JP2001325990A - Solid polymer electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid polymer electrolyte which is non-halogen having high in-combustibility, and is excellent in electric conductivity. SOLUTION: It is the solid polymer electrolyte which has a structural unit consisting of a formula A and a formula B, and has the structural unit of formula B in 20-70 weight % of all the structural unit, and contains polycarbonate whose ultimate viscosity is 0.2-2.0 dl/g and a metal salt of I group, II group carrying out ion dissociation. In the formula A, R1-R4 are H, alkyl, aryl, alkenyl, alkoxy, and aralkyl group. X is O, CO, S, SO, etc., and in the formula B, Y is a mono-polymer body or a random copolymer of Si (R16) (R17) O, or Si (R18) (R19), and R9-R19 are H, substitutable alkyl group, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ion-conductive polymer electrolyte and a polymer battery using the same.

[0002]

2. Description of the Related Art With the recent rapid market expansion of small home appliances such as video cameras, notebook computers, and mobile phones, and portable information devices, small-sized batteries using lithium ion as an electrolyte are used as batteries for these devices. Demand for thin secondary batteries is growing rapidly. In addition, there is an increasing demand for lightweight and large-capacity secondary batteries for electric assist bicycles, electric vehicles, auxiliary power supplies for fuel cell vehicles, and motorcycles. Against this background, the development of ion-conductive polymer electrolytes for realizing lightweight, thin-film batteries has been actively pursued in recent years. Ion conductive polymer electrolytes are mainly divided into polymer solid electrolytes containing no organic solvent and polymer gel electrolytes containing an organic solvent, but polymer gel electrolytes containing an organic solvent are the mainstream due to the problem of ionic conductivity. Has become.

The binder resin used for the polymer gel electrolyte is, for example, polyvinylidene fluoride in JP-A-57-143356, polyethylene oxide in JP-A-5-109310, and JP-A-4-3086.
No. 60 is a polymethyl methacrylate resin (PMM
A) was disclosed. Among them, JP-A-11-6087
No. 0 describes that the ionic conductivity is improved by blending a polyvinylidene fluoride-tetrafluoroethylene copolymer with bisphenol Z polycarbonate.

[0004] However, in today's environment where environmental problems such as soil contamination of an industrial waste landfill are becoming more and more important, a gasification and melting furnace capable of weight reduction and energy recovery rather than reclaiming and discarding expired batteries. Assuming that the waste is treated by combustion, etc., there is a demand for reducing the use of fluororesin, which is a hydrogen fluoride generation source that damages the furnace during combustion. Furthermore, polyethylene oxide and PMMA are insufficient from the viewpoint of flame retardancy in lithium ion batteries containing an organic solvent and possibly causing ignition, and the above-mentioned Japanese Patent Application Laid-Open No. Hei 11-60870 is not satisfactory in terms of conductivity. It wasn't something that could be done, and an improvement was desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a binder for a solid polymer electrolyte, which has a conventional problem and does not generate hydrogen fluoride and has flame retardancy.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the conventional problems and as a result, have found that a copolymerized polycarbonate resin derived from a specific bisphenol and a bisphenol having a polysiloxane structure has been produced. The polymer solid electrolyte used as the binder has high ionic conductivity and is non-halogen and has flame retardancy, and has been found to be a good polymer solid electrolyte for a polymer battery. Thus, the present invention has been completed.

That is, the present invention has a structural unit represented by the general formula (A) and the general formula (B), wherein the structural unit of the general formula (B) accounts for 20 to 70% by weight of all the structural units, and An object of the present invention is to provide a solid polymer electrolyte comprising a polycarbonate having an intrinsic viscosity of 0.2 to 2.0 dl / g and a metal salt of a Group I or Group II ion-dissociated, and a polymer battery using the same.

