KR20030014698A - Electrolyte composition for electric double-layer capacitor, solid polymer electrolyte, composition for polarizable electrode, polarizable electrode, and electric double-layer capacitor - Google Patents

Abstract

Electrolytic composition for electric double layer capacitor with high ion conductivity, high binder material and high dielectric material such as solid polymer electrolyte, activated carbon and conductive material can be firmly bonded to the current collector. Provided are a composition for polarizable electrodes, a polarizable electrode, and a high-function electric double layer capacitor composed thereof.

Description

ELECTROLYTE COMPOSITION FOR ELECTRIC DOUBLE-LAYER CAPACITOR, SOLID POLYMER ELECTROLYTE, COMPOSITION FOR POLARIZABLE ELECTRODE, POLARIZABLE ELECTRO ELECTRIC DOUBLE-LAYER CAPACITOR}

In the computer currently used, an electric double layer capacitor is used as a power supply for memory backup. This capacitor utilizes an electric double layer formed at the interface between the electrode and the electrolyte, and is characterized by small size, large capacity, and long repeat life.

In recent years, as portable and wireless devices for public electronic devices (for example, portable devices such as mobile phones) are rapidly developed, the demand for electric double layer capacitors is also increasing. Among them, the electric double layer capacitor using a non-aqueous electrolyte has a higher voltage and higher energy density than that of an aqueous solution, and thus, it is expected to be used for backing up various electric and electronic devices, regenerative electric vehicles, and power storage. As a result, its development is being promoted.

Conventionally, secondary batteries have been used in this field. However, the electric double layer capacitor has become widely used because the electric current of the electric double layer capacitor is excellent in terms of the reduction of the backup current, the cycle life, the operating temperature range, and the like due to the reduced power consumption of the device.

Such an electric double layer capacitor has a structure in which a separator is interposed between a pair of polarizable electrodes, and this separator is usually impregnated with an electrolyte solution. In addition, the polarizable electrode is formed by adding a high-conductor material such as activated carbon to the binder and a conductive material to improve the conductivity of the electrode, and applying the slurry onto a metal current collector such as aluminum foil to support the slurry. .

In a conventional electric double layer capacitor, as a binder for supporting high-area materials such as activated carbon, conductive materials and the like on a metal current collector, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylpyrrolidone, carboxymethyl cellulose, and the like Among them, polyvinylidene fluoride has excellent film forming ability.

However, all of these binders do not have the ability to dissolve the ion conductive salt in high concentration, and the binder itself does not have high ion conductivity. In addition, there is a problem in that when the ion conductive salt is dissolved in high concentration, crystallization and ions cannot move smoothly. In addition, in order to reduce the interfacial resistance between the polarizable electrodes / electrolyte (separator), it is desired to use a binder resin having a composition common to that used for the electrolyte (separator) as the binder for the polarizable electrodes.

As described above, the binder resin for polarizable electrodes and the electrolyte composition for electric double layer capacitors, which have been reported so far, do not have sufficient satisfactory performance, and further improvement and improvement are strongly desired.

The present invention relates to an electrolyte composition for an electric double layer capacitor, a solid polymer electrolyte, a composition for polarizable electrodes and a polarizable electrode, and an electric double layer capacitor composed thereof. It is about.

1 is a ¹³ C-NMR spectrum of the polyglycidol of Synthesis Example 1 of the present invention.

2 is a ²⁹ Si-NMR spectrum of trimethylsilylated polyglycidol in which polyglycidol of Synthesis Example 1 is trimethylsilylated.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent binder function and high ability to firmly bind an electrolyte composition for an electric double layer capacitor having high ion conductivity and a solid polymer electrolyte, a high area material and a conductive material to a current collector. An object of the present invention is to provide a composition for a polarizable electrode having a dielectric constant, shape stability, and a polarizable electrode, and a high performance electric double layer capacitor composed of these.

In order to achieve the above object, the present invention provides an electrolyte composition for an electric double layer capacitor, a composition for a solid polymer electrolyte, a polarizable electrode, and a polarizable electrode and an electric double layer capacitor.

1, (A) a unit represented by the following formula (1) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, R ¹ CO-group (R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is A polymer compound blocked by one or two or more monovalent groups selected from a group containing 2 to 4 carbon atoms, m is an integer of 1 to 100) and a person group, and (B) an ion conductive salt as main components Electrolyte composition for an electric double layer capacitor, characterized in that.

(2) a monovalent hydrocarbon group having a unit represented by the following formula (A) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted, R ¹ CO-group (R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is A polymer compound blocked by one or two or more monovalent groups selected from a group having 2 to 4 carbon atoms, m is an integer of 1 to 100) and a person group, (B) an ion conductive salt, ( C) An electrolyte composition for an electric double layer capacitor, comprising a compound having a crosslinkable functional group as a main component.

(Formula 1)

(Formula 2)

The electrolyte composition for electric double layer capacitors of the 1st or 2nd term | claim whose monovalent group which blocks the 3rd terminal is a cyano group substituted monovalent hydrocarbon group or a cyano group substituted monovalent hydrocarbon group, and R <^1> ₃ Si- group.

4, the three-dimensional network structure of the polymer obtained by crosslinking of the compound (C) component has a semi-interpenetrating polymer network structure in which the molecular chains of the polymer compound (A) component are wound together. A solid polymer electrolyte for an electric double layer capacitor, comprising an ion conductive salt as a B) component.

(A) a unit represented by the following formula (1) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, R ¹ CO-group (R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is A polymer compound sealed by one or two or more monovalent groups selected from a group having 2 to 4 carbon atoms, m is an integer of 1 to 100) and a person group, (D) a high-area material, ( E) A composition for polarizable electrodes comprising a conductive material as a main component.

(Formula 1)

(Formula 2)

(A) A monovalent hydrocarbon group having a unit represented by the following formula (A) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted, R ¹ CO-group (R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is An alkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 100) and a polymer compound blocked by one or two or more monovalent groups selected from a group containing a person group, and (C) a compound having a crosslinkable functional group And (D) a high area material and (E) a conductive material as main components.

(Formula 1)

(Formula 2)

The composition for polarizable electrodes of 5th and 6th term | claim whose monovalent group which blocks the terminal in 7 is cyano group substituted monovalent hydrocarbon group, or cyano group substituted monovalent hydrocarbon group, and R <^1> ₃ Si- group.

The polarizable electrode of Claim 8 which apply | coats the composition for polarizable electrodes of said 5th, 6th, or 7 to an electrical power collector.

In the electrical double layer capacitor formed by interposing a separator between a pair of polarizable electrodes, the polarizable electrode of said 8th is used as said pair of polarizable electrodes, and it is used as a separator to a separator base material. An electric double layer capacitor comprising a separator formed by impregnating an ion conductive salt-containing solution.

10. In the electric double layer capacitor formed by interposing a separator between a pair of polarizable electrodes, the polarizable electrode of Claim 8 is used as said pair of polarizable electrodes, and it is used as a separator to a separator base material. An electric double layer capacitor comprising a separator formed by applying or impregnating an electrolyte composition for an electric double layer capacitor according to the first, second, or third.

The electric double layer capacitor which comprises a separator between a pair of polarizable electrodes in Claim 11 WHEREIN: The polarizable electrode of 8th is used as said pair of polarizable electrodes, and said 1st as said separator is used. An electric double layer capacitor comprising a solid polymer electrolyte layer comprising an electrolyte composition for an electric double layer capacitor according to item 2 or 3.

The electric double layer capacitor formed by interposing a separator between a pair of polarizable electrodes is used for the said polarizing electrode of said 8th as said one pair of polarizable electrodes, and it is said 4th as said separator. The electric double layer capacitor characterized by using the solid polymer electrolyte for electric double layer capacitors described in the above.

As a result of intensive studies to achieve the above object, the present inventors have the ability to dissolve many ionic conductive salts, and do not crystallize even if the ionic conductive salts are dissolved at high concentrations. It is composed mainly of polyglycidol derivatives and ion-conductive salts formed by blocking the molecular chain ends of polyglycidol, which is an amorphous polymer, by entanglement of highly branched molecular chains that can move smoothly with various substituents. It was found that the electrolyte composition for electric double layer capacitors had high ionic conductivity and excellent properties such as flame retardancy, hydrophobicity, and high dielectric constant. In addition, in the three-dimensional network structure of a polymer, an electrolyte composition for an electric double layer capacitor whose main component is a compound having a crosslinkable functional group with the polyglycidol derivative and an ion conductive salt is obtained by crosslinking a compound having a crosslinkable functional group. Semi-interpenetrating polymer network in which molecular chains of glycidol derivatives are wound around each other; (semi-IPN)] structure, in addition to high ionic conductivity, the shape retention ability is dramatically improved, and it is found that it is optimal as a separator for electric double layer capacitors. Furthermore, the polyglycidol derivative has an excellent binder function and a high dielectric constant capable of firmly bonding a high-area material and a conductive material to a current collector, and thus the composition for polarizable electrodes and polarizable electrodes of an electric double layer capacitor. It was found to be very suitable as.

Further, from these findings, as a result of further studies, the electrolyte composition or solid polymer electrolyte of the electric double layer capacitor of the present invention is interposed between a pair of polarizable electrodes of the polarizable electrode composition of the present invention as a separator. The electric double layer capacitor of the present invention has a high performance of high voltage, high energy density, high capacity, long repetition life, and can be miniaturized, and is used for backup applications of various electric and electronic devices such as PCs, mobile phones, hybrid cars, The present invention has been found to be widely used for regenerative, electric power storage and the like of electric vehicles.

(The best form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The electrolyte composition for electric double layer capacitors of the present invention has the following first or second constituents.

(1) a polymer compound (polyglycidol derivative) having a unit represented by the formula (1) and a unit represented by the formula (2), wherein the terminal of the molecular chain is blocked by a predetermined substituent; ) Ionic conductive salt is the main component.

(Formula 1)

(Formula 2)

Second, the main component is a compound having a polyglycidol derivative of the component (A), an ion conductive salt (B) and a crosslinkable functional group (C).

First, the electrolyte composition for a first electric double layer capacitor of the present invention includes (A) a unit represented by Chemical Formula 1 (hereinafter referred to as A unit) and a unit represented by Chemical Formula 2 (hereinafter referred to as B unit). And a high molecular compound consisting of a polyglycidol derivative whose respective ends of the molecular chain are blocked by a predetermined substituent, and an ion conductive salt as the component (B).

