JPH11317333A - Carbon material for electric double-layer capacitor and manufacture of the same, and electric double-layer capacitor and manufacture of the same - Google Patents
Carbon material for electric double-layer capacitor and manufacture of the same, and electric double-layer capacitor and manufacture of the sameInfo
- Publication number
- JPH11317333A JPH11317333A JP11047700A JP4770099A JPH11317333A JP H11317333 A JPH11317333 A JP H11317333A JP 11047700 A JP11047700 A JP 11047700A JP 4770099 A JP4770099 A JP 4770099A JP H11317333 A JPH11317333 A JP H11317333A
- Authority
- JP
- Japan
- Prior art keywords
- electric double
- layer capacitor
- double layer
- carbon material
- carbon
- 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.)
- Pending
Links
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気二重層コンデン
サに関し、特に、電気二重層コンデンサ用炭素材料、電
気二重層コンデンサ用炭素材料の製造方法、電気二重層
コンデンサ及び電気二重層コンデンサの製造方法に関す
るものである。The present invention relates to an electric double layer capacitor, and more particularly to a carbon material for an electric double layer capacitor, a method for producing a carbon material for an electric double layer capacitor, an electric double layer capacitor, and a method for producing an electric double layer capacitor. Things.
【０００２】[0002]
【従来の技術】電気二重層コンデンサは、活性炭から作
られる１対の分極性電極をセパレータを介して対向させ
て正極および負極とする構造を有している。各分極性電
極には水溶性電解質溶液あるいは非水溶媒電解質溶液が
含浸させられ、各分極性電極はそれぞれ集電極と接触さ
せられる。分極性電極は、(1)活性炭に少量の導電剤お
よび結合剤を加えて混練圧延する、(2) 活性炭に少量の
導電剤および結合剤を加えてスラリー状に溶解して集電
極に塗布する、(3)活性炭に少量の未炭化樹脂類を混合
して焼結する、等の方法で作成される。2. Description of the Related Art An electric double layer capacitor has a structure in which a pair of polarizable electrodes made of activated carbon are opposed to each other via a separator to form a positive electrode and a negative electrode. Each polarizable electrode is impregnated with an aqueous electrolyte solution or a non-aqueous solvent electrolyte solution, and each polarizable electrode is brought into contact with a collector electrode. The polarizable electrode is (1) Activated carbon with a small amount of conductive agent and binder added and kneaded and rolled. (2) Activated carbon with a small amount of conductive agent and binder added and dissolved in slurry to be applied to the collector. And (3) a method of mixing a small amount of uncarbonized resin with activated carbon and sintering.
【０００３】従来、電気二重層コンデンサの静電容量
は、分極性電極の表面積にほぼ比例するとの考え方か
ら、電気二重層コンデンサ用炭素材料として大きな比表
面積を有する活性炭が用いられている。Conventionally, activated carbon having a large specific surface area has been used as a carbon material for an electric double layer capacitor from the idea that the capacitance of an electric double layer capacitor is almost proportional to the surface area of a polarizable electrode.
【０００４】活性炭は、800℃以下の温度で炭素質材料
を炭化した後に賦活処理を施して製造される。賦活処理
は、たとえば、水蒸気、二酸化炭素等の雰囲気中で600
ないし1000℃に加熱する、あるいは、塩化亜鉛、水酸化
カリウム等を混合して不活性雰囲気で加熱する等により
行われる。この賦活過程では炭素化過程で生じた炭素材
の表面に吸着に適した多数の細孔が生成される。[0004] Activated carbon is produced by carbonizing a carbonaceous material at a temperature of 800 ° C or less and then performing an activation treatment. The activation treatment is performed, for example, in an atmosphere of steam, carbon dioxide, etc.
To 1000 ° C. or by mixing zinc chloride, potassium hydroxide and the like and heating in an inert atmosphere. In this activation process, many pores suitable for adsorption are generated on the surface of the carbon material generated in the carbonization process.
【０００５】従来、電気二重層コンデンサの静電容量を
できるだけ大きくするために、活性炭の表面積を増大さ
せることが追求されてきた。例えば、特開昭６３−７８
５１３号公報には、石油コークスに水酸化カリウムを混
合したものを焼成することにより活性炭を得ることが提
案されている。これにより、従来最高１５００ｍ2／ｇ
程度であった比表面積が２０００ないし３５００ｍ2／
ｇに高められると記載されている。Hitherto, it has been sought to increase the surface area of activated carbon in order to maximize the capacitance of the electric double layer capacitor. For example, JP-A-63-78
No. 513 proposes that activated carbon is obtained by calcining a mixture of petroleum coke and potassium hydroxide. As a result, the conventional maximum of 1500 m 2 / g
Specific surface area of about 2000 to 3500 m 2 /
g.
【０００６】しかし、強く賦活することにより比表面積
を増大させた活性炭を分極性電極材料として用いても、
その強い賦活によって単位体積当たりの表面積が逆に低
下するため、得られる静電容量には限界があることが本
発明者によって見い出された。However, even if activated carbon whose specific surface area is increased by strong activation is used as a polarizable electrode material,
The inventor has found that the surface area per unit volume is conversely reduced by the strong activation, and thus the obtained capacitance is limited.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、静電容量の
大きな電気二重層コンデンサを得ることを目的としてい
る。より詳しくは、従来よりも大きな静電容量を得るこ
との可能な電気二重層コンデンサ用炭素材料、電気二重
層コンデンサ用炭素材料の製造方法、電気二重層コンデ
ンサ及び電気二重層コンデンサの製造方法を提供するこ
とを目的とするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide an electric double layer capacitor having a large capacitance. More specifically, the present invention provides a carbon material for an electric double layer capacitor, a method for manufacturing a carbon material for an electric double layer capacitor, an electric double layer capacitor, and a method for manufacturing an electric double layer capacitor capable of obtaining a larger capacitance than before. It is intended to do so.
【０００８】[0008]
【課題を解決するための手段】本発明の電気二重層コン
デンサ用炭素材料は、炭素材料に賦活処理を施して製造
される黒鉛類似の微結晶炭素を有する電気二重層コンデ
ンサ用炭素材料であって、その微結晶炭素の層間距離が
０．３６５ｎｍ〜０．３８５ｎｍであることを特徴とし
ている。The carbon material for an electric double layer capacitor according to the present invention is a carbon material for an electric double layer capacitor having microcrystalline carbon similar to graphite produced by activating the carbon material. The interlayer distance of the microcrystalline carbon is 0.365 nm to 0.385 nm.
【０００９】本発明の電気二重層コンデンサ用炭素材料
の製造方法は、原料を炭素化し、黒鉛類似の微結晶炭素
を成長させる熱処理工程と、該熱処理工程で得られた炭
素材料にアルカリ賦活処理を行い、微結晶炭素の層間距
離が０．３６５ｎｍ〜０．３８５ｎｍの炭素材料を得る
ことを特徴としている。The method for producing a carbon material for an electric double layer capacitor according to the present invention comprises a heat treatment step of carbonizing the raw material and growing microcrystalline carbon similar to graphite, and an alkali activation treatment for the carbon material obtained in the heat treatment step. The method is characterized in that a carbon material having an interlayer distance of microcrystalline carbon of 0.365 nm to 0.385 nm is obtained.
【００１０】本発明の電気二重層コンデンサ用炭素材料
の製造方法は、炭素材料について水蒸気賦活を行うこと
により、黒鉛類似の微結晶炭素を持ち、その微結晶炭素
の層間距離が０．３６５ｎｍ〜０．３８５ｎｍの炭素材
料を得ることを特徴とする。In the method for producing a carbon material for an electric double layer capacitor according to the present invention, the carbon material is activated by steam to have graphite-like microcrystalline carbon, and the interlayer distance of the microcrystalline carbon is from 0.365 nm to 0. .385 nm carbon material.
