JP4807128B2 - Electric double layer capacitor using carbon nanotube and method for manufacturing the same - Google Patents

Electric double layer capacitor using carbon nanotube and method for manufacturing the same Download PDF

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JP4807128B2
JP4807128B2 JP2006093205A JP2006093205A JP4807128B2 JP 4807128 B2 JP4807128 B2 JP 4807128B2 JP 2006093205 A JP2006093205 A JP 2006093205A JP 2006093205 A JP2006093205 A JP 2006093205A JP 4807128 B2 JP4807128 B2 JP 4807128B2
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carbon nanotube
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JP2007266548A (en
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研次 ▲吉▼川
大祐 藤田
暁晴 北村
正司 石川
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Hitachi Zosen Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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

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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electric double layer capacitor where there is no possibility of a leaked liquid due to a deformation caused from an impact, bending load etc., and which is thin and can storage a large capacity of electricity. <P>SOLUTION: The electric double layer capacitor is constructed in a manner such that a pair of positive/negative electrodes, in which a gelled electrolytic membrane 3 is formed on a collector 1 so as to cover a group 2 of carbon nanotubes located on the collector 1, are located so that a group of positive nanotubes and a group of negative nanotubes face each other in a non-contact manner. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

本発明は、漏液の恐れがなく、薄型で大容量の電気を蓄えることの可能な電気二重層キャパシタおよびその製造方法に関する。 The present invention relates to an electric double layer capacitor capable of storing a large amount of electricity without fear of leakage and a method for manufacturing the same .

従来、電気二重層キャパシタでは、集電体上に活性炭を主とする分極性電極層を形成した一対の分極性電極層の間にポリプロピレン不織布などのセパレータを挟んで素子とし、電極層に電解液を含浸させ、素子を金属容器に収容し、封口板とガスケットにより金属容器を密封した構造がとられていた（特許文献１参照）。   Conventionally, in an electric double layer capacitor, a separator such as a polypropylene non-woven fabric is sandwiched between a pair of polarizable electrode layers in which a polarizable electrode layer mainly composed of activated carbon is formed on a current collector, and an electrolytic solution is applied to the electrode layer. The element was housed in a metal container, and the metal container was sealed with a sealing plate and a gasket (see Patent Document 1).

また、大比表面積を有する活性炭は一般に電気伝導度が小さく、活性炭のみでは分極性電極の内部抵抗が大きくなって大電流が取出せないため、内部抵抗を下げる目的で、分極性電極中にカーボンナノチューブ群を含有させて電気伝導度を上げることにより大容量化を図る試みも行われている（特許文献２参照）。
特開平４−１５４１０６号公報 特開２０００−１２４０７９号公報 In addition, activated carbon having a large specific surface area generally has low electrical conductivity, and the activated carbon alone increases the internal resistance of the polarizable electrode, and a large current cannot be taken out. Therefore, in order to reduce the internal resistance, carbon nanotubes are included in the polarizable electrode. Attempts have been made to increase the capacity by adding groups to increase the electrical conductivity (see Patent Document 2).
JP-A-4-154106 JP 2000-1224079 A

上記のような電気二重層キャパシタは、従来の電解コンデンサに比べ大容量であり、瞬時充放電特性に優れているため、ＩＣ回路のバックアップ電源等で幅広く利用され、近年では、携帯端末等のモバイル機器への適用に向けて、さらに小型軽量かつ大容量の電気二重層キャパシタの開発が進められている。   The electric double layer capacitors as described above have a larger capacity than conventional electrolytic capacitors and are excellent in instantaneous charge / discharge characteristics. Therefore, they are widely used as backup power sources for IC circuits. The development of smaller, lighter and larger capacity electric double layer capacitors is being promoted for application to equipment.

しかしながら、通常の有機系の電解液を用いた電気二重層キャパシタでは、電極構成部材に多孔性のセパレータを使用しており、電解液の保持性や安全性の面から考慮して、５０μｍ程度の厚みが必要になっている。また、液体状の電解液であるために、デバイスの外装に、傷や破壊が生じた場合、電解液が外部に漏れ出すことになり、危険を伴う。   However, in an electric double layer capacitor using a normal organic electrolyte, a porous separator is used as an electrode constituent member, and in view of the electrolyte retention and safety, it is about 50 μm. Thickness is needed. Moreover, since it is a liquid electrolyte solution, when a damage | wound or destruction arises in the exterior of a device, electrolyte solution will leak outside and it is dangerous.

そこで、本発明では、衝撃や曲げ荷重等による変形による漏液の恐れがなく、さらに薄型で大容量の電気を蓄えることの可能な電気二重層キャパシタおよびその製造方法を提供することを課題とする。 Accordingly, it is an object of the present invention to provide an electric double layer capacitor that is capable of storing a large amount of electricity without a risk of leakage due to deformation due to impact or bending load, and a method for manufacturing the same. .

