JP3521386B2 - Electric double layer capacitor, manufacturing method thereof, and polarizable electrode material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electric double layer capacitor which has a low equivalent series resistance and is superior in stability of the capacitance value for a long time. SOLUTION: Polarizable electrodes 3A, 3B made of active carbon powder, an electrolyte solution, and a binder are dotted with pores 6 each having a volume corresponding to a grain greater than the active carbon powder and less than a grain size of 10 μm. The electrolyte solution is held also in the pores 6 to increase the absolute quantity of the electrolyte solution contained in the polarizable electrodes, compared with the conventional one. This increases the ion conductivity between the polarizable electrodes 3A, 3B by the increment of the absolute quantity of the electrolyte solution, resulting in a low equivalent series resistance and a little influence of the decrease of the electrolyte solution due to dry up. The electrolyte solution uses e.g. an acid water solution such as sulfuric acid and grains soluble in the electrolyte solution e.g. P4VP are added in the material of the polarizable electrodes and dissolved in the electrolyte solution to form pores 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric double layer capacitor, a method for manufacturing the same, and a polarizable electrode material, and more particularly to an electric double layer capacitor using a polarizable electrode in which powder of activated carbon contains an electrolytic solution and its manufacture. The present invention relates to a method and a polarizable electrode material suitable for carrying out the manufacturing method.

[0002]

2. Description of the Related Art A conventional electric double layer capacitor of this type and its manufacturing method will be described with reference to FIG. Figure 4
Is a cross section of a conventional electric double layer capacitor in the process of being manufactured.
It is a figure shown in order of a process. FIG. 4D shows a cross section of the electric double layer capacitor after completion. Referring to FIG.
First, a flat plate current collector 1 made of a conductive material is prepared,
An electrically insulating gasket 2 having a frame shape is adhered to this (FIG. 4A). For the current collector 1, for example, a butyl rubber sheet in which carbon is mixed to have conductivity is used. Alternatively, it is also possible to use a plastic film similarly containing carbon to give conductivity. The gasket 2 is made of carbon-free insulating butyl rubber or the like. To bond the current collector 1 and the gasket 2 to each other, a method of applying pressure to perform pressure bonding, or a method of using heat in combination for thermocompression bonding is used.

Although not shown, a paste-like polarizable electrode material is prepared by kneading activated carbon powder, a binder and an electrolyte solution separately from the above steps. The electrolyte solution contains
For example, an aqueous solution such as an aqueous solution of sulfuric acid, or a non-aqueous solution such as an organic solvent such as propylene carbonate or γ-butyl lactone in which a borofluoride salt or tetrafluorophosphate salt of tetraethylammonium is solute is used. Things are used. Furthermore, JP-A-59-090919
Japanese Unexamined Patent Publication No. Hei 1-196807 or Japanese Unexamined Patent Publication No. Hei 4
As the electric double layer capacitor disclosed in Japanese Patent Laid-Open No. 079308, a solution in which poly-4-vinylpyridine is previously contained in an aqueous sulfuric acid solution is used.

Next, the paste-like polarizable electrode material 30 prepared in advance is filled in the space surrounded by the gasket 2 by a doctor blade method or the like (FIG. 4).
(B)). Two current collectors filled with such polarizable electrode material are prepared. After that, when the polarizable electrode material was applied on the current collector so as to have a predetermined shape and volume, and was deposited or filled, it was formed into a predetermined shape and volume by the treatment. The later polarizable electrode material will be referred to as a polarizable electrode.

Next, the above-mentioned 2 which has been filled with the polarizable electrode material
The current collectors 1A and 1B are arranged so that the polarizable electrodes 30A and 30B face each other with the separator 5 interposed therebetween, and the gaskets 2A and 2B are bonded to each other to form the polarizable electrodes 30A and 30B. After sealing (FIG. 4 (c)), a conventional electric double layer capacitor is completed (FIG. 4 (d)). The separator 5 is non-electroconductive and ion-permeable, and for example, a microporous polypropylene sheet or the like is used. In order to bond the two gaskets 2A and 2B, for example, a method of applying heat and pressure to the gaskets 2A and 2B to thermally bond the gaskets is used.