In this case, the polyglycidol comprising the units of Formulas 1 and 2 is Andrzej Dworak et al., Macromol. Chem. Phys. Known as described in 196, 1963-1970 (1995), R. Tokar et al., Macromolecules 27, 320-322 (1994). However, this polyglycidol has electrochemical properties such as (i) high electrochemical stability, colorless and transparent, and non-toxic, such as binder binder materials of various active substances (for example, electroluminescent binders, etc.). As a substitute for materials, thickeners and alkylene glycols, which can be used in a wide range of applications, (ii) having the ability to dissolve ionic conductive salts in high concentrations, and not to crystallize even when ionic conductive salts are dissolved in high concentrations, (iii) When polyglycidol having a relatively high molecular weight is used as an electrolyte in combination with an ion conductive salt, a polyglycidol in a solid state is obtained at room temperature by the entanglement effect of the polyglycidol molecular chain, and (iv) polyglycidol It is a new inventor of the present invention that a high-area material and a conductive material can be firmly bound to a current collector, and are suitable as a binder for polarized electrodes for electric double layer capacitors. Good insight.

Here, although the said polyglycidol can be obtained by superposing | polymerizing glycidol or 3-chloro-1, 2-propanediol, it is generally recommended to superpose | polymerize using glycidol as a raw material.

As the polymerization reaction, (1) a method using a basic catalyst such as sodium hydroxide, potassium hydroxide, various amine compounds, and (2) a Lewis acid catalyst are known (Andrzej Dworak et al., Macromol. Chem. Phys. 196, 1963-1970 (1995), R. Toker., Macromolecules 27, 320-322 (1994).

(1) The method of polymerization using a basic catalyst is often performed by adding an alcoholic compound (active hydrogen compound) serving as a starting point, and a high molecular weight polymer is difficult to obtain. The reaction mechanism is as shown below.

In a specific polymerization method, a predetermined amount of glycidol is added into a flask, methylene chloride is added as a solvent, set at a predetermined temperature, a predetermined amount of potassium hydroxide is added as a catalyst, and the reaction is carried out while stirring. At this time, if necessary, an active hydrogen compound is blended. After completion of the reaction, methanol is added to stop the reaction, and methanol and methylene chloride are distilled off under reduced pressure. The obtained polymer is dissolved in water, neutralized using an ion exchange resin, the ion exchange resin is separated by filtration, water is distilled off under reduced pressure, and polyglycidol can be obtained by drying.

In this case, as an active hydrogen compound, alcohols, such as ethanol, methanol, isopropyl alcohol, benzyl alcohol, glycerin, pentaerythritol, sorbitol, diethylene glycol, ethylene glycol, threose, tetraose, pentaose, hexose, etc. High molecular compounds which have hydroxyl groups, such as polyols, polyvinyl alcohol, and polyethylenevinyl alcohol, etc. can be used.

The addition amount of the active hydrogen compound is (moles of active hydrogen groups of the added active hydrogen compound) / (number of moles of glycidol added) = 0.0001 to 1, more preferably 0.001 to 1, still more preferably 0.005 0.5, Most preferably, it is the range of 0.01-0.1.

In addition, the method of superposing | polymerizing using a Lewis acid catalyst is superposing | polymerizing in the system without water, and the reaction mechanism is as showing below.

As a specific polymerization method, a predetermined amount of glycidol is introduced into a flask, methylene chloride is used as a solvent if necessary, a predetermined amount of a catalyst (reaction initiator) is added under a predetermined reaction temperature, and stirred under a nitrogen gas stream. React. Methanol is added after completion | finish of reaction, reaction is stopped, methanol and methylene chloride are distilled off under reduced pressure. After dissolving the obtained polymer in water and neutralizing with sodium hydrogen carbonate, the solution was passed through a column filled with an ion exchange resin, the solution after the passage of the column was separated by filtration, the filtrate was distilled off under reduced pressure, and dried. Glycidol can be obtained.

In this case, trifluoroborate diethyl etherate (BF ₃ · OEt ₂ ), SnCl ₄ · HPF ₆ · OEt ₂ , or the like can be used as the catalyst (reaction initiator) (Et represents an ethyl group).

When polyglycidol obtained in this way was measured by ¹³ C-NMR (DEPT measurement using a solvent D ₂ 0 using a Varian VXR 300 NMR spectrometer), as shown in FIG. The peak which shows the carbon derived from a unit appears, and it can confirm that a polyglycidol consists of A and B two units.

Moreover, it is preferable that two or more, preferably 6 or more, more preferably 10 or more of the said polyglycidol are summed together by two units of A and B in a molecule | numerator. In this case, the upper limit is not particularly limited, but is preferably 10,000 or less. When fluidity as a liquid is required for polyglycidol, the smaller the sum of A and B units is, on the other hand, the higher the greater the total of A and B units, when higher viscosity is required.

The appearance of these A and B units does not have regularity and is random, for example, -AAA-, -AAB-, -ABA-, -BAA-, -ABB-, -BAB-, -BBA-, -BBB- and the like. Any combination of is possible.

As polyglycidol, the weight average molecular weight (Mw) of polyethyleneglycol conversion using gel filtration chromatography (GPC) becomes like this. Preferably it is 200-730,000, More preferably, it is 200-100,000, More preferably, it is 600-20,000. In this case, polyglycidol having a weight average molecular weight of about 2000 is a high viscosity liquid flowing at room temperature, but polyglycidol having a weight average molecular weight of more than 3000 is a soft paste in the form of a solid at room temperature. Moreover, it is preferable that average molecular weight ratio (Mw / Mn) is 1.1-20, More preferably, it is 1.1-10.

The polyglycidol varies in appearance from a liquid starch liquid having a high viscosity to a solid state in a rubber state at room temperature (20 ° C.) at a room temperature (20 ° C.). It becomes what can be called so-called solid (soft paste solid) with low fluidity.

Moreover, polyglycidol is not a linear polymer, but amorphous (amorphous) polymer by the entanglement of highly branched molecular chain, regardless of the magnitude of molecular weight. This confirms that no peak suggesting the presence of crystals is found from the results of the wide-angle X-ray diffraction.

In addition, the ratio of A unit and B unit in a molecule | numerator can be calculated | required by measuring ²⁹ Si-NMR of the trimethylsilylated polyglycidol which introduce | transduced the trimethylsilyl group into the hydroxyl group of polyglycidol, as shown in FIG. have. In this case, the ratio of A unit and B unit is A: B = 1 / 9-9 / 1, Preferably it is 3 / 7-7 / 3 in molar ratio.

Since the polyglycidol is colorless and transparent and has no toxicity, it can be used as an electrochemical material such as binder binder materials (e.g., binders of electroluminescence) of various active substances, thickeners, substitutes for alkylene glycol, and the like. It can be used for a wide range of applications.

In the present invention, at least 10% of the terminal OH group of the molecular chain of the polyglycidol as the (A) component is a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, R ¹ CO- group (R ¹ is unsubstituted) Or a substituted monovalent hydrocarbon group), a R ¹ ₃ Si-group (R ¹ is the same as above), an amino group, an alkylamino group, an H (OR ² ) _m -group (R ² is an alkylene group having 2 to 4 carbon atoms, m Is an integer of 1 to 100) and a polyglycidol derivative sealed by one or two or more monovalent groups selected from the group containing a person group.

In this case, in the blockade of the terminal end of the polyglycidol molecular chain by the above group, in the polymer containing the ion conductive salt at a high concentration, the dissociation of the dissociated metal cation and the counter anion easily occurs in the polymer matrix of low dielectric constant, and the conductivity Although lowering the polymer matrix increases the polarity of the polymer matrix, it is less likely to cause ionic association. Therefore, a polar group is introduced into the side chain (hydroxyl group) of the polyglycidol to increase the dielectric constant of the matrix polymer. It aims at providing the outstanding characteristic of these.

In order to increase the dielectric constant of the (1) polymer compound, polyglycidol and a hydroxyl group-reactive compound are reacted to block the molecular chain terminal (hydroxyl group) of the polyglycidol with a high polar substituent.

Although it does not restrict | limit especially as such a high polar substituent, It is more preferable that it is a neutral substituent rather than an ionic substituent. For example, an unsubstituted or substituted monovalent hydrocarbon group, a R ¹ CO-group (R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), and an H (OR ² ) _m -group (R ² has ² to 4 carbon atoms) Alkylene group, m is an integer of 1-100), etc. are mentioned. Moreover, you may block with an amino group, an alkylamino group, etc. as needed.

On the other hand, (2) In the case of imparting hydrophobicity and flame retardancy to a polymer compound, the molecular chain terminal (hydroxyl group) of polyglycidol is a halogen atom, a group containing a R ¹ ₃ Si- group (R ¹ is the same as above), and a person group. Seal with a back.

Here, when the substituent is specifically described, examples of the halogen atom include fluorine, bromine and chlorine. As a substituted or unsubstituted monovalent hydrocarbon group, a C1-C10, especially 1-8 substituted or unsubstituted monovalent hydrocarbon group is preferable, For example, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, isobutyl Alkyl groups such as groups, tert-butyl groups, pentyl groups, neopentyl groups, hexyl groups, cyclohexyl groups, octyl groups, nonyl groups and decyl groups, aryl groups such as phenyl groups, tolyl groups and xylyl groups, benzyl groups and phenyl Aralkyl groups, such as an aralkyl group, such as an ethyl group and a phenylpropyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, butenyl group, a hexenyl group, a cyclohexenyl group, an octenyl group, and some hydrogen atoms of these groups Or all are halogen atoms such as fluorine, bromine, chlorine, cyano group, hydroxyl group, H (OR ² ) _m -group (R ² is an alkylene group having 2 to 4 carbon atoms, m is an integer of 1 to 100), amino group, amino Substituted with alkyl group, phosphono group and the like, for example cyanoethyl group, cyanobenzyl group, other Substituent, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group etc. which the cyano group couple | bonded with the alkyl group are mentioned, One of these can be used individually or in combination of 2 or more types.

Examples of the R ¹ CO- group include those in which R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably ¹ to 8 carbon atoms, and preferably R ¹ is an alkyl group. Or a phenyl group, and an acyl group, a benzoyl group, a cyanobenzoyl group, and the like are preferable.

As the H (OR ² ) _m − group, R ² represents an alkylene group having 2 to 4 carbon atoms (ethylene group, propylene group, butylene group), and m is 1 to 100, preferably an integer of 2 to 70. Moreover, 2 or more types may be mixed for an ethyleneoxy group, a propyleneoxy group, and butyleneoxy group.

Examples of the R ¹ ₃ Si-group include those in which R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having the same carbon atoms as those of 1 to 10, preferably C1 to 8, and preferably R ¹ is an alkyl group, Trialkylsilyl group, especially trimethylsilyl group is preferable.

In addition, the substituent may be an amino group, an alkylamino group, a group containing a person group, or the like.

Here, the terminal blocking rate by the substituent is 10% or more, preferably 50% or more, more preferably 90% or more, and substantially all of the terminals may be blocked by the substituent (blocking rate of about 100%).

In addition, if cut off the end all of the polymer molecular chain group, including the halogen atom, R ^l ₃ Si- groups, personnel, so that if the ion-conductive salt dissolution ability of the polymer itself decreases, while taking into account the degree of solubility, an appropriate amount of It is necessary to introduce a substituent. Specifically, it is 10 to 95%, preferably 50 to 95%, and more preferably 50 to 90% with respect to the entire terminal (hydroxyl group).