[0008]

Embedded image (Wherein, R _{1 to} R ₄ are each independently hydrogen, carbon 1
An alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. When it has an atom, it may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
X is

Embedded image Wherein R _{5 and} R ₆ are each hydrogen and carbon number 1
An alkyl group having 10 to 10, an alkenyl group having 2 to 10 carbon atoms,
Represents an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group in which R _{5 to} R ₆ are bonded together to form a carbocyclic or heterocyclic ring; When it has a carbon atom, it may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ₇ ~R
₈ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a is 0
Represents an integer of -20. )

Embedded image (In the formula, R _{9 to} R ₁₀ are each independently hydrogen, carbon atom 1
An alkyl group having 5 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. When it has an atom, it may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
R _{11 to} R ₁₄ each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, and 2 to 5 carbon atoms.
An alkenyl group, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. When these groups have a carbon atom, the alkyl group having 1 to 5 carbon atoms, An alkenyl group of 2 to 5 or 1 carbon atom
It can also have up to 5 alkoxy groups. R ₁₅ represents an alkylene group having 1 to 6 carbon atoms or an alkylidene group, or simply represents a bond. Y _{is, -Si (R 16) (R} 17) O- and / or -Si (R ₁₈₎ represents (R ₁₉₎ O- homopolymers or random copolymers, polymerization degree is at 0 to 200 , R
_{16 to} R ₁₉ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or An aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a
It can also have 5 alkoxy groups. )

[0009]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate used as a material of the polymer solid electrolyte of the present invention can be prepared by a known method used for producing a polycarbonate from bisphenol A and a carbonate-forming compound, for example, a method of preparing bisphenols and phosgene. A method such as a direct reaction (phosgene method) or a transesterification reaction between a bisphenol and a bisaryl carbonate (a transesterification method) can be employed.

In the former phosgene method, the bisphenols deriving the general formula (A) and the polysiloxane compound deriving the general formula (B) in the present invention are usually combined with a phosgene in the presence of an acid binder and a solvent. And react with. Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. Furthermore, in order to promote the condensation polymerization reaction,
Tertiary amine catalysts such as triethylamine and catalysts such as quaternary ammonium salts, and for controlling the degree of polymerization,
Monofunctional compounds such as phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols, alkyl hydroxybenzoates and alkyloxyphenols are added as molecular weight regulators. Further, if desired, sodium sulfite, an antioxidant such as hydrosulfite, and phloroglucin, isatin bisphenol,
1,1,1-tris (4-hydroxyphenyl) ethane, α,
A small amount of a branching agent such as α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene may be added. The reaction is usually performed at 0 to 150 ° C., preferably 5 to 50 ° C. The reaction time depends on the reaction temperature, but is usually from 0.5 minutes to 10 hours, preferably from 1 minute to 2 hours. It is desirable to keep.

On the other hand, in the latter transesterification method,
In the present invention, a bisphenol derived from the general formula (A) and a polysiloxane compound derived from the general formula (B) are mixed with a bisaryl carbonate and reacted at a high temperature under reduced pressure. At this time, a monofunctional compound such as phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols, alkyl hydroxybenzoates and alkyloxyphenols may be added as a molecular weight regulator. The reaction is usually performed at a temperature in the range of 150 to 350 ° C, preferably 200 to 300 ° C,
Further, the degree of reduced pressure is finally preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate generated by the transesterification are distilled out of the system. The reaction time depends on the reaction temperature and the degree of pressure reduction, but is usually about 1 to 6 hours. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon. Further, if desired, the reaction may be performed by adding an antioxidant or a branching agent.

In the phosgene method and the transesterification method, the phosgene method is more preferable in consideration of the reactivity of the bisphenols deriving the general formula (A) structure and the bisphenol compounds deriving the general formula (B) structure.

The bisphenols derived from the general formula (A) used for the production of the polycarbonate in the present invention are specifically 4,4'-biphenyldiol, bis (4-hydroxyphenyl) methane, bis ( 4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4 -Hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) ) Butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2-
Bis (4-hydroxy-3-methylphenyl) propane (dimethylbisphenol A), 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol A
P; BPAP), bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-allylphenyl)
Propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane, 9,9-bis (4-hydroxy-3
-Methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol and the like. These can be used in combination of two or more. Among them, 9,9-bis (4-hydroxy
-3-methylphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane And 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (4-hydroxy-3-methylphenyl) propane are preferred.

