JP2001076979A - Electric double layer capacitor and electrode material therefor - Google Patents
Electric double layer capacitor and electrode material thereforInfo
- Publication number
- JP2001076979A JP2001076979A JP25033999A JP25033999A JP2001076979A JP 2001076979 A JP2001076979 A JP 2001076979A JP 25033999 A JP25033999 A JP 25033999A JP 25033999 A JP25033999 A JP 25033999A JP 2001076979 A JP2001076979 A JP 2001076979A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- double layer
- electric double
- layer capacitor
- carbonaceous material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 46
- 239000007772 electrode material Substances 0.000 title claims description 5
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- 238000007654 immersion Methods 0.000 claims abstract description 15
- 238000005259 measurement Methods 0.000 claims abstract description 11
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- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000008151 electrolyte solution Substances 0.000 claims description 14
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- 239000003960 organic solvent Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 11
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- 230000004043 responsiveness Effects 0.000 abstract description 2
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- 150000002500 ions Chemical class 0.000 description 12
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- 230000003213 activating effect Effects 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
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- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ALOAEEKRZQMXKD-UHFFFAOYSA-N carbonic acid pyrene Chemical compound C(O)(O)=O.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34 ALOAEEKRZQMXKD-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気二重層キャパシ
タに関するものであり、より詳しくは、バックアップ電
源、車両用電源、補助電源等の各種電源に用いられる高
出力キャパシタに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric double layer capacitor, and more particularly, to a high output capacitor used for various power supplies such as a backup power supply, a vehicle power supply, and an auxiliary power supply.
【０００２】[0002]
【従来の技術】電気二重層キャパシタの電極単位面積当
たりの静電容量は、その構成及び作動原理からして、固
体としての分極性電極と、液体としての電解液の両方の
物性、形状に大きく影響を受ける。電解液に関しては、
様々な溶媒、電解質等が検討されており、ほぼ最適化さ
れているといってよい。一方、固体側が静電容量に影響
を与える物性、形状として、比表面積、電極に電荷を与
えたり取り出したりする際の抵抗、即ち電荷の材料内部
での移動に対する抵抗、電解質イオンの拡散、吸脱着等
の移動に対する抵抗等が考えられる。比表面積を大きく
すべく、キャパシタの分極性電極として、主に活性炭等
の炭素質材料を主体とした多孔質電極が用いられている
が、比表面積に関しては現在３０００ｍ2 ／ｇ程度が最
大であり、これを用いた電気二重層キャパシタの単位体
積あたりの容量もほぼ限界に達しているのが現状であ
る。2. Description of the Related Art The capacitance per unit area of an electrode of an electric double layer capacitor is large in the physical properties and shape of both a polarizable electrode as a solid and an electrolytic solution as a liquid due to its configuration and operating principle. to be influenced. As for the electrolyte,
Various solvents, electrolytes, and the like have been studied, and it can be said that they are almost optimized. On the other hand, physical properties that affect the capacitance on the solid side, such as specific surface area, resistance when applying or removing charge to the electrode, that is, resistance to movement of charge inside the material, diffusion and adsorption / desorption of electrolyte ions And the like against the movement of the like. In order to increase the specific surface area, a porous electrode mainly composed of a carbonaceous material such as activated carbon is mainly used as a polarizable electrode of a capacitor. However, the maximum specific surface area is currently about 3000 m 2 / g. At present, the capacity per unit volume of the electric double layer capacitor using this has almost reached the limit.
【０００３】特に、微小電流下のみならず大電流下でも
高容量とするためには、キャパシタの分極性電極の主た
る材料として使用する炭素質材料の表面でのイオンの移
動度が高いことが重要となる。すなわち、キャパシタの
充電・ 放電過程においては、炭素質材料の細孔内におけ
る電解質イオンの通過移動速度によりその充電特性・放
電特性が支配される。比表面積が大きくなると炭素質材
料中のより微細な細孔の占める部分が増加し、この微細
な細孔内においては、イオンのスムーズな移動が行われ
難く、導電パスが少なくなるため、現象としてイオンの
移動に対する抵抗が大きくなるという問題がある。炭素
質材料の比表面積や、内部接続抵抗等の物理特性を測定
してキャパシタに最適な炭素質材料を選択することは有
効ではあるが、大電流下でも高容量のキャパシタを得る
ためには電解質イオンが十分に早く移動できることが必
要であり、イオンが十分に早く移動できれば電荷の蓄積
（充電）、放出（放電）が十分早くできる。このような
炭素質材料を選択するには、電極の主たる材料である炭
素質材料の電解液中での挙動を把握することが必要であ
るが、そのような試みはされていない。In particular, in order to achieve a high capacity under a large current as well as a small current, it is important that the mobility of ions on the surface of a carbonaceous material used as a main material of a polarizable electrode of a capacitor is high. Becomes That is, in the charging / discharging process of the capacitor, the charge / discharge characteristics of the capacitor are controlled by the passing speed of the electrolyte ions in the pores of the carbonaceous material. When the specific surface area increases, the portion occupied by finer pores in the carbonaceous material increases, and in these fine pores, it is difficult for ions to move smoothly, and the number of conductive paths is reduced. There is a problem that resistance to the movement of ions increases. It is effective to measure the specific surface area of the carbonaceous material and physical properties such as internal connection resistance to select the most suitable carbonaceous material for the capacitor. It is necessary that ions can move sufficiently quickly. If ions can move sufficiently quickly, charge accumulation (charge) and discharge (discharge) can be performed sufficiently quickly. In order to select such a carbonaceous material, it is necessary to understand the behavior of the carbonaceous material, which is the main material of the electrode, in the electrolytic solution, but no such attempt has been made.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは、活性炭
等の炭素質材料の電解液中での電気化学的特性を総合的
に判断する簡易な方法があれば、キャパシタに使用され
る分極性電極の主成分に最適な炭素質材料を選択するこ
とができ、高出力のキャパシタが得られることを知見し
本発明に至った。SUMMARY OF THE INVENTION The present inventors have proposed a simple method for comprehensively determining the electrochemical characteristics of a carbonaceous material such as activated carbon in an electrolytic solution. The present inventors have found that an optimum carbonaceous material can be selected as a main component of a polar electrode, and that a high-output capacitor can be obtained.
