JP2002260970A - Activated carbonaceous structure and electric double- layer capacitor using the same - Google Patents
Activated carbonaceous structure and electric double- layer capacitor using the sameInfo
- Publication number
- JP2002260970A JP2002260970A JP2001053165A JP2001053165A JP2002260970A JP 2002260970 A JP2002260970 A JP 2002260970A JP 2001053165 A JP2001053165 A JP 2001053165A JP 2001053165 A JP2001053165 A JP 2001053165A JP 2002260970 A JP2002260970 A JP 2002260970A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- carbon powder
- activated
- electric double
- layer capacitor
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、容易に活性炭粉末
の充填密度を高めることができる活性炭質構造体に関
し、特に電気二重層コンデンサの分極性電極用として好
適な活性炭質構造体およびこれを用いた電気二重層コン
デンサに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an activated carbonaceous structure capable of easily increasing the packing density of activated carbon powder, and more particularly to an activated carbonaceous structure suitable for use as a polarizable electrode of an electric double layer capacitor, and to a use thereof. Related to the electric double-layer capacitor.
【0002】[0002]
【従来技術】電気二重層コンデンサは、電極と電解液と
の界面においてイオンの分極によりできる電気二重層を
利用したコンデンサで、コンデンサと電池の両方の機能
を兼ね備えたものであり、従来のコンデンサと比較して
大きな静電容量を発現できるとともに、急速充放電が可
能であることから、小型のメモリーバックアップ電源や
自動車の駆動源等、大容量モータなどの補助電源として
注目されている。2. Description of the Related Art An electric double layer capacitor is a capacitor using an electric double layer formed by polarization of ions at an interface between an electrode and an electrolytic solution, and has both functions of a capacitor and a battery. Compared to a large electrostatic capacity and a rapid charge / discharge capability, it is attracting attention as an auxiliary power supply for a large-capacity motor, such as a small memory backup power supply or a drive source for an automobile.
【0003】従来の電気二重層コンデンサの一例として
は、一対の板状の分極性電極間に板状のセパレータを介
在させるとともに、前記分極性電極の前記セパレータ積
層面と反対の表面それぞれに板状の集電体を積層し、か
つ該積層体を封止材にて封止した構成からなる積層型電
気二重層コンデンサが知られている。As an example of a conventional electric double layer capacitor, a plate-like separator is interposed between a pair of plate-like polarizable electrodes, and a plate-like separator is provided on each surface of the polarizable electrodes opposite to the separator laminated surface. There is known a multilayer electric double layer capacitor having a configuration in which current collectors are stacked and the stacked body is sealed with a sealing material.
【0004】かかる電気二重層コンデンサにおいては、
分極性電極の内部抵抗を低減しつつ静電容量を向上する
ことが求められており、例えば、特開平3−20151
6号公報では、分極性電極をなす活性炭質構造体とし
て、20〜30μmの粒度を主体とする活性炭粉末に対
して、3〜10重量%の数(3〜8)μmの粒度を主体
とするメソカーボン粉末を混合したものにて形成するこ
とにより、内部抵抗を低減しつつ、静電容量の高い電気
二重層コンデンサが得られることが記載されている。In such an electric double layer capacitor,
It is required to improve the capacitance while reducing the internal resistance of the polarizing electrode.
In JP-A-6 (1999), as an activated carbonaceous structure constituting a polarizable electrode, a particle size of 3 to 10% by weight of a number (3 to 8) μm is mainly based on an activated carbon powder mainly having a particle size of 20 to 30 μm. It is described that an electric double layer capacitor having a high capacitance can be obtained while reducing internal resistance by forming a mixture of mesocarbon powder.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、上記特
開平3−201516公報の電気二重層コンデンサで
は、電気二重層容量の少ないメソカーボンを添加するた
め、電気二重層コンデンサの静電容量の向上が充分でな
く、内部抵抗の増加を抑制しつつさらなる静電容量の向
上が求められていた。However, in the electric double layer capacitor disclosed in Japanese Patent Laid-Open Publication No. Hei 3-201516, the mesocarbon having a small electric double layer capacity is added, so that the electrostatic capacity of the electric double layer capacitor can be sufficiently improved. Rather, there has been a demand for further improvement in capacitance while suppressing an increase in internal resistance.
【0006】本発明は、上記課題を解決するためになさ
れたもので、その目的は、内部抵抗が低く、かつ単位体
積当たりの静電容量を向上できる電気二重層コンデンサ
の分極性電極として好適な活性炭質構造体およびそれを
用いた電気二重層コンデンサを提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has as its object to be suitable as a polarizable electrode of an electric double layer capacitor having a low internal resistance and capable of improving the capacitance per unit volume. It is to provide an activated carbonaceous structure and an electric double layer capacitor using the same.