In the electric double layer capacitor obtained as described above, the polarizable electrodes 30A and 30B have a very large specific surface area due to the pores present in the activated carbon powder constituting them, and the electric double layer capacitor. It exhibits a large capacitance for two reasons: its thickness is as thin as the diameter of the molecule.

[0007]

The electric double layer capacitor has a function of accumulating charge by an electric double layer generated at a solid / liquid interface between activated carbon and an electrolyte solution.
It is characterized in that it has a much larger electrostatic capacity of about 0 to 50 F / cm ³ than that of an aluminum electrolytic capacitor known as a large capacity capacitor.

Therefore, in designing an electric double layer capacitor, it is usually important not to impair the large capacitance described above or to obtain a larger capacitance.
That is, in FIG. 4B, when the space surrounded by the gasket 2 has a constant volume, the total amount of activated carbon powder in the polarizable electrode 30 packed in the space is maximized. This is because the effective surface area of the polarizable electrode 30 is proportional to the absolute amount of the activated carbon powder contained in the polarizable electrode if the specific surface area of the activated carbon powder used is the same.
In that case, since the polarizable electrode material is a paste-like material in which activated carbon powder and an electrolyte solution are kneaded, the ratio of the activated carbon powder to the electrolyte solution does not cause an insufficient amount of the electrolyte solution to form the electric double layer. The range is as large as possible.

However, if an attempt is made to increase the capacitance as described above, the capacitance value (initial value) immediately after manufacture will increase, but the capacitance will decrease greatly during long-term use. . In addition, ESR (E
quivalent Series Resistan
The initial value of (ce) becomes worse. This is because the ratio of the activated carbon powder in the polarizable electrode is large, in other words, the absolute amount of the electrolyte solution is small. That is, in the electric double layer capacitor shown in FIG. 4D, between the current collector 1A and the gasket 2A, between the current collector 1B and the gasket 2B,
If the amount of the electrolyte solution that escapes (dry-up) through the sealing portion between the gasket 2A and the gasket 2B in a certain time is the same, the absolute amount of the electrolyte solution contained in the polarizable electrodes 30A and 30B is smaller. However, the dry-up is relatively intense. In addition, the polarizable electrode 30
If the absolute amount of the electrolyte solution in A and 30B is small, the ionic conductivity between the polarizable electrodes 30A and 30B becomes small, and the initial value of ESR becomes large.

Therefore, the present invention relates to an electric double layer capacitor using a polarizable electrode in which an activated carbon powder contains an electrolyte solution, and has a large capacitance and a low ES in the initial stage after manufacturing.
The purpose of the present invention is to provide an electric double layer capacitor that exhibits R and has a small decrease in electrostatic capacitance due to dry-up of the electrolyte solution over a long period of time.

[0011]