【０００５】[0005]
【課題を解決するための手段】即ち、本発明の電気二重
層キャパシタは、正極、負極、及び電解液を有する電気
二重層キャパシタにおいて、前記正極及び／又は前記負
極は、下記特性Ａを有する炭素質材料を主成分とする分
極性電極からなることを特徴とするものである。特性Ａ
とは、前記電解液中でクロノアンペロメトリー法により
浸漬電位から浸漬電位に対して＋５０ｍＶステップさせ
る測定において、ステップ開始時から１００ｍｓ後に測
定される電流値がステップ開始直後の最大電流値の１０
％以下であることをいう。ここで、前記電解液が有機系
溶媒に電解質を溶解した非水系電解液であるのが好まし
い。That is, an electric double layer capacitor according to the present invention is an electric double layer capacitor having a positive electrode, a negative electrode, and an electrolytic solution, wherein the positive electrode and / or the negative electrode has the following characteristic A: A polarizable electrode mainly composed of a porous material. Characteristic A
Means that the current value measured 100 ms after the start of the step is the maximum current value immediately after the start of the step in the measurement in which the immersion potential is increased by +50 mV from the immersion potential by the chronoamperometry method in the electrolytic solution.
% Or less. Here, the electrolyte is preferably a non-aqueous electrolyte obtained by dissolving an electrolyte in an organic solvent.
【０００６】本発明はまた、上記電気二重層キャパシタ
のための上記特性Ａを有する炭素質材料からなる電極材
料を提供する。The present invention also provides an electrode material made of a carbonaceous material having the above characteristic A for the electric double layer capacitor.
【０００７】[0007]
【発明の実施の形態】本発明者は、電解質イオンの炭素
質材料細孔内での移動しやすさを検討するには、電解液
中での炭素質材料単独の電気化学的挙動を測定すること
が重要であり、このような測定により、キャパシタにお
いてもイオンの移動度の高い炭素質材料を選択でき、こ
の材料を用いて分極性電極を作製すれば高出力のキャパ
シタが得られることを知見し本発明に至った。BEST MODE FOR CARRYING OUT THE INVENTION The present inventor measures the electrochemical behavior of a carbonaceous material alone in an electrolytic solution in order to examine the ease of movement of electrolyte ions within the pores of the carbonaceous material. It is important to know that such a measurement enables the selection of a carbonaceous material with high ion mobility even in a capacitor, and that a high-output capacitor can be obtained by using this material to produce a polarizable electrode. This has led to the present invention.
【０００８】特開平１１−０１１９２１号公報には、活
性炭粉末とフェノール、ポリビニルブチラール等の炭化
性樹脂とを混合して造粒体を調製し成形後炭化熱処理し
て固形状活性炭を得てこれをシート状にして静電容量を
測定する試みが開示されている。しかし、この方法で
は、固形状、または、シート状にする工程で、各工程条
件のばらつきや、雰囲気条件等を一定にすることが困難
なので、外乱を受けやすく、十分に活性炭の特徴が測定
できず、シート化する際の不具合を内包した形でしか評
価ができなかった。さらに、実際の電気二重層キャパシ
タを組立てて試験をするためには、特に非水系電解液を
使用する場合はキャパシタセル中の水分を徹底的に除去
することが必要で、１個のセルを作製するのに何日もか
かる。Japanese Patent Application Laid-Open No. 11-011921 discloses that activated carbon powder is mixed with a carbonizable resin such as phenol and polyvinyl butyral to prepare granules, which are molded, carbonized and heat-treated to obtain solid activated carbon. An attempt to measure the capacitance in the form of a sheet is disclosed. However, in this method, it is difficult to keep the process conditions uniform and the atmospheric conditions constant in the process of forming a solid or sheet, so that it is easily affected by disturbance, and the characteristics of the activated carbon can be sufficiently measured. However, the evaluation could be made only in a form that included the problem when forming the sheet. Furthermore, in order to assemble and test an actual electric double layer capacitor, it is necessary to thoroughly remove the water in the capacitor cell, especially when a non-aqueous electrolyte is used. It takes days to do.
【０００９】これに対し、本発明の方法は、非常に簡易
な測定で、高い精度で炭素質材料の電気化学的挙動を測
定でき、しかもその炭素質材料を用いてキャパシタを組
上げた際の電気特性との相関関係が高い。本発明の測定
条件を用いれば、任意に選択した炭素質材料一粒をマイ
クロエレクトロード（微小電極）としてその特性を測定
することができ、しかも実際のキャパシタに用いる同一
電解液に対して測定することができるためであると考え
られる。また、分極性電極に用いられる他の材料の影響
を受けない炭素質材料単独の電気化学的特性を評価でき
る利点もある。On the other hand, the method of the present invention can measure the electrochemical behavior of a carbonaceous material with a very simple measurement and high accuracy, and furthermore, the electric power when a capacitor is assembled using the carbonaceous material. High correlation with characteristics. By using the measurement conditions of the present invention, it is possible to measure the characteristics of one selected carbonaceous material as a microelectrode (microelectrode), and to measure the same electrolytic solution used for an actual capacitor. It is thought that it is possible. Another advantage is that the electrochemical properties of the carbonaceous material alone, which is not affected by other materials used for the polarizable electrode, can be evaluated.
