as 1,2-diethoxyethane and 1,2-dibutoxyethane, methyl propionate, methyl pivalate, octyl pivalate, and dimethylformamide.

The solid polymer electrolyte of the present invention can be prepared by, for example, casting a solution in which the oxetane compound represented by the general formula (1) and the catalyst are uniformly dissolved in the polar solvent on a flat substrate, By heating at a temperature of 40 ° C., preferably 40 to 100 ° C., the ring-opening reaction of oxetane can be carried out in parallel with the evaporation of the solvent to produce the oxetane. LiBF ₄ , LiAsF ₆ , L
When an electrolyte salt having relatively low thermal stability such as iPF ₆ is used, it is preferable to heat under reduced pressure.

In the solid polymer electrolyte of the present invention, the polymer compound as a structural material can be composed of only the polymer compound having the unit of the general formula (1). In addition to the polymer compound having the unit (1), at least one of the oxetane compounds represented by the general formulas (2) and (3) which are compatible with the polymer compound is contained and subjected to ring-opening polymerization. In addition, mechanical strength can be increased by intermolecular crosslinking. When at least one of the oxetane compounds represented by the general formulas (2) and (3) is contained, the content is not particularly limited, but if the content is excessively large, a gel-like cured product is obtained; It is preferably used in an amount of 20 to 2,000 parts by weight, particularly preferably 40 to 1500 parts by weight, per 100 parts by weight of the oxetane compound represented by the general formula (1), since the cured product has low properties. Further, it may be composed of a polymer blend obtained by blending another polymer compound.
In this case, examples of the other polymer compound include, for example, at least one polymer or copolymer of acrylates such as polyethylene oxide (PEO), ethylene carbonate methacrylate, hydroxyethyl methacrylate, and methoxytetraethylene glycol methacrylate. Can be. The blend ratio can be appropriately determined according to the ionic conductivity, flexibility, and the like required for the polymer solid electrolyte film. The amount of use is not particularly limited, but if it is excessively large, it causes bleeding, and if it is excessively small, a hard cured product is obtained.
It is preferable to use 00 parts by weight, especially 40 to 800 parts by weight.

The solid polymer electrolyte of the present invention can be used as various electrochemical device materials including high energy density batteries such as lithium batteries.

In the general formula (1) used in the present invention,
As the oxetane compound represented, for example, poly (3-
Methacryloxymethyl-3-ethyloxetane) (EH
O-MMA polymer; in the general formula (1), a = 10 to 40
0, m1 = 2, n1 = 1, R ₁= Methyl group, R₃= Echi
Group), poly (3-acryloxymethyl-3-ethyl)
Xetane) (EHO-MA polymer; in the general formula (1),
a = 10 to 400, m1 = 2, n1 = 1, R₁= Hydrogen source
Child, R₃Oxetane compounds such as
Copolymers with xylethylene acrylates
You. The polyoxyethylene catalyst in the general formula (1)
The relates are not particularly limited, but, for example,
Compounds such as (A) and (B) are exemplified. (A) Methoxy polyethylene glycol methacrylate M-20G (R₂= R₄= Methyl group, m2 = 2, n2 =
2, b = 10 to 400; manufactured by Shin-Nakamura Chemical Co., Ltd.) M-40G (R₂= R₄= Methyl group, m2 = 2, n2 =
4, b = 10 to 400; manufactured by Shin-Nakamura Chemical Co., Ltd.) M-90G (R₂= R₄= Methyl group, m2 = 2, n2 =
9, b = 10 to 400; manufactured by Shin-Nakamura Chemical Co., Ltd.) (B) Methoxy polyethylene glycol acrylate AM-90G (R₂= Hydrogen atom, R₄= Methyl group, m2
= 2, n2 = 9, b = 10-400; Shin-Nakamura Chemical
Made)

Examples of the oxetane compound represented by the general formula (2) include diethylene glycol bisoxetane (DDOE; in the general formula (2), m3 = 2 and n3 =
2, R ₅ = R ₆ = ethyl group), triethylene glycol bisoxetane (TrDOE; in the general formula (2), m3 =
_{2, n3 = 3, R 5} = R 6 = ethyl), tetraethylene glycol bisoxetane; in (TeDOE formula (2), m3 = 2, n3 = 4, R 5 = R 6 = ethyl group), and the like No.