【００１１】本発明の電気二重層コンデンサは、有機電
解液中に分極性電極が浸されてなる電気二重層コンデン
サにおいて、炭素材料に賦活処理を行って製造される黒
鉛類似の微結晶炭素を有する炭素材料であって、その微
結晶炭素の層間距離が０．３６５ｎｍ〜０．３８５ｎｍ
である炭素材料により前記分極性電極を形成したことを
特徴としている。An electric double layer capacitor according to the present invention is an electric double layer capacitor in which a polarizable electrode is immersed in an organic electrolytic solution, which has graphite-like microcrystalline carbon produced by activating a carbon material. A carbon material, wherein an interlayer distance of the microcrystalline carbon is 0.365 nm to 0.385 nm;
Wherein the polarizable electrode is formed of a carbon material.
【００１２】本発明の電気二重層コンデンサの製造方法
は、有機電解液中に分極性電極が浸されてなる電気二重
層コンデンサの製造方法において、炭素材料に賦活処理
を施して製造される黒鉛類似の微結晶炭素を有する炭素
材料であって、その微結晶炭素の層間距離が０．３６５
ｎｍ〜０．３８５ｎｍであり、前記電気二重層コンデン
サを組み立てた後に、最初に定格電圧以上の電圧を前記
分極性電極間に印加することによって、静電容量を発現
させることを特徴としている。The method for producing an electric double layer capacitor according to the present invention is a method for producing an electric double layer capacitor in which a polarizable electrode is immersed in an organic electrolytic solution, the method being similar to graphite produced by activating a carbon material. A microcrystalline carbon material having an interlayer distance of 0.365.
nm to 0.385 nm, and is characterized in that, after assembling the electric double layer capacitor, a voltage equal to or higher than a rated voltage is first applied between the polarizable electrodes to develop the capacitance.
【００１３】本発明の電気二重層コンデンサは、電圧印
加時に膨張する炭素質材料からなる分極性電極を有する
とともに、分極性電極が電圧印加時の膨張を制限する寸
法制限構造体中に保持されたことを特徴としている。The electric double-layer capacitor of the present invention has a polarizable electrode made of a carbonaceous material that expands when a voltage is applied, and the polarizable electrode is held in a dimension limiting structure that limits expansion when a voltage is applied. It is characterized by:
【００１４】[0014]
【発明の実施の形態】本発明は、電気二重層コンデンサ
を構成する分極性電極として用いた時に、大きな静電容
量が得られる電気二重層コンデンサ用炭素材料を提供す
るものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention provides a carbon material for an electric double layer capacitor which can obtain a large capacitance when used as a polarizable electrode constituting an electric double layer capacitor.
【００１５】本発明の電気二重層コンデンサ用炭素材料
は、賦活を行うものの賦活を浅くとどめた炭素材料が、
分極性電極として用いられた時、大きな静電容量を示す
という特性を有することが見い出されたことに基づいて
いる。この炭素材料は黒鉛類似の微結晶炭素を有する。
この炭素材料は、比表面積が小さいので従来の基準から
は電気二重層コンデンサの電極として適さないものであ
る。しかしながら、この炭素材料は、その微結晶炭素の
層間距離が特定の範囲すなわち０．３６５ｎｍ〜０．３
８５ｎｍにある場合、その比表面積が小さいにもかかわ
らず分極性電極として用いられた時、大きな静電容量を
示す。The carbon material for an electric double layer capacitor according to the present invention is a carbon material which is activated but whose activation is kept shallow.
It is based on the finding that it has the property of exhibiting a large capacitance when used as a polarizing electrode. This carbon material has microcrystalline carbon similar to graphite.
Since this carbon material has a small specific surface area, it is not suitable as an electrode of an electric double layer capacitor according to conventional standards. However, this carbon material has an interlayer distance of the microcrystalline carbon within a specific range, that is, 0.365 nm to 0.365 nm.
When it is at 85 nm, it shows a large capacitance when used as a polarizable electrode despite its small specific surface area.
【００１６】現在までに得られた本発明の炭素材料は、
電気二重層コンデンサの分極性電極として用いられた場
合に大きな静電容量を示すと共に、電圧の印加の際に膨
張するという特性を示す。The carbon material of the present invention obtained so far is
When used as a polarizable electrode of an electric double layer capacitor, it exhibits a large capacitance and expands when a voltage is applied.
【００１７】すなわち、現在までに得られた本発明の炭
素材料は、板状に成形して板状面の両面に集電極を積層
した電気二重層コンデンサを組み立てて、両集電極間に
電圧を印加した場合に、炭素材料が主として両集電極に
よる電圧印加方向に膨張するという特性を示した。That is, the carbon material of the present invention obtained up to the present is formed into a plate shape, and an electric double layer capacitor in which collector electrodes are laminated on both sides of the plate surface is assembled, and a voltage is applied between both collector electrodes. When applied, the carbon material expanded in the direction in which the voltage was applied by both collector electrodes.
【００１８】電極として用いた炭素材料が膨張すると電
気二重層コンデンサの体積が大きくなる。電気二重層コ
ンデンサの静電容量が増加しても体積が増加したので
は、単位体積当たりの電気二重層コンデンサの静電容量
の増加はその分減殺される。静電容量の増大を享受する
には、炭素材料の膨張による電気二重層コンデンサの体
積の増大を最小限に抑えることが効果的である。When the carbon material used as the electrode expands, the volume of the electric double layer capacitor increases. If the volume increases even if the capacitance of the electric double layer capacitor increases, the increase in the capacitance of the electric double layer capacitor per unit volume is reduced accordingly. In order to enjoy the increase in the capacitance, it is effective to minimize the increase in the volume of the electric double layer capacitor due to the expansion of the carbon material.
【００１９】本発明者の検討によれば、本発明の炭素材
料は、体積の増大を完全に押さえた場合、すなわち炭素
材料と接触した集電体間の距離の増加を許さず、電気二
重層コンデンサの容積が増加しないようにした場合であ
っても、静電容量の増加は自由に膨張させた場合と変わ
らなかった。According to the study of the present inventor, the carbon material of the present invention, when completely suppressing the increase in volume, that is, does not allow an increase in the distance between the current collector contacting the carbon material, and the electric double layer Even when the volume of the capacitor was not increased, the increase in capacitance was not different from that when the capacitor was freely expanded.
【００２０】電圧印加による膨張時に両集電体間の距離
が固定されていると、集電体には圧力が加わることとな
るが、本明細書ではこの圧力を膨張圧と称する。If the distance between the two current collectors is fixed at the time of expansion due to the application of a voltage, a pressure is applied to the current collector. In this specification, this pressure is referred to as an expansion pressure.
【００２１】本発明者の検討によれば、本発明の炭素材
料の電気二重層コンデンサ用分極性電極としての特性
は、電圧の印加によって大きく膨張するものの方が電気
二重層コンデンサとしての静電容量が大きくなるという
傾向があり、２ｋｇ／ｃｍ2以上の膨張圧が生じるもの
が好ましい。According to the study of the present inventor, the characteristics of the carbon material of the present invention as a polarizable electrode for an electric double layer capacitor are such that those which greatly expand upon application of a voltage have the capacitance as an electric double layer capacitor. Is preferred, and an expansion pressure of 2 kg / cm 2 or more is preferred.
【００２２】本発明の電気二重層コンデンサ用炭素材料
と従来の電気二重層コンデンサ用の活性炭についてその
X線回折結果を図1において比較して説明する。The carbon material for an electric double layer capacitor of the present invention and the conventional activated carbon for an electric double layer capacitor
The results of X-ray diffraction will be described in comparison with FIG.
【００２３】一般に、炭素材料の微細構造の解析には、
構造が明確な黒鉛を基準にすることが行われているが、
粉末黒鉛のX線回折による測定では、Ｃ002の回折ピーク
が層間距離ｄ002=０．３３５ｎｍに鋭く尖鋭なピークと
して観測され、いわゆるベンゼン環状平面網目構造が層
状に十分に成長している。Generally, in analyzing the microstructure of a carbon material,
Although it is based on graphite with a clear structure,
In the measurement of the powdered graphite by X-ray diffraction, a diffraction peak of C 002 is observed as a sharp and sharp peak at an interlayer distance d 002 = 0.335 nm, and the so-called benzene ring planar network structure is sufficiently grown in a layered manner.