The electric double layer capacitor of the present invention comprises an electrode material containing activated carbon powder and a binder.
An electric double layer capacitor using a polarizable electrode made and containing an electrolyte solution, wherein the polarizable electrode is interspersed with pores corresponding to particles having a particle size larger than the activated carbon powder and smaller than 10 μm, It is characterized in that the electrolyte solution is held also in the pores. According to one aspect of the invention
The method for producing an electric double layer capacitor is a method for producing an electric double layer capacitor using a polarizable electrode containing an electrolyte solution in activated carbon powder, and at least activated carbon powder,
An electrode material forming step of forming a paste-like polarizable electrode material containing a pore-forming material composed of polymer or copolymer particles soluble in the electrolyte solution and a binder; A step of forming a polarizable electrode by applying it to a predetermined portion of one surface of a conductive flat plate current collector to form a polarizable electrode, and a non-electroconductive frame on the outer periphery of the polarizable electrode of the current collector. the Jo gasket placed, and a gasket mounting step of bonding said said collector gasket, said partial polar electrostatic
The electrolyte solution is included in the electrode, and the electrolyte solution
The pore-forming material was melted, and the pore-forming material was present.
The steps of impregnation and pore formation for forming pores in a place, and a collector provided with the gasket and the polarizable electrode containing the electrolyte solution are two, and the polarizable electrodes are non-electroconductive and ion-permeable. And a gasket, and the gaskets are arranged so as to face each other with a separator interposed therebetween, and the gaskets are bonded together.
Method for manufacturing electric double layer capacitor according to another aspect of the present invention
The method consists of using a polarizable electrode in which activated carbon powder is impregnated with an electrolyte solution.
A method of manufacturing an electric double layer capacitor used,
At least activated carbon powder and a polymer or a polymer soluble in the electrolyte solution.
Is a pore-forming material composed of copolymer particles, and a binder
Electrode material forming paste-like polarizable electrode material containing
The process and the electron-conducting flat current collector
Before the gasket mounting process to bond the frame-shaped gasket
The polarizable electrode material is collected after the gasket mounting process is completed.
Polarization by filling in the space formed by the electric body and gasket
Forming a polarizable electrode with a polarizable electrode, and
An electrolyte solution is included, and the pores are formed by the electrolyte solution.
Dissolve the forming material, and place it in the place where the hole forming material was present.
The steps of impregnation and pore formation for forming pores, and
Current collecting with a sket and a polarizable electrode containing an electrolyte solution
Two bodies, two polarizable electrodes are non-electron conductive and ionic
Place them face-to-face with a permeable separator, and
And a coalescing step of adhering the skets together. The present invention
For manufacturing an electric double layer capacitor according to still another aspect of the present invention
The method consists of using a polarizable electrode in which activated carbon powder is impregnated with an electrolyte solution.
A method of manufacturing an electric double layer capacitor used,
At least activated carbon powder and a polymer or a polymer soluble in the electrolyte solution.
Is a pore-forming material composed of copolymer particles, and a binder
Electrode material forming paste-like polarizable electrode material containing
Process and collecting the polarizable electrode material in the form of electron-conducting flat plate
Apply to a certain part of one surface of the body to make a polarizable electrode
Forming a polarizable electrode, and forming the polarizable electrode of the current collector
A non-electroconductive and frame-shaped gasket is placed on the outer periphery, and
Gasket mounting work for adhering the current collector and the gasket
And an impregnation step in which the polarizable electrode contains an electrolyte solution
And the gasket and the polarizable electrode containing the electrolyte solution
Two current collectors with polarizable electrodes are non-electron conducting
To face through a permeable, ion-permeable separator
Arrangement and bonding process to bond gaskets together
In the pore forming material, poly-4-vinyl pyridine,
Li-3-vinyl pyridine or poly-2-vinyl pyridine
Using at least one or more particles selected from
Characterize. Electric Double Layer According to Yet Another Embodiment of the Present Invention
The method of manufacturing capacitors is to include activated carbon powder and electrolyte solution.
Manufacture of an electric double layer capacitor using a polarizable electrode
A method comprising at least activated carbon powder and the electrolyte solution.
Pore formation consisting of liquid-soluble polymer or copolymer particles
Material and a paste-like polarizable electrode material containing a binder
Electrode material formation process and electron-conducting flat plate current collector
A gasket that adheres a non-electroconductive, frame-shaped gasket to the body
The gasket mounting step and the polarizable electrode material.
The space formed by the current collector and gasket after the mounting process is completed.
Polarizable electrode formation process to fill the space and form a polarizable electrode
When the impregnation step to include Kaishitsu solution conductivity to the polarizable electrode
And the gasket and the polarizable electrode containing the electrolyte solution
Two current collectors with polarizable electrodes are non-electron conducting
To face through a permeable, ion-permeable separator
Arrangement and bonding process to bond gaskets together
In the pore forming material, poly-4-vinyl pyridine,
Li-3-vinyl pyridine or poly-2-vinyl pyridine
Using at least one or more particles selected from
Characterize.

[0012]

The polarizable electrode material of the present invention contains at least activated carbon powder, a binder, and a pore-forming material composed of particles of a nucleophilic polymer or copolymer.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a diagram occupying a cross section of an electric double layer capacitor according to the present invention after completion. FIG. 2 is a view showing a cross section of the capacitor in the process of manufacturing when the electric double layer capacitor shown in FIG. 1 is manufactured by the manufacturing method according to the first embodiment in the order of steps. Comparing FIG. 1 and FIG. 4 (d), the electric double layer capacitor according to the present invention has holes 6 in the polarizable electrodes 3 A and 3 B.
Is formed, and the electrolyte solution is held also in the pores 6, which is different from the conventional electric double layer capacitor. As will be described later, the pores 6 have a volume corresponding to particles having a particle size larger than the activated carbon powder and smaller than 10 μm.