【0007】[0007]
【課題を解決するための手段】本発明者等は、上記課題
に対して、活性炭質構造体を構成する粉末について検討
した結果、平均粒径(r1)が20〜50μmのフェノ
ール樹脂系活性炭粉末間に、過度の粉砕条件によらず容
易に得られ、内部抵抗の低減に寄与する平均粒径
(r2)が0.1r1〜0.4r1の比較的小さい粒径を
有する椰子殻系活性炭を充填することによって、活性炭
質構造体中の活性炭粉末の分散性が向上し、容易に活性
炭粉末の充填密度が向上することから、電気二重層コン
デンサの静電容量が向上するとともに、高い静電容量を
発現しやすいフェノール樹脂系活性炭粉末と、平均粒径
(r2)が比較的小さい椰子殻系活性炭粉末とを併せて
用いることによって、電気二重層コンデンサの内部抵抗
を低下する結果、短時間充電における電気二重層コンデ
ンサの内部抵抗を低減するとともに、単位体積当たりの
静電容量を高めることができることを知見した。Means for Solving the Problems The present inventors have examined the powder constituting the activated carbonaceous structure to solve the above-mentioned problems, and as a result, have found that the average particle diameter (r 1 ) of the phenolic resin-based activated carbon is 20 to 50 μm. between powder, excessive milling conditions easily obtained regardless, coconut shell contributes an average particle size in reduction of internal resistance (r 2) is having a relatively small particle size of 0.1r 1 ~0.4r 1 By filling the activated carbon, the dispersibility of the activated carbon powder in the activated carbon structure is improved, and the packing density of the activated carbon powder is easily improved. By using a phenolic resin-based activated carbon powder that easily exhibits capacitance and a coconut shell-based activated carbon powder having a relatively small average particle size (r 2 ), the internal resistance of the electric double layer capacitor is reduced. Short time It has been found that the internal resistance of the electric double layer capacitor during charging can be reduced and the capacitance per unit volume can be increased.
【0008】すなわち、本発明の活性炭質構造体は、平
均粒径(r1)が20〜50μmのフェノール樹脂系活
性炭粉末間に、平均粒径(r2)が0.1r1〜0.4r
1の椰子殻系活性炭粉末を充填してなることを特徴とす
るものである。That is, the activated carbonaceous structure of the present invention has an average particle size (r 2 ) of 0.1r 1 to 0.4r between phenolic resin-based activated carbon powders having an average particle size (r 1 ) of 20 to 50 μm.
It is characterized by being filled with the coconut shell activated carbon powder of No. 1 .
【0009】ここで、前記フェノール樹脂系活性炭粉末
を55〜75重量%と、前記椰子殻活性炭粉末を25〜
45重量%との比率で含有すること、構造体全量に対す
るFe、Cr、Ni、Na、K、Clの含有量が総量で
450ppm以下であることが望ましい。The phenolic resin-based activated carbon powder is 55 to 75% by weight, and the coconut shell activated carbon powder is 25 to 75% by weight.
It is desirable that the content is 45% by weight and that the total content of Fe, Cr, Ni, Na, K and Cl relative to the total amount of the structure is 450 ppm or less.
【0010】また、本発明の電気二重層コンデンサは、
セパレータを介して一対の上記活性炭質構造体に電解液
を含浸した分極性電極を配するとともに、該一対の分極
性電極の外側表面のそれぞれに集電体を配してなること
を特徴とするものである。Further, the electric double layer capacitor of the present invention comprises:
A pair of the activated carbonaceous structures is provided with a polarizable electrode impregnated with an electrolyte through a separator, and a current collector is provided on each of the outer surfaces of the pair of polarizable electrodes. Things.
【0011】[0011]
【発明の実施の形態】本発明の活性炭質構造体につい
て、その模式図である図1を基に説明する。図1によれ
ば、活性炭質構造体1は、平均粒径(r1)が20〜5
0μmのフェノール樹脂系活性炭粉末2間に、平均粒径
(r2)が0.1r1〜0.4r1の椰子殻系活性炭粉末
3を充填してなることが大きな特徴であり、これによっ
て、活性炭粉末間に大きな空隙が残存することなく、ま
た、活性炭粉末同士が凝集して凝集粒子内に大きな空隙
が残存することなく、活性炭粉末の充填密度を高めて電
気二重層コンデンサの静電容量を向上することができる
とともに、構造体として高い機械的強度を有するものと
なる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The activated carbonaceous structure of the present invention will be described with reference to FIG. According to FIG. 1, the activated carbonaceous structure 1 has an average particle size (r 1 ) of 20 to 5.
Between phenolic resin activated carbon powder 2 0 .mu.m, the average particle diameter (r 2) is 0.1r 1 ~0.4r 1 of coconut shell-based activated carbon powder 3 that a large technical feature made by filling a, thereby, There is no large void remaining between the activated carbon powders, and no large voids remain in the aggregated particles due to the aggregation of the activated carbon powders. The structure can be improved, and the structure has high mechanical strength.
【0012】また、平均粒径(r2)の小さい椰子殻系
活性炭粉末3は、粉末の内部にまでわたって形成されて
いる細孔内部へ電解液イオンが容易に拡散することがで
き、拡散抵抗が小さくなるために、電気二重層のやり取
り速度が速くでき、特に充放電初期の電流の応答性が向
上することから、特に充放電初期の電流の応答性を高め
て内部抵抗の低減を図ることができる。Further, in the coconut shell-based activated carbon powder 3 having a small average particle diameter (r 2 ), the electrolyte ions can easily diffuse into the pores formed extending to the inside of the powder. Since the resistance is reduced, the exchange speed of the electric double layer can be increased, and the responsiveness of the current at the initial stage of charging and discharging is particularly improved, so that the responsiveness of the current at the initial stage of charging and discharging is particularly increased to reduce the internal resistance. be able to.