The polysiloxane compound derived from the general formula (B) used in the production of the polycarbonate in the present invention includes, specifically,

Embedded image And the like.

These can be used in combination of two or more. Among them, in particular, random copolymerization of dimethylsiloxane having a 3- (2-hydroxyphenyl) propyl group at both terminals and diphenylsiloxane, or α, ω-bis [3
-(o-Hydroxyphenyl) propyl] polydimethylsiloxane is preferred.

On the other hand, examples of the carbonate-forming compound include phosgene, diphenyl carbonate, and di-carbonate.
Examples include bisallyl carbonates such as p-tolyl carbonate, phenyl-p-tolyl carbonate, and dinaphthyl carbonate. These compounds can be used in combination of two or more.

In the present invention, phloroglucin, isatin bisphenol, 1,1,1-bisphenols derived from the general formula (A) are generally used in an amount of 0.1 to 4 mol% relative to the bisphenols.
Tris (4-hydroxyphenyl) ethane, α, α ', α "-
It is possible to add a branching agent such as tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene to obtain a branched polycarbonate. Branching may result in a structure that can more easily hold the metal salt.

The polycarbonate polymer synthesized by these reactions can be molded by known molding methods such as extrusion molding, injection molding, blow molding, compression molding, and wet molding. It is desirable that the resin can be easily formed by wet molding, film forming by extrusion, and compression stretching. The range for maintaining the moldability and mechanical strength required for that purpose is the intrinsic viscosity of 0.2 to
It is preferably in the range of 2.0 dl / g.

Further, the structural unit of the general formula (B) preferably accounts for 20 to 70% by weight of all the structural units. If the general formula (B) is less than 20% by weight, the flame retardant effect is small, and if it exceeds 70% by weight, the mechanical strength required for the polymer solid electrolyte is insufficient.

The above solid polymer electrolytes include other polycarbonates, ethylene-vinyl acetate copolymers, poly (meth)
The polymer alloy may contain one or more of acrylate, polyethylene oxide, polyacrylonitrile, vinylidene fluoride-6-acetone fluoride copolymer, polyvinylidene fluoride and the like. However, the amount of the fluorinated resin is preferably 30% by weight or less for the purpose of the present invention.

Next, a specific method for producing a solid polymer electrolyte will be described. The production is preferably carried out in a dry room or a glove box with low moisture content. First, a polymer is dispersed and dissolved in a solvent. The solvent at this time may be appropriately selected from various solvents in which the polymer can be dissolved, for example, tetrahydrofuran (THF), dioxane, toluene,
It is preferable to use cyclohexanone, methyl acetate, acetone, dimethylformamide and the like. The concentration of the polymer with respect to the solvent is preferably 5 to 25% by weight.

Next, an electrolytic solution is added to the polymer solution.
You. The electrolyte is a solution in which the electrolyte is dissolved in an organic solvent.
Suitable for use in lithium secondary batteries.
It is sufficient to select and use as appropriate. As the electrolyte, metal salts
And the general formula M⁺X^-Is exemplified, and M⁺Is
Li⁺, Na⁺, K⁺One selected from the group of
X ^-Is ClO_Four ^-, BF_Four ^-, PF₆ ^-, CF_ThreeSO_Three
^-, (CF_ThreeSO_Two)_TwoN ^-, (C_TwoF_FiveSO_Two)_TwoN
^-, (CF_ThreeSO_Two)_ThreeC^-, (C_TwoF_FiveSO_Two) _ThreeC
^-Being at least one member selected from the group consisting of
preferable. Further, when applied as a lithium secondary battery
Is LiPF₆, LiClO_Four, LiBF_Four, LiCF
_ThreeSO_Three, LiN (CF_ThreeSO_Two)_TwoEtc. are used.
The concentration of such a non-aqueous solvent-based electrolyte salt is preferably
It is 0.5 to 3 mol / l.