【００２４】これに対して、大きな静電容量密度を目的
とした従来の電気二重層コンデンサに用いられる、強く
賦活した活性炭では、Ｃ002のピークは一般に少なく、
多少あってもｄ002は０．４０ｎｍ以上に広がってい
て、鮮明には認められないことが普通である。On the other hand, a strongly activated activated carbon used in a conventional electric double layer capacitor aimed at a large capacitance density generally has a small peak of C 002 ,
Even if there is a little, d 002 extends to 0.40 nm or more, and it is usual that it is not clearly recognized.
【００２５】ところが、本発明に用いる炭素質材料は、
ｄ002が０．３６５ｎｍ〜０．３８５ｎｍに、黒鉛に比
べれぱかなりブロードではあるが、積分強度としては高
い強度でＣ002の回折ピークが認められることから、黒
鉛類似の微結晶炭素の結晶子を有することが分かる。図
１においてＡで黒鉛化の過程にある材料のX線回折曲線
を示し、Ｂに比表面積を２０００ｃｍ2／ｇまで深く賦
活した従来の電気二重層コンデンサ用の活性炭のX線回
折曲線を示し、Ｃに本発明にかかる賦活の程度が浅い炭
素材料のX線回折曲線を示す。However, the carbonaceous material used in the present invention is:
d 002 is 0.365 nm to 0.385 nm, which is considerably broader than graphite, but a diffraction peak of C 002 is recognized at a high intensity as an integrated intensity, so that a crystallite of microcrystalline carbon similar to graphite can be obtained. It can be seen that it has. In FIG. 1, A shows an X-ray diffraction curve of a material in the process of graphitization, and B shows an X-ray diffraction curve of a conventional activated carbon for an electric double layer capacitor having a specific surface area deeply activated to 2000 cm 2 / g. C shows an X-ray diffraction curve of the carbon material having a low degree of activation according to the present invention.
【００２６】本発明の電気二重層コンデンサ用炭素材料
は、賦活が進んでいない低温焼成した炭素材料を用いる
ことができ、活性炭原料として用いられる木材、果実
殻、石炭、ピッチ、石油コークス等の種々の材料を用い
て製造することができる。例えば、賦活前に不活性雰囲
気中において熱処理して、賦活が大きく進行しないよう
にしたり、あるいは賦活操作を短時間とする等の処理に
よって製造することができ、熱処理温度としては、６０
０℃ないし１０００℃程度の比較的低温で焼成を行った
ものが好ましい。As the carbon material for an electric double layer capacitor of the present invention, a low-temperature fired carbon material that has not been activated can be used, and various materials such as wood, fruit husk, coal, pitch, and petroleum coke used as a raw material for activated carbon Can be manufactured using the above materials. For example, it can be manufactured by performing a heat treatment in an inert atmosphere before the activation so that the activation does not greatly proceed, or a process such as shortening the activation operation.
Those fired at a relatively low temperature of about 0 ° C. to 1000 ° C. are preferred.
【００２７】また、本発明の電気二重層コンデンサ用炭
素材料は、電圧の印加によって膨張をした時、含浸して
いる電解質をアセトニトリル等の揮発性溶媒で十分沸騰
洗浄し、しかる後に乾燥してX線回折測定を行うと、Ｃ
002回折ピーク強度と層間距離ｄ002の値は・電圧印加前
の炭素材料の値を示す。Further, when the carbon material for an electric double layer capacitor of the present invention is expanded by application of a voltage, the impregnated electrolyte is sufficiently boiled and washed with a volatile solvent such as acetonitrile, and then dried and dried. When a line diffraction measurement is performed, C
The values of the 002 diffraction peak intensity and the interlayer distance d 002 indicate the values of the carbon material before voltage application.
【００２８】本発明の炭素材料を分極性電極とした電気
二重層コンデンサの膨張圧力の測定は、電極対の外側に
ストレーンゲージなどによる圧力センサーを置き、その
背後から機械的に押さえて厚さすなわち膨張を制限する
ことによって行うことが可能である。To measure the expansion pressure of the electric double layer capacitor using the carbon material of the present invention as a polarizable electrode, a pressure sensor such as a strain gauge is placed outside the electrode pair, and the thickness is reduced by mechanically pressing the pressure sensor from behind. This can be done by limiting inflation.
【００２９】図２は、静電容量及び膨張圧を測定する装
置の一例を説明する断面図である。この装置１は、基台
２上にストレーンゲージ等の圧力センサー３を有する。
圧力センサー３上には下部金属ブロック４と上部金属ブ
ロック７が配置される。２つのブロックの間に、合成樹
脂フイルム５で気密に被覆した電気二重層コンデンサ６
が挟まれて配置される。この電気二重層コンデンサ６
は、アルミニウム製集電極と炭素電極とセパレータを、
集電極／炭素電極／セパレータ／炭素電極／集電極の順
序で積み重ね、電解液を含浸した構造を有している。上
部金属ブロック７の上には、スラストベアリング８が載
置され、このスラストベアリング８上に先端が当接する
ようにネジ９が強固なフレーム１１に取り付けられてい
る。FIG. 2 is a sectional view for explaining an example of an apparatus for measuring the capacitance and the expansion pressure. This apparatus 1 has a pressure sensor 3 such as a strain gauge on a base 2.
A lower metal block 4 and an upper metal block 7 are arranged on the pressure sensor 3. An electric double layer capacitor 6 airtightly covered with a synthetic resin film 5 between two blocks.
Are arranged in between. This electric double layer capacitor 6
Is an aluminum collector electrode, carbon electrode and separator,
It has a structure in which a collector electrode / carbon electrode / separator / carbon electrode / collector electrode is stacked in this order and impregnated with an electrolytic solution. A thrust bearing 8 is mounted on the upper metal block 7, and a screw 9 is attached to a rigid frame 11 so that a tip of the thrust bearing 8 abuts on the thrust bearing 8.
【００３０】電気二重層コンデンサ６の集電極にリード
線10を介して電源11から電圧が印加される。圧力センサ
ーの出力は記録計１２に供給され、記録される。A voltage is applied from a power supply 11 to the collector of the electric double layer capacitor 6 via a lead wire 10. The output of the pressure sensor is supplied to the recorder 12 and recorded.
【００３１】図3は、図２の装置を用いて測定した本発
明の炭素材料を分極性電極として用いた電気二重層コン
デンサに関する充電・放電特性と、膨張圧を示す図であ
る。図３には、本発明の炭素材料を用いて作成された直
径２０ｍｍ、厚さ０．５ｍｍの分極性電極を有する電気
二重層コンデンサを組み立てた後に初めて行った１０ｍ
Ａの定電流での繰り返し充放電の、１サイクル目と２サ
イクル目が示されている。膨張圧は、初期設定圧力から
上昇し、放電開始時に最大となり、放電終了時まで降下
を続けるが初期値までは復帰しないことを示している。FIG. 3 is a graph showing the charge / discharge characteristics and the expansion pressure of an electric double layer capacitor using the carbon material of the present invention as a polarizable electrode, measured using the apparatus of FIG. FIG. 3 shows the first 10 m measurement after assembling an electric double layer capacitor having a polarizable electrode having a diameter of 20 mm and a thickness of 0.5 mm made using the carbon material of the present invention.
The first cycle and the second cycle of repeated charging and discharging at a constant current of A are shown. The inflation pressure increases from the initial set pressure, reaches a maximum at the start of discharge, continues to decrease until the end of discharge, but does not return to the initial value.
