JPH06203874A - Ionic conductive high-polymer electrolyte - Google Patents

Abstract

(57) [Abstract] [Purpose] To achieve long-term reliability and low-temperature characteristics improvement of aluminum electrolytic capacitors, lithium batteries, and electric double-layer capacitors made up of liquid electrolytes. [Structure] At least one kind of molecule having a specific molecular chain or a mixture thereof. An electrolyte is formed by combining a solvent and a polymer material such as polyethylene oxide having ether type oxygen in the structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion conductive electrolyte and an electrochemical device such as a lithium battery, an aluminum electrolytic capacitor and an electric double layer capacitor.

[0002]

2. Description of the Related Art Lithium batteries, aluminum electrolytic capacitors,
Electrolytes for driving electrochemical devices such as electric double layer capacitors have high decomposition voltage, high electrical conductivity, high boiling point, low freezing point,
Although conditions such as low vapor pressure are required, those with a high boiling point generally have a property of high viscosity and low electrical conductivity.

Therefore, as an electrolytic solution for driving an aluminum electrolytic capacitor, a solution in which an organic ammonium salt is dissolved in an organic solvent such as ethylene glycol or γ-butyl lactone has been conventionally used, with a particular emphasis on improving the electric conductivity.

Electrolyte solutions for driving electrochemical devices such as lithium batteries and battery double layer capacitors are also focused on high electrical conductivity, and inorganic lithium salts and organic ammonium salts are used as high dielectric constants such as propylene carbonate. What has been dissolved in a solvent has been used.

[0005]

However, low-viscosity solvents such as diethylene glycol have a low boiling point, and electrochemical devices such as electrolytic capacitors using such electrolytes have long-term reliability because of evaporation and dissipation of organic solvents. Was difficult to obtain. Further, there is a problem that the conductivity of the electrolytic solution greatly decreases as the temperature decreases.

Further, an electrolytic solution using a high dielectric constant solvent such as γ-butyl lactone or propylene carbonate has a sufficiently high conductivity at room temperature, but originally has a high viscosity.
In particular, there was a problem that the electrical conductivity at 0 ° C. or lower was remarkably reduced.

An electric double layer capacitor using an electrode prepared by mixing an electrolytic solution prepared by dissolving an organic ammonium salt in these high dielectric constant solvents and activated carbon is
In particular, there is a problem that the impedance greatly increases at -10 ° C or lower.

Further, LiClO is added to these high dielectric constant solvents.
_When an electrolytic solution prepared by dissolving a lithium salt such as ₄ , LiBF ₄ , LiPF ₆ or the like is used for driving a lithium battery having a voltage of 4 V or more composed of CoO ₂ or the like as a positive electrode active material, especially 70 When the battery is stored in a temperature atmosphere of about ℃ in a charged state, the electrolytic solution is decomposed with the lapse of time to generate gas, which causes a problem of impairing the device performance.

[0009]

In order to effectively solve such problems, the electrolyte of the present invention uses the specific compounds described in the claims.

[0010]

Function: General formulas (Formula 7), (Formula 8), (Formula 9), (Formula 1)
The solvents represented by the formulas (0) and (Chem. 11) can adjust the boiling point and the viscosity by changing the number n of ethylene oxide and the terminal alkyl group R, so that an electrolyte having a long life and high conductivity can be obtained. can get. In particular, when, for example, an ammonium salt or a lithium salt is dissolved in a solvent limited to specific R and n, and this is combined with a polymer material having ether type oxygen in the structure, it has the electrical conductivity required for practical use. In addition, an electrolyte having a high boiling point and a low vapor pressure, which has never been achieved, could be constructed.

[0011]

[Chemical 7]

[0012]

[Chemical 8]

[0013]

[Chemical 9]

[0014]

[Chemical 10]

[0015]

[Chemical 11]

[0016]

[Chemical 12]

Further, the polymer composition having ether type oxygen in its structure has a polyether skeleton as a basic skeleton, and the polyether moiety is a random copolymer of oxyethylene and oxypropylene (Chemical Formula 12). It was found that the conductivity is further improved by substituting a compound having a polymerizable double bond such as an acrylic group and irradiating the compound with an electron beam to perform a three-dimensional crosslinking reaction.