The oxetane compound represented by the general formula (3) includes, for example, polyethylene glycol monomethyl ether oxetane (En3;
4 = 2, n4 = 3, R ₇ = ethyl group, R ₈ = methyl group), polyethylene glycol monomethyl ether oxetane (En9; in the general formula (3), m4 = 2, n4 =
9, R ₇ = ethyl group, R ₈ = methyl group), polyethylene glycol monomethyl ether oxetane (En12;
In the general formula (3), m4 = 2, n4 = 12, R ₇ = ethyl group, R ₈ = methyl group), polyethylene glycol monoethyl ether oxetane (m 4 = 2 in the general formula (3),
n4 = 3, R ₇ = ethyl group, R ₈ = ethyl group), polyethylene glycol monoiso-propyl ether oxetane (in the general formula (3), m4 = 2, n4 = 3, R ₇ = ethyl group, R ₈ = iso-propyl group), polyethylene glycol mono n-butyl ether oxetane (in the general formula (3), m4 = 2, n4 = 3, R ₇ = ethyl group, R ₈
= N-butyl group), polyethylene glycol monomethyl ether oxetane (m4 = 2, n4 in the general formula (3))
= 2, R ₇ = ethyl group, R ₈ = methyl group), polyethylene glycol monoethyl ether oxetane (m4 = 2, n4 = 2, R ₇ = ethyl group, R _{8 in the} general formula (3))
= Ethyl group), polyethylene glycol mono n-butyl ether oxetane (m4 = 2, n4 in the general formula (3))
= 2, R ₇ = ethyl group, R ₈ = n-butyl group) and the like. In addition, polypropylene glycol monomethyl ether oxetane (in the general formula (3), m4 =
3, n4 = 2, R ₇ = ethyl group, R ₈ = methyl group), polypropylene glycol monomethyl ether oxetane (in the general formula (3), m4 = 3, n4 = 3, R ₇ = ethyl group, R ₈ = methyl Group), polypropylene glycol mono n-propyl ether oxetane (m in formula (3)
4 = 3, n4 = 3, R ₇ = ethyl group, R ₈ = n-propyl group) and the like. Furthermore, polyethylene glycol monomethyl ether oxetane (m4 = 2, n4 = 6, R ₇ = ethyl group, R _{8 in the} general formula (3))
= Methyl group) and the like.

The oxetane compound represented by the general formula (1) used in the present invention, for example, EHO-MMA / A
The M-90G copolymer can be produced by the following method.

[EHO-MMA / AM-90G copolymer (in the general formula (1), R ₁ = methyl group, R ₂ = hydrogen atom,
R ₃ = ethyl group, R ₄ = methyl group, m1 = 2, n1 =
1, m2 = 2, n2 = 9, a = 10 to 400, b = 10
To 400)] First, Pattison (JA)
m. Chem. Soc. Reaction of trimethylolpropane with diethyl carbonate according to the method of 3-ethyl-3-hydroxymethyloxetane (E
HO). Then methyl methacrylate (MM
A) and the transesterification reaction between EHO and 3-methacryloxymethyl-3-ethyloxetane (EHO-M
MA). EHO-MMA and AM-9 obtained
0G (R ₂ = hydrogen atom, R ₄ = methyl group, m2 = 2, n
2 = 9, b = 10-400; manufactured by Shin-Nakamura Chemical Co., Ltd.) in the presence of a polymerization initiator such as 2,2′-azobis (isobutyronitrile) in a toluene solvent to obtain EHO-MMA. A copolymer can be obtained.

The oxetane compound represented by the general formula (2) suitably used in the present invention can be produced, for example, by the following method.