【0013】さらに、本発明によれば、活性炭として平
均粒径(r1)が20〜50μmのフェノール樹脂系活
性炭粉末2と、平均粒径(r2)が0.1r1〜0.4r
1の椰子殻系活性炭粉末3とを組み合わせて含有せしめ
るものである。Further, according to the present invention, phenolic resin-based activated carbon powder 2 having an average particle size (r 1 ) of 20 to 50 μm as activated carbon, and an average particle size (r 2 ) of 0.1 r 1 to 0.4 r
Are those allowed to contain a combination of a 1 coconut shell based activated carbon powder 3.
【0014】すなわち、フェノール樹脂系活性炭粉末2
は高い静電容量を有するものの、粉末自体が硬く、粉砕
によって粉砕機や粉砕メディアからFe、Cr、Ni、
Na、K、Cl等のコンタミネーションが混入しやす
い。このために、フェノール樹脂系活性炭粉末2の平均
粒径(r1)が20μmよりも小さくなると活性炭粉末
中に上記不純物が多量に混入して、電解液との反応によ
りガスが発生して電解液が劣化し、電気二重層コンデン
サの静電容量が低下するという問題が生じる。That is, phenolic resin-based activated carbon powder 2
Has a high capacitance, but the powder itself is hard, and the powder itself is fed from a pulverizer or a pulverizing medium to Fe, Cr, Ni,
Contaminants such as Na, K, and Cl are easily mixed. For this reason, when the average particle diameter (r 1 ) of the phenolic resin-based activated carbon powder 2 is smaller than 20 μm, a large amount of the above impurities are mixed into the activated carbon powder, and a gas is generated by the reaction with the electrolytic solution to form the electrolytic solution. And the capacitance of the electric double layer capacitor decreases.
【0015】逆に、フェノール樹脂系活性炭粉末2の平
均粒径(r1)が50μmを越えると、構造体中の活性
炭粉末の含有比率が低下する。フェノール樹脂系活性炭
粉末2の平均粒径(r1)の望ましい範囲は35〜45
μmである。Conversely, when the average particle size (r 1 ) of the phenolic resin-based activated carbon powder 2 exceeds 50 μm, the content ratio of the activated carbon powder in the structure decreases. Desirable range of the average particle diameter of the phenol resin-based activated carbon powder 2 (r 1) is 35 to 45
μm.
【0016】また、平均粒径が20〜50μmのフェノ
ール樹脂系活性炭粉末2を添加しないと、平均粒径が小
さい椰子殻系活性炭粉末3間に凝集が起こって凝集粒子
の内部等に大きな空隙が生じてしまう結果、構造体中の
活性炭の充填密度が低下して強度および静電容量が低下
する。If the phenolic resin-based activated carbon powder 2 having an average particle diameter of 20 to 50 μm is not added, aggregation occurs between the coconut shell-based activated carbon powders 3 having a small average particle diameter, and large voids are formed inside the aggregated particles. As a result, the packing density of the activated carbon in the structure decreases, and the strength and the capacitance decrease.
【0017】逆に、平均粒径(r2)が0.1r1〜0.
4r1の椰子殻系活性炭粉末3を添加しない場合には、
フェノール樹脂系活性炭粉末2間に多くの空隙が生じて
静電容量が低下するとともに、特に充放電初期時の内部
抵抗が高くなってしまう。また、椰子殻系活性炭粉末3
の平均粒径(r2)が0.1r1よりも小さい場合には、
粉末間の凝集力が増大し、分散性が低下して椰子殻系活
性炭粉末3同士が凝集してしまう結果、フェノール樹脂
系活性炭粉末2間の空隙を有効に埋めることができず内
部抵抗が増加してしまう。Conversely, when the average particle size (r 2 ) is between 0.1 r 1 and 0.1.
If 4r 1 coconut shell activated carbon powder 3 is not added,
Many voids are formed between the phenolic resin-based activated carbon powders 2 to lower the capacitance and increase the internal resistance particularly at the beginning of charging and discharging. In addition, coconut shell activated carbon powder 3
When the average particle size (r 2 ) of is less than 0.1 r 1 ,
As the cohesive force between the powders increases, the dispersibility decreases and the coconut shell-based activated carbon powders 3 aggregate, so that the voids between the phenolic resin-based activated carbon powders 2 cannot be effectively filled and the internal resistance increases. Resulting in.
【0018】さらに、椰子殻系活性炭粉末3の平均粒径
(r2)が0.4r1よりも大きい場合には、フェノール
樹脂系活性炭粉末2間に生じた空隙を充分に埋めること
ができず、活性炭の充填性が低下する。椰子殻系活性炭
粉末3の平均粒径(r2)の望ましい範囲は0.15r1
〜0.3r1である。Further, when the average particle size (r 2 ) of the coconut shell activated carbon powder 3 is larger than 0.4 r 1 , the voids formed between the phenolic resin activated carbon powders 2 cannot be sufficiently filled. In addition, the fillability of the activated carbon decreases. The desirable range of the average particle size (r 2 ) of the coconut shell activated carbon powder 3 is 0.15r 1
0.30.3 r 1 .
【0019】また、本発明によれば、活性炭質構造体1
中の活性炭の充填密度を高めるとともに、電気二重層コ
ンデンサの内部抵抗の低減および静電容量の向上を図る
ために、フェノール樹脂系活性炭粉末2を55〜75重
量%と、椰子殻活性炭粉末3を25〜45重量%との比
率で含有することが望ましい。Further, according to the present invention, the activated carbonaceous structure 1
In order to increase the packing density of the activated carbon therein, to reduce the internal resistance of the electric double layer capacitor and to improve the capacitance, 55 to 75% by weight of the phenol resin-based activated carbon powder 2 and the coconut shell activated carbon powder 3 were used. Desirably, the content is 25 to 45% by weight.