【００１０】以下に、本発明を詳細に説明する。本発明
の電気二重層キャパシタは、正極、負極、及び非水系電
解液を有する構成であるが、この正極及び負極の少なく
とも一方が、高レスポンス性である炭素質材料を主成分
とする分極性電極であることを特徴としている。Hereinafter, the present invention will be described in detail. The electric double layer capacitor of the present invention has a configuration including a positive electrode, a negative electrode, and a non-aqueous electrolyte. At least one of the positive electrode and the negative electrode is a polarizable electrode mainly composed of a highly responsive carbonaceous material. It is characterized by being.
【００１１】本発明の電気二重層キャパシタを構成する
正極及び負極の少なくとも一方の電極の主成分をなす炭
素質材料としては、比表面積が大きい材料を挙げること
ができ、活性炭、ポリアセン、カーボンブラック等から
なりかつ比表面積が２００ｍ 2 ／ｇ〜３５００ｍ2 ／ｇ
である粉末を好ましく挙げることができる。また、カー
ボンファイバ、カーボンウィスカ、グラファイト等の繊
維又は粉末も比表面積が２００ｍ2 ／ｇ〜３５００ｍ2
／ｇであれば好ましく使用することができる。Constituting the electric double layer capacitor of the present invention
Charcoal that forms the main component of at least one of the positive and negative electrodes
Materials with a large specific surface area should be used as material
From activated carbon, polyacene, carbon black, etc.
200m Two/ G ~ 3500mTwo/ G
The following powder can be preferably mentioned. Also the car
Fibers such as Bonfiber, carbon whisker, and graphite
The specific surface area of fiber or powder is 200mTwo/ G ~ 3500mTwo
/ G can be preferably used.
【００１２】活性炭は、石油等の鉱物系、やしがら系、
フェノール系、レーヨン系、アクリル系、ピッチ系等の
それぞれ単独及び、同一系、あるいは異なる系の複合材
料を炭化、賦活することで得ることができる。賦活方法
としては、水蒸気賦活による方法、例えばアルカリ賦活
のような薬品賦活による方法、酸化性雰囲気中で活性炭
源を部分的に酸化させる酸化性雰囲気賦活による方法、
及びそれらの単独、あるいは複数の手法の複数回賦活に
より得ることができる。 活性炭の粒径は、電極の薄膜化が容易になり、キャパシ
タの容量密度も高くなりやすいため、０．１μｍ〜１０
０μｍであることが好ましく、更に好ましくは１μｍ〜
２０μｍである。Activated carbon includes minerals such as petroleum, palms,
It can be obtained by carbonizing and activating a phenolic, rayon-based, acryl-based, pitch-based, etc. alone or composite material of the same or different system. Examples of the activation method include a method based on steam activation, a method based on chemical activation such as alkali activation, a method based on oxidizing atmosphere activation in which an activated carbon source is partially oxidized in an oxidizing atmosphere,
And single or multiple activation by a plurality of techniques. The particle size of the activated carbon is 0.1 μm to 10 μm because the electrode can be easily formed into a thin film and the capacitance density of the capacitor is easily increased.
0 μm, more preferably 1 μm
20 μm.
【００１３】本発明で使用される炭素質材料は、高レス
ポンス性であり、その炭素質材料単独で、特性Ａを有す
る。本発明で使用される炭素質材料は、クロノアンペロ
メトリー法により浸漬電位から浸漬電位に対して＋５０
ｍＶステップさせる測定において、ステップ開始時から
１００ｍｓ後に測定される電流値がステップ開始直後の
最大電流値の１０％以下であり（特性Ａ）、５％以下で
あることが好ましい。１０％以下であると、大電流によ
る急速充放電においても高容量の電気二重層キャパシタ
が得られる。The carbonaceous material used in the present invention has high responsiveness, and has the characteristic A by itself. The carbonaceous material used in the present invention has a immersion potential of +50 with respect to the immersion potential by chronoamperometry.
In the measurement in which the step is performed in mV steps, the current value measured 100 ms after the start of the step is 10% or less of the maximum current value immediately after the start of the step (characteristic A), and is preferably 5% or less. If it is 10% or less, a high-capacity electric double layer capacitor can be obtained even in rapid charging and discharging with a large current.
【００１４】本発明において、炭素質材料の特性を確認
するためのクロノアンペロメトリー（ポテンシャルステ
ップ）法の測定条件及び測定方法は以下の通りである。 使用機器：北斗電工社製、ＨＡ−１５０ 作用電極：炭素質材料 対極：Ｐｔ板 参照電極：Ａｇ／Ａｇ+ 電極 電解液組成：実際のキャパシタに用いるものと同じもの 印加電圧：浸漬電位から、浸漬電位に対して＋５０ｍＶ
ステップさせて、電流値を連続して測定し、その間の最
大電流と、ステップ開始時から１００ｍｓ後に流れてい
る電流値を測定する。In the present invention, the measuring conditions and the measuring method of the chronoamperometry (potential step) method for confirming the characteristics of the carbonaceous material are as follows. Equipment used: HA-150, manufactured by Hokuto Denko Co., Ltd. Working electrode: Carbonaceous material Counter electrode: Pt plate Reference electrode: Ag / Ag + electrode Electrolyte composition: Same as that used for actual capacitors Applied voltage: Immersion potential from immersion potential +50 mV with respect to potential
The current value is continuously measured by stepping, and the maximum current during the measurement and the current value flowing 100 ms after the start of the step are measured.