This effect was the same when the terminal hydrogen of (Chemical Formula 12) was converted to isocyanate and this was heated for three-dimensional crosslinking reaction.

Further, an ion conductive polymer electrolyte containing at least one kind of ammonium salt selected from quaternary ammonium borate, quaternary ammonium phosphate, ammonium carboxylate or quaternary ammonium carboxylate as a salt is used. It has been found that when used as an electrolyte for driving an electrolytic capacitor, sufficient withstand voltage and low impedance are realized, and high-temperature storage deterioration and low-temperature characteristics, which have been technical problems in the past, are significantly improved.

Further, as a salt, CF ₃ S is used as a cationic species.
The ion-conductive degradable material containing at least one salt selected from tetraalkylammonium or tetraalkylphosphonium having O ₃ , ClO ₄ , and BF ₄ , or tetraalkylammonium carboxylate, tetraalkylphosphonium carboxylate is used as an electrolyte. It was found that when used in a double-layer capacitor, the high-temperature storage deterioration and low-temperature characteristics, which were the conventional technical problems, were greatly improved.

Further, when an ion conductive polymer electrolyte containing a lithium salt such as LiBF _{4 is used} as a salt in a lithium battery, it has been found that the high temperature storage deterioration and the low temperature characteristics, which have been the technical problems of the prior art, are greatly improved. did.

[0022]

【Example】

(Example 1) The ionic conductivity and long-term reliability of the ion conductive polymer electrolyte will be described.

In the structural formula (Formula 6), (l + m) × n =
100 g of a base polymer obtained by acrylated terminal hydrogen of a polymer composition represented by 50 is represented by the general formulas (Formula 1), (Formula 2), (Formula 3), (Formula 4) and (Formula 5). As an example of the solvent, the one shown in (Table 1) is added, and a predetermined amount of the salt shown in Table 1 is dissolved and cast in a stainless steel vat to a thickness of 0.5 mm. The stock solution was cured by irradiating it with an electron beam in a nitrogen atmosphere to obtain seven kinds of ion conductive polymer electrolyte sheets of the present invention. The irradiation conditions of the electron beam are accelerating voltage of 750 keV and irradiation dose of 1M.
rad.

As a comparative example, an electrolytic solution generally used for aluminum electrolytic capacitors, electric double layer capacitors and lithium batteries was prepared at the same time, and its composition is shown in (Table 2). The ionic conductivity of the above electrolyte at 20 ° C. was measured by a known complex ion impedance method.
The results are shown in (Table 3). In addition, FIG. 1 shows a change with time in conductivity when left in an atmosphere of 100 ° C. in nitrogen without being sealed. As shown in (Table 3) and FIG. 1, the ion-conductive polymer electrolyte of the present invention has a practically usable conductivity, a small decrease rate of conductivity in a low temperature region, and is unprecedented. It turned out to have high reliability.

In (Table 1), the ion conductive polymer electrolyte (1) is represented by the general formula (Formula 1),
Similarly, in (2) and (3), the general formula (Formula 2) is replaced by (4),
(5) and (6) are represented by the general formula (Formula 3), (7) is represented by the general formula (Formula 4), and (8), (9), and (10) are represented by the general formula (Formula 5). Although an example is shown, the same effects were obtained even when the solvent defined by (Chemical formula 1) to (Chemical formula 5) and having a solvent having another unit number n of the alkyl group or ethylene oxide was used.

Further, in the present embodiment, a base polymer in which the terminal hydrogen is acrylated in the structural formula (Formula 6) is used,
It was cured by irradiating it with an electron beam, but it was prepared by curing it by curing it for 24 hours in a nitrogen gas atmosphere kept at a temperature of 80 ° C. by using an isocyanate of the terminal hydrogen. The molecular electrolyte also obtained similar characteristics.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

(Example 2) Hereinafter, a specific example of an aluminum electrolytic capacitor will be described in detail as an example of an electrochemical element prepared by using the ion conductive polymer electrolyte described in the claims as a constituent element.