【0020】さらに、本発明によれば、活性炭粉末中に
特に粉砕等によって混入するFe、Cr、Ni、Na、
KおよびClが構造体全量に対して総量で450ppm
以下あることが望ましい。Further, according to the present invention, Fe, Cr, Ni, Na,
K and Cl are 450 ppm in total amount with respect to the total amount of the structure
It is desirable to have the following.
【0021】また、活性炭質構造体1中には、例えば、
平均粒径が200nm以下、特に50〜100nmのケ
ッチェンブラック等の導電性カーボンやポリテトラフル
オロエチレン(PTFE)等のテフロン(登録商標)樹
脂が結合剤4として含有されていてもよく、また、ケッ
チェンブラックの一部はけん糸性を有し繊維状をなして
いることが構造体の強度向上の点で望ましい。なお、各
成分の含有量は、例えば、活性炭粉末の総量80〜85
重量%と、ケッチェンブラック5〜10重量%とPTF
E5〜10重量%の比率からなることが望ましい。In the activated carbonaceous structure 1, for example,
Conductive carbon such as Ketjen black having an average particle diameter of 200 nm or less, particularly 50 to 100 nm, or Teflon (registered trademark) resin such as polytetrafluoroethylene (PTFE) may be contained as the binder 4, It is desirable that a part of Ketjen Black has a toughness and is in a fibrous form from the viewpoint of improving the strength of the structure. In addition, the content of each component is, for example, the total amount of activated carbon powder 80 to 85.
Wt%, Ketjen Black 5-10 wt% and PTF
It is desirable to have a ratio of E5 to 10% by weight.
【0022】さらに、結合剤としては上記成分以外に
も、ポリビニリデンフルオライト(PVDF)、フェノ
ール、コールタール、ポリブチルブチラール(PVB)
等を好適に添加することができ、また、これら結合剤4
は炭化してかーボンとして存在してもよい。Further, as the binder, in addition to the above components, polyvinylidenefluorite (PVDF), phenol, coal tar, polybutylbutyral (PVB)
And the like, and these binders 4
May be carbonized to exist as a carbon.
【0023】また、コンデンサの静電容量を高める等、
活性炭質構造体としての特性を最大限発揮しつつ、構造
体として必要な強度を得るため、活性炭質構造体1は、
比表面積が1000〜2500m2/gであることが望
ましい。In addition, the capacitance of the capacitor is increased,
In order to maximize the properties of the activated carbonaceous structure and obtain the required strength as a structure, the activated carbonaceous structure 1
It is desirable that the specific surface area is 1000 to 2500 m 2 / g.
【0024】(電気二重層コンデンサの構成)次に、上
記活性炭質構造体の好適な適応例として、活性炭質構造
体1内に電解液を含浸し、これを電気二重層コンデンサ
の分極性電極として用いた一例について図2の概略断面
図を基に説明する。(Structure of Electric Double Layer Capacitor) Next, as a preferred application example of the above-mentioned activated carbonaceous structure, an active carbonaceous structure 1 is impregnated with an electrolytic solution, and this is used as a polarizable electrode of the electric double layer capacitor. One example used will be described with reference to the schematic sectional view of FIG.
【0025】図2によれば、電気二重層コンデンサ11
は、セパレータ13を介して一対の2枚の分極性電極1
2、12を積層するとともに、該分極性電極12、12
の外側の表面それぞれに集電体14、14を積層した集
電体14−分極性電極12−セパレータ13−分極性電
極12−集電体14の電極体セル15を具備している。According to FIG. 2, the electric double layer capacitor 11
Is a pair of two polarizable electrodes 1 via a separator 13.
2 and 12, and the polarizable electrodes 12 and 12
An electrode body cell 15 of a current collector 14, a polarizable electrode 12, a separator 13, a polarizable electrode 12, and a current collector 14 in which current collectors 14 and 14 are laminated on the outer surfaces of the current collector 14, respectively is provided.
【0026】ここで、分極性電極12は、上述した活性
炭質構造体1中に電解液を含浸したものからなることか
ら、上述したとおり、電気二重層コンデンサ11は内部
抵抗が低く、かつ静電容量の高いものとなり、特に、短
時間充電において電気二重層コンデンサ11の静電容量
を高めることができる。Here, since the polarizable electrode 12 is made of the above-described activated carbonaceous structure 1 impregnated with an electrolytic solution, as described above, the electric double layer capacitor 11 has a low internal resistance, The capacitance is high, and the capacitance of the electric double layer capacitor 11 can be increased particularly in short-time charging.
【0027】また、分極性電極12中に含浸される電解
液としては、硫酸や硝酸などの水溶液や、エチレンカー
ボネート(EC)、プロピレンカーボネート(PC)、
ブチレンカーボネート(BC)、γ−ブチロラクトン
(γ−BL)、N,N−ジメチルホルムアミド、スルホ
ラン、3−メチルスルホラン等の非水溶媒とテトラアン
モニウムテトラフルオロボレート等の4級アンモニウム
塩、4級スルホニウム塩、4級ホスホニウム塩等の電解
質を組み合わせた非水系電解液が使用可能であるが、特
に分解電圧の高い非水系電解液を用いることが望まし
い。さらに、安定で高い静電容量を得るためには、前記
電解質の前記溶媒に対する溶解量は0.5〜2mol/
lとすることが望ましい。The electrolytic solution impregnated in the polarizable electrode 12 may be an aqueous solution such as sulfuric acid or nitric acid, ethylene carbonate (EC), propylene carbonate (PC), or the like.
