JP2009246136A - Organic electrolyte capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electrolyte capacitor allowing lithium ions to be uniformly and easily carried by a negative electrode, capable of obtaining high energy density, high output and low resistance, and allowing industrial production. <P>SOLUTION: The organic electrolyte capacitor includes a positive electrode, the negative electrode, and an organic electrolyte capable of transferring lithium ions. The organic electrolyte capacitor is structured such that each of the positive electrode and the negative electrode includes a collector having a through-hole penetrating the front and back surfaces; and lithium ions are previously carried by the negative electrode by moving the lithium ions through the through-holes formed on the collectors respectively constituting the positive electrode and the negative electrode by electrochemical contact between a lithium ion supply source arranged opposite to the positive electrode or the negative electrode, and the negative electrode and/or the positive electrode. The organic electrolyte capacitor is characterized in that at least either of the collector constituting the positive electrode and the collector constituting the negative electrode is formed of metal foil with a through-hole formed thereon by mechanical punching. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic electrolyte capacitor, and more particularly to an organic electrolyte capacitor including an organic electrolyte capable of transporting a positive electrode, a negative electrode, and lithium ions.

  Conventionally, as an organic electrolyte capacitor, a positive electrode and a negative electrode have been proposed that have an electric device element and an organic electrolyte solution that are wound or alternately stacked via a separator, Although the organic electrolyte capacitor having such a configuration is expected to have high performance, a lithium ion supply source (metal ion supply source) made of, for example, lithium foil is disposed on the negative electrode so as to face the negative electrode or the positive electrode, for example. Therefore, it is necessary to dope lithium ions (metal ions) in advance, and this doping process takes a very long time, and it is not easy to uniformly carry lithium ions on the entire negative electrode, so that practical application is difficult. It was.

  Thus, in recent years, as an organic electrolyte capacitor, comprising an electric device element and an organic electrolyte having a configuration in which a positive electrode and a negative electrode are wound or alternately stacked via a separator, the positive electrode and the negative electrode, The thing of the structure provided with the electrical power collector which has a through-hole which penetrates front and back is proposed (refer patent document 1 and patent document 2).

  In the organic electrolyte capacitor having such a configuration, since the current collector constituting the positive electrode and the negative electrode is provided with a through-hole penetrating the front and back surfaces, the lithium ion is not blocked by the current collector. Since the electric device element has a configuration in which the positive electrode and the negative electrode are wound or alternately stacked via a separator, the lithium can pass through the through hole. Lithium ions can be electrochemically supported not only on the negative electrode located in the vicinity of the ion supply source but also on the negative electrode located at a location distant from the lithium ion supply source.

  However, the current collector constituting the positive electrode and the negative electrode is, for example, a metal as a raw material, such as expanded metal obtained by making a staggered cut in a metal foil and forming a mesh while spreading the cut. When a through-hole is formed in a flat metal material such as a foil, since the metal material is processed with deformation, metal stress occurs in the processing process, and the metal Due to stress, the metal strength of the resulting current collector decreases, and as a result, it is difficult to increase the coating speed, it is difficult to reduce the thickness, and it is difficult to design a higher energy density. There is a problem that.

JP 2006-286919 A JP 2008-60477 A

  The present invention has been made based on the above circumstances, and the object thereof is to uniformly and easily carry lithium ions on the negative electrode, and to obtain high energy density, high output and low resistance. And providing an organic electrolyte capacitor capable of industrial production.

The organic electrolyte capacitor of the present invention includes a positive electrode containing a material capable of reversibly supporting lithium ions and / or anions as an active material, a negative electrode containing a material capable of reversibly supporting lithium ions as an active material, An organic electrolyte capable of transporting lithium ions,
The positive electrode and the negative electrode each include a current collector having a through-hole penetrating the front and back surfaces, and the negative electrode includes a lithium ion supply source disposed opposite the positive electrode or the negative electrode, and the negative electrode and / or the positive electrode An organic electrolyte capacitor having a structure in which lithium ions are supported in advance by moving lithium ions through a through-hole provided in a current collector constituting each of a positive electrode and a negative electrode by electrochemical contact,
At least one of the current collector that constitutes the positive electrode and the current collector that constitutes the negative electrode is made of a metal foil in which through holes are formed by mechanical punching.

