JPH08225626A - Ionically conductive high-molecular solid electrolyte, composition, and production - Google Patents

Abstract

PURPOSE: To obtain an ionically conductive high-molecular solid olectrolyte having a high ionic conductivity, excellent film forming properties and a high film strength by mixing a hydroxyalkylpolysaccharide (derivative) with a specified ester compound and an ionically conductive metal salt. CONSTITUTION: The ionically conductive high-molecular solid electrolyte comprising 100 pts.wt. hydroxyalkylpolysaccharide or its derivative, 100-500 pts.wt. diester compound containing a polyoxyalkylene component [e.g. a compound of formula I (wherein R1 , R2 and R3 are each H or 1-6C alkyl; and the conditions: X>=1 and Y>=0 or the conditions: X>=0 and Y>=1 are satisfied] and monoester compound containing a polyoxyalkylene component [e.g. a compound of formula II (wherein R4 , R5 and R6 are each H or 1-6C alkyl; and the conditions: A>=1 and B>=0 or the conditions: A>=0 and B>=1 are satisfied)], and 5-1000 pts.wt. ionically conductive metal salt. This solid electrolyte has a high ionic conductivity, excellent film forming properties, and a high film strength, and is excellent in especially handleability in industrial production.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion conductive polymer solid electrolyte which can be used as an electrochemical material such as a secondary battery and a capacitor.

[0002]

2. Description of the Related Art Conventionally, liquid substances such as water, propylene carbonate and tetrahydrofuran have been mainly used as electrolytes for secondary batteries and capacitors.

However, the liquid electrolyte is liable to cause liquid leakage, and it is necessary to increase the airtightness of the container in order to ensure long-term stability.

For this reason, electric and electronic devices using a liquid electrolyte have the drawbacks that the weight is heavy and the manufacturing process is complicated.

On the other hand, an electrolyte made of an ion-conductive solid has almost no fear of liquid leakage, has advantages that it is easy to achieve simplification of manufacturing and weight reduction of products, and is actively studied.

Ion conductive solid electrolytes are classified into inorganic materials and organic materials, but their weight, moldability,
In terms of flexibility, the organic ion conductive solid electrolyte is superior to the inorganic ion conductive solid electrolyte.

The organic ion conductive solid electrolyte is generally composed of a matrix polymer and a low molecular weight ion conductive metal salt.

In particular, the matrix polymer plays the role of both solidifying the electrolyte and the solvent of dissolving the ion conductive metal salt, and is therefore the most important element in the organic ion conductive solid electrolyte.

In 1978, Almond et al., University of Grenoble, France, found that lithium perchlorate was dissolved in polyethylene oxide, and this system was 10 ^-7 S / cm.
Since it was reported that it has ionic conductivity, similar studies have been conducted on a wide variety of polymer substances such as polypropylene oxide, polyethyleneimine, polyurethane and polyester, focusing on its related polymers.

Utilizing the advantages of the organic polymer such as excellent film formability and flexibility and high energy characteristics when used as a battery, its application as an electrolyte for a solid secondary battery is progressing.

[0011]

Polyethylene oxide, which has been most studied, is a polymer having a high ability to dissolve an ion conductive metal salt, but it is a semi-crystalline polymer, and when a large amount of a metal salt is dissolved, it is a metal. The salt forms a pseudo-crosslinking structure between the polymer chains and the polymer further crystallises, so that the conductivity is considerably lower than expected.

An ionic conductor dissolved in a linear polyether polymer matrix such as polyethylene oxide has local segmental motion of polymer chains in an amorphous region above the glass transition temperature of the polymer matrix. Move with.

The cation responsible for ionic conductivity is strongly coordinated by the polymer chain, and its mobility is strongly affected by the local motion of the polymer.

Therefore, it is not a good idea to select a linear polymer as the matrix polymer of the ion conductive polymer solid electrolyte from the viewpoint of the mobility of the ion conductor.

In the reports so far, polyethylene oxide,
The conductivity of an ionic conductive polymer solid electrolyte consisting of only linear polymers such as polypropylene oxide and polyethyleneimine is about 10 ^-7 S / cm at room temperature, or at most about 10 ^-6 S / cm at room temperature.

On the other hand, in order to secure high ionic conductivity at room temperature, it is important to have many amorphous regions in the matrix polymer in which the ionic conductor easily moves, and the glass transition temperature of the polymer is low. The molecular design must be done.

An attempt was made to introduce a branched structure into polyethylene oxide as this method, and an ion conductive polymer solid electrolyte of a polyethylene oxide derivative having high conductivity (about 10 ⁻⁴ S / cm at room temperature) was synthesized. (Ogata
Naoya et al., Journal of Textile Society, P52-57, 1990). However, it has not been commercialized because the method of synthesizing the polymer is complicated.

Further, a method of ensuring ionic conductivity by causing a matrix polymer to have a three-dimensional network structure and inhibiting the crystal structure has been reported.

As an example of this method, there is an ion conductive polymer solid electrolyte obtained by crosslinking and curing a polyoxyalkylene derivative of glycerin with a polyisocyanate compound (Japanese Patent Laid-Open No. 4-112460, 5-36483, etc.).

However, according to this method, the isocyanate is liable to react with water and it is difficult to control the storage of the isocyanate and the reaction activity. O The urethane-forming cross-linking reaction of the polyoxyalkylene derivative of glycerin and the polyisocyanate compound is affected by the ion conductive metal salt or the auxiliary solvent component, and the reactivity is significantly lowered or the reaction is accelerated. Therefore, a method of impregnating an ion conductive metal salt with an appropriate solvent (impregnation method) is often used after first synthesizing a polymer matrix, resulting in poor industrial productivity. ○ General-purpose aromatic isocyanates are susceptible to electrochemical deterioration. Aliphatic isocyanates have low reactivity. ○ When molding into a film, a long-time heating reaction is necessary. Issues such as remain unsolved.

As another example of using a polymer having a three-dimensional network structure as a polymer matrix, a method for polymerizing an acrylic monomer or a methacrylic monomer containing a polyoxyalkylene component has been applied (Japanese Patent Laid-Open No. 25353/1993). However, since the solubility of the ion conductive metal salt in the monomer is low, there are problems that a third component such as vinylene carbonate must be added and that the obtained polymer has low physical strength.