Non-aqueous solvents such as butylene carbonate (BC), γ-butyrolactone (γ-BL), N, N-dimethylformamide, sulfolane, and 3-methylsulfolane; and quaternary ammonium salts such as tetraammonium tetrafluoroborate and quaternary sulfonium salts Although a non-aqueous electrolytic solution in which an electrolyte such as a quaternary phosphonium salt is combined can be used, it is particularly preferable to use a non-aqueous electrolytic solution having a high decomposition voltage. Furthermore, in order to obtain a stable and high capacitance, the amount of the electrolyte dissolved in the solvent is 0.5 to 2 mol / mol.
It is desirable to be 1.
【0028】一方、分極性電極12、12間に配される
セパレータ13は、パルプやポリエチレン、ポリプロピ
レン等の有機フィルムまたはガラス繊維不織布等および
セラミックス等により形成され、正極および負極をなす
一対の分極性電極12、12間を絶縁するために形成さ
れるものであるが、前記電解液中のイオンを透過させる
ことができる多孔質体により形成され、セパレータ13
内にも電解液が含浸される。On the other hand, the separator 13 disposed between the polarizable electrodes 12, 12 is formed of an organic film such as pulp or polyethylene or polypropylene, a glass fiber nonwoven fabric, ceramics, or the like, and a pair of polarizers forming a positive electrode and a negative electrode. The separator 12 is formed to insulate the electrodes 12 from each other, and is formed of a porous material through which ions in the electrolytic solution can pass.
The electrolyte is also impregnated inside.
【0029】また、集電体14は、導電性を有するアル
ミニウム、銀、金、ニッケル、ステンレス鋼等の金属、
特に、20〜100μm厚みの金属箔またはステンレス
鋼等により形成され、分極性電極12との間で電荷をや
り取りする。The current collector 14 is made of a conductive metal such as aluminum, silver, gold, nickel, stainless steel, or the like.
In particular, it is formed of a metal foil or stainless steel having a thickness of 20 to 100 μm, and exchanges electric charges with the polarizable electrode 12.
【0030】さらに、電極体セル15は分極性電極12
に含浸される電解液の外部への漏れを防止するととも
に、前記積層体を固定、保護するため、外装材16内に
収納、封止される。外装材16としては、非導電性の材
料、例えば、ポリプロピレン、アクリル等のプラスチッ
クや、ガラス、セラミックス、さらには、アルミニウム
箔等の金属箔の両面を有機樹脂フィルムで被覆した、い
わゆるラミネートフィルム等により形成される。Further, the electrode assembly cell 15 is provided with the polarizable electrode 12.
In order to prevent the electrolyte solution impregnated in the laminate from leaking to the outside and to fix and protect the laminate, the laminate is housed and sealed in the exterior material 16. The exterior material 16 is made of a non-conductive material, for example, a plastic such as polypropylene or acrylic, glass, ceramics, or a so-called laminate film in which both surfaces of a metal foil such as an aluminum foil are covered with an organic resin film. It is formed.
【0031】また、図2においては、分極性電極12、
セパレータ13、集電体14が板状体からなり、これら
板状体を積層したものであったが、本発明はこれに限定
されるものではなく、集電体−分極性電極−セパレータ
の長尺テープ状の積層体を巻回して形成したものであっ
てもよい。In FIG. 2, the polarizable electrode 12,
Although the separator 13 and the current collector 14 were formed of a plate-like body and these plate-like bodies were laminated, the present invention is not limited to this, and the length of the current collector-polarizable electrode-separator It may be formed by winding a length tape-shaped laminate.
【0032】(製造方法)次に、上述した電気二重層コ
ンデンサを作製する方法について説明する。まず、分極
性電極を形成する固形状活性炭質構造体(以下、活性炭
質構造体と略す。)を作製するには、粒径の異なる2種
類の活性炭原料を準備する。平均粒径(r1)が20〜
50μmのフェノール樹脂系活性炭は、フェノール樹脂
を出発原料として水蒸気賦活、薬品賦活やガス賦活さ
れ、所望により粗粉砕して作製される。一方、平均粒径
(r2)が0.1r1〜0.4r1の椰子殻系活性炭は、
安価な椰子殻を出発原料として水蒸気賦活、薬品賦活や
ガス賦活により作製され、所望により粉砕して作製され
る。(Manufacturing Method) Next, a method for manufacturing the above-described electric double layer capacitor will be described. First, in order to produce a solid activated carbon structure (hereinafter, abbreviated as activated carbon structure) forming a polarizable electrode, two types of activated carbon raw materials having different particle sizes are prepared. Average particle size (r 1 ) of 20 to
The phenolic resin-based activated carbon having a thickness of 50 μm is produced by using a phenolic resin as a starting material, being steam-activated, chemical-activated or gas-activated, and roughly pulverized if desired. On the other hand, coconut shell activated carbon having an average particle size (r 2 ) of 0.1 r 1 to 0.4 r 1 is
It is produced by using a cheap coconut shell as a starting material by steam activation, chemical activation, or gas activation, and pulverized if necessary.