FIG. 2 is a sectional view showing the structure of an aluminum electrolytic capacitor formed by using the electrolyte of the present invention. Thickness 0.0
5mm, etching hole diameter 1 to 5 microns, size 3
An anode connector 2 is spot-welded to one side of an electrode 1 made of a cm × 100 cm aluminum foil. Next, an aqueous solution for boric acid (concentration 80 g, which was kept at a temperature of 90 ° C.)
/ L) and oxidize the aluminum surface for 15 minutes at a current of 30 A to form a dielectric layer 3 composed of aluminum oxide to form an anode.

Further, a cathode connector 5 is provided on one side of an electrode 4 made of aluminum foil having a thickness of 0.05 mm, an etching hole diameter of about 1 to 5 microns, and a size of 3 cm × 100 cm.
An electrode for a cathode was prepared by spot welding.

Next, in the structural formula (Formula 6), (l +
m) × n = 50, a polymer material 100 in which the terminal hydrogen of a polymer compound having a structure represented by the formula is isocyanated
g, ammonium borodisalicylate 20 g, and CH ₃
A stock solution of the ion conductive polymer electrolyte of the present invention was prepared by stirring and mixing 100 g of a solvent represented by O (C ₂ H ₄ O) ₅ CH ₃ and 200 g of n-butanone as a diluent.

Subsequently, using the coating apparatus shown in FIG.
The polymer electrolyte layer 5 was bonded to the dielectric electrode 3. Shown in Figure 3
The coating device used was a nozzle with a liquid hole diameter of 0.5 mm and 3 kg
/cm ²The nitrogen pressure of 1 l / hr. The above spray amount
Stock solution of polymer electrolyte is applied from the vertical direction of the dielectric electrode 3.
To do. The coating method is as follows:
Fix it at a height of 10 cm in the vertical direction and set the dielectric electrode 1 in the horizontal direction.
Run at a constant speed of 0 cm / sec, and nozzle jet
It was carried out by applying at an angle of 22 degrees.

The polyelectrolyte stock solution thus coated had a thickness of 0.06 mm and a difference within 20%. The undiluted solution is semi-dried by leaving it in the air at 30 ° C. for 1 hour, and then the aluminum electrode 4 for the negative electrode is pressure-bonded to the surface of the electrolyte in opposition
By leaving this in air at 50 ° C. for 3 hours, dielectric layer / polymer electrolyte layer / electrode was formed.

Finally, this was wound into a roll together with a separator made of Manila hemp to prepare an unsealed aluminum electrolytic capacitor A using the ion conductive polymer electrolyte of the present invention.

Next, as a comparative example, an unsealed aluminum electrolytic capacitor B similar to the capacitor A was prepared by using a known electrolyte prepared by dissolving 1 g of ammonium adipate in 9 g of ethylene glycol. The manufacturing method is the same as that used in the aluminum electrolytic capacitor A, the anode foil and the cathode foil, and the roll shape with the porosity of 50%, the thickness of 0.1 mm, and the size of 3 cm x 4 cm, which is made of this Manila hemp. After that, the electrolytic solution was impregnated under reduced pressure for 1 minute at room temperature and a pressure of 5 Torr.

In the aging process, the element A is 4 ° C. at 80 ° C.
00V was applied for 2 hours, and element B was applied at room temperature by applying 400V for 24 hours.

As an accelerated test for evaluating the stability of the electrolyte stored at high temperature with respect to the electrolytic capacitor A of the example and the electrolytic capacitor B of the comparative example prepared by the above method, the tangent of the loss angle in the unsealed state stored at 85 ° C. (Tan δ) and equivalent series resistance (ESR) were measured over time, and the results are shown in FIGS. 4 and 5, respectively. The measurement was performed at 20 ° C. and 120 Hz.

In FIG. 4 and FIG. 5, the capacitor B of the comparative example using an electrolyte using ethylene glycol as a solvent, which has been conventionally used, is deteriorated in characteristics by the present invention in comparison with the characteristics which are deteriorated early by high temperature storage. It has been found that the capacitor A composed of a certain electrolyte has sufficient reliability.

(Third Embodiment) In the second embodiment described above, CH ₃
An example of an electrolyte prepared by dissolving an organic ammonium salt in a solvent represented by O (C ₂ H ₄ O) ₅ CH ₃ is shown, but in this example, another solvent described in the claims is used. An example of an aluminum electrolytic capacitor using the ion-conductive polymer electrolyte thus prepared will be shown.