  The organic electrolyte capacitor of the present invention preferably has a structure in which positive electrodes and negative electrodes are alternately stacked via separators.

  In the capacitor for knowing organic electrolysis of the present invention, it is preferable to have a structure in which a positive electrode and a negative electrode are wound through a separator.

  According to the organic electrolyte capacitor of the present invention, the current collectors constituting the positive electrode and the negative electrode are each provided with a current collector having through holes penetrating the front and back surfaces, and the current collector is through-holed by mechanical punching. Therefore, the lithium ion can be reliably supported electrochemically from the lithium ion supply source to the negative electrode through the through hole, and the through hole is formed. The metal foil is not deformed with the processing for the purpose, so that metal stress does not occur in the manufacturing process, and as a result, before being subjected to processing for forming a through hole in the current collector itself. Since the metal strength of the metal foil as the raw material can be maintained, the current collector can be made thin, and high energy density, high output, and low resistance can be obtained. Moreover possible productivity is high coating speed is capable of high industrial production.

  Hereinafter, embodiments of the present invention will be described in detail.

FIG. 1 is an assembled perspective view for explaining an example of the configuration of the organic electrolyte capacitor of the present invention.
This organic electrolyte capacitor 10 is a lithium ion capacitor which is a kind of organic electrolyte capacitor.
In the electric device element 11 constituting the organic electrolyte capacitor 10, a plurality of plate-like positive electrodes and plate-like negative electrodes are alternately laminated via separators, and a lithium foil is further placed on the metal support via the separators. A lithium electrode (lithium ion supply source) attached to the electrode is laminated, and the plurality of positive electrodes are electrically connected to a positive electrode terminal 12A made of, for example, aluminum as a common positive electrode lead member, and a plurality of negative electrodes The lithium electrode and the negative electrode lead member are commonly connected to a negative electrode terminal 12B made of, for example, copper, and the tips of the positive electrode terminal 12A and the negative electrode terminal 12B protrude from each other. The outer peripheral film 22B is sandwiched between the upper outer film 22A and the lower outer film 22B. That.
By injecting the organic electrolyte into the airtight space for accommodating the electric device elements inside the outer container, electrochemical contact is generated between the lithium electrode and the negative electrode and / or the positive electrode, and the positive electrode and the negative electrode. The lithium ion is moved through the through-hole provided in the electric body, and the lithium ion is supported on the negative electrode and / or the positive electrode, whereby the organic electrolyte capacitor 10 can be manufactured.

〔Electrolytes〕
The organic electrolyte that constitutes the organic electrolyte capacitor is not particularly limited as long as it can transfer lithium ions, and the electrolyte is dissolved in an appropriate solvent. Examples of the solvent include ethylene carbonate, Non-protons such as propylene carbonate, 1-fluoroethylene carbonate, 1- (trifluoromethyl) ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane Organic solvents may be mentioned, and these may be used alone or in combination of two or more. Further, as the electrolyte, for example, LiI, LiCIO ₄ , LiAsF ₄ , LiBF ₄ , LiPF ₆ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiN ( FSO ₂ ) _{2 and the} like.

[Positive electrode active material]
The positive electrode active material constituting the organic electrolyte capacitor of the present invention is a material that can reversibly carry lithium ions and / or anions such as tetrafluoroborate.
As such a positive electrode active material, various materials can be cited, and polyacene having a hydrogen atom / carbon atom ratio of 0.50 to 0.05, which is a heat-treated product of activated carbon and an aromatic condensation polymer. Preferred examples include polyacenic organic semiconductors (PAS) having a skeleton structure, and activated carbon is particularly preferable.

Since PAS has an amorphous structure, it does not undergo structural changes such as swelling / shrinkage with respect to insertion / extraction of lithium ions, and the obtained lithium ion capacitor has excellent cycle characteristics. In addition, since the molecular structure is isotropic with respect to insertion / extraction of lithium ions (higher order structure), the obtained lithium ion capacitor can be rapidly charged and rapidly discharged.
The aromatic condensation polymer that is a precursor of PAS is a condensate of an aromatic hydrocarbon compound and an aldehyde. Examples of the aromatic hydrocarbon compound include phenols such as phenol, cresol, and xylenol; Examples thereof include methylene and bisphenols represented by (1); hydroxy and biphenyls; hydroxynaphthalenes, and among these, phenols can be particularly preferably used.