【００３２】図４は、本発明の電気二重層コンデンサに
対して充電及び完全放電を１６回繰り返した際の端子間
電圧の変化を示している。充電電圧は、充放電サイクル
１から９までは定格電圧の２．３Ｖ、充電サイクル１０
から１５までは定格を超える４Ｖ、充電サイクル１６で
は３．５Ｖである。図４には、充電サイクル１，３，１
０，１２，１６における結果のみが示されている。横軸
が時間、縦軸が端子間電圧で充放電は定電流で行ってい
るから、充放電曲線の勾配は静電容量に反比例してい
る。FIG. 4 shows a change in voltage between terminals when charging and discharging are repeated 16 times with respect to the electric double layer capacitor of the present invention. The charge voltage is 2.3 V of the rated voltage in charge / discharge cycles 1 to 9, and the charge cycle is 10
To 15 are 4 V exceeding the rating, and 3.5 V in the charging cycle 16. FIG. 4 shows charging cycles 1, 3, 1
Only the results at 0, 12, 16 are shown. Since the horizontal axis is time and the vertical axis is voltage between terminals and charging and discharging are performed at a constant current, the gradient of the charging and discharging curve is inversely proportional to the capacitance.
【００３３】図４から分かるように、製造後初めて充電
が行われる充放電サイクル１では、充電開始時は極端に
小さな静電容量のために、端子間電圧が急激に直線的に
上昇し、１．５Ｖ付近から急に端子間電圧の上昇が遅く
なり、ここから静電容量が増加していることを示してい
る。As can be seen from FIG. 4, in charge / discharge cycle 1 in which charging is performed for the first time after manufacturing, at the start of charging, the voltage between terminals sharply increases linearly due to an extremely small capacitance. The rise of the inter-terminal voltage is suddenly slowed from around 0.5 V, which indicates that the capacitance is increasing.
【００３４】この充放電サイクル１の充電期間の後半に
おいて増加した静電容量は、放電後も維持される。すな
わち、充放電サイクル３では、充電時の端子間電圧の上
昇速度が充放電サイクル１のほぼ半分となっている。こ
れは、充放電サイクル３における静電容量が、充放電サ
イクル１における充電開始時に比べおよそ２倍になった
ことを示している。The capacitance that has increased in the latter half of the charge period of the charge / discharge cycle 1 is maintained after discharge. That is, in the charge / discharge cycle 3, the rate of rise of the voltage between terminals during charging is almost half that in the charge / discharge cycle 1. This indicates that the capacitance in the charging / discharging cycle 3 was about twice as large as that at the start of charging in the charging / discharging cycle 1.
【００３５】充放電サイクル１０以降、充電電圧は４Ｖ
に上げられた。充放電サイクル１０では、端子間電圧は
２．６Ｖまでは充放電サイクル３と同じ速度で上昇して
いる。これは、端子間電圧２．６Ｖの時点まで静電容量
が充放電サイクル３の時と同じ値であることを示してい
る。ところが、端子間電圧が２．６Ｖあたりを過ぎる
と、端子間電圧の上昇速度が減少している。これは、こ
の時点から静電容量が増大したことを示している。After the charge / discharge cycle 10, the charge voltage is 4 V
Was raised to. In the charge / discharge cycle 10, the terminal voltage rises to 2.6 V at the same rate as the charge / discharge cycle 3. This indicates that the capacitance is the same as that in the charge / discharge cycle 3 until the time of the terminal voltage of 2.6 V. However, when the inter-terminal voltage exceeds about 2.6 V, the rising speed of the inter-terminal voltage decreases. This indicates that the capacitance has increased from this point.
【００３６】この充電電圧を上げた充放電サイクル１０
における静電容量の増加は、完全放電後も維持される。
すなわち、充放電サイクル１２では、端子間電圧の上昇
速度は充電当初から充放電サイクル３の場合よりも遅
く、静電容量が充放電サイクル３の時よりも更に増加し
ていることを示している。The charge / discharge cycle 10 in which the charging voltage is increased
Is maintained even after complete discharge.
That is, in the charge / discharge cycle 12, the rising speed of the inter-terminal voltage is lower than in the charge / discharge cycle 3 from the beginning of charging, and the capacitance is further increased compared to the charge / discharge cycle 3. .
【００３７】この様にして増加した静電容量は、その後
に充放電サイクル１６のように充電電圧を３．５Ｖに下
げても増加した状態を維持している。The capacitance thus increased maintains the increased state even when the charging voltage is reduced to 3.5 V as in the charge / discharge cycle 16 thereafter.
【００３８】一方、電極の膨張圧は、静電容量の増加に
ほぼ比例して充放電サイクルに同期して増減する。その
振幅、すなわち最大圧力と最小圧力の差は炭素質材料と
電解液の濃度、種類、充電状態等によって変化するが２
〜２０ｋｇ／ｃｍ2程度の値を示す。On the other hand, the expansion pressure of the electrode increases and decreases in synchronization with the charge / discharge cycle almost in proportion to the increase in capacitance. The amplitude, that is, the difference between the maximum pressure and the minimum pressure varies depending on the concentration, type, charge state, etc. of the carbonaceous material and the electrolytic solution.
It shows a value of about 20 kg / cm 2 .
【００３９】以上のことから、本発明の炭素材料を用い
た電気二重層コンデンサは、黒鉛類似の微結晶炭素を有
する電気二重層コンデンサ用炭素材料であって、その微
結晶炭素の層間距離が０．３６５ｎｍ〜０．３８５ｎｍ
である炭素材料を用いて従来の電気二重層コンデンサと
同様にして製造し、初期充電の際に電気二重層コンデン
サとして使用する際の定格電圧よりも高い電圧を印加す
ることによって、大きな静電容量を示す電気二重層コン
デンサを得ることができる。From the above, the electric double layer capacitor using the carbon material of the present invention is a carbon material for an electric double layer capacitor having microcrystalline carbon similar to graphite, and the interlayer distance of the microcrystalline carbon is 0. .365 nm to 0.385 nm
It is manufactured in the same way as a conventional electric double-layer capacitor using a carbon material that has a large capacitance by applying a voltage higher than the rated voltage when used as an electric double-layer capacitor during initial charging. Can be obtained.
【００４０】また、本発明の電気二重層コンデンサは、
充電時の電気二重層コンデンサの容積の増加を抑制する
ために、電極に生じる膨張圧に抗する構造とすることが
好ましいし、そのように容積の増加を抑制しても、静電
容量の増加のメリットを享受できるという特徴を持って
いる。Further, the electric double layer capacitor of the present invention
In order to suppress the increase in the capacity of the electric double layer capacitor during charging, it is preferable to adopt a structure that resists the expansion pressure generated in the electrodes. It has the feature that you can enjoy the benefits of.
【００４１】図５は、単位電気二重層コンデンサを気密
容器中に設けた本発明の電気二重層コンデンサの一例を
説明する断面図である。FIG. 5 is a sectional view illustrating an example of the electric double layer capacitor of the present invention in which the unit electric double layer capacitor is provided in an airtight container.
【００４２】コンデンサ容器２１内部には、前述したア
ルミニウム製集電極と炭素電極とセパレータを、集電極
／炭素電極／セパレータ／炭素電極／集電極の順序で積
み重ね、電解液を含浸した構造を持ち、合成樹脂フイル
ムで気密に封止された単位電気二重層コンデンサ６の多
数を積層した電気二重層コンデンサ積層体２２が収容さ
れており、各電気二重層コンデンサは直列あるいは並列
に接続されるよう電気的結線がされている。Inside the capacitor container 21, the above-mentioned aluminum collector electrode, carbon electrode and separator are stacked in the order of collector electrode / carbon electrode / separator / carbon electrode / collector electrode and have a structure impregnated with an electrolyte. An electric double layer capacitor laminated body 22 in which many unit electric double layer capacitors 6 are hermetically sealed with a synthetic resin film is accommodated, and the electric double layer capacitors are electrically connected in series or in parallel. Connection is made.