Examples of the solvent for the electrolyte include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolan,
Non-aqueous solvents such as methyldioxolan, γ-butyrolactone, sulfolane, 3-methylsulfolane, dimethoxyethane, diethoxyethane, ethoxymethoxyethane, and ethyldiglyme can be used. The content of the electrolyte is preferably a weight ratio of polymer: electrolyte = 50: 50 to 20:80.

A mixed solution of a polymer solution and an electrolytic solution (hereinafter abbreviated as “gel electrolyte solution”) is applied on a substrate. This substrate may be anything as long as it is smooth. For example, polyester film, glass, polytetrafluoroethylene film, and the like. The means for applying the gel electrolyte solution to the substrate is not particularly limited, and may be appropriately determined according to the material and shape of the substrate. Generally, a metal mask printing method, an electrostatic coating method, a dip coating method, a spray coating method, a roll coating method, a doctor blade method, a gravure coating method, a screen printing method, and the like are used. Thereafter, if necessary, a rolling treatment is performed by a flat plate press, a calender roll, or the like.

After the coating, if the solvent in which the polymer is dissolved is evaporated, a polymer solid electrolyte film is completed. The temperature at which the solvent is evaporated may be room temperature, but may be heated. The resulting solid polymer electrolyte is translucent and elastic.

The electrolytic solution may be mixed at the time of preparing the gel electrolyte solution as described above, but it may be impregnated with the electrolytic solution after preparing a film containing no electrolytic solution in advance. In order to increase the film strength and swelling property,
iO ₂ or the like may be added as a filler.

The structure of the secondary battery using the polymer solid electrolyte of the present invention, in particular, the structure of the lithium secondary battery is not particularly limited. Usually, it is applied to a stacked battery, a cylindrical battery, and the like.

The electrode used in combination with the solid polymer electrolyte of the present invention preferably uses a composition comprising an electrode active material, the solid polymer electrolyte, and if necessary, a conductive additive.

For the negative electrode, a negative electrode active material such as a carbon material, lithium metal, lithium alloy or oxide material is used. For the positive electrode, an oxide or carbon capable of intercalating / deintercalating lithium ions is used. It is preferable to use a suitable positive electrode active material. By using such an electrode, a lithium secondary battery having excellent characteristics can be obtained.

The carbon material used as the electrode active material may be appropriately selected from, for example, mesocarbon microbeads (MCMB), natural or artificial graphite, resin fired carbon material, carbon black, carbon fiber and the like. These are used as powders.

As the oxide capable of intercalating / deintercalating lithium ions, a composite oxide containing lithium is preferable. For example, LiCoO ₂ , LiM
_{n 2 O 4, LiNiO 2,} LiV 2 O 4 and the like. The average particle size of the oxide powder is preferably about 1 to 40 μm.

[0032] The conductive additive optionally added includes
Preferable are metals such as graphite, carbon black, carbon fiber, nickel, aluminum, copper, silver and the like, and graphite is particularly preferable.

The electrode composition is such that a positive electrode has an active material: a conductive auxiliary agent:
Polymer solid electrolyte = 30 to 90: 3 to 10:10 to 70
And the total amount of the active material, the conductive additive and the solid polymer electrolyte is preferably 100 parts by weight. In the negative electrode, the active material: the conductive auxiliary agent: the polymer solid electrolyte is in a weight ratio of 30 to 90: 0 to 10:10 to 70, and the total amount of the active material, the conductive auxiliary agent, and the solid polymer electrolyte is Preferably it is 100 parts by weight.

In the present invention, the above-mentioned negative electrode active material and / or positive electrode active material, preferably both active materials are mixed in the above-mentioned gel electrolyte solution and adhered to the surface of the current collector.

For example, an electrode coating solution obtained by mixing a gel electrolyte solution with an active material and, if necessary, a conductive material such as a carbon material and a metal is placed on a current collector such as a copper foil or an aluminum foil. It is prepared by coating and evaporating the solvent. Note that a metal foil, a metal mesh, or the like is usually used as the current collector. Although the metal mesh has a smaller contact resistance with the electrode than the metal foil, in the case of the polymer solid electrolyte of the present invention, the contact resistance is sufficiently reduced even with the metal foil.