[In said general formula (1), x and y are the integers of 0-2 each independently. ]

  As the aromatic condensed polymer, a part of the aromatic hydrocarbon compound having a phenolic hydroxyl group is substituted with an aromatic hydrocarbon compound having no phenolic hydroxyl group, such as xylene, toluene, aniline, etc. A modified aromatic condensation polymer, specifically, a condensate of phenol, xylene and formaldehyde, a modified aromatic polymer substituted with melamine or urea, and the like can also be used. Moreover, furan resin can also be used suitably.

Such a PAS can be manufactured as follows. That is, the aromatic condensation polymer is gradually heated to a suitable temperature of 400 to 800 ° C. in a non-oxidizing atmosphere (including a vacuum), whereby a hydrogen atom / carbon atom ratio (hereinafter referred to as “H”). / C ") is an insoluble and infusible substrate having a thickness of 0.5 to 0.05, preferably 0.35 to 0.10, and this insoluble and infusible substrate is subjected to a non-oxidizing atmosphere (including vacuum). ), Gradually heated to an appropriate temperature of 350 to 800 ° C., preferably 400 to 750 ° C., and then thoroughly washed with water or dilute hydrochloric acid, so that H / C is in the above range, And PAS whose BET specific surface area is 600 m < ² > / g or more can be obtained, for example.
In the PAS obtained as described above, the position of the main peak is present at 24 ° or less expressed by 2θ by X-ray diffraction (CuKα), and between 41 to 46 ° in addition to the main peak. It is detected that other broad peaks are present. That is, the PAS has a polyacene-based skeleton structure in which an aromatic polycyclic structure is appropriately developed and has an amorphous structure, and thus it is considered that lithium ions can be stably doped. .

As the positive electrode active material, those having a wide particle size distribution are preferably used. For example, those having a 50% volume cumulative diameter (D ₅₀ ) of 2 μm or more are preferable, more preferably 2 to ₅₀ μm, and particularly preferably 2 to 20 μm. It is.
Moreover, as a positive electrode active material, that whose average pore diameter is 10 nm or less is preferable, that whose specific surface area is 600-3000 m < ² > / g is preferable, More preferably, it is 1300-2500 m < ² > / g.

[Method for producing positive electrode]
The positive electrode constituting the organic electrolyte capacitor of the present invention is manufactured from a positive electrode active material, a binder, and a conductive agent used as necessary.
Specifically, for example, a positive electrode active material, a binder, and a conductive agent used as necessary are dispersed in an aqueous medium to form a slurry, and the slurry is applied to a current collector, or the above slurry Can be formed in advance into a sheet shape, which is preferably attached to a current collector using a conductive adhesive.

  The amount of the binder used varies depending on the electrical conductivity of the positive electrode active material, the shape of the positive electrode to be formed, etc., but it is preferably 1 to 20% by mass, more preferably 2 to 10%, based on the positive electrode active material. % By mass.

Examples of the conductive agent used as necessary to form the positive electrode include acetylene black, ketjen black, furnace black, channel black, lamp black, graphite, and metal powder.
The amount of the conductive agent used varies depending on the electrical conductivity of the positive electrode active material, the shape of the positive electrode to be formed, etc., but is preferably 1 to 20 parts by mass, more preferably 2 to 20 parts per 100 parts by mass of the positive electrode active material. The mass part.

[Negative electrode active material]
The negative electrode active material constituting the organic electrolyte capacitor of the present invention is a material that can reversibly carry lithium ions.
Examples of such negative electrode active materials include carbon materials such as graphite, non-graphitizable carbon, hard carbon, and coke, and polyacene organic semiconductors (PAS) described above as positive electrode active materials. As the negative electrode active material, specifically, a carbonized phenol resin or the like, activated as necessary, and then pulverized can be used.