【００１５】ここで、浸漬電位とは電流を流すことなく
電解液に炭素質材料を浸漬させたときの電位であり、 本
発明においてはこの電位を基準に電気化学的測定を行な
っている。通常炭素質材料を電解液中でクロノアンペロ
メトリー法で測定すると、測定される電流値は、静電容
量と抵抗成分からなる時定数により決められる減少曲線
を示す。ここで抵抗成分は、電気的な電子の抵抗分のみ
ならず、イオンの拡散、吸脱着抵抗も含めた全抵抗で測
定されるため、本発明において測定される電流値による
曲線は単純減少曲線に限定されない。Here, the immersion potential is a potential when a carbonaceous material is immersed in an electrolytic solution without passing an electric current. In the present invention, electrochemical measurement is performed based on this potential. Usually, when a carbonaceous material is measured in an electrolytic solution by a chronoamperometry method, the measured current value shows a decreasing curve determined by a time constant composed of a capacitance and a resistance component. Here, the resistance component is measured not only by the resistance of electric electrons but also by the total resistance including the diffusion and adsorption / desorption resistance of ions, so that the curve based on the current value measured in the present invention is a simple decrease curve. Not limited.
【００１６】なお、本発明においては電位の変化を浸漬
電位から、浸漬電位に対して＋５０ｍＶにステップ状に
変化させた場合で検討を行なっている。ステップ電位が
高過ぎると、電解液、電解質、炭素質材料の内部や外部
の反応性物質による不本意な反応電流が測定に関与する
可能性が高くなり、反対にステップ電位が低過ぎると、
電気化学的測定ノイズの影響が増加するためステップ電
位として５０ｍＶを選択している。異なるステップ電位
で測定すれば、１００ｍｓ後に流れる電流値の、最大電
流に対する割合が変化する事は容易に予想される。同様
に、本発明では、電位を変化させてから１００ｍｓ後に
流れている電流値の、最大電流に対する割合を検討して
いるが、この測定時間を変える事によって、その値自体
が変化する事は容易に予測される。In the present invention, a study is made on the case where the potential is changed stepwise from the immersion potential to +50 mV with respect to the immersion potential. If the step potential is too high, there is a high possibility that an undesired reaction current due to a reactive substance inside or outside the electrolyte, the electrolyte, and the carbonaceous material will be involved in the measurement. Conversely, if the step potential is too low,
Since the influence of the electrochemical measurement noise increases, 50 mV is selected as the step potential. If measured at different step potentials, it is easily expected that the ratio of the value of the current flowing after 100 ms to the maximum current changes. Similarly, in the present invention, the ratio of the value of the current flowing 100 ms after the potential is changed to the maximum current is examined. However, the value itself can be easily changed by changing the measurement time. Is predicted.
【００１７】本発明において、炭素質材料に対する、電
解質のプラスイオン、及びマイナスイオンの拡散速度、
吸脱着速度の影響により、電気二重層キャパシタを構成
する正極及び負極のうち少なくともどちらか一方が、上
述した特性Ａを満たす炭素質材料を主成分とする分極性
電極からなればよく、残りのもう一方の電極は特性Ａを
満たさない材料からなる分極性電極であってもよく、ま
た分極性電極でなくてもよい。例えば負極はリチウムイ
オン二次電池の負極に使用されるリチウムイオンを吸
蔵、脱離できる炭素質材料であってもよい。In the present invention, the diffusion rates of positive ions and negative ions of the electrolyte with respect to the carbonaceous material,
Due to the influence of the adsorption / desorption speed, at least one of the positive electrode and the negative electrode constituting the electric double layer capacitor only needs to be formed of a polarizable electrode mainly composed of a carbonaceous material satisfying the above-mentioned property A, and the remaining one is not. One electrode may be a polarizable electrode made of a material that does not satisfy the characteristic A, and may not be a polarizable electrode. For example, the negative electrode may be a carbonaceous material capable of inserting and extracting lithium ions used for the negative electrode of a lithium ion secondary battery.
【００１８】本発明において、キャパシタの正極及び負
極のうち少なくとも一方は、分極性電極であり、上述し
た特性Ａを有する炭素質材料を主成分とし、特に限定さ
れないが、結合材、さらに好ましくは導電材を加えて構
成される。この分極性電極は、例えば、炭素質材料の粉
末とポリテトラフルオロエチレン等の結合材と好ましく
は導電材とをアルコール等の溶媒の存在下で混練してシ
ート状に成形し、乾燥した後、導電性接着剤等を介して
集電体と接合して得られる。また、炭素質材料の粉末と
結合材及び好ましくは導電材とを溶媒と混合してスラリ
ーとし、集電体金属箔の上にコートし、乾燥して集電体
と一体化された電極を得ることもできる。In the present invention, at least one of the positive electrode and the negative electrode of the capacitor is a polarizable electrode, which is mainly composed of the carbonaceous material having the above-mentioned characteristic A, and is not particularly limited. It is constructed by adding materials. This polarizable electrode, for example, after kneading a carbonaceous material powder and a binder such as polytetrafluoroethylene and preferably a conductive material in the presence of a solvent such as alcohol to form a sheet, and after drying, It is obtained by bonding to a current collector via a conductive adhesive or the like. Also, a powder of a carbonaceous material and a binder and preferably a conductive material are mixed with a solvent to form a slurry, coated on a current collector metal foil, and dried to obtain an electrode integrated with the current collector. You can also.