In the present invention, among these substituents, in particular, it is preferable to use a cyano group-substituted monovalent hydrocarbon group or a cyano group-substituted monovalent hydrocarbon group and an R ¹ ₃ Si- group together, specifically, a cyanoethyl group, cyanobenzyl group, and cya The thing which combined the substituent which the cyano group couple | bonded with the nobenzoyl group and other alkyl groups, or these cyano group substituted monovalent hydrocarbon group and trimethylsilyl group, etc. are mentioned.

In addition, 70 of the cyano case where a cyano group-substituted ethyl group such as one of a combination of a group R ¹ ₃ Si- group such as trimethylsilyl group hydrocarbon, the ratio of the two is a cyano group-substituted monovalent entire ends of the molecular chain hydrocarbon group (hydroxyl group) -97%, Preferably it is 90-97%, R <_3> Si-group is 30 to ₃ % of the whole terminal, Preferably it is ^{10 to} ₃ %. Thus, the polymer introduced by combining the cyano group-substituted monovalent hydrocarbon group and the R ¹ ₃ Si- group has excellent conductivity and hydrophobicity.

As a method of blocking (introducing) a polyglycidol molecular chain with such a substituent, when a cyanoethyl group is introduced, for example, polyglycidol is mixed with dioxane and acrylonitrile, and this mixed solution By adding sodium hydroxide solution and reacting with stirring, cyanoethylated polyglycidol having a cyanoethyl group introduced into part or all of the side chains can be obtained.

When introducing an acetyl group, for example, polyglycidol is mixed with acetic acid and methylene chloride, an aqueous solution of perchloric acid and acetic anhydride are added to the mixed solution, stirred at room temperature, the reaction solution is poured into cold water, and the precipitate precipitates. The precipitates obtained are dissolved in acetone and added to water again. After adding sodium hydrogencarbonate and neutralizing, it filtered. The precipitates can be collected and placed in a dialysis tube with water, dialyzed with ion-exchanged water, the precipitates collected, washed with water and dried under reduced pressure to obtain acetylated polyglycidol.

In the case of introducing a cyanobenzoyl group, for example, polyglycidol is mixed with dioxane, pyridine is added, and then a solution in which cyanobenzoyl chloride is dissolved in dioxane is added dropwise. Thereafter, the solution was allowed to react at a predetermined temperature, the reactant was poured into a solution of methanol: water = 3: 4, and the precipitated precipitate was collected. The cyanobenzoylated polyglycidol can be obtained by dissolving the precipitate in N, N-dimethylsulfoxide, placing it in a dialysis tube, dialysis to collect the precipitate, washing with water and drying under reduced pressure.

In the case of introducing a trimethylsilyl group, for example, polyglycidol is dissolved in dimethylacetamide, bis (trimethylsilyl) acetamide is added to this solution, stirred at room temperature, and the reaction solution is cooled with ice water. Pour into cooled methanol: water = 4: 1 solution. Precipitated precipitate is separated by filtration, the filtrate is dissolved in acetamide, filtered through a filter paper, and the solution is dried under reduced pressure to obtain trimethylsilylated polyglycidol.

In addition, other substituents can also be blocked using a known method for introducing various groups into the terminal OH group.

Next, ion conductivity is imparted to the polyglycidol derivative as the component (A) in the electrolyte composition for an electric double layer capacitor of the present invention by adding the ion conductive salt as the component (B).

In this case, as the ion conductive salt, any one can be used without particular limitation as long as it is used for a general electrochemical device, and in particular, the general formula: R ¹ R ² R ³ R ⁴ N ⁺ or R ¹ R ² R ³ R ⁴ P ⁺ (Wherein R ¹ to R ⁴ are each an alkyl group having 1 to 10 carbon atoms which may be the same or different from each other), and a quaternary onium cation represented by BF ₄ ⁺ , N (CF ₃ SO ₂ ) ₂ ⁻ , PF ₆ ⁻ Salts which combine anions such as, ClO ₄ ^- and the like are preferable.

Specifically, (C ₂ H ₅ ) ₄ PBF ₄ , (C ₃ H ₇ ) ₄ PBF ₄ , (C ₄ H ₉ ) ₄ PBF ₄ , (C ₆ H _l3 ) ₄ PBF ₄ , (C ₄ H ₉ ) ₃ CH ₃ PBF ₄ , (C ₂ H ₅ ) ₃ (Ph-CH ₂ ) PBF ₄ , (Ph represents a phenyl group), (C ₂ H ₅ ) ₄ PPF ₆ , (C ₂ H ₅ ) PCF ₃ SO ₂ , (C ₂ H ₅ ) ₄ NBF ₄ , (C ₄ H ₉ ) ₄ NBF ₄ , (C ₆ H ₁₃ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₆ NPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ These can be mentioned and one type can be used individually or in combination of 2 or more types.

Although the compounding quantity of the ion conductive salt which is this (B) component differs according to the kind of ion conductive salt to be used, the molecular weight of a high molecular compound, etc., it cannot determine uniformly, Usually, 100 weight of polyglycidol derivatives which are (A) component 5 to 1000 parts by weight of the ion conductive salt, preferably 10 to 500 parts by weight, more preferably 10 to 100 parts by weight, still more preferably 10 to 50 parts by weight relative to the part. When the compounding quantity of an ion conductive salt is too small, the density | concentration of an ion conductor will become thin, and the result may be too low practically. On the other hand, when too large, the solubility with respect to the ion conductive salt of a polymer matrix may exceed, and precipitation of salt may arise.

In the electrolyte composition for the first electric double layer capacitor of the present invention, in addition to the components (A) and (B), a solvent capable of dissolving an ion conductive salt can be added in a normal capacity. As such a solvent, dibutyl ether, 1, 2-dimethoxyethane, 1, 2-ethoxymethoxyethane, methyl diglyme, methyl triglyme, methyl tetraglyme, ethyl glyme, ethyl diglyme, butyl Chain ethers such as glycol ethers (ethyl cellosolve, ethyl carbitol, butyl cellosolve, butyl carbitol, etc.) such as diglyme, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-di Heterocyclic ethers such as oxofuran, 4, 4-dimethyl-1, 3-dioxane, γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3-methyl-1, 3-oxazolidine Butyrolactones such as 2-one, 3-ethyl-1, 3-oxazolidin-2-one, and amide solvents (N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidinone, etc., carbonate solvents (diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene car) Nate, ethylene carbonate, styrene carbonate, etc.), an imidazolidinone solvent (1, 3- dimethyl- 2-imidazolidinone, etc.) etc. are mentioned, One type is single or two or more types are mixed in these solvents. It can also be used.

The electrolyte composition for the first electric double layer capacitor of the present invention varies in appearance from a high viscosity starch liquid to a rubbery solid state at room temperature (20 ° C.), and the higher the weight average molecular weight, the higher the room temperature (20 ° C.). ) Is low fluidity, that is to say solid (soft paste solid).

In the electrolyte composition for the first electric double layer capacitor of the present invention, it is confirmed that the ion conductive salt is completely dissociated in the high molecular compound. The conductivity measured by the alternating current impedance method shows that, based on 100 parts by weight of the polyglycidol derivative as the component (A), it contains about 10 to about ³ parts by weight of the ion conductive salt as the component (B). It shows high conductivity of about -10 ^-4 S / cm. Furthermore, according to the electrolyte composition for the first electric double layer capacitor of the present invention, the substituents that block the terminal OH group with high ionic conductivity can impart desirable properties such as high dielectric constant, hydrophobicity, and flame retardancy.

In the first electrolyte composition of the present invention, when a polyglycidol derivative having a small weight average molecular weight is used, the polymer becomes a liquid polyelectrolyte, but has a large weight average molecular weight (3000 or more). When glycidol derivatives are used, they become solid polymer electrolytes and all have high ion conductivity. In this case, even if it is a solid, since it is a rubber | gum state which is easy to plastic deformation, it is easy to stress-strain and can be easily formed in film form.

Next, the electrolyte composition for the second electric double layer capacitor of the present invention is a polymer compound comprising a polyglycidol derivative as the component (A), an ion conductive salt as the component (B), and a crosslinkable component as the component (C). The compound which has a functional group is a main component. In this case, as a high molecular compound which consists of the polyglycidol derivative which is said (A) component, the same thing as the polyglycidol derivative which is (A) component of the electrolyte composition for 1st electrical double layer capacitors can be used. As a solvent which can dissolve the ion conductive salt which is (B) component, and also an ion conductive salt, the solvent which can dissolve the (B) component ion conductive salt and ion conductive salt in the said electrolyte composition for electric double layer capacitors of said 1st. The same can be used.

The compound which has a crosslinkable functional group which is the said (C) component can raise shape retention ability further by making this compound react and forming a three-dimensional network structure.

That is, a compound having a crosslinkable functional group as the component (C) is added to a mixture of the polyglycidol derivative as the component (A) and the ion conductive salt as the component (B), and the compound is reacted to form a three-dimensional network structure. In this three-dimensional network structure, a semi-interpenetrating polymer network (semi-IPN) structure, in which a polymer compound composed of a highly branched polyglycidol derivative as the component (A) is enclosed, is formed. By forming, the compatibility between heterogeneous polymer chains is improved, the correlation bonding force is increased, and as a result, the shape retaining ability is remarkably improved.

Examples of the compound having a crosslinkable functional group as the component (C) include (1) a compound having an epoxy group in a molecule and a compound having two or more active hydrogen groups capable of reacting with the epoxy group, and (2) a compound having an isocyanate group in the molecule and 2 capable of reacting with the isocyanate group. Compounds having two or more active hydrogen groups, ③ Compounds having two or more reactive double bonds in the molecule can be used.

(1) Examples of the compound having an epoxy group in the molecule include sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, and diglycerol polyglycidyl. Ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, glycerol polyglycidyl ether, trimethylpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, diglycidyl ether of ethylene propylene glycol copolymer, polytetramethylene glycol diglycidyl ether, adipic acid diglyc The compound which has two or more epoxy groups in molecules, such as cyl ether, is mentioned.

A semi-IPN structure can be formed by reacting a compound having two or more active hydrogen groups, for example, an amine compound, an alcohol compound, a carboxylic acid compound, or a phenol compound, with the compound having the epoxy group. Examples thereof include polymer polyols such as polyethylene glycol, polypropylene glycol and ethylene glycol propylene glycol copolymers, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 3-butanediol, 1, 4 Butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2, 2-dimethyl-1, 3-propanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanedimethanol, 1, 4 -Bis (βhydroxyethoxy) benzene, p-xylenediol, phenyl diethanol amine, methyl diethanol amine, polyethylene imine, other polyfunctional amine, polyfunctional carboxylic acid, etc. are mentioned.