【００４３】単位電気二重層コンデンサは、分極性電
極、集電極および電解液からなるコンデンサ要素を、少
なくとも一層の合成樹脂フイルムあるいは合成樹脂フィ
ルムと金属フィルムとの積層フィルムからなる袋状体に
収容し・袋状体の内部を減圧して密封して袋状体とコン
デンサ要素を密着したものからなることが好ましい。In the unit electric double layer capacitor, a capacitor element comprising a polarizable electrode, a collecting electrode and an electrolytic solution is accommodated in at least one layer of a synthetic resin film or a bag made of a laminated film of a synthetic resin film and a metal film. -It is preferable that the inside of the bag-shaped body is reduced in pressure and hermetically sealed so that the bag-shaped body and the capacitor element are in close contact with each other.
【００４４】また、単位電気二重層コンデンサは、分極
性電極、集電極、セパレータおよび電解液からなるコン
デンサ要素を、少なくとも一層の合成樹脂フィルムある
いは合成樹脂フィルムと金属フィルムとの積層フイルム
からなり、コンデンサ要素収容室およびコンデンサ要素
収容室と連通したトラップを有する袋状体内に以下のよ
うにして収納した構造とすることができる。The unit electric double layer capacitor comprises a capacitor element comprising a polarizable electrode, a collecting electrode, a separator and an electrolytic solution comprising at least one synthetic resin film or a laminated film of a synthetic resin film and a metal film. A structure in which the bag is housed in a bag-like body having a trap communicating with the element housing chamber and the capacitor element housing chamber as follows.
【００４５】(１)コンデンサ要素を袋状体に収容し、袋
状体内を減圧脱気した後に、袋状体を封口し、コンデン
サ要素に通電を行って充放電を行う。(２)トラップ内部
の圧力よりも圧力が低い減圧室内においてトラップを冷
却してトラップにコンデンサ要素からの発生物質を集め
る。(３)トラップとコンデンサ要素収容室の間を融着密
封する。(４)トラップを切り離して単位電気二重層コン
デンサを得る。(1) The capacitor element is housed in a bag-shaped body, and after the bag-shaped body is degassed under reduced pressure, the bag-shaped body is sealed, and the capacitor element is energized to perform charging and discharging. (2) The trap is cooled in a decompression chamber having a pressure lower than the pressure inside the trap, and generated substances from the condenser element are collected in the trap. (3) The space between the trap and the capacitor element storage chamber is fusion-sealed. (4) Separate the trap to obtain a unit electric double layer capacitor.
【００４６】なお、上記(２)のステップにおいて、コン
デンサ要素から発生したガスなどの物質及び余分の電解
液を、トラップ内部に吸引ノズルを挿入して吸引し取り
除くことも可能である。In the above step (2), it is also possible to insert a suction nozzle inside the trap and remove the substance such as gas generated from the capacitor element and the excess electrolyte by suction.
【００４７】以上のような処理により、初期充放電時に
電気二重層コンデンサの各構成要素から発生する電気二
重層コンデンサの特性にとって好ましくない物質をトラ
ップに集めて除去することができる。その結果、特性の
優れた単位電気二重層コンデンサを得ることができる。By the above-described processing, substances which are not preferable for the characteristics of the electric double layer capacitor and are generated from each component of the electric double layer capacitor at the time of initial charge and discharge can be collected and removed in the trap. As a result, a unit electric double layer capacitor having excellent characteristics can be obtained.
【００４８】コンデンサ容器２１の底部には、内部と外
部の圧力差に抗するように、凹面状底板２３が設けられ
ている。凹面状底板上には、多数収容されたコンデンサ
をそれぞれの膨張圧に抗して圧縮状態に保持するため
に、底部押板２４が設けられている。また、電気二重層
コンデンサの上部には、上部押板２５が設けられてい
る。底部押板及び上部押板には、剛性の大きな金属板を
用いることが好ましい。At the bottom of the condenser container 21, a concave bottom plate 23 is provided so as to resist a pressure difference between the inside and the outside. On the concave bottom plate, a bottom push plate 24 is provided to hold a large number of accommodated capacitors in a compressed state against their respective expansion pressures. An upper pressing plate 25 is provided above the electric double layer capacitor. It is preferable to use a metal plate having high rigidity for the bottom pressing plate and the upper pressing plate.
【００４９】上部押板２５上には、膨張圧に抗して電気
二重層コンデンサの寸法の増加を制限する機能を有する
加圧手段２６が設けられている。On the upper pressing plate 25, a pressurizing means 26 having a function of restricting an increase in the size of the electric double layer capacitor against the inflation pressure is provided.
【００５０】加圧手段２６には、各種のものを用いるこ
とができる。図５に示した加圧手段は、内部に高圧流体
(例えばガス)を封入したゴムなどの弾性体から形成さ
れ、注入口２７から注入した高圧流体によって、単位電
気二重層コンデンサの膨張圧に抗して電気二重層コンデ
ンサの寸法を制限する圧力を発生することができる。ま
た、本実施例の電気二重層コンデンサでは、加圧手段に
注入する流体の圧力を調整によって膨張圧に抗して電気
二重層コンデンサの寸法の増加を制限する圧力を調整す
ることが容易である。また、本発明の電気二重層コンデ
ンサにおいては、膨張圧は主として電圧印加方向に発生
するので電圧印加方向以外に寸法制限構造体を設けなく
ても実用上は問題が生じない。Various means can be used as the pressure means 26. The pressurizing means shown in FIG.
(E.g., gas) is formed from an elastic body such as rubber, and a high-pressure fluid injected from the injection port 27 generates a pressure that limits the size of the electric double layer capacitor against the expansion pressure of the unit electric double layer capacitor. can do. Further, in the electric double layer capacitor of the present embodiment, it is easy to adjust the pressure of the fluid to be injected into the pressurizing means to adjust the pressure limiting the increase in the size of the electric double layer capacitor against the inflation pressure. . Also, in the electric double layer capacitor of the present invention, since the expansion pressure is mainly generated in the voltage application direction, there is no practical problem even if the dimension limiting structure is not provided in the direction other than the voltage application direction.
【００５１】図５の電気二重層コンデンサでは、合成樹
脂フイルムによって気密に保持された電気二重層コンデ
ンサが、気密容器内に収納されているので、電気二重層
コンデンサが外部の環境による悪影響を受ける可能性が
小さい。In the electric double-layer capacitor shown in FIG. 5, the electric double-layer capacitor airtightly held by the synthetic resin film is housed in an airtight container, so that the electric double-layer capacitor may be adversely affected by the external environment. The nature is small.
【００５２】また、本発明の電気二重層コンデンサは、
上下の押板によって常に加圧されているので、各電気二
重層コンデンサの集電体と電極との導電接触を良好に維
持することができるという特徴も有している。Further, the electric double layer capacitor of the present invention
Since it is always pressurized by the upper and lower push plates, it also has a feature that the conductive contact between the current collector and the electrode of each electric double layer capacitor can be favorably maintained.
【００５３】コンデンサ容器内へ収容する電気二重層コ
ンデンサは、外部において加圧した状態で、定格電圧よ
りも１０ないし２０％高い電圧で充電し、合成樹脂フイ
ルムで形成した気密性の袋に設けた予備室に、電気二重
層コンデンサから発生する気泡等を集めた後に予備室を
分離する等の方法によって電気二重層コンデンサの初期
充電時に発生する物質を分離した後に収容することが好
ましい。The electric double layer capacitor housed in the capacitor container was charged at a voltage 10 to 20% higher than the rated voltage in a pressurized state outside, and provided in an airtight bag made of a synthetic resin film. It is preferable to collect the air bubbles and the like generated from the electric double layer capacitor in the preliminary chamber and then separate the preliminary chamber to separate the substances generated during the initial charging of the electric double layer capacitor and then store the separated substances.