The present invention provides an ion conductive polymer solid electrolyte having high ion conductivity, excellent film formability, tough film strength, and excellent handling characteristics during industrial production. The purpose is to

[0023]

The present invention provides (1) 100 parts by weight of a hydroxyalkyl polysaccharide or a hydroxyalkyl polysaccharide derivative, a diester compound containing a polyoxyalkylene component and a monoester containing a polyoxyalkylene component. A composition for a polymer solid electrolyte comprising 10 to 500 parts by weight of a compound and 5 to 1000 parts by weight of an ion conductive metal salt, and a weight ratio of (2) diester compound / monoester compound is 1 to 0.2 ( 1) The composition according to 1), 3) The hydroxyalkyl polysaccharide derivative according to 1), wherein part or all of the hydroxyl groups in the hydroxyalkyl polysaccharide have a substituent introduced through an ester bond or an ether bond. Composition for polymer solid electrolyte, which is a polysaccharide derivative, (4) Polyoxyalkoxy according to (1) Diester compound containing a down component (Formula 1) is

Embedded image (Provided that R ₁ , R ₂ and R ₃ represent H or an alkyl group having 1 to 6 carbon atoms and satisfy the conditions of X ≧ 1 and Y ≧ 0,
Or, those satisfying the conditions of X ≧ 0 and Y ≧ 1. ), And the monoester compound (Chemical Formula 2) containing a polyoxyalkylene component is

[Chemical 4] (However, R ₄ , R ₅ , and R ₆ represent H or an alkyl group having 1 to 6 carbon atoms and satisfy the conditions of A ≧ 1 and B ≧ 0, or the conditions of A ≧ 0 and B ≧ 1. The polymer solid electrolyte according to (1), further comprising: (5) a solvent capable of dissolving an ion conductive metal salt. Composition, the composition for polymer solid electrolyte as described in (6) (1), ultraviolet ray, electron beam, X-ray, gamma ray, microwave,
By irradiating with high frequency or by heating, a diester compound containing a polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component are polymerized, and the resulting polymer chain is a hydroxyalkyl polysaccharide, or A method for producing a polymer solid electrolyte, which comprises forming a three-dimensional crosslinked network structure in which molecular chains of a hydroxyalkyl polysaccharide derivative are intertwined with each other, and a polymer obtained by the production method according to (7) or (6). Solid electrolyte.

The ion conductive polymer solid electrolyte of the present invention comprises a hydroxyalkyl polysaccharide containing an ion conductive metal salt, or a hydroxyalkyl polysaccharide derivative containing a diester compound containing a polyoxyalkylene component and a polyoxyalkylene component. It is synthesized by three-dimensional meshing with the contained monoester compound.

In particular, when a diester compound containing a polyoxyalkylene component and a monoester compound containing a polymethoxyoxyalkylene component undergo a polymerization reaction to form a three-dimensional network structure, a hydroxyalkyl polysaccharide or its hydroxyalkyl polysaccharide Molecular chain of derivative and semi-interpenetrating polymer network
rating polymer network; s
EMI-IPN) structure is formed. Schematic diagrams of the semi-IPN structure are shown in FIGS. The formation of the semi-IPN structure has advantages such as improvement in compatibility between different polymer chains and increase in interphase bonding force, unlike the case of simply mixing different polymers.

Attempts to form an IPN structure and improve the film strength have been made for a long time. Recently, Nishio et al. Of Nagaoka University of Technology reported a review of cellulosic IPN (Polymer, 43 , 549 (1994)).

However, the cellulosic IP shown in the present invention
The composition of N has not been reported so far, and there is no application of cellulosic IPN to the field of batteries.

The inventors have found that, even in the case of the hydroxyalkyl polysaccharide of the present invention or the hydroxyalkyl polysaccharide derivative thereof, the formation of a semi-IPN structure dramatically improves the film properties.

[0029] Further, the inventors of the present invention, in the course of research to find a good combination of interaction between a polymer and an ion conductive metal salt, hydroxyalkyl polysaccharides and hydroxyalkyl polysaccharide derivatives satisfactorily dissolve the ion conductive metal salt. However, they have found that it is a material that satisfies all the conditions necessary for the polymer used as the ion conductive polymer solid electrolyte and exhibits high conductivity.

Further, in the hydroxyalkyl polysaccharide and the hydroxyalkyl polysaccharide derivative, it is considered that the ion conductive metal salt is mainly dissolved in the side chain.

That is, since the metal salt responsible for conductivity can move without any restriction of local movement of the polysaccharide main chain,
It was found that the conductivity is higher than that of a linear polymer matrix such as polyethylene oxide by one digit or more.
It is clear when comparing Example 1 and Comparative Example 3.

The hydroxyalkyl polysaccharides include hydroxyethyl polysaccharides obtained by reacting naturally occurring polysaccharides such as cellulose and starch with ethylene oxide, hydroxypropyl polysaccharides obtained by reacting propylene oxide, It refers to three hydroxyalkyl polysaccharides, dihydroxypropyl polysaccharides obtained by reacting glycidol or 3-chloro-1,2-propanediol.

Further, the hydroxyalkyl polysaccharide derivative means a polysaccharide derivative in which some or all of the hydroxyl groups in the hydroxyalkyl polysaccharide molecule are blocked with a substituent group through an ester bond or an ether bond.

Polysaccharides that can be used are cellulose,
Examples include starch, amylose, amylopectin, pullulan, curdlan, mannan, glucomannan, arabinan, chitin, chitosan, alginic acid, carrageenan, and dextran. There are no restrictions on the type, array, etc.

However, cellulose and starch are particularly preferable from the viewpoint of easy availability. Hydroxyethyl cellulose, hydroxyethyl starch, hydroxypropyl cellulose, and hydroxypropyl starch are commercially available in various molar substitution (MS) products (molar degree of substitution; A value indicating whether a substituent is introduced.).

A method for synthesizing dihydroxypropyl cellulose is described in US Pat. No. 4,096,326 (1978). In addition, other dihydroxypropyl polysaccharides can be synthesized with reference to a known method (Reference, Sato et al., Makromol. Cem., 193 , 6).
47 (1992), or Macromolecule
es 24 , 4691 (1991)).

These hydroxyalkyl polysaccharides can be used as the ion conductive polymer solid electrolyte.

The hydroxyalkyl polysaccharide that can be used in the present invention has a degree of molar substitution of 2 or more. When the molar substitution degree is less than 2, the ability to dissolve the ion conductive metal salt is too low to be used. The upper limit of the molar substitution degree is 30,
It is preferably 20. It is difficult to industrially synthesize a hydroxyalkyl polysaccharide having a degree of molar substitution of higher than 30, considering the industrial production cost and the complexity of the synthetic operation. Even if it is produced by force and the molar substitution degree is increased to more than 30, it is considered that the increase in conductivity due to the increased molar substitution degree cannot be expected so much.