【００１９】結合材としては、例えばポリテトラフルオ
ロエチレン、ポリフッ化ビニリデン、フルオロオレフィ
ン／ビニルエーテル共重合体架橋ポリマー、カルボキシ
メチルセルロース、ポリビニルピロリドン、ポリビニル
ブチラール（ＰＶＢ）等のポリビニルアルコール、又は
ポリアクリル酸、フェノール、コールタール等が使用で
きる。電極中の結合材の含有量は炭素質材料と結合材の
合量中０．５重量％〜２０重量％程度とするのが好まし
い。結合材の量が０．５重量％未満であると電極の強度
が不足し、２０重量％を超えると電気抵抗の増大や容量
の低下が起き好ましくない。電極の強度と容量バランス
から、結合材の配合量は０．５重量％〜１０重量％とす
るのがより好ましい。なお、架橋ポリマーの架橋剤とし
ては、アミン類、ポリアミン類、ポリイソシアネート
類、ビスフェノール類又はパーオキサイド類が好まし
い。Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, crosslinked polymer of fluoroolefin / vinyl ether copolymer, carboxymethyl cellulose, polyvinyl alcohol such as polyvinyl pyrrolidone and polyvinyl butyral (PVB), or polyacrylic acid, phenol , Coal tar and the like can be used. The content of the binder in the electrode is preferably about 0.5% to 20% by weight based on the total amount of the carbonaceous material and the binder. If the amount of the binder is less than 0.5% by weight, the strength of the electrode becomes insufficient, and if it exceeds 20% by weight, the electric resistance increases and the capacity decreases, which is not preferable. From the viewpoint of the strength and capacity balance of the electrode, the amount of the binder is more preferably 0.5% by weight to 10% by weight. As the crosslinking agent for the crosslinked polymer, amines, polyamines, polyisocyanates, bisphenols or peroxides are preferable.
【００２０】導電材としては、カーボンブラック、天然
黒鉛、人造黒鉛、酸化チタン、酸化ルテニウム等の粉末
が用いられる。これらのうち、少量でも導電性を向上さ
せる効果が大きいことから、カーボンブラックの１種で
あるケッチェンブラック又はアセチレンブラックを使用
するのが好ましい。また、カーボンブラックの粒径は、
０．００１μｍ〜１μｍであることが好ましく、更に好
ましくは、０．０１μｍ〜０．５μｍである。また、そ
の比表面積は、２００ｍ2 ／ｇ〜１５００ｍ2／ｇであ
ることが好ましく、更に好ましくは５００ｍ2 ／ｇ〜１
３００ｍ2 ／ｇである。電極中のカーボンブラック等の
導電材の配合量は、導電性を向上させられるように、炭
素質材料との合量中５重量％以上、特には１０重量％以
上配合するのが好ましい。導電材の配合量が多すぎる
と、炭素質材料の配合割合が減って電極の静電容量が減
るため電極中の導電材の配合量は４０重量％以下、特に
は３０重量％以下とするのが好ましい。As the conductive material, powders of carbon black, natural graphite, artificial graphite, titanium oxide, ruthenium oxide and the like are used. Among them, it is preferable to use Ketjen black or acetylene black, which is a kind of carbon black, since the effect of improving conductivity is large even in a small amount. The particle size of carbon black is
It is preferably from 0.001 μm to 1 μm, more preferably from 0.01 μm to 0.5 μm. The specific surface area thereof, 200m 2 / g~1500m is preferably 2 / g, more preferably 500 meters 2 / g to 1
300 m 2 / g. The amount of the conductive material such as carbon black in the electrode is preferably 5% by weight or more, more preferably 10% by weight or more based on the total amount with the carbonaceous material so as to improve the conductivity. If the compounding amount of the conductive material is too large, the compounding ratio of the carbonaceous material is reduced and the capacitance of the electrode is reduced. Therefore, the compounding amount of the conductive material in the electrode is set to 40% by weight or less, particularly 30% by weight or less. Is preferred.
【００２１】スラリーを形成する溶媒としては、上記結
合材を溶解できるものが好ましく、Ｎ−メチルピロリド
ン、ジメチルホルムアミド、トルエン、キシレン、イソ
ホロン、メチルエチルケトン、酢酸エチル、酢酸メチ
ル、エチルアセテート、ジメチルフタレート、メタノー
ル、エタノール、イソプロパノール、ブタノール、水等
が適宜選択される。As the solvent for forming the slurry, those capable of dissolving the above binder are preferable, and N-methylpyrrolidone, dimethylformamide, toluene, xylene, isophorone, methyl ethyl ketone, ethyl acetate, methyl acetate, ethyl acetate, dimethyl phthalate, methanol , Ethanol, isopropanol, butanol, water and the like are appropriately selected.
【００２２】電極の集電体としては、電気化学的、化学
的に耐食性のある導電体であればよい。炭素質材料を主
成分とする電極の集電体としては、ステンレス鋼、アル
ミニウム、チタン、タンタル、ニッケル等が用いられ
る。なかでも、ステンレス鋼とアルミニウムが性能と価
格の両面で好ましい集電体である。集電体の形状は箔で
もよいし、三次元構造を有するニッケルやアルミニウム
の発泡金属やステンレス鋼のネットやウールでもよい。The current collector of the electrode may be any conductor that is electrochemically and chemically resistant to corrosion. Stainless steel, aluminum, titanium, tantalum, nickel, or the like is used as a current collector for an electrode mainly composed of a carbonaceous material. Among them, stainless steel and aluminum are preferred current collectors in terms of both performance and cost. The shape of the current collector may be a foil, a nickel or aluminum foam metal having a three-dimensional structure, or a stainless steel net or wool.