【００５４】図6は、本発明の他の積層した電気二重層
コンデンサの一実施例を説明する斜視図である。図６に
おいて、底部押板２４と上部押板２５の間には、電気二
重層コンデンサ積層体２２が収容されている。この底部
押板２４と上部押板２５の間には、滑車２８を介してワ
イヤー２９が張架されている。そして、引張り部材３０
によって、各ワイヤーには所定のテンションが加えられ
ている。その結果、電気二重層コンデンサ積層体２２に
所定の押圧力が印加される。FIG. 6 is a perspective view for explaining another embodiment of the laminated electric double layer capacitor of the present invention. In FIG. 6, between the bottom push plate 24 and the upper push plate 25, the electric double layer capacitor laminate 22 is housed. A wire 29 is stretched between the bottom push plate 24 and the upper push plate 25 via a pulley 28. And the tension member 30
Thus, a predetermined tension is applied to each wire. As a result, a predetermined pressing force is applied to the electric double layer capacitor laminate 22.
【００５５】底部押板、上部押板には、軽量で剛性が大
きなアルミニウム合金等の金属材料を用いることが好ま
しく、またワイヤーには、ステンレス鋼製のものを用い
ることが好ましい。For the bottom pressing plate and the upper pressing plate, it is preferable to use a metal material such as an aluminum alloy which is lightweight and has high rigidity, and it is preferable to use a stainless steel wire for the wire.
【００５６】例えば、電気二重層コンデンサの面積が４
４ｃｍ2の場合には、２ｋｇ／ｃｍ2の圧力を印加するた
めには、押板に８８ｋｇｆの荷重を加えるが必要とな
る。滑車の数を増加することによって、ワイヤーに加わ
るテンションを小さくすることが可能となる。For example, if the area of the electric double layer capacitor is 4
In the case of 4 cm 2 , in order to apply a pressure of 2 kg / cm 2 , it is necessary to apply a load of 88 kgf to the pressing plate. By increasing the number of pulleys, it is possible to reduce the tension applied to the wire.
【００５７】[0057]
【実施例】以下に、実施例を示し本発明を説明する。 ［実施例１］石油コークスを不活性雰囲気中で７５０℃
において２時間の熱処理を行い、これと重量比で２倍量
の水酸化カリウムを混合し不活性雰囲気で８００℃の熱
処理を行って炭素質材料を得た。不活性雰囲気中であら
かじめ行った熱処理による炭素化の効果によリ賦活は充
分に進行せず、得られた炭素質材料のＢＥＴ比表面積は
３００ｍ2／ｇ程度にとどまった。この値は、電気二重
層コンデンサで大静電容量密度を得る活性炭としては使
用することができないものであった。この炭素質材料の
X線回折結果は、図１おいてＣで示されているものであ
る。The present invention will be described below with reference to examples. [Example 1] Petroleum coke was heated at 750 ° C in an inert atmosphere.
, A heat treatment at 800 ° C. was performed in an inert atmosphere, and a carbonaceous material was obtained. The reactivation did not sufficiently proceed due to the effect of carbonization by a heat treatment performed in advance in an inert atmosphere, and the BET specific surface area of the obtained carbonaceous material was only about 300 m 2 / g. This value cannot be used as activated carbon for obtaining a large capacitance density with an electric double layer capacitor. This carbonaceous material
The X-ray diffraction result is shown by C in FIG.
【００５８】このようにして得られた炭素質材料を３０
μｍ程度の粒度に粉砕し、炭素質材料８２ｍｇ、導電性
補助剤としてカーボンブラック９ｍｇ、および結着剤と
してポリテトラフルオロエチレン粉末９ｍｇを混合して
混練し、圧延により厚さ０．５ｍｍのシートを作成し
た。このシートから直径２０ｍｍの円盤状電極を複数切
り出し、これを１０Ｔｏｒｒに減圧した真空デシゲータ
中に配置し、１２０℃において４時間乾燥する。The carbonaceous material obtained in this way is
Pulverized to a particle size of about μm, 82 mg of a carbonaceous material, 9 mg of carbon black as a conductive auxiliary, and 9 mg of polytetrafluoroethylene powder as a binder were mixed and kneaded, and a sheet having a thickness of 0.5 mm was rolled. Created. A plurality of disc-shaped electrodes having a diameter of 20 mm are cut out from the sheet, placed in a vacuum desiccator reduced to 10 Torr, and dried at 120 ° C. for 4 hours.
【００５９】その後、低湿度に保ったグローブボックス
内で圧縮状態で１００μｍ程度となるガラスセパレータ
を介して上記電極２枚を重ね、さらにその最外側を二枚
のアルミニウム板製集電極で挟み電気二重層コンデンサ
本体とする。Thereafter, in a glove box kept at a low humidity, the above two electrodes are overlapped with each other via a glass separator of about 100 μm in a compressed state, and the outermost electrode is sandwiched between two aluminum plate collecting electrodes. It is a multilayer capacitor body.
【００６０】コンデンサ本体をＯリングでシールしたア
ルミニウム製気密容器に入れ、テトラエチルアンモニウ
ム・テトラフルオロボーレートの１モルを溶解したプロ
ピレンカーボネートを電解液として充分含浸させて、試
験用電気二重層コンデンサを得た。The capacitor body was placed in an aluminum hermetic container sealed with an O-ring, and sufficiently impregnated with propylene carbonate in which 1 mol of tetraethylammonium / tetrafluoroborate was dissolved as an electrolyte to obtain an electric double layer capacitor for testing. .
【００６１】得られた電気二重層コンデンサを４Ｖまで
１サイクルだけ充放電した。充電及び放電電流は５ｍＡ
である。その後２．３Ｖで充放電して特性を測定した。
充放電及び特性の測定は図２の装置を用いて行われた。
その測定結果を表１に示す。 ［比較例１］実施例１と同じ石油コークスを用い、実施
例１と違って格別の熱処理をせず、重量比で１．７倍の
水酸化カリウムを混合し窒素雰囲気で４００℃で１時間
加熟後８００℃で２時間の賦活を行い炭素質材料(活性
炭)を得た。この活性炭の比表面積は、２５００ｍ2／ｇ
であった。この値は、電気二重層コンデンサで大静電容
量密度を得る活性炭として十分に使用することができる
ものである。この様にして得た活性炭を用いて、実施例
１と同様に電気二重層コンデンサを作製し、作製した電
気二重層コンデンサの特性を実施例１と同様に測定し
た。その結果を表１に示す。また、比較例１で用いた活
性炭のX線回折結果を図１においてＢで示す。 ［実施例２］やしがらを炭化処理して得たやしがら炭に
対して１０００℃で水蒸気賦活を行い、炭素質材料を得
た。賦活に当たっては、水蒸気の量を少量とすることに
より、賦活が十分に行われないようにした。この結果、
比表面積４００ｍ2／ｇの電気二重層コンデンサ用電極
材料の活性炭としては性能の不充分なものとなった。こ
の炭素質材料を用い、実施例１と同様に電気二重層コン
デンサを作製し、得られた電気二重層コンデンサの特性
を測定した。その結果を表１に示す。また、実施例２で
作成した活性炭のX線回折結果を図１においてＤで示
す。 ［比較例２］やしがらを炭化処理して得たやしがら炭を
１０００℃で水蒸気賦活して比表面積約１６００ｍ2の
活性炭を得た。この値は、電気二重層コンデンサで大静
電容量密度を得る活性炭として十分に使用することがで
きるものである。この活性炭を用いて実施例１と同様に
電気二重層コンデンサを作製し、得られた電気二重層コ
ンデンサの特性を測定した。その結果を表１に示す。ま
た、比較例２で作成した活性炭のX線回折結果を図１に
おいてＥで示す。 ［表１］ 静電容量密度 膨張圧力 比表面積 (Ｆ／ｍｌ) (ｋｇ／ｃｍ2) (ｍ2／ｇ) 実施例１ ２８．５ ７．５ ３００ 比較例１ ２０．５ １．０以下 ２５００ 実施例２ １８．８ ３．０ ４００ 比較例２ １３．４ １．０以下 １６００ 表１から、実施例の炭素質材料による電気二重層コンデ
ンサは、従来の活性炭で製造された電気二重層コンデン
サに比べていずれも４０％以上の大きな静電容量密度が
得られる点で優れている。またいずれも比較例に比べて
大きな膨張圧力を示すものであった。また、比表面積
は、電解液イオンが電極に進入する以前の状態で測定さ
れた値であるが、小さな比表面積の活性炭でも大きな静
電容量が得られ、電気二重層コンデンサの静電容量が必
ずしも電極材料の比表面積に依存しないことを示してい
る。The obtained electric double layer capacitor was charged and discharged to 4 V for one cycle. Charge and discharge current is 5mA
It is. Thereafter, the battery was charged and discharged at 2.3 V, and the characteristics were measured.