(2) Examples of the compound having an isocyanate group in the molecule include tolylene diisocyanate, xylene diisocyanate, naphthylene diisocyanate, diphenylmethane diisocyanate, biphenylene disocyanate, diphenyl ether diisocyanate and tolidine disocyanate. And compounds having two or more isocyanate groups in molecules such as hexamethylene diisocyanate and isophorone disocyanate.

Moreover, the isocyanate terminal polyol compound which made the said isocyanate compound and the polyhydric polyol compound react can also be used. These can be obtained by making isocyanate compounds, such as diphenylmethane disocyanate and tolylene diisocyanate, react with the polyol compounds listed below.

In this case, the stoichiometric ratio of [NCO] of the isocyanate compound and [OH] of the polyol compound is [NCO]> [OH], specifically [NCO]: [OH] = 1.03 / 1 to 10/1. Range, Preferably it is the range of 1.10 / 1-5/1.

As a polyol compound, For example, high molecular polyols, such as polyethylene glycol, a polypropylene glycol, an ethylene glycol propylene glycol copolymer, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 3-butanediol, 1 , 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2, 2-dimethyl-1, 3-propanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanedimethanol, 1 , 4-bis- (βhydroxyethoxy) benzene, p-xylylenediol, phenyldiethanol amine, methyldiethanol amine, 3, 9-bis- (2-hydroxy-1, 1-dimethyl)- 2, 4, 8, 10- tetraoxaspiro [5, 5] -undecane etc. are mentioned.

In place of the polyol compound, an amine compound having two or more active hydrogen groups may be reacted with an isocyanate compound. As an amine compound, although the thing which has a primary and a secondary amino group can be used, the compound which has a primary amino group is more preferable. For example, diamines such as ethylene diamine, 1, 6-diaminohexane, 1, 4-diaminobutane, piperazine, polyamines such as polyethylene amine, amino alcohols such as N-methyldiethanolamine, aminoethanol and the like These are mentioned, Among these, diamines which have the same reactivity of a functional group are more preferable. Also in this case, the stoichiometric ratios of [NCO] of the isocyanate compound and [NH ₂ ], [NH] of the amine compound are [NCO]> [NH ₂ ] + [NH].

With only the compound which has these isocyanate groups, semi-IPN structure cannot be formed. In order to form a semi-IPN structure, a semi-IPN structure can be formed by reacting these compounds with a compound having two or more active hydrogen groups, for example, an amine compound, an alcohol compound, a carboxylic acid compound, and a phenol compound. . As a compound which has such two or more active hydrogen groups, For example, high molecular polyols, such as polyethylene glycol, a polypropylene glycol, an ethylene glycol propylene glycol copolymer, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol , 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2, 2-dimethyl-1, 3-propanediol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanedimethanol, 1,4-bis (βhydroxyethoxy) benzene, p-xylylenediol, phenyldiethanol amine, methyldiethanol amine, polyethylene imine, other polyfunctional amines, polyfunctional carboxes Acids and the like.

(3) As the compound having a reactive double bond, divinylbenzene, divinyl sulfone, allyl methacrylate, dimethacrylate ethylene glycol, dimethacrylate diethylene glycol, dimethacrylate triethylene glycol, dimethacrylic acid Polyethylene glycol (average molecular weight 200-1000), dimethacrylic acid 1, 3-butylene glycol, dimethacrylic acid 1, 6-hexanediol, dimethacrylic acid neopentyl glycol, dimethacrylic acid polypropylene glycol (average Molecular weight 400), 2-hydroxy-1, 3-dimethacryloxypropane, 2, 2-bis- [4- (methacryloxyethoxy) phenyl] propane, 2, 2-bis- [4- (meta Krilloxyethoxy diethoxy) phenyl] propane, 2, 2-bis- [4- (methacryloxyethoxy polyethoxy) phenyl] propane, diacrylate ethylene glycol, diacrylate diethylene glycol, diacrylate Ethylene glycol, polyethylene glycol diacrylate (average molecular weight 200-1000), diacrylic acid 1, 3-butylene Recall, diacrylic acid 1,6-hexanediol, diacrylate neopentylglycol, diacrylate polypropylene glycol (average molecular weight 400), 2-hydroxy-1, 3-diacryloxypropane, 2, 2-bis- [4 -(Acryloxyethoxy) phenyl] propane, 2,2-bis- [4- (acryloxyethoxy diethoxy) phenyl] propane, 2,2-bis- [4- (acryloxyethoxypolye Methoxy) phenyl] propane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, water soluble urethane diacrylate, water soluble urethane dimethacrylate, And compounds having two or more reactive double bonds in molecules such as tricyclodecane dimethanol acrylate, hydrogenated dicyclopentadiene diacrylate, polyester diacrylate, and polyester dimethacrylate.

If necessary, for example, acrylic or methacrylic acid esters such as glycidyl methacrylate, glycidyl acrylate and methacrylic acid tetrahydrofurfuryl, methacryloyl isocyanate and 2-hydroxymethyl methacryl The compound which has one acrylic acid group or a methacrylic acid group can be added in molecule | numerators, such as acid, N, N- dimethylaminoethyl methacrylic acid, and the like. Furthermore, acrylamide compounds such as N-methylol acrylamide, methylenebisacrylamide, diacetone acrylamide, vinyl compounds such as vinyloxazolines and vinylene carbonate, or other compounds having reactive double bonds may be added. It may be.

Even in this case, in order to form a semi-IPN structure, it is necessary to add a compound having two or more reactive double bonds in the molecule. That is, since only a compound having only one reactive double bond such as methyl methacrylate cannot form a semi-IPN structure, a compound having at least two reactive double bonds must be added to a part.

Among the compounds containing the reactive double bond, particularly preferred reactive monomers include a diester compound containing a polyoxyalkylene component represented by the following formula (3), and a polyoxyalkylene component represented by the following formula (4). It is recommended to use the monoester compound containing these in combination.

(Wherein, R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms, or a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl An alkyl group having 1 to 6 carbon atoms, in particular, 1 to 4, such as a group, and X ≥ 1 also satisfies the condition of Y ≥ 0, or X ≥ 0 also satisfies the condition of Y ≥ 1, X + Y Is preferably 100 or less, particularly 1 to 30. Particularly, R ⁴ , R ⁵ and R ⁶ are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and s-butyl Group, t-butyl group is preferred.)

(Wherein R ⁷ , R ⁸ , and R ⁹ are hydrogen atoms or methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl An alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms such as a group, and A ≥ 1 or B ≥ 0, or A ≥ 0 and B ≥ 1, X + Y Is preferably 100 or less, in particular 1 to 30. In particular, R ⁷ , R ⁸ and R ⁹ are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and s-butyl Group, t-butyl group is preferred.)

The diester compound containing the polyoxyalkylene component and the monoester compound containing the polyoxyalkylene component include ultraviolet rays, electron beams, X-rays, γ-rays, microwaves, and radiofrequency waves in a mixture of a polyglycidol derivative and an ion conductive salt. Or by heating the mixture to form a three-dimensional crosslinked network structure of semi-IPN structure.

In this case, generally, the diester compound containing a polyoxyalkylene component can be added to the polyglycidol derivative which is (A) component using only this, and can superpose | polymerize, and can form semi-IPN structure, As mentioned above, it is preferable to further add the monoester compound containing the polyoxyalkylene component which is a monofunctional monomer to the diester compound containing this polyoxyalkylene component. This is because the polyoxyalkylene branched chain can be introduced onto the three-dimensional network by the addition of this monoester compound.

In addition, the composition ratio of the diester compound containing a polyoxyalkylene component and the monoester compound containing a polyoxyalkylene component is although it does not specifically limit, [The diester compound / poly containing a polyoxyalkylene component by weight ratio]. Monoester compound containing an oxyalkylene component] = 1 to 0.5, particularly 1 to 0.2 is preferable in view of improving the film strength.

The compounding quantity of the compound which has a crosslinkable functional group which is the said (C) component is 10-500 weight part with respect to 100 weight part of polyglycidol derivatives which are (A) component, Preferably it is 10-150 weight part, More preferably, 20-100 weight part. If the compound having a crosslinkable functional group is less than 10 parts by weight, the film strength may not increase. On the other hand, when it exceeds 500 weight part, the ion-conductive metal salt dissolving ability of the whole matrix may fall, and a disadvantage may arise, such that a salt precipitates and the film | membrane which becomes easy to break | breaks arises.

Further, in addition to the components (A), (B) and (C), the same ion conductive salt as the first electrolyte composition for the electric double layer capacitor is dissolved in the electrolyte composition for the second electric double layer capacitor of the present invention. The solvent which can be added can be combined with a normal volume.

In the present invention, by irradiating ultraviolet rays, electron beams, X-rays, γ-rays, microwaves, high-frequency rays, or the like to the composition obtained by blending the components (A) to (C) and optional components as necessary, or by heating (C) Reacting or polymerizing a compound having a crosslinkable functional group as a component to form a three-dimensional crosslinked network (semi-IPN) structure intertwined with a molecular chain of a highly branched polyglycidol derivative. The solid polymer electrolyte for electric double layer capacitors of the present invention excellent in high ion conductivity and shape stability is obtained.

The polymerization reaction can form a semi-IPN structure mainly by radical reaction. When carrying out the polymerization reaction, in the case of using an electron beam, it is not necessary to add a polymerization initiator (catalyst). In other cases, a polymerization initiator is usually added.

The polymerization initiator (catalyst) is not particularly limited and may be acetophenone, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylisopropiophenone, and 1-hydroxycyclo. Photoinitiators, such as hexyl ketone, benzoin ether, 2, 2- diethoxy acetophenone, and benzyl dimethyl ketal, can be used.

Moreover, as a thermal polymerization initiator, high-temperature initiators, such as cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, persulfate, azobisisobuty Common initiators such as ronitrile, hydrogen peroxide, ferrous salt, persulfate, acidic sodium sulfite, cumene hydroperoxide ferrous salt, low-temperature initiators such as benzoyl peroxide, dimethylaniline, redox initiator, and peroxide organic metal alkyl , Triethyl boron, diethyl zinc, oxygen-organometallic alkyl and the like can be used.

These polymerization initiators can be used individually by 1 type or in mixture of 2 or more types. The addition amount of this radical reaction catalyst is 0.1-1 weight part with respect to 100 weight part of compounds which have a crosslinkable functional group which is the said (C) component, Preferably it is the range of 0.1-0.5 weight part. If the amount of the catalyst added is less than 0.1 part by weight, the polymerization rate may remarkably decrease. On the other hand, even more than 1 part by weight does not affect the reactivity, only the reagent is wasted.

Although the conditions of the said polymerization reaction are not specifically limited, For example, reaction conditions in the case of photopolymerization can be performed by irradiating an ultraviolet-ray with air quantity of 1-50 mW / cm <^2> or more in 5 to 30 minutes in air at room temperature.