Further, a hydroxyalkyl polysaccharide derivative obtained by blocking a part or all of the hydroxyl groups of the above hydroxyalkyl polysaccharide with a substituent through an ester bond or an ether bond can also be used as the ion conductive polymer solid electrolyte. I can.

That is, a hydroxyalkyl polysaccharide derivative in which a substituent containing an alkyl group having 1 to 6 carbon atoms, an aromatic substituent or a cyano group is introduced into a hydroxyalkyl polysaccharide by an ester bond or an ether bond also has high ion conductivity. It can be used as a molecular solid electrolyte.

For example, a derivative obtained by substituting a hydroxy group of hydroxypropylcellulose with a methyl group through an ether bond is hydroxypropylmethylcellulose, which is commercially available.

Further, for example, cyanoethylated hydroxypropyl cellulose obtained by cyanoethylating hydroxypropyl cellulose also shows good properties as an ion conductive polymer solid electrolyte (Example).

The concentration of the ion conductive metal salt is considerably high in the ion conductive polymer solid electrolyte, and the association of the ions easily occurs in the polymer matrix having a low dielectric constant, and the decrease in the conductivity due to the association of the ions is reduced. To be In this case, if the polarity of the matrix is improved, the association of ions will be less likely to occur.

It is significant to cap the hydroxyl group of the hydroxyalkyl polysaccharide with a polar group in terms of increasing the dielectric constant of the matrix polymer.

Ion-conductive metal salts are dissolved in the above-mentioned hydroxyalkyl polysaccharides and hydroxyalkyl polysaccharide derivatives, and a diester compound and a monoester compound described below are added and reacted to give an ion-conductive polymer. Use solid electrolyte.

In the present invention, the ion conductive metal salt is not particularly limited as long as it is used in a usual electrochemical element, and examples thereof include LiClO ₄ , LiBF ₄ , LiA.
sF ₆ , LiPF ₆ , LiSbF ₆ , LiCF ₃ SO ₃ , L
iCF ₃ COO, NaClO ₄ , NaBF ₄ , NaSC
N, KBF ₄ , Mg (ClO ₄ ) ₂ , Mg (BF ₄ ) ₂ ,
(C ₄ H ₉ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NBF ₄ , (C ₄ H ₉ )
One or a mixture of two or more of ₄ NClO _{4 and the} like can be mentioned. The blending amount is preferably 5 to 1000 parts by weight, more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the hydroxyalkyl polysaccharide or the hydroxyalkyl polysaccharide derivative.
It is 300 parts by weight.

When the amount is less than 5 parts by weight, the ionic conductor concentration is low, and therefore the conductivity is too low for practical use.

When the amount is more than 1000 parts by weight, the solubility of the polymer matrix in the ion conductive metal salt is exceeded in many cases, and salts are precipitated.

On the other hand, the ion conductive polymer solid electrolyte is often used in the form of a film sandwiched between electrodes. Therefore, practically, high film-forming property and film strength are required.

The composite of the present invention in which an ion conductive metal salt is dissolved in a hydroxyalkyl polysaccharide and a hydroxyalkyl polysaccharide derivative is insufficient in film forming property and film strength as an ion conductive polymer solid electrolyte as it is. There is.

For example, a certain hydroxyalkyl polysaccharide derivative having a high degree of molar substitution exhibits a liquid crystal state at room temperature,
Wax-like and low film strength. Moreover, the appearance of many hydroxyalkyl polysaccharides and hydroxyalkyl polysaccharide derivatives with a high degree of molar substitution is waxy.

Therefore, as a result of intensive research to overcome this drawback, the present inventors have found that a diester compound containing a polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component are treated with a hydroxyalkyl polysaccharide or hydroxyalkyl. It is mixed with a mixture of a polysaccharide derivative and an ion-conductive metal salt, and this mixture is irradiated with ultraviolet rays,
Semi by reacting by irradiating with electron beam, X-ray, gamma ray, microwave, high frequency, or by heating the ion conductive electrolyte.
-It was found that good film-forming property and film strength can be imparted by forming a three-dimensional crosslinked network structure having an IPN structure.

The reactive monomer which can be used as the crosslinking agent in the present invention is a diester compound (Chemical formula 1) containing a polyoxyalkylene component.

[0054]

Embedded image

(However, R ₁ , R ₂ and R ₃ are H or methyl,
Ethyl, n-propyl, i-propyl, n-butyl, i
-Butyl, s-butyl, t-butyl, amino group isomer,
A hexyl group isomer, which satisfies the condition of X ≧ 1 and Y ≧ 0, or the condition of X ≧ 0 and Y ≧ 1, preferably R ₁ , R ₂ and R ₃ are Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl. ), And the monoester compound (Chemical Formula 2) containing a polyoxyalkylene component is

[0056]

[Chemical 6]

(However, R ₄ , R ₅ , and R ₆ are H or methyl,
Ethyl, n-propyl, i-propyl, n-butyl, i
-Butyl, s-butyl, t-butyl, amino group isomer,
A hexyl group isomer, which satisfies the condition of A ≧ 1 and B ≧ 0, or the condition of A ≧ 0 and B ≧ 1, preferably R ₁ , R ₂ and R ₃ are Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl. ).

The diester compound containing a polyoxyalkylene component and the ester compound containing a polyoxyalkylene component are used in a mixture of a hydroxyalkyl polysaccharide or a hydroxyalkyl polysaccharide derivative and an ion conductive metal salt with ultraviolet rays, electron beams, X-rays, By irradiating with gamma rays, microwaves, high frequencies, or by reacting by heating the mixture, s
Form a three-dimensional crosslinked network structure of an emi-IPN structure.

When the diester compound containing the polyoxyalkylene component and the monoester compound containing the polyoxyalkylene component are polymerized to form a three-dimensional network structure, the hydroxyalkyl polysaccharide or its hydroxyalkyl polysaccharide derivative is Molecular chain and semi-interpenetrating polymer network (semi-interpenetrating)
polymer network; semi-IP
N) Form a structure.

The formation of the semi-IPN structure has advantages such as improvement in compatibility between different polymer chains and increase in interphase bonding force, unlike the case where different polymers are simply mixed.

In the case of the hydroxyalkyl polysaccharide of the present invention or the hydroxyalkyl polysaccharide derivative thereof, the film properties thereof are remarkably improved by forming the semi-IPN structure.