The charge and discharge and the measurement of the characteristics were performed using the apparatus of FIG.
Table 1 shows the measurement results. [Comparative Example 1] The same petroleum coke as in Example 1 was used, and no special heat treatment was performed, unlike Example 1, but 1.7 times by weight of potassium hydroxide was mixed, and the mixture was heated at 400 ° C for 1 hour in a nitrogen atmosphere. After ripening, activation was performed at 800 ° C. for 2 hours to obtain a carbonaceous material (activated carbon). The specific surface area of this activated carbon is 2500 m 2 / g
Met. This value can be sufficiently used as activated carbon for obtaining a large capacitance density with an electric double layer capacitor. Using the activated carbon thus obtained, an electric double layer capacitor was produced in the same manner as in Example 1, and the characteristics of the produced electric double layer capacitor were measured in the same manner as in Example 1. Table 1 shows the results. The result of X-ray diffraction of the activated carbon used in Comparative Example 1 is indicated by B in FIG. [Example 2] Steam activated at 1000 ° C was applied to palm charcoal obtained by carbonizing palmite to obtain a carbonaceous material. In the activation, the amount of water vapor was reduced to a small amount so that the activation was not sufficiently performed. As a result,
Activated carbon as an electrode material for an electric double layer capacitor having a specific surface area of 400 m 2 / g had insufficient performance. Using this carbonaceous material, an electric double layer capacitor was manufactured in the same manner as in Example 1, and the characteristics of the obtained electric double layer capacitor were measured. Table 1 shows the results. The result of X-ray diffraction of the activated carbon prepared in Example 2 is indicated by D in FIG. [Comparative Example 2] Coconut charcoal obtained by carbonizing palmite was steam-activated at 1000 ° C to obtain activated carbon having a specific surface area of about 1600 m 2 . This value can be sufficiently used as activated carbon for obtaining a large capacitance density with an electric double layer capacitor. Using this activated carbon, an electric double layer capacitor was produced in the same manner as in Example 1, and the characteristics of the obtained electric double layer capacitor were measured. Table 1 shows the results. The X-ray diffraction result of the activated carbon prepared in Comparative Example 2 is indicated by E in FIG. [Table 1] Capacitance density Expansion pressure Specific surface area (F / ml) (kg / cm 2 ) (m 2 / g) Example 1 28.5 7.5 300 Comparative Example 1 20.5 1.0 or less 2500 Example 2 18.8 3.0 400 Comparative Example 2 13.4 1.0 or less 1600 From Table 1, the electric double layer capacitor made of the carbonaceous material of the example is different from the conventional electric double layer capacitor made of activated carbon. All of them are excellent in that a large capacitance density of 40% or more can be obtained. In addition, each of them showed a larger expansion pressure than the comparative example. The specific surface area is a value measured before the electrolyte ions enter the electrode.A large capacitance can be obtained even with activated carbon having a small specific surface area. This shows that it does not depend on the specific surface area of the electrode material.
【００６２】[0062]
【発明の効果】本発明の電気二重層コンデンサ用炭素材
料により、従来に比べ静電容量密度の大きな電気二重層
コンデンサを得ることができる。According to the carbon material for an electric double layer capacitor of the present invention, it is possible to obtain an electric double layer capacitor having a larger capacitance density than the conventional one.
【図１】X線回折による炭素質材料の測定結果を説明す
る図である。FIG. 1 is a diagram for explaining a measurement result of a carbonaceous material by X-ray diffraction.
【図２】静電容量／膨張圧測定装置の一例を説明する図
である。FIG. 2 is a diagram illustrating an example of a capacitance / expansion pressure measuring device.
【図３】充電・放電特性及び同時に測定した膨張圧の変
化を示す図である。FIG. 3 is a graph showing changes in charge / discharge characteristics and simultaneously measured expansion pressure.
【図４】本発明の電気二重層コンデンサに対して種々の
電圧で充放電を行った際の充放電特性の変化を示す図で
ある。FIG. 4 is a diagram showing changes in charge / discharge characteristics when the electric double layer capacitor of the present invention is charged / discharged at various voltages.
【図５】本発明の電気二重層コンデンサの一例を説明す
る断面図である。FIG. 5 is a cross-sectional view illustrating an example of the electric double layer capacitor of the present invention.
【図６】本発明の他の電気二重層コンデンサの一実施例
を説明する斜視図である。FIG. 6 is a perspective view illustrating another embodiment of the electric double layer capacitor of the present invention.
１：膨張圧測定装置、２：基台、３：圧力センサー、
４：下部金属ブロック、５：合成樹脂フイルム、６：電
気二重層コンデンサ、７：上部金属ブロック、８：スラ
ストベアリング、９：取り付けねじ、１０：リード線、
１１：電源、１２：記録計、２１：コンデンサ容器、２
２：電気二重層コンデンサ積層体、２３：凹面状底板、
２４：底部押板、２５：上部押板、２６：加圧手段、２
７：注入口、２８：滑車、２９：ワイヤー、３０：引張
り部材1: inflation pressure measuring device, 2: base, 3: pressure sensor,
4: Lower metal block, 5: Synthetic resin film, 6: Electric double layer capacitor, 7: Upper metal block, 8: Thrust bearing, 9: Mounting screw, 10: Lead wire,
11: power supply, 12: recorder, 21: condenser container, 2
2: electric double layer capacitor laminate, 23: concave bottom plate
24: bottom push plate, 25: top push plate, 26: pressing means, 2
7: injection port, 28: pulley, 29: wire, 30: tension member
Claims (14)
黒鉛類似の微結晶炭素を有する電気二重層コンデンサ用
炭素材料であって、その微結晶炭素の層間距離が０．３
６５ｎｍ〜０．３８５ｎｍであることを特徴とする電気
二重層コンデンサ用炭素材料。1. A carbon material for an electric double layer capacitor having graphite-like microcrystalline carbon produced by activating a carbon material, wherein the interlayer distance of the microcrystalline carbon is 0.3.
A carbon material for an electric double layer capacitor, having a thickness of 65 nm to 0.385 nm.
を成長させる熱処理工程と、該熱処理工程で得られた炭
素材料にアルカリ賦活処理を行い、微結晶炭素の層間距
離が０．３６５ｎｍ〜０．３８５ｎｍの炭素材料を得る
ことを特徴とする電気二重層コンデンサ用炭素材料の製
造方法。2. A heat treatment step of carbonizing the raw material and growing microcrystalline carbon similar to graphite, and performing an alkali activation treatment on the carbon material obtained in the heat treatment step, wherein the interlayer distance of the microcrystalline carbon is 0.365 nm or more. A method for producing a carbon material for an electric double layer capacitor, comprising obtaining a carbon material having a thickness of 0.385 nm.
により、黒鉛類似の微結晶炭素を持ち、その微結晶炭素
の層間距離が０．３６５ｎｍ〜０．３８５ｎｍの炭素材
料を得ることを特徴とする電気二重層コンデンサ用炭素
材料の製造方法。3. An electric power characterized by obtaining a carbon material having microcrystalline carbon similar to graphite and having an interlayer distance of 0.365 nm to 0.385 nm by performing steam activation on the carbon material. Manufacturing method of carbon material for double layer capacitor.