【0033】上記2種の活性炭粉末を所定の範囲となる
ように配合し、高速混合攪拌機やボールミル等にて湿式
または乾式で充分に混合を行い、均一混合を行い2種の
活性炭粉末の分散させた後に、この活性炭混合原料にケ
ッチェンブラック等の導電性カーボンやポリテトラフル
オロエチレン(PTFE)等のテフロン樹脂等の結合剤
を所定量添加して、高速混合撹拌機にて混合する。な
お、結合剤としては、上記以外にも、ポリビニリデンフ
ルオライド(PVDF)、フェノール、コールタール、
ポリビニルブチラール(PVB)等を好適に添加するこ
とができるが、とりわけ成形性および得られる固形状活
性炭質構造体の強度の観点からポリテトラフルオロエチ
レン(PTFE)が最適である。The above two types of activated carbon powders are blended so as to be in a predetermined range, thoroughly mixed in a wet or dry system using a high-speed mixing stirrer, a ball mill or the like, and uniformly mixed to disperse the two types of activated carbon powders. After that, a predetermined amount of a binder such as conductive carbon such as Ketjen black or a Teflon resin such as polytetrafluoroethylene (PTFE) is added to the activated carbon mixed raw material, and mixed with a high-speed mixing stirrer. In addition, as the binder, in addition to the above, polyvinylidene fluoride (PVDF), phenol, coal tar,
Polyvinyl butyral (PVB) or the like can be suitably added, but polytetrafluoroethylene (PTFE) is most suitable from the viewpoint of moldability and the strength of the obtained solid activated carbonaceous structure.
【0034】得られた混合粉体をプレス成形、押出成
形、ロール成形や、ドクターブレード法、カレンダーロ
ール法等のテープ成形法等の公知の成形法によってシー
ト状の活性炭質構造体を作製する。また、該シート状の
活性炭質構造体を複数枚積層、圧着してもよい。また、
所望により、該活性炭質構造体を炭化してもよい。The obtained mixed powder is formed into a sheet-like activated carbonaceous structure by a known molding method such as press molding, extrusion molding, roll molding, or a tape molding method such as a doctor blade method or a calendar roll method. Further, a plurality of the sheet-like activated carbonaceous structures may be laminated and pressure-bonded. Also,
If desired, the activated carbonaceous structure may be carbonized.
【0035】得られた2枚の活性炭質構造体間にセパレ
ータを配し、活性炭質構造体の外側表面それぞれに集電
体を配することによって、集電体−活性炭質構造体(分
極性電極)−セパレータ−活性炭質構造体(分極性電
極)−集電体の電極体セルを形成し、所望によって該電
極体セルを複数積層する。なお、電極体セルの作成方法
としては、集電体−活性炭質構造体(分極性電極)−セ
パレータ−活性炭質構造体(分極性電極)の長尺テープ
状の積層体を巻回して形成してもよい。By arranging a separator between the obtained two activated carbonaceous structures and disposing a current collector on each of the outer surfaces of the activated carbonaceous structures, a current collector-activated carbonaceous structure (polarizable electrode) -)-Separator-Activated carbonaceous structure (polarizable electrode)-A current collector electrode body cell is formed, and a plurality of the electrode body cells are laminated as required. The electrode body cell is formed by winding a long tape-shaped laminate of a current collector-activated carbonaceous structure (polarizable electrode) -separator-activated carbonaceous structure (polarizable electrode). You may.
【0036】そして、この電極体セルを外装材内に収納
し、該外装材内の前記活性炭質構造体内に電解液を注入
して分極性電極とするとともに、セパレータ内にも電解
液を注入した後、前記外装材を封口することにより電気
二重層コンデンサを作製することができる。Then, the electrode body cell was housed in an exterior material, and an electrolyte was injected into the activated carbonaceous structure in the exterior material to form a polarizable electrode, and an electrolyte was also injected into the separator. Thereafter, the electric double layer capacitor can be manufactured by sealing the exterior material.
【0037】[0037]
【実施例】フェノール樹脂を炭化賦活して得たBET値
が1500m2/gで表1に示す平均粒径(r1)からな
るフェノール樹脂系活性炭粉末と、椰子殻を炭化賦活し
たBET値が1500m2/gで表1に示す平均粒径
(r2)からなる椰子殻系活性炭粉末とを表1に示す重
量比率にて混合して高速混合攪拌機にて混合する。EXAMPLE A phenolic resin-based activated carbon powder having a BET value of 1500 m 2 / g and an average particle size (r 1 ) shown in Table 1 obtained by carbonizing a phenol resin, and a BET value obtained by carbonizing a coconut shell were obtained. A coconut shell-based activated carbon powder having an average particle size (r 2 ) shown in Table 1 at 1500 m 2 / g is mixed at a weight ratio shown in Table 1 and mixed with a high-speed mixing stirrer.