Table 5 shows the composition of the electrolyte used in (Table 4) and the characteristics of the capacitor having the same constitution as that of Example 2 using the same. From Table 5, it is found that the capacitors made of the electrolytes of the present example significantly deteriorated in high temperature deterioration, whereas the capacitors made of the electrolytes of the present example largely deteriorated in characteristics when stored at 85 ° C. for 100 hours.

In this example, the characteristics of an aluminum electrolytic capacitor were shown as an example of an electrochemical element made of an ion conductive polymer electrolyte, but a dielectric material obtained by electrolytically oxidizing tantalum foil or titanium foil was used. The produced electrolytic capacitor also had excellent life characteristics.

[0044]

[Table 4]

[0045]

[Table 5]

(Example 4) An electric double layer capacitor will be described in detail below as an example of an electrochemical device prepared by using the ion conductive polymer electrolyte described in the claims as a constituent element. A typical configuration of the electric double layer capacitor that is an embodiment of the present invention is shown in FIG.

In the figure, 7 is an electrode made of activated carbon and an ion conductive polymer composition, 8 is an electrolyte layer made of the same material as the ion conductive polymer composition, and 9 is a collector electrode made of a metal foil. 10 is an electrode terminal made of nickel, 1
Is an aluminum can and 12 is a sealant. The metal material used for 9 may be aluminum, stainless steel or the like, and is not particularly limited to this material.

First, the ion conductive polymer composition used in the construction of the electric double layer capacitor of this example, and the method of constructing an electrode prepared by mixing this with activated carbon will be described.

Average particle size 2 μm, specific surface area 2500 m ² /
g, 100 g of activated carbon having an average diameter of micropores of 20 angstrom, (l + m) in the structural formula (Formula 6)
50 g of a base polymer in which the terminal hydrogen of the polymer composition represented by xn = 50 is acrylated, HO
150 g of a solvent (Chemical formula 1) represented by (C ₂ H ₄ O) ₃ H,
20 g of a quaternary ammonium salt represented by (C ₄ H ₉ ) ₄ NCF ₃ SO ₃ and 100 g of methyl ethyl ketone were placed in an alumina ball mill and stirred and pulverized for 24 hours to prepare an electrode stock solution.

Subsequently, the electrode stock solution was applied to a thickness of 100 μm on a 20 μm thick aluminum foil having stainless steel electrode terminals attached by spot welding using a roll coater. Next, it was cured by irradiation with an electron beam in a nitrogen atmosphere to obtain an electrode sheet. The electron beam irradiation conditions are an acceleration voltage of 500 keV and an irradiation dose of 4 Mra.
d.

Next, 100 g of the base polymer,
The solvent represented by HO (C ₂ H ₄ O) ₃ H
g, and a mixture of 40 g of a quaternary ammonium salt represented by (C ₄ H ₉ ) ₄ NCF ₃ SO ₃ with stirring, and using a wire rod on the electrode coated surface of the electrode sheet, a thickness of 50 μm.
After casting to m, it is cured again by electron beam irradiation. The electron beam irradiation conditions are an acceleration voltage of 180 keV and an irradiation dose of 1
It was Mrad.

The electrode sheet prepared in this manner was used for 2.
Cut into a size of 5 cm x 40 cm, and then press-bond the two electrode sheets to each other on the electrode coated surfaces. Then, insulate polypropylene paper into a roll and store it in an aluminum tube. A capacitor D was prepared by sealing with.

The last capacitor D was aged by applying 2.3 V at 100 ° C. for 5 hours and then short-circuiting for 1 hour.

As a comparative example, an electric double layer capacitor E was prepared using an electrolytic solution in which (C ₂ H ₅ ) ₄ NBF ₄ was dissolved at 0.8 mol / l using propylene carbonate as a solvent.

As in the above example, the average particle diameter was 2 μm, the specific surface area was 2500 m ² / g, and the average diameter of the micropore was 20.
After thoroughly stirring 100 g of Angstrom activated carbon, 10 g of acetylene black and 200 g of tetrafluoroethylene dispersion / methanol solution (5% by weight), this was roll-coated on the same aluminum foil as used in Example D above. Was cast to a thickness of 100 μm, and then cured by storing in a nitrogen atmosphere at a temperature of 100 ° C. for 13 hours.