The negative electrode active material preferably has a 50% volume cumulative diameter (D ₅₀ ) of, for example, 0.5 to 30 μm, more preferably 0.5 to 15 μm, and particularly preferably 0.5 to 6 μm.
As the negative electrode active material preferably has a specific surface area of 0.1~2000m ² / g, more preferably 0.1~1000m ² / g, even more preferably at 0.1~600m ² / g is there.

[Method for producing negative electrode]
The negative electrode constituting the organic electrolyte capacitor of the present invention is manufactured from a negative electrode active material, a binder, and a conductive agent used as necessary.
Specifically, as in the positive electrode described above, the same means as in the positive electrode can be used. That is, for example, a negative electrode active material, a binder, and a conductive agent that is used as necessary are dispersed in an aqueous medium to form a slurry, and the slurry is applied to a current collector, or the above slurry is preliminarily sheeted. Examples of the method include forming the film into a shape and sticking it to a current collector, preferably using a conductive adhesive.

Examples of the binder for forming the negative electrode include rubber binders such as styrene-butadiene rubber (SBR) and nitrile rubber (NBR); fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride; polypropylene and polyethylene A thermoplastic resin such as polyacrylate can be used.
Although the usage-amount of a binder changes also with the electrical conductivity of a negative electrode active material, the shape of the negative electrode to form, etc., it is preferable to add in the ratio of 1-20 mass parts with respect to 100 mass parts of negative electrode active materials.

  Examples of the conductive agent used as necessary to form the negative electrode include the same conductive agents used as necessary to form the positive electrode, and the amount used is also the same. Range.

[Current collector]
As the positive electrode current collector and the negative electrode current collector constituting the organic electrolyte capacitor of the present invention, it is necessary that at least one of them is made of a metal foil in which through holes are formed by mechanical punching. Is done.
Here, the current collector constituting the positive electrode and the negative electrode may be made of a metal foil in which one of the holes is formed by mechanical punching, but a higher effect can be obtained. Both are preferably made of a metal foil in which through holes are formed by mechanical punching.

  As a method for forming a through-hole by mechanical punching of a metal foil as a raw material of a current collector, for example, a punching method or a pressing method for making a hole by reciprocating a pin, a number of methods on the surface A method such as a rotary roll punching method in which a hole is made by allowing a metal foil to pass through a roll having a pin placed thereon may be used.

The current collector constituting the positive electrode is made of, for example, aluminum or stainless steel, and the thickness is preferably 5 to 50 μm, and particularly preferably 7 to 35 μm.
When the thickness of the current collector of the positive electrode is less than 5 μm, the current collector itself is insufficient in strength and may be difficult to handle, whereas when the thickness exceeds 50 μm, As the weight of the current collector itself increases, the weight of the positive electrode increases and the energy density tends to decrease.

The current collector constituting the negative electrode is made of, for example, copper, stainless steel, nickel, etc., and the thickness is preferably 5 to 40 μm, and particularly preferably 7 to 25 μm.
When the thickness of the current collector of the negative electrode is less than 5 μm, the current collector itself is insufficient in strength and may be difficult to handle, whereas when the thickness exceeds 50 μm, As the weight of the current collector itself increases, the weight of the negative electrode increases and the energy density tends to decrease.

  The through hole formed in the current collector may have any shape, for example, a circular shape, a cross shape, a triangular shape, a triangular shape with rounded corners, a rhombus shape, a square shape, and a corner. A rounded square shape, a rectangular shape, a rectangular shape with rounded corners, a hexagonal shape, an elliptical shape, a circular shape, and the like are preferable, and a circular shape is particularly preferable.

Further, the current collector is preferably formed with a plurality of through holes, and the arrangement position of the plurality of through holes is not particularly limited, but is preferably a staggered arrangement.
Here, the current collector preferably has a configuration in which circular through holes are arranged in a staggered arrangement.

Regarding the size of the through hole in the current collector, the opening area is preferably 4 mm ² or less, more preferably 2 mm ² or less, and particularly preferably 1 mm ² or less.
When the opening area of the through hole exceeds 4 mm ² , the retention of the active material layer formed on the current collector is lowered, and the long-term reliability tends to be lowered.

The aperture ratio of the current collector is preferably 10% or more, more preferably 30% or more, and particularly preferably 40% or more.
When the aperture ratio is less than 10%, the pre-doping property is lowered and the productivity tends to be lowered.