When forming a semi-IPN structure,
Generally, only the diester compound containing the polyoxyalkylene component may be added to the hydroxyalkyl polysaccharide or the hydroxyalkyl polysaccharide derivative to carry out polymerization.

However, in the present invention, a monoester compound containing a polyoxyalkylene component which is a monofunctional monomer is intentionally added.

This is because polyoxyalkylene branches are introduced on the three-dimensional network by adding the monoester compound (see FIGS. 1 and 2).

In the ion conductive polymer solid electrolyte of the present invention, the metal salt responsible for the ion conductivity is mainly a branched hydroxyalkyl group of a hydroxyalkyl polysaccharide or a hydroxyalkyl polysaccharide derivative, or a diester compound containing a polyoxyalkylene component. It is considered that the monoester compound containing the polyoxyalkylene component strongly interacts with the hydroxyalkyl side chain portion of the branched portion on the three-dimensional network formed by polymerization.

Since the metal salt responsible for conductivity can move without any restriction of the local movement of the polysaccharide main chain, the conductivity is higher by one digit or more than that of a linear polymer matrix such as polyethylene oxide. Shows sex. It is clear when comparing Example 1 and Comparative Example 3.

The addition amount of the diester compound containing the polyoxyalkylene component and the monoester compound containing the polyoxyalkylene component is 10 to 100 parts by weight of the hydroxyalkyl polysaccharide or the hydroxyalkyl polysaccharide derivative in total. A range of 500 parts by weight is preferred.

If the amount is less than 10 parts by weight, the film strength will not increase. If the amount is more than 500 parts by weight, the ability of the entire matrix to dissolve the ion-conductive metal salt is lowered, resulting in inconveniences such as salt precipitation and the resulting film becoming brittle.

The composition ratio of the diester compound containing the polyoxyalkylene component and the monoester compound containing the polyoxyalkylene component is not particularly limited, but the weight ratio is (diester compound containing the polyoxyalkylene component) / (polyoxyalkylene component). The range of monoester compound containing alkylene component) = 1 to 0.2 is preferable from the viewpoint of film strength.

When an electron beam is used during the polymerization reaction, it is not necessary to add a polymerization initiator, but in other cases,
Usually, a polymerization initiator is added.

The polymerization initiator is not particularly limited, but
Light such as acetophenone, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylisopropiophenone, 1-hydroxycyclohexyl ketone, benzoin ether, 2,2-diethoxyacetophenone, benzyldimethylketal A polymerization initiator can be used.

As the thermal polymerization initiator, high temperature initiators such as cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide and di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, persulfate, Ordinary initiators such as azobisisobutyronitrile, low temperature initiators such as hydrogen peroxide / ferrous salt, persulfate / sodium acid sulfite, cumene hydroperoxide / ferrous salt, benzoyl peroxide / dimethylaniline (Redox initiator), peroxide / organometallic alkyl, triethylboron, diethylzinc, oxygen / organometallic alkyl and the like can be used.

These polymerization initiators may be used alone or in combination of two or more. The polymerization initiator is a diester compound containing a polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component 10
It is added in the range of 0.1 to 1 part by weight with respect to 0 part by weight.

If the amount is less than 0.1 part by weight, the polymerization rate is remarkably reduced, which is not preferable. It is a waste of reagent to use more than 1 part by weight.

The conditions of the polymerization reaction are not particularly limited, but for example, the reaction conditions in the case of photopolymerization are carried out by irradiating ultraviolet rays in the air at room temperature with a light amount of 1 to 50 mW / cm ² for 5 to 30 minutes or more.

When an electron beam is used, the temperature is 150-150 at room temperature.
An acceleration voltage of 300 kV is sufficient. 50-in case of heat polymerization
It reacts by heating at 120 ° C. for 0.5 to 6 hours.

The polymer formed by photopolymerization is entangled with the polymer chain of the hydroxyalkyl polysaccharide or the hydroxyalkyl polysaccharide derivative, and is a strong semi-I.
A PN three-dimensional network structure is formed, but no crystal structure is formed and the matrix is amorphous.

The polymerization reaction is preferably UV irradiation or heat polymerization in view of the simplicity of the apparatus and the running cost.

Since the polymerization reaction of the diester compound containing the polyoxyalkylene component and the monoester compound containing the polyoxyalkylene component proceeds without being hindered by the influence of the ion conductive metal salt mixed in the system,
Conventionally, in the case of polyurethane-based cross-linking agents, three-dimensionalization is performed in a system without ion-conductive metal salts, and then the ion-conductive metal salts are dissolved in a solvent and the matrix polymer is impregnated with the solvent (impregnation. Method) 2
There is no need to adopt a step system.

The ion conductive polymer solid electrolyte of the present invention is usually produced as follows. A predetermined amount of hydroxyalkyl polysaccharide or hydroxyalkyl polysaccharide derivative,
A predetermined amount of ion conductive metal salt, a diester compound containing a predetermined amount of polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component are put in an appropriate amount of solvent and mixed.

The mixed solution is heated under reduced pressure to evaporate the solvent to a desired concentration. The solvent may be evaporated until the mixed solution has a viscosity that makes it easy to cast on the electrode.

Further, the solvent is completely evaporated for the purpose of increasing the amount of ion conductive metal salts dissolved in the ion conductive polymer solid electrolyte of the present invention and improving the mobility of the dissolved metal ions in the polymer matrix. It is also possible to leave an arbitrary amount remaining without causing it.

In the ion conductive polymer solid electrolyte, the copolymerized polymer chains of a diester compound containing a polysaccharide molecular chain and a polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component are entangled with each other.
Hydroxyalkyl polysaccharide or hydroxyalkyl polysaccharide derivative 1 because it has an emi-IPN network structure
Even if 1 to 8000 parts by weight, preferably 1 to 300 parts by weight, of solvent is left with respect to 00 parts by weight, the film strength is not affected at all.

However, if it is higher than 8000 parts by weight,
No matter how strong the semi-IPN network structure is formed, the film strength is lowered, which is not preferable. If it is less than 1 part by weight, the effect of leaving the solvent cannot be obtained.

When there is no hydroxyalkyl polysaccharide or hydroxyalkyl polysaccharide derivative in the system, that is, the polymerization reaction is performed only with the diester compound containing the polyoxyalkylene component and the monoester compound containing the polyoxyalkylene component. When a three-dimensional network structure is formed, the amount of solvent that can be retained in this matrix is about 250% at the maximum, and it is difficult to handle as a self-supporting film a solvent to which 100% or more of solvent is added in practice. Too much solvent deprives the membrane of its independence. The effect of semi-IPN is clear from this example as well.