【００２３】本発明の電気二重層キャパシタの電解液と
しては、水系電解液、または非水系電解液を使用するこ
とができ、耐電圧が高いという観点から、有機系溶媒に
電解質を溶解した非水系電解液を使用することが好まし
い。As the electrolyte for the electric double layer capacitor of the present invention, an aqueous electrolyte or a non-aqueous electrolyte can be used. From the viewpoint of high withstand voltage, a non-aqueous electrolyte prepared by dissolving an electrolyte in an organic solvent is used. It is preferable to use an electrolyte.
【００２４】有機系溶媒としては、電気化学的に安定な
エチレンカーボネート、プロピレンカーボネート、ブチ
レンカーボネート、γ−ブチロラクトン、スルホラン、
スルホラン誘導体、３−メチルスルホラン、１，２−ジ
メトキシエタン、アセトニトリル、グルタロニトリル、
バレロニトリル、ジメチルホルムアミド、ジメチルスル
ホキシド、テトラヒドロフラン、ジメトキシエタン、メ
チルフォルメイト、ジメチルカーボネート、ジエチルカ
ーボネート及びエチルメチルカーボネートから選ばれる
１種以上からなる溶媒が好ましい。これらは混合して使
用することも可能である。Examples of the organic solvent include electrochemically stable ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, sulfolane,
Sulfolane derivative, 3-methylsulfolane, 1,2-dimethoxyethane, acetonitrile, glutaronitrile,
Solvents comprising at least one selected from valeronitrile, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dimethoxyethane, methylformate, dimethylcarbonate, diethylcarbonate and ethylmethylcarbonate are preferred. These can be used as a mixture.
【００２５】非水系電解液の電解質としては、Ｒ1 Ｒ2
Ｒ3 Ｒ4 Ｎ+ 若しくはＲ1 Ｒ2 Ｒ3Ｒ4 Ｐ+ （Ｒ1 、Ｒ
2 、Ｒ3 、Ｒ4 はそれぞれ独立に炭素数１〜６のアルキ
ル基を示す。）で表される第４級オニウムカチオンと、
ＢＦ4 - 、ＰＦ4 - 、ＣｌＯ 4 - 、ＣＦ3 ＳＯ3 - 又は
（ＳＯ2 Ｒ5 ）（ＳＯ2 Ｒ6 ）Ｎ- （Ｒ5 、Ｒ6 はそれ
ぞれ独立に炭素数１〜４のアルキル基又はアルキレン基
を示し、Ｒ5 とＲ6 が環を形成していてもよい。）から
選ばれるアニオンとからなる塩が好ましい。具体的に
は、例えば、（Ｃ2 Ｈ5 ）4 ＮＢＦ4 、（Ｃ2 Ｈ5 ）3
（ＣＨ3 ）ＮＢＦ4 、（Ｃ2 Ｈ5 ）4 ＰＢＦ4 及び（Ｃ
2 Ｈ5 ）3 （ＣＨ3 ）ＰＢＦ4 等が好ましいものとして
挙げられる。電解液中のこれらの塩の濃度は０．１ｍｏ
ｌ／ｌ〜２．５ｍｏｌ／ｌ、さらには０．５ｍｏｌ／ｌ
〜２ｍｏｌ／ｌ程度とするのが好ましい。（Ｃ2 Ｈ5 ）
4 ＮＢＦ4 、（Ｃ2 Ｈ5 ）3 （ＣＨ3 ）ＮＢＦ4 のプロ
ピレンカーボネート溶液を電解質とすると、電気二重層
キャパシタの静電容量を大きくでき、充放電サイクル耐
久性に優れているため特に好ましい。As the electrolyte of the non-aqueous electrolyte, R1RTwo
RThreeRFourN+Or R1RTwoRThreeRFourP+(R1, R
Two, RThree, RFourAre each independently an alkyl having 1 to 6 carbon atoms
Represents a hydroxyl group. A quaternary onium cation represented by
BFFour -, PFFour -, ClO Four -, CFThreeSOThree -Or
(SOTwoRFive) (SOTwoR6) N-(RFive, R6Is it
Each independently an alkyl or alkylene group having 1 to 4 carbon atoms
And RFiveAnd R6May form a ring. From)
Salts comprising the selected anion are preferred. Specifically
Is, for example, (CTwoHFive)FourNBFFour, (CTwoHFive)Three
(CHThree) NBFFour, (CTwoHFive)FourPBFFourAnd (C
TwoHFive)Three(CHThree) PBFFourEtc. are preferred
No. The concentration of these salts in the electrolyte is 0.1 mol
1 / l to 2.5 mol / l, further 0.5 mol / l
It is preferably about 2 mol / l. (CTwoHFive)
FourNBFFour, (CTwoHFive)Three(CHThree) NBFFourProfessional
When the pyrene carbonate solution is used as the electrolyte, the electric double layer
Capacitor capacitance can be increased and charge / discharge cycle resistance
It is particularly preferable because of its excellent durability.
