JP2002150836A - Polymer solid electrolyte, and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer solid electrolyte which has high ion conductivity at room temperature, excellent film forming property, elasticity, and mechanical strength. SOLUTION: The polymer solid electrolyte contains a ring-opening polymer of oxetane compound with acrylate skeleton expressed by the formula (1), and electrolytic salt, (in the formula, a is 10-400, m1 is 1-6 independent with each other, n1 is 1<=n1<=20 independent with each other, and R1 and R2 are alkyl groups or hydrogen atoms with 1-12 carbons which may have side chain).

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 batteries using these compositions are numerous. 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) (where a is 10 to 400,
Are each independently 1 to 6, n1 is each independently 1 ≦ n1 ≦ 20, and R ₁ and R ₂ are each independently an optionally branched alkyl having 1 to 12 carbons. Group or a hydrogen atom. 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]

Embedded image

In the present invention, in the polymer compound, an oxetane compound represented by the following general formula (2) or (3) (wherein, in the formulas (2) and (3), m2 and m3 are each independently N is independently 1 ≦ n2 ≦ 20, and n3 is independently 1 ≦ n3 ≦ 2.
0 and R _{3 to} R ₆ are each independently an alkyl group having 1 to 12 carbon atoms which may be branched. By incorporating the ring-opening polymer of the above), a polymer solid electrolyte having further excellent mechanical strength can be obtained.

[0012]

Embedded image

[0013]

Embedded image

Further, the present invention is represented by the following general formula (1).
Oxetane compounds having an acrylate skeleton
In the formula (1), a is 10 to 400, and m1 is
Each independently represents 1 to 6, and n1 independently represents 1
≦ n1 ≦ 20 and R ₁And R_TwoAre independent
An alkyl group having 1 to 12 carbon atoms which may be branched
Is a hydrogen atom. ) In the presence of a catalyst
And a method for producing a solid polymer electrolyte.

[0015]

Embedded image

In the present invention, ring-opening polymerization is carried out by adding at least one of the oxetane compounds represented by the general formulas (2) and (3) to the oxetane compound represented by the general formula (1). By doing so, a polymer solid electrolyte having excellent mechanical strength can be manufactured.

[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, n represented by the general formulas (2) and (3)
Compounds having units in which n2 and n3 are specified can be used alone or in combination, and compounds having a plurality of types of units can be used alone or in combination.

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 Inc. (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, acetonitrile and the like. At least one kind of polar solvent is preferable, but other organic solvents can be used alone or in combination with the above-mentioned polar solvent as long as they do not extremely inhibit the ring-opening reaction of oxetane.

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 it is excessively large, a gel-like cured product is obtained.
If the amount is excessively small, a cured product having low flexibility will be obtained. Therefore, it is preferable to use 20 to 2000 parts by weight, particularly 40 to 1500 parts by weight, per 100 parts by weight of the oxetane compound represented by the general formula (1). 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 blending 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. Therefore, 20 to 10 parts by weight based on 100 parts by weight of the oxetane compound represented by the formula (1) is used.
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, R_Two= Ethyl
Group), poly (3-acryloxymethyl-3-ethyloxy)
Cetane) (EHO-MA polymer; in the general formula (1), a
= 10 to 400, m1 = 2, n1 = 1, R₁= Hydrogen source
Child, R_Two= Ethyl group) and the like.

Examples of the oxetane compound represented by the general formula (2) include diethylene glycol bisoxetane (DDOE; in the general formula (2), m2 = 2 and n2 =
2, R ₃ = R ₄ = ethyl group), triethylene glycol bisoxetane (TrDOE; in the general formula (2), m2 =
2, n2 = 3, R ₃ = R ₄ = ethyl group), tetraethylene glycol bisoxetane (TeDOE; general formula (2)
And m2 = 2, n2 = 4, and R ₃ = R ₄ = ethyl group.