Solvents usable for the ion conductive polymer solid electrolyte of the present invention include dibutyl ether, 1,2-
Dimethoxyethane, 1,2-ethoxymethoxyethane,
Chain ethers such as methyl diglyme, methyl triglyme, methyl tetraglyme, ethyl glyme, ethyl diglyme, butyl diglyme, glycol ethers (ethyl cellosolve, ethyl carbitol, butyl cellosolve, butyl carbitol, etc.) , Tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, heterocyclic ethers such as 4,4-dimethyl-1,3-dioxane, γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3-methyl Butyrolactones such as -1,3-oxazolidin-2-one, 3-ethyl-1,3-oxazolidin-2-one, and other solvents commonly used in electrochemical devices such as water and alcohol solvents (methanol, ethanol, Butanol, ethylene glycol, propylene Glycol, diethylene glycol, 1,4-butanediol, glycerin, etc.), polyoxyalkylene polyol (ethylene oxide, polypropylene oxide, polyoxyethylene / oxypropylene glycol and a combination of two or more thereof), amide solvent (N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidinone, etc., carbonate solvent (propylene carbonate, ethylene carbonate, styrene carbonate, etc.), imidazolidinone solvent (1,3-dimethyl-2-
Imidazolidinone, etc.) and the like. It is also possible to use a mixture of two or more of these solvents.

After the mixed solution is adjusted to a desired composition, a predetermined amount of a polymerization initiator is mixed and cast on a substrate to a desired thickness using a knife coater.

By irradiating this film with ultraviolet rays, electron beams, X-rays, gamma rays, microwaves, high frequencies, or by heating the ion conductive electrolyte, an ion conductive polymer solid having good ion conductivity is obtained. An electrolyte is obtained.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these. Also,
Parts represent parts by weight.

[0090]

【Example】

[0091]

Example 1 To 10 parts of tetrahydrofuran as a solvent, 1 part of hydroxypropyl cellulose (molar degree of substitution (MS) = 4.65, manufactured by Nippon Soda Co., Ltd.) and 1 part of anhydrous lithium perchlorate were added. Dissolved and 0.5 parts of polyethylene glycol dimethacrylate (the number of oxyethylene units = 9, manufactured by NOF CORPORATION) and 1.5 parts of methoxy polyethylene glycol monomethacrylate (the number of oxyethylene units = 9, Japan) Yushi Co., Ltd.)
Was added and mixed.

This mixed solution was kept under reduced pressure at 40 ° C., and tetrahydrofuran was removed until the weight of the mixed solution became 4.2 parts by weight.

0.05 part of benzyl dimethyl ketal was added as a polymerization initiator and dissolved, and the mixture was cast on a substrate (copper plate) using a doctor knife applicator.

At room temperature, ultraviolet rays of 6 mW / cm ² were applied in the air.
The polymerization reaction was performed by irradiating with the light amount of 20 minutes to obtain an ion conductive polymer solid electrolyte.

[0095]

Example 2 One part of hydroxypropyl cellulose (molar degree of substitution (MS) = 4.6 as an example without using a solvent)
5, Nippon Soda Co., Ltd., 2 parts of anhydrous lithium perchlorate and 2.5 parts of polyethylene glycol dimethacrylate (the number of oxyethylene units = 9, manufactured by NOF CORPORATION)
And 2.5 parts of methoxy polyethylene glycol monomethacrylate (the number of oxyethylene units = 9, manufactured by NOF CORPORATION) were added and mixed with stirring at 70 ° C.

To this mixed solution, 0.05 part of benzyl dimethyl ketal as a polymerization initiator was added, and the mixture was cast on a substrate (copper plate) using a doctor knife applicator.

At room temperature, ultraviolet rays of 6 mW / cm ² were emitted in the air.
The polymerization reaction was performed by irradiating with the light amount of 20 minutes to obtain an ion conductive polymer solid electrolyte.

[0098]

Example 3 1 part of hydroxypropyl cellulose (molar degree of substitution (MS) = 4.6) was added to a solvent prepared by mixing 10 parts of tetrahydrofuran and 10 parts of propylene carbonate.
5, manufactured by Nippon Soda Co., Ltd. and 1 part of anhydrous lithium perchlorate were added and dissolved, and 1.5 parts of polyethylene glycol dimethacrylate (the number of oxyethylene units =
9, NOF CORPORATION, and 1.5 parts of methoxypolyethylene glycol monomethacrylate (the number of oxyethylene units = 9, NOF Corporation) were added and mixed.

This mixed solution was put under reduced pressure to adjust the viscosity.
The temperature was kept at 0 ° C., and the solvent was removed until the total amount of the mixed solution reached 15 parts. 0.05 part of benzyl dimethyl ketal was added as a polymerization initiator and dissolved, and the mixture was cast on a base (Teflon plate) using a doctor knife applicator.

At room temperature, ultraviolet rays of 6 mW / cm ² were emitted in the air.
The polymerization reaction was performed by irradiating with the light amount of 20 minutes to obtain an ion conductive polymer solid electrolyte.

[0101]

Example 4 The mixed solution before the addition of the polymerization initiator of Example 3 was cast on a substrate (Teflon plate) using a doctor knife applicator. An electron beam irradiation device with an accelerating voltage of 200 kV was used to irradiate an electron beam to carry out a polymerization reaction to obtain an ion conductive polymer solid electrolyte.

[0102]

Example 5 (Cyanoethylation of hydroxypropyl cellulose [I]); 8 g of hydroxypropyl cellulose (molar degree of substitution (MS) = 4.65, Nippon Soda Co., Ltd.)
4w) and suspended in 400 ml of acrylonitrile.
1 ml of a t% aqueous sodium hydroxide solution was added, and the mixture was stirred at 30 ° C. for 4 hours.

The above reaction mixture was neutralized with acetic acid and then poured into a large amount of methanol to obtain cyanoethylated hydroxypropyl cellulose.

To remove impurities, cyanoethylated hydroxypropyl cellulose was dissolved in acetone, filled in a dialysis membrane tube, and dialyzed and purified using ion-exchanged water.

The cyanoethylated hydroxypropyl cellulose precipitated during dialysis was collected, dried and used for the production of ion conductive polymer solid electrolyte.

When the obtained cyanoethylated hydroxypropyl cellulose was subjected to elemental analysis, N weight% was 7.
It was found to be 3%. From this value, the cap ratio of the hydroxyl groups in hydroxypropyl cellulose due to cyanoethyl groups is 94%.