In addition, when using an electron beam, the acceleration voltage of 150-300 kV is used at room temperature. In the case of heat polymerization, it is made to react by heating at 50-120 degreeC for 0.5 to 6 hours.

In addition, the polymerization reaction is preferably ultraviolet irradiation or heat polymerization in consideration of the simplicity of the apparatus and the surface of the running cost.

The solid polymer electrolyte for an electric double layer capacitor of the present invention is a three-dimensional network structure formed by a crosslinkable compound as a component (C), and a highly branched polyglycidol derivative as a component is entangled in a complicated manner. It has a semi-IPN structure, and the shape retention ability is dramatically improved. Since the molecular structure is an amorphous polymer and is not crystallized, the ion conductor can move smoothly in the molecule. It has a high conductivity of about 10 ⁻³ to 10 ⁻⁴ S / cm at room temperature, has no fear of evaporation and liquid leakage, and is suitable as an electrolyte for electric double layer capacitors (separators).

Moreover, the solid polymer electrolyte for electric double layer capacitors of this invention is a (C) component after coating the mixed solution which mixed the said (A)-(C) component, a dilution solvent, etc. on a support body, for example. A compound having a crosslinkable functional group can be crosslinked to form a film, and further, a roller coating such as an applicator roll, a screen coating, a doctor blade method, spin coating, a bar coater or the like can be used to form an electrolyte membrane having a uniform thickness. Can be.

Next, the composition for polarizable electrodes of this invention has the following 1st or 2nd structural component.

First, the main component is a polymer compound composed of a polyglycidol derivative as the component (A), a high-area material as the component (D), and a conductive material as the component (E).

2nd, the polymer compound which consists of polyglycidol derivative which is (A) component, the compound which has a crosslinkable functional group which is (C) component, the high-area material which is (D) component, and the electrically conductive material which is (E) component It has as a main component.

First, the high molecular compound which consists of polyglycidol derivative which is (A) component of the composition for 1st polarizable electrodes of this invention is the (A) composition of the electrolyte composition for 1st and 2nd said double layer capacitors of this invention. The same thing as the high molecular compound which consists of polyglycidol derivative which is a component can be used.

As a high area material which is the said (D) component, a specific surface area is 500 m <^2> / g or more, Preferably it is 1000 m <^2> / g or more, More preferably, it is 1500-3000 m <^2> / g, Moreover, 30 micrometers or less of average particle diameters are preferable. Preferably, the carbon material of 5-30 micrometers is used suitably. If the specific surface area and the average particle diameter are out of the above ranges, the capacitance may be large, and an electric double layer capacitor of low resistance may not be obtained.

As such a high area material, activated carbon is particularly preferable. The raw materials of activated carbon include plant wood, sawdust, palm husk, pulp waste liquid, fossil fuel coal, petroleum heavy oil or pyrolyzed coal and petroleum oil, pitch, tar pitch fibers, synthetic polymer, phenol resin, Furan resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyimide resin, polyamide resin, liquid crystal polymer, plastic waste, waste tire, and the like. These raw materials are carbonized and then revitalized. The resurrection method is roughly classified into a gas regeneration method and a chemical regeneration method. The gas revival method is a method in which carbonized raw materials are brought into contact with water vapor, carbon dioxide gas, oxygen, other oxidizing gases and the like at high temperature to obtain activated carbon. The chemical revival method is a method of impregnating a raw material with an activating chemical evenly, heating in an inert gas atmosphere, and obtaining activated carbon by dehydration and oxidation of the chemical. In this case, the chemicals to be used include zinc chloride, phosphoric acid, sodium phosphate, calcium chloride, potassium sulfide, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium sulfate, potassium sulfate, calcium carbonate and the like. The activated carbon has various shapes such as crushing, granulation, granules, fibers, felts, fabrics, sheets, and the like, and all of them can be used in the present invention. Among these activated carbons, activated carbon obtained by the chemical revival method using KOH is particularly preferable because the capacity of the activated carbon tends to be larger than that of the steam activated product.

The compounding quantity of the high area material which is this (D) component is 800-2300 weight part with respect to 100 weight part of polyglycidol derivatives which are (A) component, Preferably it is 1300-2000 weight part. When the addition amount of a high area material is too large, the adhesive force of the composition for polarizable electrodes may fall, and adhesiveness with an electrical power collector may be inferior. On the other hand, when too small, the resistance of a polarizable electrode may become high and the capacitance of the created polarized electrode may become low.

The conductive material as the component (E) is not particularly limited as long as it can impart conductivity to the composition for polarizable electrodes. For example, carbon black, ketjen black, acetylene black, carbon whisker, carbon fiber, natural graphite, artificial Metal fibers, such as graphite, titanium oxide, ruthenium oxide, aluminum, and nickel, etc. are mentioned, One of these can be used individually or in combination of 2 or more types. Among these, Ketjen black and acetylene black which are a kind of carbon black are preferable. Moreover, it is preferable that the average particle diameter of an electrically conductive material powder is 10-100 nm especially 20-40 nm.

The compounding quantity of the electrically conductive material which is this (E) component is 50-500 weight part with respect to 100 weight part of polyglycidol derivatives which are (A) component, Preferably it is 100-300 weight part. When the compounding quantity of an electrically conductive material is too big | large, the ratio of high area material may fall and a capacitance may fall. On the other hand, when too small, the electroconductive provision effect may become inadequate.

A dilution solvent can be added to the composition for polarizable electrodes of this invention in addition to the said (A), (D), (E) component. As this dilution solvent, N-methyl- 2-pyrrolidone, acetonitrile, tetrahydrofuran, acetone, methyl ethyl ketone, 1, 4- dioxane, ethylene glycol dimethyl ether, etc. are mentioned, for example. Moreover, it is preferable that the addition amount of a dilution solvent is 80-150 weight part with respect to 100 weight part of whole compositions for polarizable electrodes.

Next, as a high molecular compound which consists of a polyglycidol derivative which is (A) component of the composition for 2nd polarizable electrodes of this invention, the electrolyte composition of the 1st, 2nd electric double layer capacitor of this invention (A The same thing as the high molecular compound which consists of polyglycidol derivative which is a component can be used. As a compound which has a crosslinkable functional group which is (C) component, the thing similar to the compound which has a crosslinkable functional group which is (C) component of the electrolyte composition for 2nd electric double layer capacitors of the said invention can be used. Moreover, as the high area material which is (D) component, and the electrically conductive material which is (E) component, the thing similar to (D) and (E) component of the composition for 1st polarizable electrodes of the said invention can be used.

Moreover, the compounding quantity of the compound which has a crosslinkable functional group which is (C) component is 10-100 weight part with respect to 100 weight part of polyglycidol derivatives which are (A) component, Preferably it is 20-80 weight part. In addition, the compounding quantity of the high area material which is (D) component, and the electrically conductive material which is (E) component is the same as the said 1st polarizable electrode composition.

The composition for polarizable electrodes of this invention has the outstanding binder function which can firmly bind a high area material and a electrically conductive material to an electrical power collector.

Next, the polarizable electrode of the present invention is obtained by applying the first or second polarizable electrode composition of the present invention onto a current collector.

It is preferable that it is a metal as said collector. Examples of the metal current collector include aluminum, titanium, tantalum, stainless steel, and the like, and aluminum and stainless steel are preferable because of their high corrosion resistance. Aluminum is particularly preferable because it is light and its electrical resistance is low.

The shape of an electrical power collector may be any form, such as foil shape, an expanded metal shape, a fiber sintered sheet shape, and a plate-shaped metal foam. It is especially preferable at the point that 20-100 micrometers thin thing is easy to wind up or laminate, and it is comparatively cheap. In the case where the metal foil is used for the current collector, when the surface is roughened by chemical, electrochemical or physical methods, the adhesion between the polarizable electrode and the metal current collector can be improved and the resistance can be lowered.

In the polarizable electrode of the present invention, the first or second polarizable electrode composition is coated on a current collector, for example, roller coating such as an applicator roll, screen coating, doctor blade method, spin coating, bar coater. It can form by apply | coating to uniform thickness using means, such as these.

In addition, when using the composition for 2nd polarizable electrodes, after apply | coating the 2nd polarizable electrode composition on an electrical power collector, it heats at 60-100 degreeC for 1 to 6 hours, and this invention of a semi-solid state A polarizable electrode is obtained.

Next, the electric double layer capacitor of the present invention is formed by interposing a separator between a pair of polarizable electrodes. In this case, as a pair of polarizable electrodes, while using the polarizable electrode formed by apply | coating the composition for 1st or 2nd polarizable electrode of this invention on an electrical power collector, these pair of polarizable electrodes are It is preferable to use the thing of the same structure.

As the separator, first, a separator obtained by impregnating an ion conductive salt-containing solution with a separator substrate is used. As this separator base material, what is normally used as a separator base material for electric double layer capacitors can be used. For example, a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a PTFE porous body film, a kraft paper, a rayon fiber sisal fiber blend sheet, a manilama sheet, a glass fiber sheet, a cellulose electrolyte, a paper made of rayon fiber, It is possible to use a mixed paper of cellulose and glass fibers, or a combination of these and a plurality of layers.

The ion conductive salt and the solvent capable of dissolving the ion conductive salt are the same as those of the ion conductive salt exemplified in the electrolyte composition for the first electric double layer capacitor of the present invention and the solvent capable of dissolving the ion conductive salt. Can be used. Moreover, it is preferable that the density | concentration of the ion conductive salt in the ion conductive salt containing solution is 0.5-2.5 mol / L.

The present invention electric double layer capacitor is obtained by interposing a separator formed by impregnating the ion conductive salt-containing solution in a separator substrate between a pair of the present invention polarizable electrodes and applying a predetermined pressure.

As the separator, a separator formed by applying or impregnating the electrolyte composition for the first or second electric double layer capacitor of the present invention to the separator substrate is used as the second separator. In this case, the same thing as the above can be used as a separator base material.

Specifically, the separator formed by applying or impregnating the electrolyte composition for the first or second electric double layer capacitor of the present invention to the separator substrate is interposed between the pair of the present invention polarizable electrodes to apply a predetermined pressure. The electric double layer capacitor of the present invention is obtained.

In addition, a separator formed by applying or impregnating the electrolyte composition for a second electric double layer capacitor of the present invention to a separator substrate is interposed between a pair of the present invention polarizable electrodes, and a predetermined pressure is applied thereto. The electric double layer capacitor of this invention is obtained by heating for 8 hours and hardening.

Moreover, as a separator, the solid polymer electrolyte layer which consists of electrolyte composition for the 1st or 2nd electric double layer capacitor of this invention is used for 3rd. In this case, the polymer compound composed of the polyglycidol derivative as the component (A) constituting the electrolyte composition for the first or second electric double layer capacitor has a large weight average molecular weight (weight average molecular weight of 3000 or more, preferably 10000 or more), it is preferable to use a solid or semi-solid state.