As described above, by using the same polymer material as the polymer solid electrolyte also for the electrode, the adhesion to the polymer solid electrolyte is improved, and the internal resistance is reduced. When lithium metal or lithium alloy is used as the negative electrode active material, the composition of the negative electrode active material and the solid polymer electrolyte may not be used.

[0037]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

EXAMPLE 1 75.6 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was added to 450 ml of an 8.8% (w / v) aqueous sodium hydroxide solution.
(Hereinafter abbreviated as BCFL, 0.2 mol) and hydrosulfite
1 g was added and dissolved. 360 ml of methylene chloride is added thereto, and while stirring at 15 ° C., 34 g of phosgene is added to 30 ml.
I blew it over a minute. After the completion of the blowing, the reaction solution was emulsified by vigorous stirring, and after 1 minute, 2.2 g of p-tert-butylphenol (hereinafter abbreviated as PTBP, 0.015 mol
l) and 81 g of the following polysiloxane compound (hereinafter abbreviated as Si1; 0.022 mol) were added, and the mixture was further stirred for 10 minutes and then 0.2 m
l of triethylamine was added, and stirring was continued for another 50 minutes to carry out polymerization.

[0039]

Embedded image

The polymer solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the washing was repeated until the conductivity of the washing solution became 10 μS or less, to obtain a purified resin solution. The obtained purified resin solution was slowly dropped into 60 ° C. warm water under vigorous stirring to solidify the polymer while removing the solvent.
The solid was filtered and dried to obtain a white powdery polymer. This polymer has a concentration of 0.5 g using methylene chloride as a solvent.
/ Dl solution at 20 ° C intrinsic viscosity [η] is 0.39dl
/ G. (Huggins calculation as a constant 0.45) results obtained above polymer was analyzed from the infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, carbonate It was confirmed to have a bond.
Further, absorption derived from siloxane was also observed at the positions of 1100 to 1020 cm ^-1 . From the results, this polymer was confirmed to be a polycarbonate polymer having the following structural units.

[0041]

Embedded image

Next, in an argon glove box, a water content of 3 was placed in a 300 ml Erlenmeyer flask as follows.
0 ppm or less of tetrahydrofuran (hereinafter abbreviated as THF)
22.5 g, 10.5 g of 1M LiClO ₄ / (ethylene carbonate + propylene carbonate having a volume mixing ratio of 50%) solution and 4.5 g of the above polycarbonate polymer (hereinafter abbreviated as CP1) were added, and the mixture was allowed to stand at room temperature for 90 minutes. Upon mixing, a homogeneous solution was obtained. This gel electrolyte solution was applied to a polyethylene terephthalate (PET) film to a width of 50 mm with an applicator having a gap of 0.8 mm.
This was air-dried for 1 hour, and THF was evaporated to obtain a transparent polymer solid electrolyte film comprising a CP1 / 1M LiClO ₄ solution. This film was elastic and had sufficient strength to handle. The thickness of this film is 0.
It was 2 mm. The composition charged this time CP1: 1M concentration LiClO ₄ solution = 36: 64 and a weight ratio of.

The conductivity was measured by complex impedance measurement (measurement voltage: 10 mA). The measurement was carried out by cutting out the polymer solid electrolyte to a diameter of 12 mm and sandwiching it between SUS304 electrodes having a diameter of 15 mm. The conductivity at 25 ° C. is 1.2 × 10
^-3 S / cm.

In the flame retardancy test, CP1 itself was heated and compression molded at 300 ° C. to prepare a test piece of 1.5 cm × 3 cm × 2 mm in thickness, and the burning time after contact with a vertical flame Bunsen burner was measured. The dried solid polymer electrolyte film was precisely weighed to 1 g, and a vertical flame Bunsen burner was contacted and burned, and the residue weight after spontaneous extinguishing was measured and used as a measure of flame retardancy.