Next, two sheets of this sheet were cut into a size of 2.5 cm × 40 cm, and the porosity of polypropylene was 4
After covering with a separator of 0% and thickness of 40 μm, winding it into a roll, storing it in an aluminum tube, injecting an electrolyte solution, vacuum impregnating for 1 minute at a pressure of 5 Torr, and finally using epoxy resin for the connector part. Capacitor F was created by sealing. Finally, the capacitor E was aged by applying 2.3 V at 50 ° C. for 24 hours and then short-circuiting for 1 hour.

For the above two types of capacitors E and F,
The temperature characteristics of capacitance and internal resistance were evaluated. The results are shown in FIGS. 7 and 8, respectively.

The discharge capacity was measured by applying a voltage of 2.3 V for 30 minutes at each temperature, discharging at a constant current of 10 mA, and initializing the amount of electricity (coulomb) flowing until the element voltage reached 0 V. The value obtained by dividing the applied voltage by 2.3 V was taken as the electrostatic capacity (F). Further, the internal resistance was measured with an impedance of 1 kHz.

In FIG. 7, the horizontal axis represents temperature and the vertical axis represents capacitance. From this figure, it was found that the element F of the comparative example dropped to 50% of the capacity at 20 ° C. at −25 ° C., while the reduction rate of the element E of the example remained below 10%.

Further, in FIG. 8, the element F of the comparative example is
It was found that at 25 ° C., the increase ratio of the element E of the example was less than 50%, compared with the impedance increased to 3 times the impedance at 20 ° C.

Further, as a reliability test of high temperature storage, the capacitors E and F were not sealed with epoxy resin 8
The sample was stored in a nitrogen atmosphere kept at 5 ° C., and the change in capacitance with time was measured. The results are shown in Fig. 9. As is clear from this figure, it was found that the element of this example has a much longer life than the comparative example.

Example 5 In Example 4, 100 g of the base polymer, 300 g of the solvent, and 40 ammonium salts were used.
Although an example in which g is added to form an ion conductive polymer electrolyte is shown, in this example, an electric double layer capacitor having particularly excellent characteristics is used by using other claimed ammonium salt or phosphonium salt and a solvent. Created. (Table 6)
The ammonium salt used in the above, the name of the plasticizer, and the addition amount with respect to 10 g of the base polymer are shown. The reliability test of high temperature storage of these devices was evaluated by the same method as in Example 4, and the results are shown in (Table 7). In (Table 7), the capacity ratio is the capacity after storage for 500 hours / initial capacity, and the impedance ratio is the impedance after storage for 500 hours / initial impedance. From Table 7, it was found that the life of these devices was remarkably improved as compared with the conventional electrolytic solution type device described in Example 4.

[0063]

[Table 6]

[0064]

[Table 7]

(Example 6) A lithium secondary battery will be described in detail as an example of an electrochemical device prepared by using the ion conductive polymer electrolyte described in the claims as a constituent element.

A typical constitution of the lithium secondary battery which is an embodiment of the present invention is shown in FIG. 13 is a positive electrode terminal, 1
4 is a positive electrode current collector made of nickel having a thickness of 0.05 mm, 15 is a positive electrode made of LiCoO ₂ , acetylene black, and a polymer electrolyte, 16 is a polymer electrolyte layer, 17 is graphite, acetylene black, and A negative electrode made of a molecular electrolyte, 18 is a negative electrode current collector electrode made of nickel having a thickness of 0.05 mm like l, 19 is a negative electrode terminal, 20 is an aluminum can, and 21 is a sealant. Hereinafter, the manufacturing method of each component will be described.

In the structural formula (Formula 6), (l + m) × n =
100 g of a base polymer in which the terminal hydrogen of the polymer compound represented by 50 is acrylated, 9.4 g of LiBF ₄ ,
100 ml of a solvent represented by CH ₃ O (C ₂ H ₄ O) ₅ C ₄ H ₉
Was weighed in dry air and then mixed with stirring to prepare a stock solution of the polymer electrolyte.