[Organic electrolyte capacitor]
In particular, the organic electrolyte capacitor of the present invention is a stacked cell in which three or more layers of a plate-like positive electrode and a negative electrode are laminated via a separator, and a laminate in which a positive electrode and a negative electrode configured in a strip shape are laminated via a separator. A large-capacity body such as a wound cell wound through a separator so that adjacent positive and negative electrodes do not contact each other, or a film type cell in which a laminated cell is enclosed in an exterior film is realized. It can consist of a cell structure. These cell structures are disclosed in International Publication WO00 / 07255, International Publication WO03 / 003395, Japanese Patent Application Laid-Open No. 2004-266091, and the like.

  According to the organic electrolyte capacitor as described above, the lithium ion is reversibly supported (doping) on the negative electrode and / or the positive electrode, so that a particularly high capacity is obtained, a high energy density, a high output, and a low In addition to obtaining resistance, high withstand voltage is obtained, high durability is obtained, and high reliability is obtained.

Since the current collector is made of a metal foil in which through holes are formed by mechanical punching, the metal foil is not deformed along with the processing for forming the through holes. Therefore, metal stress does not occur in the manufacturing process, and as a result, the current collector itself can maintain the metal strength of the metal foil as a raw material before being subjected to processing for forming a through hole. . Therefore, the coating speed of the active material layer on the current collector can be increased, and productivity is increased. Furthermore, thin film processing becomes possible, and high energy density design becomes possible.
Therefore, according to the organic electrolyte capacitor of the present invention, lithium ions can be uniformly and easily supported on the negative electrode, high energy density, high output, and low resistance can be obtained, and industrial production becomes possible. .

Although the organic electrolyte capacitor of the present invention has been specifically described above, the present invention is not limited to the above examples, and various modifications can be made.
For example, the electric device element may have a structure in which a positive electrode and a negative electrode are wound through a separator.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

(Binder synthesis example)
The interior of an autoclave with an internal volume of about 6 liters equipped with an electromagnetic stirrer was thoroughly purged with nitrogen, then charged with 2.5 liters of deoxygenated pure water and 15 g of ammonium perfluorodecanoate as an emulsifier, and stirred at 350 rpm The temperature was raised to 60 ° C. Next, a mixed gas consisting of 44.2% vinylidene fluoride (VDF) and 55.8% propylene hexafluoride (HFP) was charged until the internal pressure reached 20 kg / cm ² G. Thereafter, 25 g of Freon 113 solution containing 20% of diisopropyl peroxydicarbonate as a polymerization initiator was injected using nitrogen gas to initiate polymerization. During the polymerization, a mixed gas consisting of 60.2% VDF and 39.8% HFP was successively injected so that the internal pressure was maintained at 20 kg / cm ² G. Further, since the polymerization rate decreased as the polymerization progressed, after 3 hours, the same amount of polymerization initiator as that of the previous one was injected using nitrogen gas, and the reaction was further continued for 3 hours. Thereafter, the reaction solution was cooled and the stirring was stopped, the unreacted monomer was released to stop the reaction, and latex [D] containing fine particles [D] made of a fluoropolymer was obtained. The average particle size of the fine particles [D] made of the fluoropolymer was 200 nm. Further, the mass composition ratio of each monomer determined from ¹⁹ F-NMR was VdF / HFP = 85/15.

After fully replacing the inside of a 7-liter separable flask with nitrogen, 11 parts of the latex [D] obtained (in terms of solid content), a polymerizable emulsifier “ADEKA rear soap SR1025” (manufactured by Asahi Denka) 0.1 1 part, 10 parts of methyl methacrylate, 0.5 part of acrylic acid and 170 parts of water were added, 0.3 parts of potassium persulfate and 0.1 part of sodium sulfite were added as polymerization initiators, and the reaction was carried out at 50 ° C. for 2 hours. I let you.
On the other hand, in another container, 80 parts of water, 0.5 part of “ADEKA rear soap SR1025” (manufactured by Asahi Denka), 60 parts of 2-ethylhexyl acrylate, 19 parts of methyl methacrylate, 10 parts of styrene and 0.5 parts of acrylic acid Part was added and mixed, and uniformly emulsified to obtain an emulsion. This emulsion was put into the separable flask and reacted at 50 ° C. for 3 hours and further at 80 ° C. for 1 hour. Thereafter, the reaction is stopped by cooling, the pH is adjusted to 7 with an aqueous sodium hydroxide solution, and 0.05 part of “Nopco NXZ” (manufactured by San Nopco) is added as an antifoaming agent, whereby binder particles [1] are contained. An aqueous dispersion [1] was obtained.
The number average particle diameter of the binder particles [1] in the obtained aqueous dispersion [1] was 350 nm.