Example 2 45.6 g (hereinafter abbreviated as BPA, 0.2 mol) of 2,2-bis (4-hydroxyphenyl) propane instead of BCFL, and 50.8 g of the following polysiloxane compound (abbreviated as Si2 hereinafter) instead of Si1
0.015mol), PTBP was changed to 0.67g (0.0045mol), and 0.61, g of 1,1,1-tris (4-hydroxyphenyl) ethane (hereinafter abbreviated as TPE, 0.002mol) was added at the same time as BPA was added. Was polymerized in the same manner as in Example 1.

[0046]

Embedded image

The resulting polymer has an intrinsic viscosity [η] of 0.70 dl.
As a result of analysis from an infrared absorption spectrum at / g, the product was identified as a polycarbonate polymer having the following structure (hereinafter abbreviated as CP2).

[0048]

Embedded image

In the same manner as in Example 1, a polymer solid electrolyte having a weight ratio of CP2: 1M LiPF ₆ solution = 36: 64 was prepared. The 1M concentration L used here
The iPF ₆ solution was dissolved in the same solvent as in Example 1. The conductivity at 25 ° C. was 9.7 × 10 ⁻⁴ S / cm.

Example 3 53.6 g (hereinafter abbreviated as BPZ, 0.2 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane instead of BCFL, and 58 g of a polysiloxane compound (abbreviated as Si2, hereinafter) instead of Si1
0.015mol), change PTBP to 0.7g (0.0047mol), and
Polymerization was carried out in the same manner as in Example 1, except that 0.61 g (0.002 mol) of TPE was added at the same time as the addition of BPZ.

[0051]

Embedded image

The resulting polymer had an intrinsic viscosity [η] of 0.61 dl.
As a result of analysis by infrared absorption spectrum at / g, it was recognized as a polycarbonate polymer having the following structure (hereinafter abbreviated as CP3).

[0053]

Embedded image

[0054] In the same manner as in Example 1, CP3: 1M concentration LiPF ₆ solution = 36: 64 to prepare a solid polymer electrolyte in a weight ratio of. The 1M concentration L used here
The iPF ₆ solution was dissolved in the same solvent as in Example 1. The conductivity at 25 ° C. was 8.2 × 10 ⁻⁴ S / cm.

Example 4 Instead of BCFL, 29 g of 1,1-bis (4-hydroxyphenyl) -1-phenylethane (hereinafter abbreviated as BPAP, 0.1 mol) and 2,2-
Bis (4-hydroxy-3-methylphenyl) propane 25.6
g (hereinafter abbreviated as BPC, 0.1mol), Si2 instead of Si1
Change 60g (0.018mol) and PTBP to 1.0g (0.0067mol)
At the same time as the introduction of BPAP and BPC, 0.61 g of 1,1,1-tris (4-hydroxyphenyl) ethane (hereinafter abbreviated as TPE, 0.002 g)
The polymerization was carried out in the same manner as in Example 1 except that mol) was added. The resulting polymer was analyzed by infrared absorption spectrum at an intrinsic viscosity [η] of 0.57 dl / g, and was found to be a polycarbonate polymer having the following structure (hereinafter abbreviated as CP4).

[0056]

Embedded image

In the same manner as in Example 1, CP4: 1M concentrated
Degree LiPF₆Solution = polymer solid having a weight ratio of 36:64
A body electrolyte was prepared. The 1M concentration L used here
iPF ₆The solution was dissolved in the same solvent as in Example 1.
is there. Conductivity at 25 ° C. is 7.8 × 10^-FourIn S / cm
there were.