Specifically, the electrolyte composition for the first or second electric double layer capacitor of the present invention is applied on the polarizable electrode surface by means of roller coating such as an applicator roll, screen coating, doctor blade method, spin coating, bar coater and the like. Using a uniform thickness and cast using a doctor knife applicator. Next, the present invention double layer capacitor is obtained by superimposing the same polarized electrodes having the same configuration on the cast side and applying a pressure so as to have a predetermined thickness.

As another separator, a solid polymer electrolyte layer formed by curing the electrolyte composition for the second electric double layer capacitor of the present invention is used for the fourth. In this case, the electrolyte composition for the second electric double layer capacitor of the present invention is used on the polarizable electrode surface of the present invention by means of roller coating such as an applicator roll, screen coating, doctor blade method, spin coating, bar coater, or the like. The coating is applied to a uniform thickness and cast using a doctor knife applicator. Next, the polarized electrode of the same structure which is separate is piled on this casting side, the pressure is made to become a predetermined thickness, it heats at 60-100 degreeC for 1 to 8 hours, and hardens | cures it, and is obtained by this invention double layer capacitor. Lose.

The electric double layer capacitor of the present invention firmly couples a high-area material and a conductive material to the current collector by using a pair of polarizable electrodes coated with the first or second polarizable electrode composition on the current collector. As a separator interposed between these pairs of polarizable electrodes while exhibiting excellent binder function, a polarizable electrode and a separator (particularly, by using an electrolyte composition for a first or second electric double layer capacitor) Since the electrolytic composition for the electric double layer capacitor or the solid polymer electrolyte) has a common composition, the interfacial resistance between the polarizable electrode / separator can be lowered, and a high quality electric double layer capacitor having excellent performance with high capacity and long life is obtained.

Moreover, although the film form is suitable as a shape of the electric double layer capacitor of this invention, it is not limited to this, The element is formed by winding a pair of elongate electrode body through an elongate separator, The device is formed by alternately stacking a cylindrical and rectangular electrode body formed by impregnating the device with a non-aqueous electrolyte solution and storing it in a bottomed cylindrical case as a positive electrode and a negative electrode through a separator. Various shapes, such as a square formed by impregnating electrolyte solution and accommodating in a bottomed square case, can be used.

The electric double layer capacitor of the present invention can be used for backup power supply of a memory such as a PC or a mobile terminal, as well as for power supply for instantaneous power failure measures such as a PC, for application to an electric vehicle or a hybrid vehicle, and for storing solar power generation in combination with a solar cell. It can be used suitably for various uses such as a load leveling power supply combined with a system and a battery.

Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example.

Synthesis Example 1 Synthesis of Polyglycidol (1)

Methylene chloride was added as a solvent so that a glycidol concentration might be 4.2 mol / L in the flask, and the reaction temperature was set at -10 ° C.

As a catalyst (reaction initiator), trifluoroborate diethyl etherate (BF ₃ · OEt ₂ ) was added so as to be 1.2 × 10 ⁻² mol / L, and the reaction was stirred under a nitrogen gas stream for 3 hours. After the reaction was completed, methanol was added to terminate the reaction. Thereafter, methanol and methylene chloride were distilled off under reduced pressure.

The obtained crude polymer was dissolved in water and neutralized with sodium hydrogen carbonate, and then the solution was passed through a column packed with an ion exchange resin (trade name: Amberlite IRC-76; manufactured by Organo Corporation). The solution after the passage of the column was separated by 5C filter paper, and the filtrate was distilled off under reduced pressure and dried.

The obtained purified polyglycidol was analyzed by gel filtration chromatography (GPC) having 0.1 M saline as a mobile phase, and the weight average molecular weight in terms of polyethylene glycol was measured. In addition, crystallinity was evaluated by wide-angle X-ray diffraction, and the state at room temperature was visually observed. The results are shown in Table 2. ¹³ C-NMR spectrum was also measured (DEPT measurement in solvent D ₂ 0 using a Varian VXR 300 NMR spectrometer). The results are shown in FIG.

Synthesis Examples 2 to 8

Based on the addition amount, reaction time, and temperature shown in Table 1, the polyglycidol of the synthesis examples 2-8 was synthesize | combined by the method similar to the synthesis example 1.

The obtained polyglycidol was analyzed by gel filtration chromatography (GPC) having 0.1 M saline as a mobile phase, and the weight average molecular weight in terms of polyethylene glycol was measured. In addition, crystallinity was evaluated by wide-angle X-ray diffraction, and the state at room temperature was visually observed. The results are shown in Table 2.

Synthesis Example 9 Synthesis of Polyglycidol (2)

100 weight part of glycidol was put into the flask, 1000 weight part of methylene chlorides were added, and it set at 20 degreeC. 20 weight part of potassium hydroxide was added as a catalyst, and it was made to react, stirring for 22 hours. After the reaction was completed, methanol was added to terminate the reaction. Thereafter, methanol and methylene chloride were distilled off under reduced pressure.

The obtained crude polymer was dissolved in water, neutralized using an ion exchange resin (trade name: Amberlite IRC-76; manufactured by Organo Corporation), the ion exchange resin was filtered off, and the water was distilled off under reduced pressure and dried.

The obtained purified polyglycidol was analyzed by gel filtration chromatography (GPC) having 0.1 M saline as a mobile phase, and the weight average molecular weight in terms of polyethylene glycol was measured. In addition, crystallinity was evaluated by wide-angle X-ray diffraction, and the state at room temperature was visually observed. The results are shown in Table 4.

Synthesis Example 10, 11

Based on the addition amount, temperature, and reaction time shown in Table 3, the polyglycidol of the synthesis examples 10 and 11 was synthesize | combined by the method similar to the synthesis example 9. As the active hydrogen compound, glycerin in Synthesis Example 10 and ethanolamine in Synthesis Example 11 were used.

The obtained polyglycidol was analyzed by gel filtration chromatography (GPC) having 0.1 M saline as a mobile phase, the weight average molecular weight of polyethylene glycol was measured, and crystallinity was evaluated by wide-angle X-ray diffraction. Moreover, the state at room temperature was visually observed. The results are shown in Table 4.

Synthesis Example 12 Cyanoethylation of Polyglycidol

3 parts by weight of polyglycidol obtained in Synthesis Example 9 was mixed with 20 parts by weight of dioxane and 14 parts by weight of acrylonitrile. The sodium hydroxide solution which melt | dissolved 0.16 weight part of sodium hydroxide in 1 weight part water was added to this mixed solution, and it stirred at 25 degreeC for 10 hours. After the reaction was completed, 20 parts by weight of water was added to the mixed solution, followed by neutralization using an ion exchange resin (trade name: Amberlite IRC-76 Organo Co., Ltd.). After the ion exchange resin was separated by filtration, 50 parts by weight of acetone was added to the solution, and the insoluble portion was separated by filtration. The filtered solution was concentrated under reduced pressure to obtain crude cyanoethylated polyglycidol. This crude cyanoethylated polyglycidol was dissolved in acetone, filtered through a 5 A filter paper, and then precipitated in water to collect the precipitated components. After repeating this operation of dissolving acetone and precipitation in water twice, it was dried under reduced pressure at 50 ° C to obtain purified cyanoethylated polyglycidol.

When the infrared absorption spectrum of the obtained purified cyanoethylated polyglycidol was measured, it was understood that absorption of hydroxyl groups was not observed and that all hydroxyl groups were substituted with cyanoethyl groups. Moreover, when crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous at room temperature. In addition, the state at room temperature was visually observed. The results are shown in Table 5.

Synthesis Example 13 Cyanoethylation of Polyglycidol

Purified cyanoethylated polyglycidol was obtained in the same manner as in Synthesis Example 12 using the polyglycidol obtained in Synthesis Example 1.

When the infrared absorption spectrum of the obtained purified cyanoethylated polyglycidol was measured, it was understood that absorption of hydroxyl groups was not observed and that all hydroxyl groups were substituted with cyanoethyl groups. Moreover, when crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous at room temperature. In addition, the state at room temperature was visually observed. The results are shown in Table 5.

Synthesis Example 14 Cyanoethylation of Polyglycidol

Purified cyanoethylated polyglycidol was obtained in the same manner as in Synthesis Example 12 using the polyglycidol obtained in Synthesis Example 8.

When the infrared absorption spectrum of the obtained purified cyanoethylated polyglycidol was measured, it was understood that absorption of hydroxyl groups was not observed and that all hydroxyl groups were substituted with cyanoethyl groups. Moreover, when crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous at room temperature. In addition, the state at room temperature was visually observed. The results are shown in Table 5.

Synthesis Example 15 Cyanoethyl trimethylsilylation of polyglycidol

3 parts by weight of polyglycidol obtained in Synthesis Example 1 was mixed with 20 parts by weight of dioxane and 14 parts by weight of acrylonitrile. The sodium hydroxide solution which melt | dissolved 0.16 weight part of sodium hydroxide in 1 weight part water was added to this mixed solution, and it stirred at 25 degreeC for 5 hours. After the reaction was completed, 20 parts by weight of water was added to the mixed liquid. Subsequently, neutralization was performed using an ion exchange resin (trade name: Amberlite IRC-76; manufactured by Organo Corporation). After the ion exchange resin was separated by filtration, 50 parts by weight of acetone was added to the solution, and the insoluble portion was separated by filtration. The filtered solution was concentrated under reduced pressure to obtain crude cyanoethylated polyglycidol. 1 part by weight of this crude cyanoethylated polyglycidol was dissolved in dimethylacetamide, 2 parts by weight of bis (trimethylsilyl) acetamide was added to this solution, and the mixture was stirred at room temperature for 5 hours. The reaction solution was cooled with ice water and poured into a methanol: water = 4: 1 solution cooled to 0 ° C. The precipitate which precipitated was separated by filtration, and the filtrate was dissolved in acetamide. After filtering this solution with the filter paper of 5C, the solution was dried under reduced pressure and cyanoethyl trimethylsilylated polyglycidol was obtained.

When the infrared absorption spectrum of the obtained cyanoethyl trimethylsilylated polyglycidol was measured, absorption of the hydroxyl group was not observed. The result of elemental analysis showed that the cyanoethylation rate of the hydroxyl group was 87%, and the remaining 13% hydroxyl group was trimethylsilylated. Moreover, when crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous at room temperature. In addition, the state at room temperature was visually observed. The results are shown in Table 5.

Synthesis Example 16 Acetylation of Polyglycidol

1 part by weight of polyglycidol obtained in Synthesis Example 1 was mixed with 30 parts by weight of acetic acid and 30 parts by weight of methylene chloride. 0.4 weight part of 60% aqueous perchloric acid solutions, and 40 weight part of acetic anhydride were added to this mixed solution, and it stirred at room temperature for 8 hours. The reaction solution was poured into cold water, and the precipitated precipitate was collected. The obtained precipitate was dissolved in acetone, poured into water again, and neutralized by adding sodium hydrogencarbonate, followed by filtration with a 5C filter paper. The precipitate was collected, put in a dialysis tube with water, and dialyzed with ion exchange water for 3 days. The precipitate was collected, washed with water and dried under reduced pressure to obtain an acetylated polyglycidol.