<Production Example 1 of Positive Electrode>
(Preparation Example 1 of conductive paint)
Ion exchange water is added to and mixed with 95 parts by weight of carbon powder (average particle size: 4.5 μm) and 5 parts by weight of carboxymethyl cellulose, and a slurry having a solid content concentration of 30% (hereinafter also referred to as “conductive paint (1)”). Was made.
The viscosity of the obtained conductive paint (1) was measured with a B-type viscometer and found to be 510 mPa · s (50 rpm, 20.3 ° C.).

(Preparation example 1 of positive electrode paint)
Add ion-exchanged water to 87 parts by weight of activated carbon (phenolic activated carbon having a specific surface area of 2030 m ² / g and an average particle diameter of 4 μm), 4 parts by weight of acetylene black powder, 6 parts by weight of binder particles [1] and 3 parts by weight of carboxymethyl cellulose. To prepare a slurry having a solid content concentration of 35% (hereinafter also referred to as “positive electrode paint (1)”).
When the viscosity of the obtained positive electrode paint (1) was measured with a B-type viscometer, it was 2850 mPa · s (50 rpm, 19.2 ° C.).

(Coating Example 1 for Current Collector for Positive Electrode)
A current collector having an aperture ratio of 42%, having a configuration in which a plurality of circular through-holes having an opening area of 0.79 mm ² are arranged in a staggered manner on a band-shaped aluminum foil having a width of 200 mm and a thickness of 15 μm by a punching method, was obtained. . Applying the conductive paint (1) to a part of the current collector using a vertical die type double-side coating machine and applying the coating width of 130 mm and coating speed of 8 m / min on both sides. After coating on both sides with a value of 20 μm, it was dried under reduced pressure at 200 ° C. for 24 hours to form a conductive layer on the front and back surfaces of the current collector.
Thereafter, on the conductive layers formed on the front and back surfaces of the current collector, the positive electrode paint (1) is applied to both sides under a coating condition of a coating speed of 8 m / min using a vertical die type double-side coating machine. After the double-side coating was performed with the combined coating thickness target value being 150 μm, it was dried under reduced pressure at 200 ° C. for 24 hours to form a positive electrode layer on the conductive layer formed on the current collector.
A material in which a conductive layer and a positive electrode layer are laminated on a part of a strip-shaped current collector, and a portion in which the conductive layer and the positive electrode layer are laminated (hereinafter also referred to as “coating portion”) is 98 × 128 mm. The portion (hereinafter also referred to as “uncoated portion”) where no layer is formed is cut into a size of 98 × 143 mm so that it becomes 98 × 15 mm, and this is cut into a positive electrode (hereinafter “positive electrode (1 ) ").

<Preparation Examples 2 and 3 of the positive electrode>
In the positive electrode production example 1, the positive electrode (hereinafter referred to as “the positive electrode” in the same manner as in the positive electrode production example 1 except that the current collector was obtained by performing the processing shown in Table 1 on the strip-shaped aluminum foil. , Also referred to as “positive electrode (2)” and “positive electrode (3)”).

<Production Example 4 of Positive Electrode>
In the positive electrode production example 1, the positive electrode was produced except that the current collector was obtained by performing the processing shown in Table 1 (processing not mechanical punching processing according to the present invention) on the strip-shaped aluminum foil. The positive electrode was produced in the same manner as in Example 1. However, since the current collector was cut off during the process, specifically, during the application to the current collector, the positive electrode was It could not be produced.

<Fabrication Example 5>
In the positive electrode production example 1, the current collector was obtained by performing the processing shown in Table 1 (processing not mechanical punching processing according to the present invention) on the strip-shaped aluminum foil, the conductive layer, and the positive electrode layer A positive electrode (hereinafter, also referred to as “positive electrode (5)”) was produced in the same manner as in Production Example 1 of the positive electrode except that the coating speed related to the formation was 2 m / min.