【００２６】本発明の電気二重層キャパシタは、ケース
内に、少なくとも一方の電極が上述した分極性電極であ
るシート状電極一対と、この一対の電極間に介在するセ
パレータと、電極に接続するリードと、シート状電極及
びセパレータに含浸される電解液とを少なくとも収容す
るものであればどのような構成をとってもよい。例え
ば、電極一対の間にセパレータを挟んだ素子を、電解液
と共に金属ケースと金属蓋と両者を絶縁するガスケット
によって金属ケース中に密封したコイン型、一対の正極
と負極をセパレータを介して巻回してなる巻回型、セパ
レータを介して多数のシート状電極を積み重ねた積層型
等いずれの構成もとることができる。The electric double layer capacitor according to the present invention has a pair of sheet-like electrodes in which at least one electrode is the above-described polarizable electrode, a separator interposed between the pair of electrodes, and a lead connected to the electrodes. Any configuration may be used as long as it accommodates at least the sheet electrode and the electrolytic solution impregnated in the separator. For example, an element in which a separator is interposed between a pair of electrodes, a coin type sealed in a metal case with a gasket that insulates a metal case and a metal lid with an electrolytic solution, and a pair of positive and negative electrodes are wound through a separator. Any of a wound type, a laminated type in which a large number of sheet electrodes are stacked via a separator, and the like can be adopted.
【００２７】本発明において正極と負極との間に挿入さ
れるセパレータとしては、例えばポリプロピレン繊維不
織布、ガラス繊維不織布、合成セルロース紙等が好適に
使用できる。In the present invention, as the separator inserted between the positive electrode and the negative electrode, for example, a polypropylene fiber nonwoven fabric, a glass fiber nonwoven fabric, a synthetic cellulose paper, or the like can be suitably used.
【００２８】[0028]
【実施例】以下、本発明を実施例及び比較例によって具
体的に説明するが、本発明はこれらに限定されない。炭
素質材料としては活性炭を使用し、石油等の鉱物系、や
しがら等の天然物系、及び、フェノール樹脂等の合成物
系を、既存の賦活方法、例えば、水蒸気賦活、アルカリ
賦活及びそれらの複数回賦活することにより得られる各
種活性炭より選んで用いた。活性炭単独の電気化学的物
性測定は、活性炭一粒に対して１ｍｏｌ／ｌ濃度の（Ｃ
2 Ｈ5 ）4 ＮＢＦ4 を含有するプロピレンカーボネート
溶液を電解液とし、測定機器として、北斗電工社製のＨ
Ａ−１５０を用い、Ｐｔ板を対極、Ａｇ／Ａｇ+ 電極を
参照電極として用いて、クロノアンペロメトリー法によ
り、浸漬電位から浸漬電位に対して＋５０ｍＶステップ
させた場合の電流波形を測定し、ステップ開始時から１
００ｍｓ後に流れている電流の値がステップ開始直後に
おける最大電流値の何％であるかを算出して、その結果
を電流値比として表１に示した。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Activated carbon is used as the carbonaceous material, and minerals such as petroleum, natural products such as palms, and synthetic materials such as phenolic resins can be activated by existing activation methods, for example, steam activation, alkali activation and the like. From various activated carbons obtained by activating a plurality of times. The measurement of the electrochemical properties of the activated carbon alone was carried out at a concentration of 1 mol / l (C
A propylene carbonate solution containing 2 H 5 ) 4 NBF 4 was used as an electrolyte, and Hokuto Denko H.
Using A-150, a Pt plate was used as a counter electrode, and an Ag / Ag + electrode was used as a reference electrode, and a current waveform was measured by a chronoamperometry method when a step of +50 mV was performed from the immersion potential to the immersion potential. 1 from the start of the step
The value of the current flowing after 00 ms was calculated as a percentage of the maximum current value immediately after the start of the step, and the result is shown in Table 1 as a current value ratio.
【００２９】次に各活性炭を用い、下記の方法で実際の
電気二重層キャパシタを作製した。電気二重層キャパシ
タは、上記で選定した特性を有する活性炭の粉末を８０
重量％、カーボンブラックの一種であるケッチェンブラ
ックＥＣを１０重量％、及びポリテトラフルオロエチレ
ンを１０重量％含有する混合物を、エタノールを添加し
つつ混練し、ロール圧延した後、２００℃で２時間乾燥
して、幅１０ｃｍ、長さ１０ｃｍ、厚さ０．６５ｍｍの
電極シートを得た。このシートから直径１２ｍｍの２枚
の円盤状電極を打ち抜き、黒鉛系の導電性接着剤でそれ
ぞれステンレス３１６製ケース及び上蓋に接着した。こ
の上蓋とケースを３００℃で４時間真空乾燥した後、乾
燥アルゴン雰囲気中で１ｍｏｌ／ｌの濃度の（Ｃ
2 Ｈ5 ）4 ＮＢＦ4 を含有するプロピレンカーボネート
溶液を電極に含浸させた。次いで、ポリプロピレン製不
織布セパレータを介して両極を対向させ、ポリプロピレ
ン製絶縁ガスケットを用いてかしめ封口した。なお、こ
のコイン型電気二重層キャパシタは直径１８．３ｍｍ、
厚さ２．０ｍｍであった。Next, an actual electric double layer capacitor was manufactured by the following method using each activated carbon. The electric double layer capacitor is made by adding activated carbon powder having the characteristics selected above to 80.
A mixture containing 10% by weight of Ketjen Black EC, which is a kind of carbon black, and 10% by weight of polytetrafluoroethylene, was kneaded while adding ethanol, and roll-rolled. After drying, an electrode sheet having a width of 10 cm, a length of 10 cm and a thickness of 0.65 mm was obtained. Two disc-shaped electrodes having a diameter of 12 mm were punched out of this sheet, and bonded to a stainless steel 316 case and a top lid, respectively, with a graphite-based conductive adhesive. The upper lid and the case are vacuum-dried at 300 ° C. for 4 hours, and then dried at a concentration of 1 mol / l (C) in a dry argon atmosphere.