る電気二重層コンデンサにおいて、炭素材料に賦活処理
を行って製造される黒鉛類似の微結晶炭素を有する炭素
材料であって、その微結晶炭素の層間距離が０．３６５
ｎｍ〜０．３８５ｎｍである炭素材料により前記分極性
電極を形成したことを特徴とする電気二重層コンデン
サ。4. An electric double layer capacitor comprising a polarizable electrode immersed in an organic electrolytic solution, wherein the carbon material has graphite-like microcrystalline carbon produced by performing an activation treatment on the carbon material. 0.365 interlayer distance of microcrystalline carbon
An electric double layer capacitor, wherein the polarizable electrode is formed of a carbon material having a thickness of from 0.3 nm to 0.385 nm.
おいて、前記有機電解液の溶質は、４フッ化ホウ酸塩で
あることを特徴とする電気二重層コンデンサ。5. The electric double layer capacitor according to claim 4, wherein the solute of the organic electrolyte is a tetrafluoroborate.
おいて、前記有機電解液の溶質は、テトラエチルアンモ
ニウムの４フッ化ホウ酸塩であることを特徴とする電気
二重層コンデンサ。6. The electric double layer capacitor according to claim 4, wherein the solute of the organic electrolyte is tetrafluoroammonium tetrafluoroborate.
る電気二重層コンデンサの製造方法において、炭素材料
に賦活処理を施して製造される黒鉛類似の微結晶炭素を
有する炭素材料であって、その微結晶炭素の層間距離が
０．３６５ｎｍ〜０．３８５ｎｍであり、前記電気二重
層コンデンサを組み立てた後に、最初に定格電圧以上の
電圧を前記分極性電極間に印加することによって、静電
容量を発現させることを特徴とする電気二重層コンデン
サの製造方法。7. A method for manufacturing an electric double layer capacitor in which a polarizable electrode is immersed in an organic electrolytic solution, wherein the carbon material has a microcrystalline carbon similar to graphite produced by activating the carbon material. Then, the interlayer distance of the microcrystalline carbon is 0.365 nm to 0.385 nm, and after assembling the electric double layer capacitor, a voltage equal to or higher than the rated voltage is first applied between the polarizable electrodes. A method for producing an electric double-layer capacitor, characterized by expressing electric capacity.
時に膨張する炭素質材料からなる分極性電極を有すると
ともに、分極性電極が電圧印加時の膨張を制限する寸法
制限構造体中に保持されたことを特徴とする電気二重層
コンデンサ。8. An electric double-layer capacitor having a polarizable electrode made of a carbonaceous material that expands when a voltage is applied, and wherein the polarizable electrode is held in a size-limiting structure that limits expansion when a voltage is applied. An electric double layer capacitor.
方向の電極の膨張を制限することを特徴とする請求項８
記載の電気二重層コンデンサ。9. The dimensional restriction structure restricts expansion of an electrode in a voltage application direction when a voltage is applied.
The electric double-layer capacitor as described.
寸法を制限した状態で、電極には２ｋｇ／ｃｍ2以上の
膨張圧が発生することを特徴とする請求項８記載の電気
二重層コンデンサ。10. An electric device according to claim 8, wherein an expansion pressure of 2 kg / cm 2 or more is generated in the electrode in a state where the size is limited against expansion of the polarizable electrode when voltage is applied. Multilayer capacitors.
として非水溶媒電解質を使用するとともに、分極性電極
を構成する炭素材料の層間距離ｄ002が０．３６５ｎｍ
〜０．３８５ｎｍに存在し、電圧印加時の膨張を制限す
る寸法制限構造体中に保持されていることを特徴とする
電気二重層コンデンサ。11. An electric double-layer capacitor, wherein a non-aqueous solvent electrolyte is used as an electrolytic solution, and an interlayer distance d 002 of a carbon material constituting a polarizable electrode is 0.365 nm.
An electric double layer capacitor, which is held in a size limiting structure that limits expansion when a voltage is applied.
め加熱処理した後、水酸化カリウムと混合して不活性雰
囲気中で熱処理したものであることを特徴とする請求項
８ないし１１のいずれかに記載の電気二重層コンデン
サ。12. The carbonaceous material according to claim 8, wherein petroleum coke is heat-treated in advance, mixed with potassium hydroxide and heat-treated in an inert atmosphere. The electric double-layer capacitor as described.
気中あるいは水蒸気を含む雰囲気中で熱処理したもので
あることを特徴とする請求項８ないし１１のいずれかに
記載の電気二重層コンデンサ。13. The electric double layer according to claim 8, wherein the carbonaceous material is obtained by heat-treating coconut charcoal in an inert atmosphere or an atmosphere containing steam. Capacitors.
充電することを特徴とする請求項８ないし１１のいずれ
かに記載の電気二重層コンデンサ。14. The electric double layer capacitor according to claim 8, wherein in the initial charging, the charging is performed at a voltage higher than the rated voltage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11047700A JPH11317333A (en) | 1998-03-03 | 1999-02-25 | Carbon material for electric double-layer capacitor and manufacture of the same, and electric double-layer capacitor and manufacture of the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-50862 | 1998-03-03 | ||
| JP5086298 | 1998-03-03 | ||
| JP11047700A JPH11317333A (en) | 1998-03-03 | 1999-02-25 | Carbon material for electric double-layer capacitor and manufacture of the same, and electric double-layer capacitor and manufacture of the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005107936A Division JP2005294850A (en) | 1998-03-03 | 2005-04-04 | Carbon material for electric double-layer capacitor and method of producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11317333A true JPH11317333A (en) | 1999-11-16 |
Family
ID=26387859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11047700A Pending JPH11317333A (en) | 1998-03-03 | 1999-02-25 | Carbon material for electric double-layer capacitor and manufacture of the same, and electric double-layer capacitor and manufacture of the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11317333A (en) |
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| JP2000150318A (en) * | 1998-11-18 | 2000-05-30 | Okamura Kenkyusho:Kk | Electric double layer capacitor |
| EP1113468A2 (en) * | 1999-12-28 | 2001-07-04 | Honda Giken Kogyo Kabushiki Kaisha | Activated carbon for electric double-layer capacitor |
| US6442015B1 (en) * | 1999-01-07 | 2002-08-27 | Ngk Insulators, Ltd. | Electrochemical capacitors |
| JP2003272967A (en) * | 2002-03-19 | 2003-09-26 | Nissan Diesel Motor Co Ltd | Electric double layer capacitor |
| WO2006098525A1 (en) * | 2005-03-18 | 2006-09-21 | Japan Gore-Tex Inc. | Electrode for electric double layer capacitor and electric double layer capacitor |
| WO2006098518A1 (en) * | 2005-03-18 | 2006-09-21 | Japan Gore-Tex Inc. | Production method for electric double layer capacitor |
| JP2006295153A (en) * | 2005-03-18 | 2006-10-26 | Japan Gore Tex Inc | Electrode for electric double layer capacitor and electric double layer capacitor |
| JP2007019491A (en) * | 2005-06-10 | 2007-01-25 | Japan Gore Tex Inc | Electric double layer capacitor and electrode therefor |
| EP1770727A1 (en) | 2005-08-05 | 2007-04-04 | Power Systems Co., Ltd. | Method for conducting electric activation of electric double layer capacitors |
| WO2007037523A1 (en) | 2005-09-30 | 2007-04-05 | Cataler Corporation | Carbon material for electric double layer capacitor and electric double layer capacitor |
| WO2007052742A1 (en) * | 2005-11-04 | 2007-05-10 | Stella Chemifa Corporation | Electrical storage device |
| US7232790B2 (en) | 2001-09-11 | 2007-06-19 | Showa Denko K.K. | Activated carbon, method for production thereof and use thereof |
| JP2007169126A (en) * | 2005-12-26 | 2007-07-05 | Jfe Chemical Corp | Porous material and electric double layer capacitor |
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