<Negative electrode production example 1>
(Preparation example 1 of negative electrode paint)
Carbon ion (specific surface area 16 m ² / g, average particle diameter 4 μm) 87 parts by weight, acetylene black powder 4 parts by weight, SBR binder (JSR “TRD2001”) 6 parts by weight and carboxymethyl cellulose 3 parts by weight ion-exchanged water Were added and mixed to prepare a slurry having a solid concentration of 35% (hereinafter also referred to as “negative electrode paint (1)”).

(Coating Example 1 for Current Collector for Negative Electrode)
A current collector having an aperture ratio of 42%, having a configuration in which a plurality of circular through-holes having an opening area of 0.79 mm ² are arranged in a staggered manner on a strip-like copper foil having a width of 200 mm and a thickness of 10 μm by a punching method, was obtained. . Part of this current collector was coated with negative electrode paint (1) using a vertical die-type double-side coating machine, with a coating width of 130 mm and a coating speed of 8 m / min. After coating on both sides, the film was dried under reduced pressure at 200 ° C. for 24 hours to form negative electrode layers on the front and back surfaces of the current collector.
The material in which the negative electrode layer is formed on a part of the current collector is 1010 × 138 mm where the negative electrode layer is formed (coated part), and the part where the negative electrode layer is not formed (uncoated part) is 100. It cut | disconnected to the magnitude | size of 100x145 mm so that it might become * 15mm, and this was made into the negative electrode (henceforth "negative electrode (1)").

<Negative electrode production examples 2 and 3>
In the negative electrode production example 1, a negative electrode (hereinafter referred to as “respectively”) was prepared in the same manner as in the negative electrode production example 1 except that a current collector was obtained by performing the processing shown in Table 1 on the strip-shaped copper foil. , “Negative electrode (2)” and “Negative electrode (3)” were prepared.

<Negative electrode production example 4>
In the production example 1 of the negative electrode, the production of the negative electrode was performed except that the current collector was obtained by performing the processing shown in Table 1 on the strip-shaped copper foil (processing not mechanical punching processing according to the present invention). A positive electrode was produced in the same manner as in Example 1. However, during the process, specifically, during the application to the current collector, the current collector was cut off. It could not be produced.

<Negative electrode fabrication example 5>
In the negative electrode production example 1, the current collector was obtained by performing the processing shown in Table 1 (processing that is not mechanical punching processing according to the present invention) on the strip-shaped copper foil, and formation of the negative electrode layer A negative electrode (hereinafter also referred to as “negative electrode (5)”) was produced in the same manner as in Production Example 1 of the negative electrode except that the coating speed was 2 m / min.

[Example 1]
(Production Example 1 of Organic Electrolyte Capacitor)
First, the positive electrode (1) and the negative electrode (5) are arranged such that the coated portions overlap but the uncoated portions are on the opposite side and do not overlap, and the separator (thickness 50 μm), negative electrode, separator, positive electrode In order, using a total of 22 separators, a total of 11 negative electrodes (5), and a total of 10 positive electrodes (1), both outermost layers are formed of separators and laminated so that both lower layers are negative electrodes. An electrode laminate unit was prepared by tape-fastening the four sides of the laminate.
Next, a lithium foil having a thickness of 260 μm was prepared, the lithium foil was cut so as to be 550 mAh / g for each negative electrode active material constituting the electrode laminate unit, and this lithium foil was pressure-bonded to a stainless steel net having a thickness of 40 μm. The ion supply source was disposed on the upper side of the electrode stacking unit so as to face the negative electrode.