Continuing, 100 g of the above-mentioned polyelectrolyte stock solution
To the above, 40 g of graphite having an average particle size of 5 μm and 2 g of acetylene black were added, and the mixture was mixed with an alumina ball mill for 24 hours.
A negative electrode stock solution was prepared by stirring and mixing for a period of time.

In addition, 100 g of the above polymer electrolyte stock solution,
Add 40 g of LiCoO ₂ powder having an average particle size of 5 μm and ₂ g of acetylene black, and add 24 by a ball mill made of alumina.
A stock solution for a positive electrode was prepared by stirring and mixing for a time.
The LiCoO ₂ powder was prepared by mixing commercially available Li ₂ CO ₃ and Co ₃ O ₄ in predetermined amounts, pre-sintering at 400 ° C. for 5 hours, and then heating and reacting at 850 ° C. for 5 hours.

The stock solutions for the positive electrode and the negative electrode prepared by the above method were cast on a titanium foil having a thickness of 20 μm with a thickness of 0.2 mm and 0.5 mm, respectively, using a wire rod and irradiated with an electron beam. After being cured by the above method, the polymer electrolyte stock solution is cast again on the surface of the positive electrode and the negative electrode sheet on which the electrode material is coated to a thickness of 0.5 mm, and is cured by irradiating it with an electron beam. And a negative electrode sheet were obtained.

The electron beam irradiation is performed by accelerating voltage of 750 keV,
Irradiation dose was 2 Mrad in a nitrogen atmosphere.

Next, the positive electrode sheet and the negative electrode sheet were 2.5 cm ×
After cutting into a size of 40 cm, these sheets were wound into a roll in the order of positive electrode sheet / negative electrode sheet / electrically insulating separator. Next, this was stored in an aluminum tube, a direct current voltage of 4.3 V was applied at a temperature of 30 ° C. for 5 hours, and then a connector part was sealed with an epoxy resin to prepare a battery G of an example of the present invention. .

Next, as a comparative example, a lithium secondary battery H was prepared using an electrolytic solution in which 1 mol / l of LiBF ₄ was dissolved in propylene carbonate.

As in the above example, 50 g of graphite having an average particle size of 5 μm, acetylene black 3 g, tetrafluoroethylene dispersion / methanol solution (5% by weight product)
A negative electrode stock solution was prepared by adding 50 g and stirring and mixing with an alumina ball mill for 24 hours.

Further, 50 g of LiCoO ₂ powder having an average particle size of 5 μm, 3 g of acetylene black and 50 g of ethylene tetrafluoride dispersion / methanol solution (5 wt% product) were added, and the mixture was stirred and mixed by an alumina ball mill for 24 hours. A positive electrode stock solution was prepared. The positive electrode stock solution and the negative electrode stock solution were applied to the same titanium foil as that used in Example H using a wire rod to obtain 100 μm of each.
m and 50 μm, and then cast in nitrogen atmosphere for 20
It was cured by storing it at a temperature of 0 ° C. for 24 hours.

Next, two sheets of this sheet were cut into a size of 2.5 cm × 40 cm, and the porosity of polypropylene was 4
After covering with a separator of 0% and thickness of 40 μm, it was wound into a roll, stored in an aluminum tube whose inner surface was coated with titanium, and injected with an electrolytic solution, then at a pressure of 5 Torr for 1
After impregnating in vacuum for 30 minutes, applying a direct current voltage of 4.3 V for 5 hours at a temperature of 30 ° C., and finally sealing the connector portion with an epoxy resin, an element H of a comparative example was prepared.

For the batteries G and H produced by the above method,
A charge / discharge cycle test was conducted at 80 ° C. in a constant current mode of 8 mA at an upper limit voltage of 4.3 V and a lower limit voltage of 3 V, and the results are shown in FIG.

In FIG. 11, the horizontal axis represents the number of charging / discharging cycles and the vertical axis represents the discharge capacity. The battery G of the example has a capacity deterioration of 10% even after exceeding 200 cycles.
It was within.

In this example, one example of a lithium secondary battery prepared by using the ion conductive polymer electrolyte described in the claims as a constituent element was shown. The effect of the ion conductive polymer electrolyte of the present invention is as follows. It goes without saying that the material is not limited to this.