When the infrared absorption spectrum of the obtained acetylated polyglycidol was measured, absorption of hydroxyl group was not observed, the peak derived from C = 0 group was observed, and it turned out that all the hydroxyl groups are acetylated. Moreover, when crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous at room temperature. In addition, the state at room temperature was visually observed. The results are shown in Table 5.

Synthesis Example 17 Cyanobenzoylation of Polyglycidol

0.4 weight part of polyglycidol obtained by the synthesis example 1 was mixed with 10 weight part of dioxane, and 1.24 weight part of pyridine was added. Then, the solution which melt | dissolved 2.05 weight part of cyano benzoyl chlorides in 10 weight part of dioxanes was dripped. Then, the solution was set at 80 degreeC and made to react for 12 hours. The reaction was poured into a solution of methanol: water = 3: 4, and the precipitated precipitate was collected. The obtained precipitate was dissolved in N, N-dimethylsulfoxide, put into a dialysis tube, and dialyzed with ion-exchanged water for 3 days. The precipitate was collected, washed with water and dried under reduced pressure to obtain cyanobenzoylated polyglycidol.

When the infrared absorption spectrum of the obtained cyanobenzoylated polyglycidol was measured, absorption of hydroxyl group was not observed, and the peak derived from C = O group and the peak derived from C≡N group were observed, and all hydroxyl groups were cyanobenzoyl. I could see that it was mad. Moreover, when crystallinity was evaluated by wide-angle X-ray diffraction, it was amorphous at room temperature. In addition, the state at room temperature was visually observed. The results are shown in Table 5.

Examples 1 to 6 Electrolyte Composition (1) for Electric Double Layer Capacitors

The polyglycidol derivatives prepared in Synthesis Examples 12 to 17 and tetraethylammonium tetrafluoroborate [(C ₂ H ₅ ) ₄ NBF ₄ ] were dissolved in tetrahydrofuran, respectively. At this time, 1 mol of tetraethylammonium tetrafluoroborate [(C ₂ H ₅ ) ₄ NBF ₄ ] was added so that the weight of (C ₂ H ₅ ) ₄ NBF ₄ + the weight of the polyglycidol derivative = 1 kg.

The solution was left under reduced pressure and tetrahydrofuran was evaporated to obtain polyglycidol derivatives and supporting electrolyte composites (electrolyte composition for electric double layer capacitors) of Examples 1 to 6.

Each obtained composition (composite) was sandwiched between two copper plates having a gap of 200 μm, the conductivity measurement was performed by the AC impedance method, and the state at room temperature was visually judged (S: soft paste solid, L: high viscosity). Liquid). Moreover, wide angle X-ray measurement was performed about the obtained composition and the crystallinity was confirmed. Furthermore, the obtained composition was heated at 100 degreeC for 5 hours, and the weight loss ratio according to evaporation was measured. The results are shown in Table 6.

Comparative Example 1

A polyethylene glycol-supporting electrolyte composite (electrolyte composition for electric double layer capacitors) was prepared in the same manner as in Example 1 except that polyethylene glycol having a molecular weight of 200 was used instead of the polyglycidol derivative.

The obtained composition (composite) was sandwiched between two copper plates having a gap of 200 µm, the conductivity was measured by the alternating current impedance method, and the state at room temperature was visually judged (S: soft paste solid, L: high viscosity liquid). . Moreover, wide-angle X-ray measurement was performed about the obtained composition and the crystallinity was confirmed. Furthermore, the obtained composition was heated at 100 degreeC for 5 hours, and the weight loss ratio according to evaporation was measured. The results are shown in Table 7.

Comparative Example 2

A polyethylene glycol-supporting electrolyte composite (electrolyte composition for electric double layer capacitors) was prepared in the same manner as in Example 1 except that polyethylene glycol having a molecular weight of 2000 was used instead of the polyglycidol derivative.

The obtained composition (composite) was sandwiched between two copper plates having a gap of 200 µm, the conductivity was measured by the alternating current impedance method, and the state at room temperature was visually judged (S: soft paste solid, L: high viscosity liquid). ). Moreover, wide-angle X-ray measurement was performed about the obtained composition and the crystallinity was confirmed. Furthermore, the obtained composition was heated at 100 degreeC for 5 hours, and the weight loss ratio according to evaporation was measured. The results are shown in Table 7.

* PEG200: Polyethylene Glycol 200

* PEG2000: Polyethylene Glycol 2000

Condition at room temperature

S: soft paste solid

L: high viscosity liquid

Examples 7 to 9 Electrolyte Composition (2) and Solid Polymer Electrolyte (1) for Electric Double Layer Capacitors

In the combination shown in Examples 7 to 9 of Table 8, polyglycidol derivatives and tetraethylammonium tetrafluoroborate [(C ₂ H ₅ ) ₄ NBF ₄ ] were dissolved in tetrahydrofuran, respectively. This solution was left under reduced pressure, and tetrahydrofuran was evaporated. A predetermined amount of polyethylene glycol methacrylate (oxyethylene unit number = 9) and methoxy polyethylene glycol monomethacrylate (oxyethylene unit number = 9) were added. In addition, azobisisobutyronitrile was added and added so that tetraethylammonium tetrafluoroborate [(C ₂ H ₅ ) ₄ NBF ₄ ] would be 1 mol per 1 kg of the combined weight of the respective components.

That is, (C ₂ H ₅ ) ₄ NBF _{4 to} 1 mol (C ₂ H ₅ ) ₄ NBF ₄ weight + polyglycidol derivative weight + polyethylene glycol dimethacrylate + methoxypolyethylene glycol monomethacrylate + azobis It injected | threw-in so that isobutyronitrile = 1 kg, and the polyglycidol derivative and support electrolyte composite (electrolyte composition for electric double layer capacitors) of Examples 7-9 were obtained.

Each obtained composition (composite) was sandwiched between two copper plates having a gap of 200 μm, heated at 80 ° C. for 2 hours, and cured to obtain a solid polymer electrolyte (cured product) of Examples 7-9.

The conductivity of each obtained solid polymer electrolyte was measured by AC impedance method measurement. Moreover, wide angle X-ray measurement was performed about the obtained solid polymer electrolyte, and crystallinity was confirmed, and the state at room temperature of the solid polymer electrolyte was visually observed. In addition, the obtained solid polymer electrolyte was heated at 100 ° C. for 5 hours, and the weight loss due to evaporation was measured. The results are shown in Table 8.

Examples 10 to 12 Electrolyte Composition (3) and Solid Polymer Electrolyte (2) for Electric Double Layer Capacitors

Polyglycidol derivatives and tetraethylammonium tetrafluoroborate [(C ₂ H ₅ ) ₄ NBF ₄ ] were dissolved in tetrahydrofuran in the combinations shown in Examples 10 to 12 of Table 8. This solution was left under reduced pressure, and tetrahydrofuran was evaporated. Next, a predetermined amount of polyurethane crosslinking agent was added. As the polyurethane crosslinking agent, a mixture of the polyol solution and the isocyanate solution shown in Table 8 was used. In this case, glycerin-based ethylene oxide: polyethylene oxide = (8/2) copolymer polymer polyol (OH value = 1.215 mg / kg) is used as the polyol solution, and polyisocyanate (NCO value = 7.381 mg) is used as the isocyanate solution. / kg).

Each of these components was added to (C ₂ H ₅ ) ₄ NBF ₄ weight + polyglycidol derivative weight + polyol liquid weight + isocyanate liquid based on 1 mol of tetraethylammonium tetrafluoroborate [(C ₂ H ₅ ) ₄ NBF ₄ ] The polyglycidol derivative and the supporting electrolyte composite (electrolyte composition for electric double layer capacitor) of Examples 10 to 12 were obtained by adding so that the weight was 1 kg.

Each obtained composition (composite) was sandwiched between two copper plates having a 200 μm gap, heated at 80 ° C. for 2 hours, and cured to obtain solid polymer electrolytes (cured products) of Examples 10 to 12.

The conductivity of each obtained solid polymer electrolyte was measured by the alternating current impedance method. Moreover, the wide angle X-ray measurement was performed about the obtained solid polymer electrolyte, the crystallinity was confirmed, and the state at room temperature of the solid polymer electrolyte was visually observed. Furthermore, the obtained solid polymer electrolyte was heated at 100 ° C. for 5 hours, and the weight loss due to evaporation was measured. The results are shown in Table 8.

Comparative Example 3

A polyethylene glycol-supported electrolyte composite (electrolyte composition for an electric double layer capacitor) was prepared in the same manner as in Example 8 except that polyethylene glycol having a molecular weight of 2000 was used instead of the polyglycidol derivative, and the crosslinking agent shown in Table 8 was used. did.

The obtained composition (composite) was sandwiched between two copper plates having a gap of 200 µm, and the conductivity measurement was performed by the alternating current impedance method. Moreover, the wide angle X-ray measurement was performed about the obtained composition, the crystallinity was confirmed, and the state at room temperature of the composition was visually observed. Furthermore, the obtained composition was heated at 100 degreeC for 5 hours, and the weight loss ratio according to evaporation was measured. The results are shown in Table 8.

Crosslinking agent 1: polyethylene glycol dimethacrylate

Crosslinking agent 2: methoxy polyethylene glycol monomethacrylate

Crosslinking agent 3: ethylene oxide / polyethylene oxide copolymer polymer polyol

Crosslinking agent 4: polyisocyanate

Condition at room temperature

S: soft paste solid

L: high viscosity liquid

The electrolyte composition for an electric double layer capacitor and the solid polymer electrolyte of the present invention have high ion conductivity, and in particular, Examples 7 to 12 also have excellent shape retention, and thus, a solid polymer electrolyte (separator) for an electric double layer capacitor. Suitable as.

Example 13 Composition for Polarizable Electrode and Polarizable Electrode 1

Phenol-derived activated carbon (manufactured by Kansai Thermochemistry Co., Ltd., specific surface area: 1860 m 2 / g, average particle diameter: 16 µm) as a high-area material, and carbon black (average particle diameter: 20 nm) as the conductive material: activated carbon: carbon black = 18: 2 ( Weight ratio) and added.

The obtained mixed powder, the polyglycidol derivative of the synthesis example 12, and N-methylpyrrolidone are mixed powder by weight ratio: The polyglycidol derivative of the synthesis example 12: N-methyl-pyrrolidone = 20: 1: 30 It was mixed so that the composition for polarizable electrodes was created.

After casting the obtained composition for polarizable electrodes on an aluminum collector using a doctor knife applicator, it heated at 80 degreeC for 2 hours, N-methyl-pyrrolidone was evaporated, and the polarizable electrode of Example 13 was created. .