[Diethylene glycol bisoxetane (DDOE; in the general formula (2), m3 = 2, n3 = 2, R
₅ = R ₆ = ethyl group) Synthesis example] 50 g of diethylene glycol (DEG) and 13 of triethylamine (Et ₃ N) 13
6 g with a solvent such as 300 ml of chloroform,
Under a nitrogen atmosphere, methanesulfonyl chloride (MsCl)
140 g are added dropwise so as not to exceed 10 ° C. After the completion of the dropping, the temperature is gradually returned to room temperature to cause a reaction. Next, water is added to the reaction solution to recover an organic layer. The organic layer is washed with water, dehydrated, and then chloroform is distilled off to obtain an oil layer. Then 3-
Ethyl-3-hydroxymethyloxetane (EHO) 9
2 g and 68 g of a 35% sodium hydroxide solution were added to a solvent such as 300 ml of toluene, and after a predetermined amount of water was removed by azeotropic distillation, the oil layer previously synthesized was slowly added at a temperature of 40 to 50 ° C. After reacting at 60 ° C for about 1 hour,
For about 4 hours. Next, water is added to collect a toluene layer, and the toluene layer is washed with water, dried, and distilled under reduced pressure to obtain DDOE (1 mmHg, 178 ° C.) as a target substance.

By using triethylene glycol or tetraethylene glycol in place of ethylene glycol in the same manner as described above, triethylene glycol bisoxetane (TrDOE (1 mm
Hg, 195 ° C.); m3 = 2, n in the general formula (2)
3 = 3, R ₅ = R ₆ = ethyl group) or tetraethylene glycol bisoxetane (TeDOE (1 mmHg, 2
03 ° C.); m3 = 2, n3 = 4 in the general formula (2);
R ₅ = R ₆ = ethyl group) can be synthesized.

The oxetane compound represented by the general formula (3) can be produced, for example, by the following method.

[En3 (in the general formula (3), m4 = 2, n
Synthesis example of 4 = 3, R ₇ = ethyl group, R ₈ = methyl group)
3-ethyl-3-hydroxymethyloxetane (EH
O) 91 g and triethylamine (Et ₃ N) 115 g are added to a solvent of 300 ml of toluene, methanesulfonyl chloride (MsCl) is slowly added dropwise at a temperature not exceeding 10 ° C., and the mixture is stirred and reacted at room temperature. After the reaction,
Water and toluene are added, the toluene layer is collected, the toluene layer is further washed with water, dried and distilled under reduced pressure to give 3-ethyl-3- (methanesulfonyl) oxymethyloxetane (EHO-Ms (2 mmHg, 120 ℃))
Is obtained.

Next, the obtained EHO-Ms is reacted with a sodium salt of triethylene glycol monomethyl ether (NaO (CH ₂ CH ₂ O) ₃ CH ₃ ) in a solvent such as toluene, washed with water and distilled under reduced pressure. Thereby, En3 is obtained. En9 and En12 can be obtained in the same manner as in En3, except that purification is performed by a toluene extraction operation.

[0039]

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

Example 1 EHO-MMA / AM-90G copolymer (general formula (1)
Where, m1 = 2, n1 = 1, m2 = 2, n2 = 9, R ₁ =
Synthesis of methyl group, R ₂ = hydrogen atom, R ₃ = ethyl group, R ₄ = methyl group) First, Pattison (J. Am. Chem. So
c. Reaction of trimethylolpropane with diethyl carbonate by the method of 3-ethyl-3
-Hydroxymethyloxetane (EHO) was synthesized.
Next, transesterification of methyl methacrylate (MMA) and the EHO was performed. That is, 232 g of EHO and M were added to a four-necked flask equipped with a condenser, a thermometer and a stirrer.
MA 200g, dibutyltin oxide 10g and 2,6-te
After 6 g of rt-butyl-4-methylphenol was taken out and reacted for 2 hours while distilling methanol by heating in a hot water bath, unreacted MMA was removed under reduced pressure. Then n-
Hexane was added, washed with water, dried, and then 100 ° C., 2 mmHg
To give 3-methacryloxymethyl-3-ethyloxetane (EHO-MMA; a = 10 to 400) (yield 60%). The obtained EHO-MMA (5 g) and A
M-90G (10 g; manufactured by Shin-Nakamura Chemical Co., Ltd., m2 = 2, n
2 = 9, b = 10-400) were added to toluene (15 ml), and EHO-MMA and AM-
2,2′- in an amount of 0.5 mol% based on the total amount of 90G
Add azobis (isobutyronitrile) and polymerize at 80 ° C under nitrogen atmosphere to make EHO-MMA / AM-90G
Copolymer solution 1 (Mn38000, GPC measurement,
Standard polystyrene conversion) was obtained. Also, EHO-MMA
(10g) and AM-90G (5g) except for EH
An EHO-MMA / AM-90G copolymer solution 2 (Mn44000, GPC measurement, standard polystyrene conversion) was obtained in the same manner as in the O-MMA / AM-90G copolymer solution 1.