【0038】次に、得られた混合活性炭80重量%に対
して、ケッチェンブラック10重量%、ポリテトラフル
オロエチレン(PTFE)10重量%を混合して、再び
高速混合撹拌機にて撹拌し、得られた粉体を40メッシ
ュでメッシュパスを行った後、ロール成形によって15
0μmの厚みのシート状の活性炭質成形体を作製し、1
00mm×100mmの形状にカットした。Next, 10% by weight of Ketjen black and 10% by weight of polytetrafluoroethylene (PTFE) were mixed with 80% by weight of the obtained mixed activated carbon, and the mixture was again stirred by a high-speed mixing stirrer. The obtained powder was subjected to a mesh pass with 40 mesh, and then roll-formed to form a powder.
A sheet-like activated carbonaceous molded article having a thickness of 0 μm was prepared, and
It was cut into a shape of 00 mm x 100 mm.
【0039】得られた、前記活性炭質構造体内に1mo
l/lのテトラエトキシアンモニウムテトラフルオロボ
レート(Et4NBF4)のプロピレンカーボネート(P
C)溶液を電解液として含浸させた後、ガラス性不織布
からなる多孔質セパレータを介して積層して積層体セル
を形成し、該積層体セルをアルミラミネートによって封
止して電気二重層コンデンサを作製した。In the obtained activated carbonaceous structure, 1 mo was added.
1 / l of tetraethoxyammonium tetrafluoroborate (Et 4 NBF 4 ) propylene carbonate (P
C) After the solution is impregnated as an electrolyte, the laminate is formed through a porous separator made of a glassy nonwoven fabric to form a laminate cell, and the laminate cell is sealed with aluminum laminate to form an electric double layer capacitor. Produced.
【0040】そして、得られた電気二重層コンデンサに
ついて、2.7Vの電圧で30分間充電した後、3mA
/cm2の電流で定電流放電法にてコンデンサの静電容
量(F)を求めた。また、内部抵抗は、放電時電圧が0
になった直後に放電を中止し、その際の電圧上昇から、
放電中止10分後の電圧Vを測定して内部抵抗(R)=
V/Iより求めた。Then, the obtained electric double layer capacitor was charged at a voltage of 2.7 V for 30 minutes, and then charged at 3 mA.
The capacitance (F) of the capacitor was determined by a constant current discharge method at a current of / cm 2 . In addition, the internal resistance is such that the discharge voltage is 0.
Discharge is stopped immediately after it becomes, and from the voltage rise at that time,
The voltage V 10 minutes after the discharge was stopped was measured to determine the internal resistance (R) =
It was determined from V / I.
【0041】[0041]
【表1】 [Table 1]
【0042】表1より明らかなように、椰子殻系活性炭
粉末を含有しない試料No.1では静電容量が低く、内
部抵抗が高いものであった。また、フェノール樹脂系活
性炭粉末を含有しない試料No.8では椰子殻系活性炭
粉末同士の凝集によって静電容量が低く、内部抵抗も増
大した。さらに、椰子殻系活性炭粉末の平均粒径
(r 2)が0.1r1(r1:フェノール樹脂系活性炭粉
末の平均粒径)よりも小さい試料No.2、0.4r1
よりも大きい試料No.10、11では、粉末の充填性
が悪く内部抵抗が増加した。As is clear from Table 1, coconut shell activated carbon
Sample No. containing no powder 1, the capacitance is low.
Partial resistance was high. In addition, phenolic resin-based
Sample No. containing no charcoal powder 8 is coconut shell activated carbon
Low capacitance and increased internal resistance due to agglomeration of powders
Great. Furthermore, the average particle size of the coconut shell activated carbon powder
(R Two) Is 0.1r1(R1: Phenolic resin activated carbon powder
(Average particle size of the powder). 2, 0.4r1
Sample no. In 10 and 11, powder filling
However, the internal resistance increased.
【0043】さらに、フェノール樹脂系活性炭粉末の平
均粒径(r1)が20μmよりも小さい試料No.11
では、粉末作製時の粉砕により不純物成分が多量に混入
して内部抵抗が増大し、静電容量が低下した。逆にフェ
ノール樹脂系活性炭粉末の平均粒径(r1)が50μm
を越える試料No.14では、活性炭粉末の充填性が低
下し、静電容量が低く、かつ内部抵抗が高いものであっ
た。Further, the phenolic resin-based activated carbon powder having the average particle size (r 1 ) of less than 20 μm was used for sample No. 11
In this case, a large amount of impurity components were mixed by pulverization at the time of powder production, the internal resistance increased, and the capacitance decreased. Conversely, the average particle size (r 1 ) of the phenolic resin-based activated carbon powder is 50 μm.
Sample no. In No. 14, the packing property of the activated carbon powder was reduced, the capacitance was low, and the internal resistance was high.
【0044】これに対して、平均粒径(r1)が20〜
50μmのフェノール樹脂系活性炭粉末(A粉末)と平
均粒径(r2)が0.1r1〜0.4r1の椰子殻系活
性炭粉末(B粉末)とを組み合わせて用い、A粉末の間
にB粉末を充填してなる試料No.3〜7、9、12、
13では、活性炭粉末の分散性および充填性を高めるこ
とができ、いずれも内部抵抗31Ω以下、静電容量14
F/cc以上の優れた特性を有するものであった。ま
た、ICP分析を行った結果、試料No.11以外の試
料については、Fe、Cr、Ni、Na、KおよびCl
の含有量が総量で450ppm以下であった。On the other hand, when the average particle size (r 1 ) is 20 to
A phenolic resin-based activated carbon powder (A powder) of 50 μm and a coconut shell-based activated carbon powder (B powder) having an average particle size (r 2 ) of 0.1r1 to 0.4r1 are used in combination. Sample No. 3-7, 9, 12,
In No. 13, the dispersibility and the filling property of the activated carbon powder can be enhanced, and in each case, the internal resistance is 31Ω or less, and the capacitance is 14
It had excellent characteristics of F / cc or more. As a result of the ICP analysis, the sample No. For samples other than 11, Fe, Cr, Ni, Na, K and Cl
Was 450 ppm or less in total.