The electrode was impregnated with a propylene carbonate solution containing 2 H 5 ) 4 NBF 4 . Next, the two electrodes were opposed to each other with a polypropylene nonwoven fabric separator interposed therebetween, and sealed with a polypropylene insulating gasket. This coin-type electric double layer capacitor has a diameter of 18.3 mm,
The thickness was 2.0 mm.
【００３０】静電容量は、上記コイン型電気二重層キャ
パシタを０．１Ａ及び０．５Ａの定電流でそれぞれ放電
した場合の電位の傾きよりそれぞれ算出し、その結果を
表２に示した。更に、０．５Ａで放電した場合の静電容
量を、０．１Ａで放電した場合の静電容量で割った静電
容量比を求めて、併せて表２に示した。The capacitance was calculated from the potential gradients when the coin-type electric double layer capacitor was discharged at a constant current of 0.1 A and 0.5 A, respectively. The results are shown in Table 2. Further, a capacitance ratio obtained by dividing the capacitance at the time of discharging at 0.5 A by the capacitance at the time of discharging at 0.1 A was obtained, and also shown in Table 2.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】表２より、本発明によれば比較例に比べ、
小電流時の静電容量に対する大電流時の静電容量低下が
小さく、高出力電気二重層キャパシタが得られる。From Table 2, according to the present invention, compared to the comparative example,
A high output electric double layer capacitor is obtained with a small decrease in the capacitance at a large current with respect to the capacitance at a small current.
【００３４】[0034]
【発明の効果】本発明によれば、電気二重層キャパシタ
を組み立てずに電極材料用の炭素質材料を電気化学的に
評価できる。そして、大電流の条件下において容量が大
きいため、高出力電気二重層キャパシタを提供できる。According to the present invention, a carbonaceous material for an electrode material can be electrochemically evaluated without assembling an electric double layer capacitor. Since the capacitance is large under the condition of a large current, a high-output electric double layer capacitor can be provided.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 平塚 和也 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社内 Ｆターム(参考） 4G046 CA04 CA06 CB01 CB02 CB09 HA01 HA03 HA06 HB05 HC03 HC09 4J037 AA01 AA02 AA08 AA22 CC02 CC14 CC15 CC16 CC22 DD05 DD09 DD23 EE08 EE28 FF11 5E082 AB09 BB10 BC14 EE28 MM35 PP01 PP05 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuya Hiratsuka 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term in Asahi Glass Co., Ltd. 4G046 CA04 CA06 CB01 CB02 CB09 HA01 HA03 HA06 HB05 HC03 HC09 4J037 AA01 AA02 AA08 AA22 CC02 CC14 CC15 CC16 CC22 DD05 DD09 DD23 EE08 EE28 FF11 5E082 AB09 BB10 BC14 EE28 MM35 PP01 PP05
Claims (3)
層キャパシタにおいて、前記正極及び／又は前記負極
は、下記特性Ａを有する炭素質材料を主成分とする分極
性電極からなることを特徴とする電気二重層キャパシ
タ。 特性Ａ：前記電解液中でクロノアンペロメトリー法によ
り浸漬電位から浸漬電位に対して＋５０ｍＶステップさ
せる測定において、ステップ開始時から１００ｍｓ後に
測定される電流値がステップ開始直後の最大電流値の１
０％以下である。1. An electric double layer capacitor having a positive electrode, a negative electrode, and an electrolytic solution, wherein the positive electrode and / or the negative electrode comprises a polarizable electrode mainly composed of a carbonaceous material having the following characteristic A. Electric double layer capacitor. Characteristic A: In the measurement in which the immersion potential is increased by +50 mV from the immersion potential by the chronoamperometry method in the electrolytic solution, the current value measured 100 ms after the start of the step is one of the maximum current values immediately after the start of the step.
0% or less.
た非水系電解液であることを特徴とする請求項１に記載
の電気二重層キャパシタ。2. The electric double layer capacitor according to claim 1, wherein the electrolyte is a non-aqueous electrolyte obtained by dissolving an electrolyte in an organic solvent.
層キャパシタの少なくとも一方の電極の主成分として使
用される電気二重層キャパシタ用電極材料において、請
求項１における特性Ａを有する炭素質材料からなること
を特徴とする電気二重層キャパシタ用電極材料。3. An electrode material for an electric double layer capacitor used as a main component of at least one electrode of an electric double layer capacitor having a positive electrode, a negative electrode and an electrolytic solution, wherein the carbonaceous material having the characteristic A according to claim 1 An electrode material for an electric double layer capacitor, comprising:
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|---|---|---|---|
| JP25033999A JP4017299B2 (en) | 1999-09-03 | 1999-09-03 | Electric double layer capacitor and electrode material therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25033999A JP4017299B2 (en) | 1999-09-03 | 1999-09-03 | Electric double layer capacitor and electrode material therefor |
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| Publication Number | Publication Date |
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| JP4017299B2 JP4017299B2 (en) | 2007-12-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002296208A (en) * | 2001-03-30 | 2002-10-09 | Kuraray Co Ltd | Cell for measuring electric characteristic of activated carbon, measuring device, and method of evaluating electric characteristic |
-
1999
- 1999-09-03 JP JP25033999A patent/JP4017299B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002296208A (en) * | 2001-03-30 | 2002-10-09 | Kuraray Co Ltd | Cell for measuring electric characteristic of activated carbon, measuring device, and method of evaluating electric characteristic |
| JP4578711B2 (en) * | 2001-03-30 | 2010-11-10 | 株式会社クラレ | Cell for measuring electrical properties of activated carbon, measuring device, and electrical property evaluation method |
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| Publication number | Publication date |
|---|---|
| JP4017299B2 (en) | 2007-12-05 |
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