[0080]

EFFECTS OF THE INVENTION According to the present invention, an electrolyte having excellent low-temperature characteristics and little deterioration during high-temperature storage, and an electrochemical element using the same, such as an aluminum electrolytic capacitor, an electric double layer capacitor, and a lithium secondary battery, can be obtained. You can

[Brief description of drawings]

FIG. 1 is a storage time-ion conductivity characteristic diagram of ion conductive polymer electrolytes of different examples of the present invention.

FIG. 2 is a configuration diagram of an aluminum electrolytic capacitor including an ion conductive polymer electrolyte according to an embodiment of the present invention as a constituent element.

[Fig. 3] Configuration diagram of coating device

FIG. 4 is a characteristic diagram of storage time-tan δ of an aluminum electrolytic capacitor having an ion conductive polymer electrolyte of one example of the present invention and an electrolyte of a comparative example as constituent elements.

FIG. 5 is a storage time-equivalent series resistance characteristic diagram of an aluminum electrolytic capacitor including an ion conductive polymer electrolyte of one example of the present invention and an electrolyte of a comparative example.

FIG. 6 is a configuration diagram of an electric double layer capacitor having an ion conductive polymer electrolyte according to an embodiment of the present invention as a constituent element.

FIG. 7 is a temperature-capacitance characteristic diagram of an electric double layer capacitor having an ion conductive polymer electrolyte of one example of the present invention and an electrolyte of a comparative example as constituent elements.

FIG. 8 is a temperature-impedance characteristic diagram of the same.

[Fig. 9] Same storage time-capacitance characteristic diagram

FIG. 10 is a configuration diagram of a lithium secondary battery including an ion conductive polymer electrolyte according to an embodiment of the present invention as a component.

FIG. 11 is a cycle number and discharge capacity characteristic diagram of the lithium secondary battery and a comparative example.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location H01G 9/02 331 9375-5E // C08F 299/02 MRS 7442-4J C08G 81/00 NUT 8416- 4J

Claims (8)

[Claims] 1. A polymer composition having ether type oxygen in the structure and at least one selected from the general formulas (Chemical formula 1), (Chemical formula 2), (Chemical formula 3), (Chemical formula 4) and (Chemical formula 5). An ion-conducting polymer electrolyte, characterized in that it contains a solvent of a kind or a mixture. 2. A polymer composition having ether-type oxygen in the structure has a polyether polyol basic skeleton, and the polyether moiety is capable of polymerizing the terminal hydrogen of (Chemical Formula 6) which is a random copolymer of oxyethylene and oxypropylene. 2. The ion conductive polymer electrolyte according to claim 1, wherein the ion conductive polymer electrolyte is substituted with a compound having a different double bond. 3. A polymer composition having ether type oxygen in the structure has a polyether polyol as a basic skeleton, and a polyether moiety is a random copolymer of oxyethylene and oxypropylene. The ion-conductive polymer electrolyte according to claim 1, wherein 4. A quaternary ammonium borate, a quaternary ammonium phosphate, an ammonium carboxylate or at least one kind of ammonium salt selected from a quaternary ammonium carboxylic acid is contained, and the method according to claim 1, 2, or 3. The ion-conductive polymer electrolyte described. 5. A cationic species of CF ₃ SO ₃ , ClO ₄ , B
The tetraalkynammonium or tetraalkylphosphonium having F ₄ or at least one salt selected from tetraalkylammonium carboxylate and tetraalkylphosphonium carboxylate is contained. Ion conductive polymer electrolyte. 6. A polymer composition having ether type oxygen in the structure, a solvent comprising at least one kind or a mixture selected from the general formulas (Formula 3) and (Formula 5), and a lithium salt. A characteristic ion-conducting polymer electrolyte. 7. A polymer composition having ether type oxygen in the structure has a polyether skeleton as a basic skeleton, and the polyether moiety is a random copolymer of oxyethylene and oxypropylene. The ion-conductive polymer electrolyte according to claim 6, which is substituted with a compound having a possible double bond. 8. A polymer composition having ether type oxygen in the structure has a polyether skeleton as a basic skeleton, and the polyether moiety is a random copolymer of oxyethylene and oxypropylene. The ion-conductive polymer electrolyte according to claim 6, wherein the ion-conductive polymer electrolyte is formed. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6]