An ion conductive polymer solid electrolyte was obtained in the same manner as in the case of preparing the ion conductive polymer solid electrolyte of Example 3 using 1 part of this cyanoethylated hydroxypropyl cellulose.

[0108]

Example 6 (Cyanoethylation [II] of hydroxypropyl cellulose); 8 g of hydroxypropyl cellulose (molar degree of substitution (MS) = 4.65, Nippon Soda Co., Ltd.)
40 ml) and suspended in 400 ml of acrylonitrile.
30% by adding 1 ml of a wt% sodium hydroxide aqueous solution
And stirred for 40 minutes.

The reaction mixture was neutralized with acetic acid and then poured into a large amount of methanol to obtain cyanoethylated hydroxypropyl cellulose.

To remove impurities, cyanoethylated hydroxypropyl cellulose was dissolved in N, N-dimethylformamide, filled in a dialysis membrane tube, and dialyzed and purified using ion-exchanged water.

The dialysate was lyophilized to obtain cyanoethylated hydroxypropyl cellulose, re-dried, and then used for the production of the ion conductive polymer solid electrolyte.

When the obtained cyanoethylated hydroxypropyl cellulose was subjected to elemental analysis, N weight% was 3.
It was found to be 2%. From this value, the cap ratio of the hydroxyl groups in hydroxypropyl cellulose due to cyanoethyl groups is 34%.

An ion conductive polymer solid electrolyte was obtained in the same manner as in the case of preparing the ion conductive polymer solid electrolyte of Example 3 using 1 part of this cyanoethylated hydroxypropyl cellulose.

[0114]

Example 7 (Synthesis of dihydroxypropyl cellulose [I]); The method of Tarbak et al. (AF Turbak)
Chem. Abstr. 94 , 123426S (1
981)) and the pulp for rayon was dissolved in a mixed solvent of lithium chloride / dimethylacetamide (LiCl / DMAc) so that the cellulose concentration became 2 wt%.

10 g of powdered sodium hydroxide was added to 500 ml of this solution, and the mixture was stirred at 50 ° C. for 1 hour.

100 ml of 91 g of glycidol is added here.
The solution dissolved in dimethylacetamide was added little by little over 3 hours and then stirred for 12 hours at 50 ° C.,
It was made to react.

After the reaction, the reaction mixture was poured into a large amount of acetone to obtain a precipitate of dihydroxypropyl cellulose.
The molar substitution degree of the obtained dihydroxypropyl cellulose was found to be MS = 4.1 by analysis using ¹³ C-NMR.

Instead of the hydroxypropyl cellulose used in Example 3, dihydroxypropyl cellulose (M
S = 4.1) An ion conductive polymer solid electrolyte was obtained in the same manner as in the case of producing the ion conductive polymer solid electrolyte of Example 3 except that 1 part was used.

[0119]

[Example 8] (Synthesis of dihydroxypropyl cellulose [II]); 10 g of powdered sodium hydroxide was added to 500 ml of a lithium chloride / dimethylacetamide (LiCl / DMAc) mixed solution having a cellulose concentration of 2 wt%, and the mixture was stirred at 50 ° C for 1 hour. Stir for hours.

Here, 91 g of glycidol is added to 100 ml.
The solution dissolved in dimethylacetamide was added little by little over 3 hours and then stirred for 12 hours at 50 ° C.,
It was made to react.

Further, 91 g of glycidol is added to 100 m.
The solution dissolved in 1 dimethylacetamide was added little by little over 3 hours and then stirred at 50 ° C. for 12 hours,
The process of reacting was repeated twice.

After the reaction, the reaction mixture was poured into a large amount of acetone to obtain a precipitate of dihydroxypropyl cellulose.
The molar substitution degree of the obtained dihydroxypropyl cellulose was found to be MS = 10.5 by analysis using ¹³ C-NMR.

Instead of the hydroxypropyl cellulose used in Example 3, dihydroxypropyl cellulose (M
S = 10.5) An ion conductive polymer solid electrolyte was obtained in the same manner as in the production of the ion conductive polymer solid electrolyte of Example 3 except that 1 part was used.

[0124]

[Example 9] (Synthesis of cyanoethylated dihydroxypropyl cellulose); [I] of Example 5 except that dihydroxypropyl cellulose (MS = 4.1) was used in place of the hydroxypropyl cellulose used in Example 5. Cyanoethylation was carried out by the method to obtain cyanoethylated dihydroxypropyl cellulose.

The N weight% of the cyanoethylated dihydroxypropyl cellulose obtained was 11.9%, and the cap ratio of the hydroxyl groups in the dihydroxypropyl cellulose obtained from this value with the cyanoethyl groups was 92%.

Ion-conductive material was prepared in the same manner as in preparing the ion-conductive polymer solid electrolyte of Example 3 except that 1 part of cyanoethylated dihydroxypropyl cellulose was used in place of the hydroxypropyl cellulose used in Example 3. A polymer solid electrolyte was obtained.

[0127]

Example 10 (Synthesis of acetylated hydroxypropyl cellulose): 8 g of hydroxypropyl cellulose (degree of molar substitution (MS) = 4.65, manufactured by Nippon Soda Co., Ltd.)
Was suspended in a mixed solvent consisting of 300 ml of acetic acid and 300 ml of methylene chloride to prepare a 70 wt% perchloric acid aqueous solution 4
ml and acetic anhydride 400 ml were added, and the mixture was stirred at 25 ° C. for 1.5 hours.

Acetylated hydroxypropyl cellulose was obtained by pouring the above reaction mixture into a large amount of ethanol.

The ion conductive polymer solid electrolyte was prepared by the method of preparing the ion conductive polymer solid electrolyte of Example 3 except that 1 part of acetylated hydroxypropyl cellulose was used in place of the hydroxypropyl cellulose used in Example 3. Got

[0130]

EXAMPLE 11 1 part of hydroxyethyl starch (manufactured by Penford Products Co.) and 1 part of anhydrous lithium perchlorate were dissolved in 10 parts of distilled water as a solvent,
Add 0.5 parts of polyethylene glycol dimethacrylate (oxyethylene unit number = 9, NOF Corporation)
(Manufactured by NOF CORPORATION) and 1.5 parts of methoxypolyethylene glycol monomethacrylate (oxyethylene unit number = 9, manufactured by NOF CORPORATION) were added and mixed.

0.01 part of benzyl dimethyl ketal as a polymerization initiator was added and dissolved, and the mixture was cast on a substrate (copper plate) using a doctor knife applicator.