[Preparation of Polymer Solid Electrolyte Film] Copolymer solution 1 (3.5 g) obtained by the above method
Of LiPF ₆ dissolved in about 5 ml of acetonitrile with respect to the ether chain [Li ion] / [-O-unit]
= 0.025 to obtain a uniform solution. Next, the mixture was placed in a Teflon (registered trademark) Petri dish, reacted at 70 ° C. for 2 hours under a nitrogen atmosphere, and subsequently dried under reduced pressure at 70 ° C. for 7 hours to obtain a film of a ring-opened polymer (cured product) of an oxetane compound (cured product). Sample 1) was obtained. The obtained polymer solid electrolyte film was a flexible film. Hereinafter, samples were prepared under the conditions shown in Table 1. Sample 2 was obtained in the same manner as in Sample 1, except that the proportions of the oxetane compound and LiPF ₆ were changed. Sample 3 was obtained in the same manner as in Sample 1, except that Copolymer Solution 2 was used instead of Copolymer Solution 1. Also,
Copolymer solution 2 instead of copolymer solution 1
Sample 4 was obtained in the same manner as in Sample 2 except that Sample 5 was obtained in the same manner as in Sample 1, except that En3 (1.24 g) was mixed with Copolymer Solution 1 (3.5 g), followed by ring-opening polymerization. E
The amount of En9 shown in Table 1 was used in place of n3.
Samples 6 to 9 were obtained in the same manner as in Sample 5 except that the amount of iPF ₆ used was changed as shown in Table 1. Further, Sample 10 was obtained in the same manner as in the case of Sample 5, except that En12 in the amount shown in Table 1 was used instead of En3. In addition, DDOE as shown in Table 2 in place of En3,
Samples 11 to 13 were prepared in the same manner as in Sample 5, except that 0.03 g of each of TrDOE and TeDOE was used.
I got The thickness of the film can be appropriately adjusted to a predetermined thickness according to the purpose. However, in order to evaluate the ionic conductivity as described later,
〜150 μm was prepared.

[Evaluation of Ionic Conductivity] The ionic conductivity of the obtained polymer solid electrolyte film was evaluated as follows. That is, the polymer solid electrolyte film is pressed against an electrode of a stainless steel plate, a temperature-variable thermostat is set at a predetermined temperature, and an evaluation cell is put therein, so that the evaluation cell is in a steady state at that temperature. For about 1 hour. And
Constant voltage complex number impedance method (AC amplitude voltage 10m
V, AC frequency band 1 Hz to 500 kHz, temperature 30
C)), the ionic conductivity was analytically calculated from the semicircular arc portion obtained by the above method. The results are shown in Tables 1 and 2.

[0043]

[Table 1]

[0044]

[Table 2]

As can be seen from Tables 1 and 2, the polymer solid electrolyte films of Examples have a high ionic conductivity in a temperature range near room temperature, which is high in the conventional polymer electrolyte composed of PEO and other polymer compounds and alkali metal salts. It was confirmed that the ionic conductivity of the molecular solid electrolyte film was significantly higher than the ionic conductivity in a temperature region near room temperature.