The oxetane represented by the general formula (3)
As the compound, for example, polyethylene glycol monomer
Tyl ether oxetane (En3; in the general formula (3), m
3 = 2, n3 = 3, R_Five= Ethyl group, R₆= Methyl group),
Polyethylene glycol monomethyl ether oxetane
(En9; In the general formula (3), m3 = 2, n3 = 9, R _Five
= Ethyl group, R₆= Methyl group), polyethylene glycol
Lumonoethyl ether oxetane (in the general formula (3), m
3 = 2, n3 = 3, R_Five= Ethyl group, R₆= Ethyl group),
Polyethylene glycol mono iso-propyl ether
Oxetane (in the general formula (3), m3 = 2, n3 = 3, R
_Five= Ethyl group, R₆= Iso-propyl group), polyethylene
Glycol mono n-butyl ether oxetane (general
In the equation (3), m3 = 2, n3 = 3, R_Five= Ethyl group, R₆
= N-butyl group), polyethylene glycol monomethyl
Ether oxetane (m3 = 2, n3 in the general formula (3))
= 2, R_Five= Ethyl group, R₆= Methyl group), polyethylene
Glycol monoethyl ether oxetane (general formula
(3) where, m3 = 2, n3 = 2, R_Five= Ethyl group, R₆=
Ethyl group), polyethylene glycol mono n-butyl ether
-Teroxetane (in the general formula (3), m3 = 2, n3 =
2, R_Five= Ethyl group, R₆= N-butyl group)
Can be. In addition, polypropylene glycol monomethyl
Ruether oxetane (m3 = 3, n in the general formula (3))
3 = 2, R_Five= Ethyl group, R₆= Methyl group), polypropylene
Lenglycol monomethyl ether oxetane (general formula
(3) where m3 = 3, n3 = 3, R_Five= Ethyl group, R₆=
Methyl group), polypropylene glycol mono n-propyl
Ruether oxetane (m3 = 3, n in the general formula (3))
3 = 3, R_Five= Ethyl group, R₆= N-propyl group)
I can do it. In addition, polyethylene glycol
No methyl ether oxetane (m3 =
2, n3 = 6, R_Five= Ethyl group, R₆= Methyl group)
I can do it.

The oxetane compound represented by the general formula (1) used in the present invention, for example, an EHO-MMA polymer can be produced by the following method.

[EHO-MMA polymer (general formula (1)
Medium, m1 = 2, n1 = 1, R ₁ = methyl group, R ₂ = ethyl group) First, Pattisson (J. Am. C.)
hem. Soc. , 1957, 79) to react trimethylolpropane with diethyl carbonate.
-Ethyl-3-hydroxymethyloxetane (EHO)
Are synthesized. Next, 3-methacryloxymethyl-3-ethyloxetane (EHO-MMA) was obtained by transesterification of methyl methacrylate (MMA) and the EHO.
Are synthesized. The EHO-MMA polymer can be obtained by polymerizing the obtained EHO-MMA in the presence of a polymerization initiator such as 2,2'-azobis (isobutyronitrile).

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), m2 = 2, n2 = 2, R
Example of synthesis of ₃ = R ₄ = ethyl group) 50 g of diethylene glycol (DEG) and 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, 110 ° C
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.); m2 = 2, n in the general formula (2)
2 = 3, R ₃ = R ₄ = ethyl group) or tetraethylene glycol bisoxetane (TeDOE (1 mmHg, 20
3 ° C.); m2 = 2, n2 = 4, R in the general formula (2)
₃ = R ₄ = ethyl group).

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

[En3 (in the general formula (3), m3 = 2, n
Synthesis example of 3 = 3, R ₅ = ethyl group, R ₆ = methyl group) 3
-Ethyl-3-hydroxymethyloxetane (EHO)
91 g and 115 g of triethylamine (Et ₃ N) are added to a solvent of 300 ml of toluene, methanesulfonyl chloride (MsCl) is slowly added dropwise so as not to exceed 10 ° C., and the mixture is stirred and reacted at room temperature. After the completion of the reaction, water and toluene were added to collect a toluene layer. The toluene layer was further washed with water, dried, and distilled under reduced pressure to obtain a toluene layer.
-Ethyl-3- (methanesulfonyl) oxymethyloxetane (EHO-Ms (2 mmHg, 120 ° C)) 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 is also obtained in the same manner as 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 polymer (in the general formula (1), m1 =
2, n1 = 1, R ₁ = methyl group, R ₂ = ethyl group)] First, Pattison (J. Am. Chem. S.)
oc. Reaction of trimethylolpropane with diethyl carbonate by the method of 3-ethyl-
3-Hydroxymethyloxetane (EHO) was synthesized. Then, methyl methacrylate (MMA) and the EH
An O transesterification reaction was performed. That is, EHO232 was added to a four-necked flask equipped with a condenser, a thermometer and a stirrer.
g, MMA 200 g, dibutyltin oxide 10 g and 2,
6 g of 6-tert-butyl-4-methylphenol was taken, reacted for 2 hours while heating in a hot water bath and allowing methanol to flow out, and then unreacted MMA was removed under reduced pressure. Next, n-hexane was added to the residue, washed with water, dried,
Distillation at mmHg gave 3-methacryloxymethyl-3-ethyloxetane (EHO-MMA) (yield 60).
%). To the obtained EHO-MMA (0.5 g) and En9 (2.15 g) synthesized by the above method, 1 mol% of 2,2′-based on EHO-MMA was used as a polymerization initiator.
Azobis (isobutyronitrile) was added and polymerized at 80 ° C. under a nitrogen atmosphere to form an EHO-MMA polymer (a =
250). Further, the EHO-MMA polymer can be obtained in a solution such as toluene or xylene, and the polymerization method is not limited at all. [Preparation of polymer solid electrolyte film] The EHO-MMA polymer (a = 250, 0.5
g) was dissolved in 2 g of tetrahydrofuran, and then [Li ion] / [-O was added to the ether chain of the oxetane compound.
−unit] = 0.075 LiN (C ₂ F ₅ SO ₂ ) ₂ as an electrolyte salt to obtain a uniform solution. Next, it was placed in a Teflon (registered trademark) petri dish and reacted at 100 ° C. for 4 hours under a nitrogen atmosphere to obtain a film (sample 1) of a ring-opened polymer (cured product) of an oxetane compound. The obtained polymer solid electrolyte film was a flexible film. Samples 2 and 3 were obtained in the same manner as in Sample 1, except that the proportions of the oxetane compound and LiN (C ₂ F ₅ SO ₂ ) ₂ were changed. In addition, EHO-MMA (0.25
g) and En9 (2.15 g) were used in the same manner as in Example 1 except that the proportions of EnN (2.15 g) were changed to LiN (C) as shown in Table 1.
To obtain a sample 4-7 by the same as Sample 1 method in place of ₂ proportion of F ₅ SO _{2) 2.} In addition, EHO-MMA (0.7
5g) and En9 (2.15 g), except that the proportions used were changed to the EHO-MMA polymer (a = 300) obtained in the same manner as in Example 1 except that LiN was added as shown in Table 1.
Samples 8 to 10 were obtained in the same manner as in Sample 1, except that the proportion of (C ₂ F ₅ SO ₂ ) ₂ used was changed. Sample 11 was obtained in the same manner as in Sample 1, except that En3 (2.15 g) was used instead of En9. Also, EHO-MMA
(0.25 g) and En9 (2.15 g) with additional DDO
Sample 12 to which E (0.25 g) was added, and EHO-M
MA (0.25 g) and En9 (2.15 g) further T
Sample 13 to which rDOE (0.25 g) was added, and EH
Sample 14 in which TeDOE (0.25 g) was further added to O-MMA (0.25 g) and En9 (2.15 g) was obtained in the same manner as in Sample 1. Samples 12 to 14
In Table 1, the use ratio of LiN (C ₂ F ₅ SO ₂ ) ₂ was changed as shown in Table 1. In addition, about the thickness of a film, although it can produce suitably to predetermined thickness according to the objective, here, in order to evaluate ionic conductivity as mentioned later, the thing of 50-150 micrometers in thickness was produced. .