Then, a positive electrode terminal made of aluminum having a width of 50 mm, a length of 50 mm, and a thickness of 0.2 mm in which a sealant film is heat-sealed in advance to the uncoated portion (10 sheets) related to the positive electrode of the produced electrode laminate unit. And ultrasonic welding. In addition, the uncoated part (11 sheets) related to the negative electrode of the electrode laminate unit and the lithium foil-attached stainless steel net (one sheet) were previously sealed with a sealant film having a width of 50 mm, a length of 50 mm, A copper negative electrode terminal having a thickness of 0.2 mm was stacked and resistance welded to obtain an assembly. After that, the obtained assembly was sandwiched between two exterior aluminum laminate films, and the terminal portion 2 side and the other one side of the exterior aluminum laminate film were heat-sealed, and then the organic electrolyte was used as a propylene carbonate solvent. After injecting 50 g of a mixed solution in which LiPF ₆ was dissolved at a concentration of 1 mol / L and impregnating with vacuum, the remaining one side was heat-sealed under reduced pressure and vacuum sealing was performed. Two organic electrolyte capacitors (laminated capacitors, hereinafter also referred to as “organic electrolyte capacitors (1)”) having the configuration as shown in the drawings were manufactured.
One of the two produced organic electrolyte capacitors (1) was decomposed after 10 days, and it was confirmed that the lithium foil related to the stainless steel net with a lithium foil was completely removed.

(Capacity, internal resistance, energy density evaluation)
The obtained organic electrolyte capacitor (1) was charged with a constant current of 5 A until the cell voltage became 3.8 V, and then subjected to constant current-constant voltage charging in which a constant voltage of 3.8 V was applied for 1 hour. Next, the battery was discharged at a constant current of 5 A until the cell voltage reached 2.2V. This 3.8V-2.2V cycle was repeated, and in the third discharge, the cell capacity, the internal resistance value calculated based on the voltage drop 0.1 seconds after the start of discharge, and the energy density were measured. The results are shown in Table 2.

[Examples 2 to 5 and Comparative Example 1]
In Example 1, except that the electrodes shown in Table 2 were used, an organic electrolyte capacitor was obtained in the same manner as in Example 1, and the obtained organic electrolyte capacitor was evaluated for capacity, internal resistance, and energy density. I did it. The results are shown in Table 2.

From the results of Examples 1 to 5 and Comparative Example 1 described above, the positive electrode and the negative electrode include a current collector having a through hole penetrating the front and back surfaces, and at least one of these is a through hole by mechanical punching. It was confirmed that the energy density can be increased by being made of a metal foil in which is formed.
In addition, the organic electrolyte capacitors according to Examples 2 to 5 in which both the positive electrode and negative electrode current collectors are made of a metal foil in which through holes are formed by mechanical punching are provided as positive electrode current collectors. It was confirmed that a higher energy density can be obtained as compared with the organic electrolyte capacitor according to Example 1, which is made of a metal foil in which through holes are formed by mechanical punching.
Further, in the process of producing the positive electrode and the negative electrode (see Table 1), the current collector is applied at a high speed by using a current collector made of a metal foil having through holes formed by mechanical punching. It was confirmed that productivity could be improved.

It is an assembly perspective view for demonstrating an example of the structure of the organic electrolyte capacitor of this invention.

Explanation of symbols

10 Organic Electrolytic Capacitor 11 Electrical Device Element 12A Positive Terminal 12B Negative Terminal 22A Upper Exterior Film 22B Lower Exterior Film

Claims (3)

A positive electrode containing a material capable of reversibly supporting lithium ions and / or anions as an active material, a negative electrode containing a material capable of reversibly supporting lithium ions as an active material, and an organic electrolyte capable of transporting lithium ions And
The positive electrode and the negative electrode each include a current collector having a through-hole penetrating the front and back surfaces, and the negative electrode includes a lithium ion supply source disposed opposite the positive electrode or the negative electrode, and the negative electrode and / or the positive electrode An organic electrolyte capacitor having a structure in which lithium ions are supported in advance by moving lithium ions through a through-hole provided in a current collector constituting each of a positive electrode and a negative electrode by electrochemical contact,
An organic electrolyte capacitor, wherein at least one of the current collector constituting the positive electrode and the current collector constituting the negative electrode is made of a metal foil having a through hole formed by mechanical punching.   2. The organic electrolyte capacitor according to claim 1, wherein the organic electrolyte capacitor has a structure in which positive electrodes and negative electrodes are alternately laminated via separators.   The organic electrolyte capacitor according to claim 1, wherein the organic electrolyte capacitor has a structure in which a positive electrode and a negative electrode are wound through a separator.

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