In the electric double layer capacitor of the present invention, the pores 6 of the same size as the activated carbon powder are formed in the polarizable electrodes 3A and 3B, and the electrolyte solution is held also in the pores 6. Therefore, the absolute amount of the electrolyte solution contained in the polarizable electrodes 3A and 3B is increased as compared with the conventional one. The present invention, by increasing the absolute amount of the electrolyte solution in this way, to suppress the dry-up of the electrolyte solution, and to reduce the rate of decrease in long-term capacitance due to this,
The ionic conductivity between the polarizable electrodes 3A and 3B is improved, and the initial ESR is lowered.

The electric double layer capacitor of the present invention shown in FIG. 1 is manufactured by the manufacturing method of the first embodiment as follows. Referring to FIG. 2, first, although not shown, activated carbon powder and 7.5 wt% binder are mixed. Thereafter, particles of poly-4-vinylpyridine (hereinafter referred to as P4VP) are added to this, and the mixture is stirred to prepare a polarizable electrode material. Activated carbon powder having a particle size of 1 to 5 μm was used, and polyvinylidene fluoride was used as a binder, but polyvinyl butyrate may be used. P4VP
As the particles, solid P4VP was crushed, passed through a standard sieve of 440 mesh, and crushed to the same particle size as the activated carbon powder.

Next, the polarizable electrode material prepared as described above is applied to the current collector 1 by a method such as screen printing so as to form a thin film having a thickness of about 40 to 100 μm. It is applied and dried at a temperature of 120 ° C. to obtain the polarizable electrode 3 (FIG. 2A). In the polarizable electrode 3, P4
Particles 4 of VP are scattered. As the current collector 1, butyl rubber mixed with carbon to give conductivity is used, but a conductive plastic film can also be used.

Next, a frame-shaped gasket 2 having non-electron conductivity is placed on the outer peripheral portion of the polarizable electrode 3, and 18 kg /
A pressure of cm ² is applied to pressure-bond the current collector 1 and the gasket 2 (FIG. 2 (b)). Insulating butyl rubber is used for the gasket 2, but a thermoplastic resin film may be used.

Next, a 40 wt% sulfuric acid aqueous solution, which is an electrolyte solution, is dropped onto the polarizable electrode 3 in an amount equal to the volume of the polarizable electrode 3, and the pressure is reduced to about 1.33 × 10 ³ Pa.
The polarizable electrode 3 is impregnated with a sulfuric acid aqueous solution (see FIG. 2).
(C)).

After that, two current collectors prepared in the above steps and provided with a polarizable electrode impregnated with an electrolyte solution and a gasket are prepared, and each polarizable electrode 3A, 3B is a porous separator made of polyethylene. 5 so that they face each other, and the temperature of 120 ° C. and 18 k
Applying a pressure of g / cm ² for 20 minutes, two gaskets 2
A and 2B are heat-sealed (FIG. 2 (d)) to complete the electric double layer capacitor according to the present embodiment (FIG. 1). still,
Polypropylene fill can also be used for the porous separator 5.

In the electric double layer capacitor of the present embodiment, in the electrolyte solution impregnation step shown in FIG. 2 (c), the particles 4 of P4VP, which is a polymer containing a nitrogen atom having a nucleophilicity, are polarized electrodes. 3 was quaternized by the sulfuric acid aqueous solution impregnated in 3 and dissolved in the sulfuric acid aqueous solution, and the P4VP particles 4
After the existence of the holes, the holes 6 are formed, and at the same time, the sulfuric acid aqueous solution is retained in the holes 6 formed at the same time. As a result, the absolute amount of the electrolyte solution in the polarizable electrode 3 is increased as compared with the conventional case.
Further, it is considered that the formation of the holes 6 enables ions in the electrolyte solution to move smoothly without being affected by intermolecular force. After all, compared with the conventional electric double layer capacitor, the two polarizable electrodes 3A, 3
The ionic conductivity between B is increased, the ESR at the initial stage is improved accordingly, and the absolute amount of the original electrolyte solution is larger than that in the conventional case, so that the rate of decrease in capacitance over a long period of time becomes small.