[0046]

According to the present invention, it is possible to obtain a solid polymer electrolyte having high ionic conductivity even at around room temperature and having excellent film-forming properties, flexibility and mechanical strength.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08K 3/00 C08K 3/00 5H024 C08L 71/00 C08L 71/00 Z 5H029 H01B 1/12 H01B 1/12 Z 13 / 00 13/00 Z H01G 9/035 H01M 6/18 E 9/032 6/22 C H01M 6/18 10/40 B 6/22 H01G 9/02 311 10/40 321 F term (reference) 4J002 CH031 DD056 DD086 DE196 DG036 DG046 DH006 DK006 EG016 FD116 GQ02 4J005 AA07 BA00 BB04 4J027 AC02 AC06 BA07 CB08 4J100 AL08P AL08Q BA04Q BA08P BA08Q BC53P CA03 DA49 DA51 DA56 JA32 5G301 CA08 CA16 CD01 5H024 H01 FF01 BB01H11 FF01 BB01H11 BB01H01 FF AM16 CJ02 CJ11 DJ09 EJ12 HJ02 HJ10 HJ14

Claims (8)

[Claims] An oxetane compound having an acrylate skeleton represented by the following general formula (1)
Wherein a and b are each independently 10 to 600,
m1 and m2 are each independently 1 to 6, and n1 and n2 are each independently 1 ≦ n1 ≦ 20, 1 ≦ n2 ≦
R ₁ and R ₂ are each independently an alkyl group having 1 to 12 carbon atoms or a hydrogen atom which may be branched. R ₃ and R ₄ are independently an alkyl group having 1 to 12 carbon atoms which may be branched. A) a polymer solid electrolyte comprising a polymer compound comprising the ring-opened polymer of (a) and an electrolyte salt; Embedded image 2. The polymer compound of the following general formula (2)
Or an oxetane compound represented by (3) (wherein, in the formulas (2) and (3), m3 and m4 are each independently 1 to 6, and n3 and n4 are each independently 1 ≦ n
3 ≦ 20, 1 ≦ n4 ≦ 20, and R _{5 to} R ₈ are each independently an alkyl group having 1 to 12 carbon atoms which may be branched. 2. The polymer solid electrolyte according to claim 1, which contains the ring-opened polymer of the above (1). Embedded image Embedded image 3. An oxetane compound having an acrylate skeleton and an electrolyte salt having an ether chain [—O—]
The polymer solid electrolyte according to claim 1, wherein a molar ratio of the electrolyte salt to [(electrolyte salt) / [ether chain]) is 0.01 to 0.9. 4. An oxetane compound having an acrylate skeleton represented by the following general formula (1) (provided that the formula (1)
Wherein a and b are each independently 10 to 600,
m1 and m2 are each independently 1 to 6, and n1 and n2 are each independently 1 ≦ n1 ≦ 20, 1 ≦ n2 ≦
R ₁ and R ₂ are each independently an alkyl group having 1 to 12 carbon atoms or a hydrogen atom which may be branched. R ₃ and R ₄ are independently an alkyl group having 1 to 12 carbon atoms which may be branched. ) In which ring-opening polymerization is carried out in the presence of a catalyst. Embedded image 5. The polymer compound of the following general formula (2)
Or an oxetane compound represented by (3) (wherein, in the formulas (2) and (3), m3 and m4 are each independently 1 to 6, and n3 and n4 are each independently 1 ≦ n
3 ≦ 20, 1 ≦ n4 ≦ 20, and R _{5 to} R ₈ are each independently an alkyl group having 1 to 12 carbon atoms which may be branched. 5. The method for producing a solid polymer electrolyte according to claim 4, wherein the ring-opening polymerization is carried out in the presence of a catalyst after the addition of the compound (1). Embedded image Embedded image 6. The ring-opening polymerization is carried out by heating an organic solvent containing the catalyst at 30 to 150 ° C.
6. The method for producing a polymer solid electrolyte according to 5. 7. The method for producing a polymer solid electrolyte according to claim 4, wherein the catalyst is an electrolyte salt and / or a cationic initiator. 8. The organic solvent according to claim 6, wherein the organic solvent is a polar solvent.
The method for producing a solid polymer electrolyte according to the above.