At room temperature, ultraviolet rays of 6 mW / cm ² were emitted in the air.
The polymerization reaction was performed by irradiating with the light amount of 20 minutes to obtain an ion conductive polymer solid electrolyte.

[0133]

Example 12 (Synthesis of dihydroxypropyl dextran); Dextran (manufactured by Wako Pure Chemical Industries, molecular weight 60,000)
-90000) 5.0 g dispersed in 150 ml of acetone,
To the suspended solution at room temperature, add 1.5 ml of 10 ml of distilled water.
A solution of g of sodium hydroxide was added dropwise, and the mixture was stirred for 20 minutes.

Further, 12 g of glycidol was added to 4 parts of acetone.
A solution dissolved in 0 ml was added dropwise, and the mixture was reacted at 50 ° C. for 6 hours.

A gum-like substance was taken out from the reaction mixture, dissolved in distilled water, neutralized with acetic acid, filled in a cellulose dialysis membrane tube and dialyzed with distilled water.

The solution after dialysis was lyophilized to obtain dihydroxypropyl dextran. The molar substitution degree of the obtained dihydroxypropyl dextran was found to be MS = 2.5 by analysis using ¹³ C-NMR.

An ion conductive polymer solid electrolyte was obtained in the same manner as in Example 11 except that 1 part of dihydroxypropyl dextran was used in place of the hydroxyethyl starch used in Example 11.

[0138]

[Example 13] (Synthesis of cyanoethylated hydroxyethyl starch): Hydroxyethyl starch (manufactured by Penford Products) was used for cyanoethylation by the method of Example 5 [I] to synthesize cyanoethylated hydroxyethyl starch. did. The N weight% of the obtained cyanoethylated hydroxyethyl starch was 7.1%.

Ion-conductive material was prepared in the same manner as in preparing the ion-conductive polymer solid electrolyte of Example 3 except that 1 part of cyanoethylated hydroxyethyl starch was used in place of the hydroxypropyl cellulose used in Example 3. A polymer solid electrolyte was obtained.

[0140]

Example 14 To 10 parts of tetrahydrofuran as a solvent, 1 part of hydroxypropyl cellulose (molar degree of substitution (MS) = 4.65, manufactured by Nippon Soda Co., Ltd.) and 1 part of anhydrous lithium perchlorate were added. Dissolved and 0.5 parts of polyethylene glycol dimethacrylate (the number of oxyethylene units = 9, manufactured by NOF CORPORATION) and 1.5 parts of methoxy polyethylene glycol monomethacrylate (the number of oxyethylene units = 9, Japan) Yushi Co., Ltd.)
Was added and mixed.

The mixed solution was kept under reduced pressure at 40 ° C., and tetrahydrofuran was removed until the weight of the mixed solution became 4.2 parts by weight.

As a polymerization initiator, 0.05 part of azobisisobutyronitrile was added and dissolved, and the mixture was cast on a substrate (copper plate) using a doctor knife applicator. This one
Hold in an oven at 05 ℃ for 1 hour to carry out heat polymerization reaction,
An ion conductive polymer solid electrolyte was obtained.

[0143]

Example 15 An ionic conductive polymer solid electrolyte was obtained in the same manner as in Example 3 except that 25 parts of propylene carbonate was used as the solvent in Example 3 and the solvent in the mixed solution was not removed at all.

[0144]

Example 16 An ionic conductive polymer solid electrolyte was obtained in the same manner as in Example 3 except that 0.5 part of polyethylene glycol dimethacrylate and 2.5 parts of methoxy polyethylene glycol monomethacrylate were used. It was

[0145]

Example 17 In Example 3, 3 parts of propylene carbonate was used, 0.1 part of polyethylene glycol dimethacrylate and 0.1 part of methoxy polyethylene glycol monomethacrylate were used, and the total weight of the mixed solution was 2.4.
An ionic conductive polymer solid electrolyte was obtained in the same manner except that the solvent was removed until the amount became part by weight.

[0146]

[Comparative Example 1] 1 part of hydroxypropyl cellulose (molar degree of substitution (MS) = 4.
65, manufactured by Nippon Soda Co., Ltd. and 1 part of anhydrous lithium perchlorate were added and dissolved, and then 10 parts of propylene carbonate was added and mixed.

The mixed solution was kept under reduced pressure at 40 ° C., and the solvent was removed until the total amount of the mixed solution became 12 parts. It was cast on a base (copper plate) using a doctor knife applicator to obtain an ion conductive composition.

When the substrate (copper plate) was placed vertically, the obtained ion conductive composition was deformed by deformation of the complex, and it could not be said to be solid.

[0149]

Comparative Example 2 To 10 parts of propylene carbonate, 1 part of anhydrous lithium perchlorate was added and dissolved, and 0.5 parts of polyethylene glycol dimethacrylate (the number of oxyethylene units = 9, manufactured by NOF Corporation) ) And 1.5 parts of methoxy polyethylene glycol monomethacrylate (the number of oxyethylene units = 9, manufactured by NOF CORPORATION)
Was added and mixed.

Further, 0.05 part of benzyl dimethyl ketal as a photopolymerization initiator was added and dissolved. Since this solution could not be cast using a doctor knife applicator, it was poured into a Teflon dish and at room temperature, ultraviolet rays were irradiated at a light amount of 6 mW / cm ² for 20 minutes to carry out a polymerization reaction, An ion conductive composition was obtained.

The obtained ion conductive composition was very brittle and could not be lifted. It was extremely weak.

[0152]

Comparative Example 3 In 10 parts of tetrahydrofuran as a solvent, 1 part of polyethylene oxide (Wako Pure Chemical Industries, Ltd., molecular weight 2000) and 1 part of anhydrous lithium perchlorate were added and dissolved, and 0.5 part thereof was added. Polyethylene glycol dimethacrylate (number of oxyethylene units = 9, manufactured by NOF CORPORATION) and 1.5 parts of methoxypolyethylene glycol monomethacrylate (number of oxyethylene units =)
9, Nippon Oil & Fats Co., Ltd. were added and mixed.

This mixed solution was kept under reduced pressure at 40 ° C., and tetrahydrofuran was removed until the weight of the mixed solution became 4.2 parts by weight.

As a polymerization initiator, 0.05 part of benzyldimethyl ketal was added and dissolved, and the mixture was cast on a base (copper plate) using a doctor knife applicator. At room temperature, ultraviolet rays were irradiated in the air at a light amount of 6 mW / cm ² for 20 minutes to carry out a polymerization reaction to obtain an ion conductive polymer solid electrolyte.