[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. Table 1 shows the results.

[0042]

[Table 1]

As can be seen from Table 1, the polymer solid electrolyte film of the example has a ionic conductivity in the temperature range near room temperature, and the polymer solid electrolyte film comprises a conventional PEO or other polymer compound and an alkali metal salt. It was confirmed that the film had a significantly higher ionic conductivity in the temperature region near room temperature.

[0044]

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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/02 C08L 71/02 5H024 H01B 13/00 H01B 13/00 Z 5H029 H01G 9/035 H01M 6/18 E 9/028 10/40 B // H01M 6/18 H01G 9/02 311 10/40 331G F term (reference) 4J002 CH031 CH032 DD056 DD086 DE196 DG036 DK006 EG026 EV256 EW016 FD116 GQ00 4J005 AA07 BB02 4J027 AC02 AC03 AC03 CC02 4J100 AL08P BA02P BA08P BC53P CA01 JA43 5G301 CA30 CD01 CE01 5H024 AA12 FF23 FF31 5H029 AJ01 AK00 AL00 AM16 DJ09

Claims (8)

[Claims] An ac relay represented by the following general formula (1):
Oxetane compound having a skeleton of formula (1)
Wherein a is 10 to 400, and m1 is each independently
1 to 6, wherein n1 is independently 1 ≦ n1 ≦ 20
And R ₁And R_TwoAre each independently branched
An alkyl group having 1 to 12 carbon atoms or a hydrogen atom
is there. ) A polymer compound comprising a ring-opening polymer and an electrolyte salt
And a solid polymer electrolyte comprising: 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), m2 and m3 are each independently 1 to 6, and n2 is each independently 1 ≦ n2 ≦ 2
0 and n3 each independently represent 1 ≦ n3 ≦ 20, and R _{3 to} R ₆ each independently represent 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 ac relay represented by the following general formula (1).
Oxetane compound having a skeleton of formula (1)
Wherein a is 10 to 400, and m1 is each independently
1 to 6, wherein n1 is independently 1 ≦ n1 ≦ 20
And R ₁And R_TwoAre each independently branched
An alkyl group having 1 to 12 carbon atoms or a hydrogen atom
is there. ) Ring-opening polymerization in the presence of a catalyst
A method for producing a solid polymer electrolyte. Embedded image 5. An oxetane compound represented by the following general formula (2) or (3) (wherein m2 and m2 in the formulas (2) and (3)) m3 is each independently 1 to 6, n2 is each independently 1 ≦ n2 ≦ 20, and n3 is each independently 1
≦ n3 ≦ 20, and R _{3 to} R ₆ 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.