Example 14 Composition for Polarizable Electrode and Polarizable Electrode 2

Phenol-derived activated carbon (manufactured by Kansai Thermochemistry Co., Ltd., specific surface area: 1860 m 2 / g, average particle diameter: 16 µm) as a high-area material, and carbon black (average particle diameter: 20 nm) as powder-phase conductive material; It added and mixed in (weight ratio).

0.2 part of polyethylene glycol dimethacrylate (number of oxyethylene units = 9) (crosslinking agent 1) and methoxy polyethylene glycol monomethacrylate (number of oxyethylene units = 9) per 1 part of polyglycidol derivative of Synthesis Example 12 (Crosslinking agent 2) 0.2 part was added and mixed, and binder resin was created.

The mixed powder, binder resin and N-methyl-pyrrolidone as a diluent solvent were mixed in a weight ratio such that the mixed powder: binder resin: N-methyl-pyrrolidone = 20: 1: 30 to form a polarizable electrode composition. Was written.

After casting the obtained composition for polarizable electrodes on an aluminum collector using a doctor knife applicator, it heated at 80 degreeC for 2 hours, N-methyl-pyrrolidone was evaporated, and the polarizable electrode of Example 14 was created. .

Example 15 Electric Double Layer Capacitor 1

A separator substrate impregnated with a nonaqueous propylene carbonate in which 1 mol / L of tetraethylammonium tetrafluoroborate [(C ₂ H ₅ ) ₄ NBF ₄ ] was dissolved between a pair of polarizable electrodes obtained in Example 13 (PTFE The film-form electric double layer capacitor was obtained by interposing the separator which consists of porous films), and applying pressure.

The obtained film-form electric double layer capacitor takes the structure of [aluminum electrical power collector / polarization electrode / separator / polarization electrode / aluminum electrical power collector], and it is confirmed that it can be charged and discharged and functions effectively as an electric double layer capacitor. do.

Example 16 Electric Double Layer Capacitor 2

A separator substrate (PTFE porous film) impregnated with a nonaqueous solvent propylene carbonate in which 1 mol / L of tetraethylammonium tetrafluoroborate (C ₂ H ₅ ) ₄ NBF ₄ was dissolved between a pair of polarizable electrodes obtained in Example 14. The film-form electric double layer capacitor was obtained by interposing the separator which consists of), and applying pressure.

The obtained film-form electric double layer capacitor takes the structure of [aluminum electrical power collector / polarization electrode / separator / polarization electrode / aluminum electrical power collector], and it is confirmed that it can be charged and discharged and functions effectively as an electric double layer capacitor. do.

Example 17 Electric Double Layer Capacitor 3

Between a pair of polarizable electrodes obtained in Example 13, a film was formed by applying pressure through a separator made of a separator substrate (PTFE porous film) coated or impregnated with the electrolyte composition for the electric double layer capacitor of Example 1. An electric double layer capacitor was obtained.

The obtained film-form electric double layer capacitor takes the structure of [aluminum electrical power collector / polarization electrode / separator / polarization electrode / aluminum electrical power collector], and it is confirmed that it can be charged and discharged and functions effectively as an electric double layer capacitor. do.

Example 18 Electric Double Layer Capacitor 4

Between a pair of polarizable electrodes obtained in Example 14, a film was formed by applying pressure through a separator made of a separator substrate (PTFE porous film) coated or impregnated with the electrolyte composition for electric double layer capacitor of Example 1. An electric double layer capacitor was obtained.

The obtained film-form electric double layer capacitor takes the structure of [aluminum electrical power collector / polarization electrode / separator / polarization electrode / aluminum electrical power collector], and it is confirmed that it can be charged and discharged and functions effectively as an electric double layer capacitor. do.

Example 19 Electric Double Layer Capacitor 5

Between a pair of polarizable electrodes obtained in Example 14, a pressure was applied through a separator made of a separator substrate (PTFE porous film) coated or impregnated with the electrolyte composition for electric double layer capacitors of Example 7, and then 80 It heated at degreeC for 2 hours. Thereby, the composition of Example 7 arrange | positioned through a separator between the pair of polarizable electrodes of Example 14 was thermally polymerized, and the film-form electric double layer capacitor was obtained.

The obtained film-form electric double layer capacitor takes the structure of [aluminum current collector / polarizable electrode / electrolyte (separator) / polarizable electrode / aluminum current collector], and can charge and discharge, and functions effectively as an electric double layer capacitor. It is confirmed.

Example 20 Electric Double Layer Capacitor 6

On the surface of the polarizable electrode obtained in Example 13, the electrolyte composition for the electric double layer capacitor of Example 1 was excessively disposed, and the polarizing electrodes of the same configuration were overlapped so as to face each other, and a pair of polarizable electrodes was placed thereon. The film-form electric double layer capacitor was obtained by applying pressure so that the gap of inside might be set to 25 micrometers.

The obtained film-form electric double layer capacitor takes the structure of [aluminum current collector / polarizable electrode / solid polymer electrolyte layer / polarizable electrode / aluminum current collector], and can be charged and discharged, and functions effectively as an electric double layer capacitor. It is confirmed.

Example 21 Electric Double Layer Capacitor 7

On the surface of the polarizable electrode obtained in Example 13, the electrolyte composition for the electric double layer capacitor of Example 7 was excessively disposed, and the polarizing electrodes of the same configuration were overlapped so as to face each other, and a pair of polarizable electrodes was placed thereon. The film-form electric double layer capacitor was obtained by applying pressure so that the gap of inside might be 25 micrometers.

The obtained film-form electric double layer capacitor takes the structure of [aluminum current collector / polarizable electrode / solid polymer electrolyte layer / polarizable electrode / aluminum current collector], and can be charged and discharged, and functions effectively as an electric double layer capacitor. It is confirmed.

Example 22 Electric Double Layer Capacitor 8

On the surface of the polarizable electrode obtained in Example 14, the electrolyte composition for the electric double layer capacitor of Example 7 was slightly excess, and the other polarizable electrodes of the same configuration were superposed so as to face each other, so that a pair of polarizable electrodes The pressure was applied so that the gap of liver was 25 micrometers, and it hardened by heating at about 80 degreeC for 2 hours.

Thereby, the electrolyte composition for electric double layer capacitors of Example 7 arrange | positioned between a pair of polarizable electrodes of Example 14 thermally polymerized, the solid polymer electrolyte layer was formed, and the film-form electric double layer capacitor was obtained.

The obtained film-form electric double layer capacitor takes the structure of [aluminum current collector / polarizable electrode / solid polymer electrolyte layer / polarizable electrode / aluminum current collector], and can be charged and discharged, and functions effectively as an electric double layer capacitor. It is confirmed.

Claims (12)

(A) a unit represented by the following formula (1) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, R ¹ CO- group ( R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is ² to 4 carbon atoms) Alkylene group, m is an integer of 1 to 100) and a polymer compound blocked by one or two or more monovalent groups selected from a group containing a person group, and (B) an ion conductive salt An electrolyte composition for an electric double layer capacitor. (Formula 1) (Formula 2) (A) a unit represented by the following formula (1) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, R ¹ CO- group ( R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is ² to 4 carbon atoms) Alkylene group, m is an integer of 1 to 100) and a polymer compound blocked by one or two or more monovalent groups selected from a group containing a person group, (B) an ion conductive salt, and (C) crosslinkable An electrolyte composition for an electric double layer capacitor, comprising a compound having a functional group as a main component. (Formula 1) (Formula 2) The electrolyte composition for an electric double layer capacitor according to claim 1 or 2, wherein the monovalent group for blocking the terminal is a cyano group-substituted monovalent hydrocarbon group or a cyano group-substituted monovalent hydrocarbon group and an R ¹ ₃ Si-group. . In the three-dimensional network structure of the polymer obtained by crosslinking of the compound as the component (C), the molecular chain of the polymer compound as the component (A) has a semi-interpenetrating polymer network structure wrapped around each other and is the component (B). A solid polymer electrolyte for an electric double layer capacitor, comprising an ion conductive salt. (A) a unit represented by the following formula (1) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, R ¹ CO- group ( R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is ² to 4 carbon atoms) , An alkylene group, m is an integer of 1 to 100) and a polymer compound blocked by one or two or more monovalent groups selected from the group containing a person group, (D) a high area material, and (E) a conductive material A composition for polarizable electrodes, comprising as a main component. (Formula 1) (Formula 2) (A) a unit represented by the following formula (1) and a unit represented by the following formula (2), wherein at least 10% of the terminal of the molecular chain is a halogen atom, an unsubstituted or substituted monovalent hydrocarbon group, R ¹ CO- group ( R ¹ is an unsubstituted or substituted monovalent hydrocarbon group), R ¹ ₃ Si-group (R ¹ is the same as above), amino group, alkylamino group, H (OR ² ) _m -group (R ² is ² to 4 carbon atoms) An alkylene group, m is an integer of 1 to 100) and a polymer compound blocked by one or two or more monovalent groups selected from a group containing a person group, (C) a compound having a crosslinkable functional group, (D ) A composition for polarizable electrodes, comprising a high-area material and (E) a conductive material as main components. (Formula 1) (Formula 2) 7. The composition for polarizable electrodes according to claim 5 or 6, wherein the monovalent group blocking the terminal is a cyano group-substituted monovalent hydrocarbon group or a cyano group-substituted monovalent hydrocarbon group and an R ¹ ₃ Si-group. The polarizable electrode formed by apply | coating the composition for polarizable electrodes in any one of Claims 5-7 on an electrical power collector. In the electric double layer capacitor formed by interposing a separator between a pair of polarizable electrodes, the polarizable electrode of Claim 8 is used as said pair of polarizable electrodes, and it is ion-conductive to a separator base material as said separator. An electric double layer capacitor, characterized by using a separator formed by impregnating a salt-containing solution. In an electric double layer capacitor formed by interposing a separator between a pair of polarizable electrodes, the polarizable electrode according to claim 8 is used as the pair of polarizable electrodes, and the separator is used for the separator substrate as the separator. An electric double layer capacitor, comprising a separator formed by applying or impregnating an electrolyte composition for an electric double layer capacitor according to any one of claims 1 to 3. In an electric double layer capacitor formed by interposing a separator between a pair of polarizable electrodes, the polarizable electrode according to claim 8 is used as said pair of polarizable electrodes, and as said separator, An electric double layer capacitor comprising a solid polymer electrolyte layer comprising an electrolyte composition for an electric double layer capacitor according to any one of claims 3 to 4. In the electric double layer capacitor formed by interposing a separator between a pair of polarizable electrodes, using the polarizable electrode of Claim 8 as said pair of polarizable electrodes, Claim 4 is used as said separator. The electric double layer capacitor characterized by using the solid polymer electrolyte for electric double layer capacitors described in the above.