[0155]

[Comparative Example 4] 1 part of polyethylene oxide (Wako Pure Chemical Industries, Ltd., molecular weight 2000) in a solvent prepared by mixing 10 parts of tetrahydrofuran with 10 parts of propylene carbonate.
And 1 part of anhydrous lithium perchlorate were added and dissolved, and 1.5 parts of polyethylene glycol dimethacrylate (the number of oxyethylene units = 9, manufactured by NOF CORPORATION)
And 1.5 parts of methoxypolyethylene glycol monomethacrylate (the number of oxyethylene units = 9, manufactured by NOF CORPORATION) was added and mixed.

This mixed solution was put under reduced pressure to adjust the viscosity.
The temperature was kept at 0 ° C., and the solvent was removed until the total amount of the mixed solution reached 15 parts.

As a polymerization initiator, 0.05 part of benzyldimethyl ketal was added and dissolved, and the mixture was cast on a base (Teflon plate) using a doctor knife applicator.

At room temperature, ultraviolet rays of 6 mW / cm ² were emitted in the air.
The polymerization reaction was performed by irradiating with the light amount of 20 minutes to obtain an ion conductive polymer solid electrolyte.

[0159]

Comparative Example 5 An ion conductive polymer solid electrolyte was obtained in the same manner as in Example 3 except that polyethylene glycol dimethacrylate was 2.5 parts and methoxy polyethylene glycol monomethacrylate was 0.5 parts. It was

[0160]

[Comparative Example 6] In Example 3, 45 parts of hydroxypropyl cellulose and 10 parts of lithium perchlorate were used.
An ion conductive polymer solid electrolyte was obtained in the same manner as in Example 3 except that the solvent was removed until the total amount of the mixed solution reached 68 parts.

[0161]

[Comparative Example 7] In Example 3, except that polyethylene glycol dimethacrylate and methoxypolyethylene glycol monomethacrylate were each 5 parts, lithium perchlorate was 3 parts, and the solvent was removed until the total amount of the mixed solution was 24 parts. An ion conductive polymer solid electrolyte was obtained in the same manner as in Example 3.

The ionic conductivities of the ion conductive polymer solid electrolytes synthesized in Examples 1 to 17 and the ion conductive compositions synthesized in Comparative Examples 1 to 7 were measured by the AC impedance method. The appearance of each electrolyte was compared. The results are summarized in Table 1. The appearance shows the following states. A: Membrane shape B: Membrane shape, but brittle and easily broken C: Membrane shape does not occur

[0163]

[Table 1]

[0164]

[Table 2]

[0165]

[Table 3]

[0166]

The ionic conductive polymer solid electrolyte of the present invention has high ionic conductivity and good retention performance.

[Brief description of drawings]

FIG. 1 semi-IPN before the crosslinking reaction of the electrolyte of the present invention
Conceptual diagram of the structure.

FIG. 2 is a conceptual diagram of a semi-IPN structure in which a three-dimensional network is formed after the crosslinking reaction of the electrolyte of the present invention.

[Explanation of symbols]

 1 Hydroxyalkyl Polysaccharide or Polysaccharide Derivative 2 Diester Containing Polyoxyalkylene Component 3 Monoester Containing Polyoxyalkylene Component

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 3/04 C08L 3/04 71/02 LQC 71/02 LQC H01B 1/06 H01B 1/06 A (72) Inventor Soichiro Takenishi 1-18-1 Nishiarai Sakaecho, Adachi-ku, Tokyo Inside Nisshin Spinning Co., Ltd. Tokyo Research Center (72) Inventor Yasunobu Kodama 222-1, Ueuchizen, Sumoto, Hyogo Sanyo Electric Co., Ltd. Inside the Energy Technology Development Laboratory (72) Inventor Tsukasa Ito 222-1 Zen Uezen, Sumoto City, Hyogo Sanyo Electric Co., Ltd. Inside Soft Energy Technology Development Laboratory (72) Inventor Takashi Sakai 221-1 Uezen Zen, Hyogo Prefecture Sanyo Electric Co., Ltd. Incorporated company Soft Energy Technology Development Laboratory

Claims (7)

[Claims] 1. A diester compound containing 100 parts by weight of a hydroxyalkyl polysaccharide or hydroxyalkyl polysaccharide derivative, a polyoxyalkylene component and a monoester compound containing a polyoxyalkylene component.
~ 500 parts by weight and a composition for polymer solid electrolyte comprising 5 to 1000 parts by weight of ion conductive metal salt. 2. The composition according to claim 1, wherein the weight ratio of diester compound / monoester compound is 1 to 0.2. 3. The hydroxyalkyl polysaccharide derivative according to claim 1, which is one of the hydroxyl groups in the hydroxyalkyl polysaccharide.
A composition for a polymer solid electrolyte, which is a hydroxyalkyl polysaccharide derivative in which a part or all of which is introduced with a substituent through an ester bond or an ether bond. 4. A diester compound (Chemical Formula 1) containing the polyoxyalkylene component according to claim 1 is (Provided that R ₁ , R ₂ and R ₃ represent H or an alkyl group having 1 to 6 carbon atoms and satisfy the conditions of X ≧ 1 and Y ≧ 0,
Or, those satisfying the conditions of X ≧ 0 and Y ≧ 1. ), And the monoester compound containing the polyoxyalkylene component (Formula 2) is (However, R ₄ , R ₅ , and R ₆ represent H or an alkyl group having 1 to 6 carbon atoms and satisfy the conditions of A ≧ 1 and B ≧ 0, or the conditions of A ≧ 0 and B ≧ 1. The composition for a polymer solid electrolyte, which satisfies: 5. The composition for a polymer solid electrolyte according to claim 1, further comprising a solvent capable of dissolving the ion conductive metal salt. 6. A polyoxyalkylene component is obtained by irradiating the composition for a polymer solid electrolyte according to claim 1 with ultraviolet rays, electron beams, X-rays, gamma rays, microwaves, high frequency waves, or by heating. By polymerizing the diester compound contained and the monoester compound containing the polyoxyalkylene component, a three-dimensional cross-linking network structure is formed in which the resulting polymer chain is entangled with the molecular chain of the hydroxyalkyl polysaccharide or the hydroxyalkyl polysaccharide derivative. A method for producing a polymer solid electrolyte, which comprises forming the solid electrolyte. 7. A polymer solid electrolyte obtained by the manufacturing method according to claim 6.