【0045】[0045]
【発明の効果】以上詳述したように、本発明の活性炭質
構造体によれば、平均粒径(r1)が20〜50μmの
フェノール樹脂系活性炭粉末間に、平均粒径(r2)が
0.1r1〜0.4r1の椰子殻系活性炭粉末を充填して
なることによって、活性炭粉末間に大きな空隙が残存す
ることなく、また、活性炭粉末同士が凝集して凝集粒子
内に大きな空隙が残存することなく、活性炭粉末の充填
密度を高めて電気二重層コンデンサの静電容量を向上す
ることができるとともに、内部抵抗を低減することがで
きることから、特に充放電初期の電流の応答性を高めて
内部抵抗の低減を図ることができる。As described above in detail, according to the activated carbon quality structures of the present invention, the average particle diameter (r 1) is between phenolic resin activated carbon powder of 20 to 50 m, an average particle diameter (r 2) Is filled with 0.1 r 1 to 0.4 r 1 of coconut shell activated carbon powder, so that no large voids remain between the activated carbon powders and the activated carbon powders aggregate to form large aggregated particles. Since no voids remain, the density of the activated carbon powder can be increased and the capacitance of the electric double layer capacitor can be improved, and the internal resistance can be reduced. And the internal resistance can be reduced.
【図1】本発明の活性炭質構造体の一例を示す模式図で
ある。FIG. 1 is a schematic view showing one example of the activated carbonaceous structure of the present invention.
【図2】本発明の活性炭質構造体を分極性電極として用
いた電二重層コンデンサの一例についての概略断面図で
ある。FIG. 2 is a schematic cross-sectional view of an example of an electric double layer capacitor using the activated carbonaceous structure of the present invention as a polarizable electrode.
1 活性炭質構造体 2 フェノール樹脂系活性炭粉末 3 椰子殻系活性炭粉末 4 結合剤 11 電気二重層コンデンサ 12 分極性電極 13 セパレータ 14 集電体 15 電極体セル 16 外装材 DESCRIPTION OF SYMBOLS 1 Activated carbonaceous structure 2 Phenolic resin type activated carbon powder 3 Coconut shell type activated carbon powder 4 Binder 11 Electric double layer capacitor 12 Polarized electrode 13 Separator 14 Current collector 15 Electrode cell 16 Exterior material
Claims (4)
ノール樹脂系活性炭粉末間に、平均粒径(r2)が0.
1r1〜0.4r1の椰子殻系活性炭粉末を充填してなる
ことを特徴とする活性炭質構造体。To 1. A mean particle diameter (r 1) is between phenolic resin activated carbon powder of 20 to 50 m, an average particle diameter (r 2) is 0.
Activated carbon membrane structure characterized by comprising filling a coconut shell based activated carbon powder 1r 1 ~0.4r 1.
5重量%と、前記椰子殻活性炭粉末を25〜45重量%
との比率で含有することを特徴とする請求項1記載の活
性炭質構造体。2. The phenolic resin-based activated carbon powder 55 to 7
5% by weight, and 25-45% by weight of the coconut shell activated carbon powder
The activated carbonaceous structure according to claim 1, which is contained in a ratio of:
a、K、Clの含有量が総量で450ppm以下である
ことを特徴とする請求項1または2記載の活性炭質構造
体。3. Fe, Cr, Ni, N based on the total amount of the structure
3. The activated carbonaceous structure according to claim 1, wherein the total content of a, K, and Cl is 450 ppm or less.
のいずれか記載の活性炭質構造体に電解液を含浸した分
極性電極を配するとともに、該一対の分極性電極の外側
表面のそれぞれに集電体を配してなることを特徴とする
電気二重層コンデンサ。4. A pair of claim 1 through 3 via a separator.
And a current collector disposed on each of the outer surfaces of the pair of polarizable electrodes, and a polarizable electrode obtained by impregnating the activated carbonaceous structure with an electrolytic solution. Multilayer capacitors.
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JP2004189586A (en) * | 2002-11-29 | 2004-07-08 | Honda Motor Co Ltd | Activated carbon, polarizable electrode for electric double-layer capacitor, and electric double-layer capacitor using the same |
JP2006269961A (en) * | 2005-03-25 | 2006-10-05 | Japan Energy Corp | Carbonaceous substance for electrode material |
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CN104064369A (en) * | 2014-06-28 | 2014-09-24 | 北京航空航天大学 | Preparation of natural nutshell carbon material and application of natural nutshell carbon material in electrochemical capacitors |
JP2017073462A (en) * | 2015-10-07 | 2017-04-13 | 太陽誘電株式会社 | Electrochemical device |
JP2019145628A (en) * | 2018-02-20 | 2019-08-29 | Tdk株式会社 | Active material particles and power storage device including the same |
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CN109801791B (en) * | 2019-01-03 | 2020-12-08 | 上海奥威科技开发有限公司 | Electrode active material, electrode thereof, and electric double layer supercapacitor |
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