In order to confirm the above effects, the present inventor has
An electric double layer capacitor in which the addition rate of P4VP in the polarizable electrode material was changed was produced and subjected to a high temperature load test to evaluate the initial value of ESR and the reduction rate of the electrostatic capacity after the test. The evaluation results are shown in Table 1. In the evaluation sample, the addition ratio of P4VP particles to activated carbon powder and 7.5 wt% binder was 0 (conventional electric double layer capacitor), 1.0,
There were 5 levels of 3.0, 10.0, and 20.0 wt%, and the number of samples at each level was 5. High temperature load test, temperature 60 ℃
0.8V to the electric double layer capacitor of each sample in the atmosphere of
The voltage was applied for a long time, and the rate of change of the capacitance value after 500 hours was measured. The values shown in Table 1 are average values of 5 samples each.

[0023]

[Table 1]

Referring to Table 1, as the added amount of P4VP particles gradually increases from 0 wt% to 10 wt%, E
The initial value of SR and the decrease in capacitance due to the high temperature load test both decrease. However, in the case of the addition ratio of 0 wt%, that is, the conventional electric double layer capacitor and 1.0 wt% of the capacitor, the reduction rate of the capacitance after the high temperature load test is almost the same, and compared with the capacitors of other addition amounts. Therefore, in order to effectively suppress the decrease in capacitance caused by dry-up, the addition rate of P4VP particles should be 3 wt%.
It can be said that the above effect must be obtained and the larger the addition rate, the greater the effect. However, P4V
When the addition rate of P particles was 20 wt%, the initial value of ESR increased as compared with the case of no addition (conventional electric double layer capacitor). It is considered that this is because the onium salt generated by quaternization of P4VP has an electrical insulating property and thus has an increased internal resistance. From the above, P4
The addition rate of VP particles is preferably in the range of 3 to 10 wt%.

Next, in order to investigate the influence of the particle size of the P4VP particles, when P4VP particles having a particle size of 10 μm were added, voids that should have occurred in the polarizable electrode 3 could not be confirmed. It is considered that this is because the pores formed due to the large diameter of the particles were crushed. From this result, it can be said that the particle size of the P4VP particles to be added must be smaller than 10 μm. However, the function and effect of the present invention are that the polarizable electrode 3 has the pores 6 of the same size as or larger than the activated carbon powder scattered and the electrolyte solution is held in the pores 6 to polarize. It can be said that the particle size of the P4VP particles 4 must be at least as large as the particle size of the activated carbon powder, since it is considered that the particle size is obtained by increasing the absolute amount of the electrolyte solution in the electrode as compared with the conventional one.

Next, a second embodiment of the present invention will be described. In the present embodiment, poly-2-vinylpyridine is used as the pore-forming material added to the polarizable electrode material, and the electric double layer capacitor shown in FIG. 1 is manufactured in the order of steps shown in FIG. It was manufactured in the same process order as when manufacturing the multilayer capacitor. Referring to FIG. 3, which shows a cross-sectional view of a process of manufacturing the electric double layer capacitor according to the second embodiment in the order of steps, first, a flat plate-shaped current collector 1 made of a conductive material is prepared, and a gasket 2 is provided thereon. Are adhered (FIG. 3 (a)).

Although not shown, in addition to the above steps, a paste-like polarizable electrode material is prepared by mixing activated carbon powder, a binder and poly-2-vinylpyridine. The added amount of poly-2-vinylpyridine is the same as the added amount in the first embodiment.

Next, the paste-like polarizable electrode material 3 is filled in the space surrounded by the gasket 2 by the doctor blade method (FIG. 3 (b)). Two such current collectors filled with polarizable electrode material are prepared. Next, a 40 wt% sulfuric acid aqueous solution, which is an electrolyte solution, is dropped onto the polarizable electrode 3 in an amount equal to the volume of the polarizable electrode 3. The pressure is reduced to impregnate the polarizable electrode 3 with a sulfuric acid aqueous solution (see FIG. 3).
(C)).

After that, two current collectors prepared in the above steps and provided with a polarizable electrode impregnated with an electrolyte solution and a gasket are prepared, and the polarizable electrodes 3A and 3B face each other via a separator 5. So that the two gaskets 2A and 2B are heat-sealed (FIG. 3 (d)) to complete the electric double layer capacitor (FIG. 3). 1).

When the electric double layer capacitor according to the present embodiment was subjected to a high temperature load test under the same conditions as in the first embodiment, the same result as in the first embodiment was obtained, and It was confirmed that poly-2-vinylpyridine is also effective as a pore-forming material.