Example 5 The gel electrolyte solution (THF / CP) prepared in Example 1 was used.
45 g of a 1 / 1M concentration LiClO ₄ solution) was placed in a homogenizer container, and 10.8 g of lithium cobalt oxide (manufactured by Seimi Chemical Co., particle size 2-3 μm) and acetylene black (HS-100 manufactured by Denki Kagaku Kogyo KK) 1.3
5 g was added and dispersed at 12,000 rpm for 5 minutes at room temperature.
Apply this coating solution to aluminum foil (30 mm long, 30 mm wide, 30 mm thick)
μm) using a metal mask printing machine to print a circle having a diameter of 15 mm, and air-dried for 1 hour to evaporate THF. The thickness of this electrode was 0.15 mm. This electrode was used as a positive electrode, and the polymer electrolyte film produced in Example 1 was placed thereon with a diameter of 2
Nickel foil (30 mm long, 3 mm wide) with a lithium foil of 20 mm diameter and 0.1 mm thickness crimped to 5 mm
0 mm and a thickness of 35 μm) in this order, and the periphery thereof is sealed with a polyolefin-based hot melt adhesive.
A secondary battery was manufactured. The internal resistance of this battery was 70Ω. Further, the battery was charged at a current of 5 mA from the charging direction until the battery voltage reached 4.5 V, and charge / discharge was repeated 100 times until the battery voltage reached 2.0 V.
Looking at the capacity after charge / discharge experiment / initial capacity × 100,
The retention was 77%.

Comparative Example 1 A commercially available BPA homo-type polycarbonate (Iupilon E-20, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used in place of CP1 in Example 1.
(00) was performed in the same manner as in Example 1. Resin is T
The mixture solution of HF and 1M LiClO ₄ solution became cloudy due to insufficient dissolution, and a high quality cast film was not obtained.
The conductivity at 25 ° C. of the solid electrolyte after removing HF was 1.2 × 10 ⁻⁶ S / cm.

Comparative Example 2 Instead of CP2 of Example 2, a commercially available BPZ homo-type polycarbonate (Iupilon Z40, manufactured by Mitsubishi Gas Chemical Co., Ltd.)
The procedure was performed in the same manner as in Example 2 except that (0) was used. The conductivity at 25 ° C. of the solid electrolyte after removing THF was 8.2 ×.
It was 10 ^-5 S / cm.

Comparative Example 3 Instead of CP2 in Example 2, a commercially available polymethyl methacrylate (Acrypet WF, manufactured by Mitsubishi Rayon Co., Ltd.)
Was performed in the same manner as in Example 2 except that The conductivity at 25 ° C. of the solid electrolyte after removing THF is 2.7 × 10 5
^-4 S / cm.

Table 1 shows the solid electrolyte properties and the flame retardant properties of Examples 1 to 4 and Comparative Examples 1 to 3.

Table 1 Example Polymer Conductivity Vertical Flame Burning Time Burning Residue Comparative Example S / cm sec mg ─────────────────────────── ─────── Example 1 CP-1 1.2 × 10 ^-3 1 386 Example 2 CP-2 9.7 × 10 ^-4 1 339 Example 3 CP-3 8.2 × 10 ^-4 2 321 Example 4 CP -4 7.8 × 10 ^-4 1 343 Comparative Example 1 BPA homo PC 1.2 × 10 ^-6 > 30 135 Comparative Example 2 BPZ homo PC 8.2 × 10 ^-5 > 30 122 Comparative Example 3 PMMA 2.7 × 10 ^-4 > 30 77 ──────────────────────────────────

(Explanation of Table) Conductivity: 25 ° C., measured voltage using an impedance analyzer (HP4285A manufactured by Hewlett-Packard)
Measured at 10 mA. Vertical flame burning time: The burning time of the test piece after the burner was removed after the test piece was brought into contact with the Bunsen burner flame tip for 10 seconds. Combustion residue: The weight of the residue after the test piece film was allowed to come into contact with the tip of the Bunsen burner flame for 2 seconds and then left standing on a stainless steel bat until it self-extinguished. BPA Homo-type PC: Homopolycarbonate using 2,2-bis (4-hydroxyphenyl) propane as a monomer. BPZ Homo type PC: A homopolycarbonate using 1,1-bis (4-hydroxyphenyl) cyclohexane as a monomer. PMMA: Polymethyl methacrylate

[0065]