When the screen printing method is used as the method of forming the polarizable electrode 3 on the current collector 1 as in the first embodiment, a thin polarizable electrode is formed with high precision in both thickness and plane dimensions. However, the device becomes complicated and expensive accordingly. In addition, subsequent steps (FIG. 2B)
Then, it becomes necessary to align the polarizable electrode 3 and the gasket 2, which complicates the process. On the other hand, as in the second embodiment, the gasket 2 is first attached to the current collector 1, and then the polarizable electrode material is applied into the gasket 2 with a doctor blade or a squeegee. By doing so, since alignment is not particularly required, a simple and inexpensive device is sufficient and the process is simplified. Although the manufacturing method of the second embodiment is inferior to the manufacturing method of the first embodiment in terms of the thickness and dimensional accuracy of the polarizable electrode, it is possible to form the polarizable electrode having a relatively large thickness and a large size at a low cost. Suitable for when.

Here, in the first and second embodiments, the holes 6 are scattered in the polarizable electrodes 3A and 3B.
Poly-4-, a polymer containing a nucleophilic nitrogen atom
Since vinyl pyridine and poly-2-vinyl pyridine are quaternized by an acidic electrolyte solution to dissolve into an osmium salt and dissolve therein, the same nucleophilic nitrogen atom is contained as a pore-forming material. It is considered that the same effect can be obtained by using poly-3-vinylpyridine having the same properties as poly-4-vinylpyridine or poly-2-vinylpyridine in the polymer.

[0033]

As described above, according to the present invention,
It is possible to provide an electric double layer capacitor having a low equivalent series resistance and excellent stability of electrostatic capacitance value for a long period of time.

[Brief description of drawings]

FIG. 1 is a diagram occupying a cross section of an electric double layer capacitor according to the present invention after completion.

FIG. 2 is a diagram showing a cross section of the electric double layer capacitor in the process of manufacturing according to the first embodiment in the order of steps.

FIG. 3 is a diagram showing a cross section of the electric double layer capacitor in the process of manufacturing according to the second embodiment in the order of steps.

FIG. 4 is a diagram showing a cross section of a conventional electric double layer capacitor in the process of being manufactured in the order of steps.

[Explanation of symbols]

1,1A, 1B Current collector 2,2A, 2B gasket 3,3A, 3B Polarizing electrodes 4 P4VP particles 5 separator 6 holes 30, 30A, 30B Polarizing electrodes

─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-59-90919 (JP, A) JP-A-2-82507 (JP, A) JP-A-63-196028 (JP, A) JP-A-2000-228334 (JP, A) JP-A-8-97101 (JP, A) JP-A-6-97004 (JP, A) JP-A-5-21274 (JP, A) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) H01G 9/058

Claims (11)

(57) [Claims] 1. An electric double layer capacitor using a polarizable electrode made of an electrode material containing activated carbon powder and a binder and containing an electrolyte solution, wherein the polarizable electrode is larger than the activated carbon powder by at least 10 μm. An electric double layer capacitor, characterized in that holes corresponding to particles of a small particle size are scattered, and the electrolyte solution is held also in the holes. 2. The electric double layer capacitor according to claim 1, wherein the electrolyte solution is an acidic aqueous solution. 3. A method of manufacturing an electric double layer capacitor using a polarizable electrode comprising an activated carbon powder and an electrolyte solution contained therein, comprising at least activated carbon powder and particles of a polymer or copolymer soluble in the electrolyte solution. An electrode material forming step of forming a paste-like polarizable electrode material containing a pore forming material and a binder; A step of forming a polarizable electrode by applying it to a part to form a polarizable electrode, arranging a non-electroconductive conductive frame-shaped gasket on the outer periphery of the polarizable electrode of the current collector, and the current collector and the gasket A step of attaching a gasket for adhering, and adding the electrolyte solution to the polarizable electrode,
Dissolves the pore-forming material by
Impregnation and vacancy formation, which creates vacancies where they were present
The step of, and a current collector comprising the gasket and a polarizable electrode containing an electrolyte solution, two, the polarizable electrodes are arranged so as to face each other via a non-electroconductive and ion-permeable separator, A method of manufacturing an electric double layer capacitor, comprising a step of adhering gaskets together. 4. A method for producing an electric double layer capacitor using a polarizable electrode comprising an activated carbon powder and an electrolyte solution contained therein, comprising at least activated carbon powder and polymer or copolymer particles soluble in the electrolyte solution. Electrode material forming process to form a paste-like polarizable electrode material containing a hole-forming material and a binder, and a non-electroconductive, frame-shaped gasket bonded to an electron-conductive, plate-shaped current collector to the gasket installation process, the polarizable electrode material, and the gasket mounting step after the end of the current collector and the gasket and is filled in the space polarizable electrode and forming polarizable electrode forming step being formed by the partial Including an electrolyte solution in the polar electrode, the electrolyte solution
Dissolves the pore-forming material by
Impregnation and vacancy formation, which creates vacancies where they were present
The step of, and a current collector comprising the gasket and a polarizable electrode containing an electrolyte solution, two, the polarizable electrodes are arranged so as to face each other via a non-electroconductive and ion-permeable separator, A method of manufacturing an electric double layer capacitor, comprising a step of adhering gaskets together. 5. Polarization in which an activated carbon powder contains an electrolyte solution
It is a method of manufacturing an electric double layer capacitor using a conductive electrode.
And at least activated carbon powder and a soluble polymer in the electrolyte solution.
For forming pores composed of particles of a polymer or a copolymer, and a binder
Electrode material for forming a paste-like polarizable electrode material containing
One of the forming step and the above-mentioned polarizable electrode material is an electronically conductive flat plate current collector.
A polarizable electrode formed by applying it to a predetermined part of the surface of the
A step of forming a pole and a non-electroconductive frame around the polarizable electrode of the current collector.
-Shaped gasket is arranged, and the current collector and the gasket are arranged.
A step of attaching a gasket for adhering to each other, an impregnation step of allowing the polarizable electrode to contain an electrolyte solution, and a polarizable electrode containing the gasket and the electrolyte solution.
Two current collectors that have polarizable electrodes
Arranged to face each other through an ion-permeable separator
And, and a coalescing step of bonding the gasket to each other, before
For the pore forming material, poly-4-vinylpyridine, poly-3
-Selected from vinyl pyridine or poly-2-vinyl pyridine
Characterized by using at least one type of particles
Method of manufacturing the electric double layer capacitor to be. 6. Polarization in which an activated carbon powder contains an electrolyte solution
It is a method of manufacturing an electric double layer capacitor using a conductive electrode.
At least activated carbon powder and a soluble polymer in the electrolyte solution.
For forming pores composed of particles of a polymer or a copolymer, and a binder
Electrode material for forming a paste-like polarizable electrode material containing
In the formation process, a non-electroconductive and frame-shaped collector is attached to the electron-conductive and flat collector.
After the gasket mounting step for adhering the sket and the polarizable electrode material after the gasket mounting step is completed.
Fill the space formed by the current collector and the gasket
It comprises a polarizable electrode forming step of forming a polar electrode, an impregnating step of impregnating the polarizable electrode with an electrolyte solution, a gasket and a polarizable electrode containing the electrolyte solution.
Two current collectors that have polarizable electrodes
Arranged to face each other through an ion-permeable separator
And a process of adhering the gaskets together.
For the pore forming material, poly-4-vinylpyridine, poly-3
-Selected from vinyl pyridine or poly-2-vinyl pyridine
Characterized by using at least one type of particles
Method of manufacturing the electric double layer capacitor to be. 7. The method of manufacturing an electric double layer capacitor according to claim 3 , wherein an acidic aqueous solution is used as the electrolyte solution. 8. The electric double layer capacitor according to claim 3 , wherein particles of a polymer or a copolymer containing a nucleophilic nitrogen atom are used as the pore forming material. Production method. 9. The pore-forming material comprises at least one kind of particles selected from poly-4-vinylpyridine, poly-3-vinylpyridine or poly-2-vinylpyridine. Item 5. A method for manufacturing an electric double layer capacitor according to items 3 to 4 . 10. In the electrode material forming step, the content ratio of the hole forming material in the polarizable electrode material is 3 wt% or more 10
7. The method for manufacturing an electric double layer capacitor according to claim 3 , wherein the content is set to not more than wt%. The particle size of 11. The pore-forming agent, characterized by less than 10μm by greater than said activated carbon powder, a manufacturing method of an electric double layer capacitor according to any one of claims 3 to 10.