The polymer solid electrolyte of the present invention has a higher conductivity than conventional non-halogen-based polymer battery binders, and exhibits excellent properties as a polymer solid (gel) electrolyte. Halogen-based materials exhibit sufficient flame retardancy.
Therefore, it is suitable as a polymer battery material such as a lithium secondary battery. Further, the polymer solid electrolyte can be applied to an electric double layer capacitor having a structure similar to a secondary battery.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CG011 CG021 CP171 DE196 DG036 DH006 DK006 FD116 GQ00 GQ02 4J029 AA09 AB02 AB07 AC02 AC03 AE18 BB12A BB12B BB13A BB13B BB15B DB07 DB11 DB13 GA02 HA01 HC01 HC02 HC04A JA091 JB061 JC031 JC091 JC231 JF021 JF031 KE02 KE03 5G301 CA30 CD01 5H029 AM16 DJ09 EJ12 HJ01 HJ02 HJ10

Claims (8)

[Claims] 1. It has a structural unit represented by the general formula (A) and the general formula (B), wherein the structural unit of the general formula (B) is 20 to 70% by weight of all the structural units, and the intrinsic viscosity is 0. .2
2.0 dl / g polycarbonate and ion-dissociated I
A polymer solid electrolyte comprising a Group II or Group II metal salt. Embedded image (Wherein, R _{1 to} R ₄ are each independently hydrogen, carbon 1
An alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. When it has an atom, it may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
X is Wherein R _{5 and} R ₆ are each hydrogen and carbon number 1
An alkyl group having 10 to 10, an alkenyl group having 2 to 10 carbon atoms,
Represents an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a group in which R _{5 to} R ₆ are bonded together to form a carbocyclic or heterocyclic ring; When it has a carbon atom, it may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ₇ ~R
₈ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a is 0
Represents an integer of -20. ) (In the formula, R _{9 to} R ₁₀ are each independently hydrogen, carbon atom 1
An alkyl group having 5 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. When it has an atom, it can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, or a C1-C5 alkoxy group as a substituent.
R _{11 to} R ₁₄ each independently represent hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, 2 to 5 carbon atoms.
Is an alkenyl group, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. When these groups have a carbon atom, the alkyl group has 1 to 5 carbon atoms, An alkenyl group having 2 to 5 carbon atoms or 1 carbon atom
It can also have up to 5 alkoxy groups. R ₁₅ represents an alkylene group having 1 to 6 carbon atoms or an alkylidene group, or simply represents a bond. Y _{is, -Si (R 16) (R} 17) O- and / or -Si (R ₁₈₎ represents (R ₁₉₎ O- homopolymers or random copolymers, polymerization degree is at 0 to 200 , R
_{16 to} R ₁₉ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or An aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a
It can also have 5 alkoxy groups. ) 2. The metal salt represented by the general formula M⁺X^-, M
⁺Is Li⁺, K⁺, Na⁺One of the group
What, X^-Is ClO_Four ^-, BF_Four ^-, PF ₆ ^-, CF_Three
SO_Three ^-, (CF_ThreeSO_Two)_TwoN^-, (C_TwoF_FiveS
O_Two)_TwoN^-, (CF_ThreeSO_Two)_ThreeC^-, (C_TwoF_FiveS
O_Two)_ThreeC^-Claims are one selected from the group consisting of
2. The polymer solid electrolyte according to 1. 3. The polymer solid electrolyte according to claim 2, wherein the metal salt M ⁺ is Li ⁺ . 4. The structural unit represented by the general formula (A) is 9,9-
Bis (4-hydroxy-3-methylphenyl) fluorene,
2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 3,3,5-
The solid polymer electrolyte according to claim 1, which is derived from trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane and 2,2-bis (4-hydroxy-3-methylphenyl) propane. 5. The polymer solid electrolyte according to claim 1, wherein R _{16 to} R _{19 in} the general formula (B) are selected from a methyl group or a phenyl group. 6. A compound represented by the general formula (A):
2. The polymer solid electrolyte according to claim 1, which has a 4 mol% branched structure. 7. The structural unit of the general formula (B) has 3-terminal at both ends.
Random copolymerization of dimethylsiloxane having a (2-hydroxyphenyl) propyl group and diphenylsiloxane,
2. The solid polymer electrolyte according to claim 1, which is derived from α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane. 8. A polymer battery comprising a positive electrode, a negative electrode, and a polymer electrolyte located therebetween, wherein the polymer electrolyte comprises the polymer solid electrolyte according to claim 1.