本発明による電気二重層キャパシタは、平板状集電体上に設けられたブラシ毛状カーボンナノチューブ群を覆うように集電体上にゲル状電解質膜を形成してなる正負一対の電極を、容器内に、正極のカーボンナノチューブ群と負極のカーボンナノチューブ群が互いに向き合うようにかつ非接触状に配置するものであり、前記カーボンナノチューブ群は、集電体の平坦な表面に対して同じ方向に傾斜しており、各カーボンナノチューブと集電体とがなす傾斜角度をθ、集電体上の隣接カーボンナノチューブの中心間距離をＬ １ として、θ＜９０かつSinθ＞１０／Ｌ １ が満たされていることを特徴とするものである。 An electric double layer capacitor according to the present invention comprises a pair of positive and negative electrodes formed by forming a gel electrolyte membrane on a current collector so as to cover a group of brush-like carbon nanotubes provided on a flat plate current collector. The carbon nanotube group of the positive electrode and the carbon nanotube group of the negative electrode are arranged so as to face each other and in a non-contact manner, and the carbon nanotube group is inclined in the same direction with respect to the flat surface of the current collector Θ <90 and Sinθ> 10 / L 1 are satisfied, where θ is the inclination angle between each carbon nanotube and the current collector, and L 1 is the distance between the centers of adjacent carbon nanotubes on the current collector. it is characterized in that there.

本発明では、従来の電極構成部材である有機系電解液を用いず、また、正極・負極を分離するためのセパレータも用いず、これらの代わりに、ゲル状電解質を用いる。カーボンナノチューブを用いた電極とゲル状電解質を組み合わせることにより、これまでにない薄いシート状の電気二重層キャパシタが作製できる。   In the present invention, an organic electrolytic solution that is a conventional electrode constituent member is not used, and a separator for separating the positive electrode and the negative electrode is not used. Instead, a gel electrolyte is used. By combining an electrode using carbon nanotubes with a gel electrolyte, an unprecedented thin sheet-shaped electric double layer capacitor can be produced.

また、ゲル状電解質を用いた電気二重層キャパシタでは、電解質成分は高分子マトリクス中に保持されており、外装材に何らかの破壊が生じた場合においても、液成分が外へ漏出することがない。さらに、ゲル状電解質は多孔性のセパレータでは困難であるような薄い膜を容易に作製できる。このような理由から、ゲル状電解質を用いた電気二重層キャパシタは極めて安全であり、かつ製品の厚さを極めて薄くすることができる。   In the electric double layer capacitor using the gel electrolyte, the electrolyte component is held in the polymer matrix, and the liquid component does not leak to the outside even when some destruction occurs in the exterior material. Furthermore, the gel electrolyte can easily produce a thin film which is difficult with a porous separator. For this reason, the electric double layer capacitor using the gel electrolyte is extremely safe and the thickness of the product can be extremely reduced.

前記カーボンナノチューブ群は、集電体となる基板に対して傾斜するように形成することが好ましい。   The carbon nanotube group is preferably formed so as to be inclined with respect to the substrate serving as a current collector.

このように、ブラシ毛状カーボンナノチューブ群を傾斜状させることによって、
（ａ）カーボンナノチューブ群の厚さを薄くすることができ、これにより電極厚みを薄くすることができる。結果として、薄膜の電気二重層キャパシタが実現できる。 Thus, by inclining the brush-like carbon nanotube group,
(A) The thickness of the carbon nanotube group can be reduced, whereby the electrode thickness can be reduced. As a result, a thin-film electric double layer capacitor can be realized.

（ｂ）体積当たりのカーボン密度（カーボンナノチューブ密度）が高まることで、体積当たりカーボン表面積が増加し、体積当たりエネルギー密度と体積当たり出力密度がともに高くなる。 (B) By increasing the carbon density per volume (carbon nanotube density), the carbon surface area per volume increases, and both the energy density per volume and the output density per volume increase.

（ｃ）正極集電体と負極集電体間の距離が縮まるので、極間の抵抗成分である溶液抵抗などの直流抵抗成分が小さくなり、電気二重層キャパシタの抵抗が小さくなる。 (C) Since the distance between the positive electrode current collector and the negative electrode current collector is reduced, a direct current resistance component such as a solution resistance that is a resistance component between the electrodes is reduced, and the resistance of the electric double layer capacitor is reduced.

前記ゲル状電解質は、イオン性液体をベースとするゲル前駆体を加熱ゲル化することによって得られる。   The gel electrolyte is obtained by heat-gelling a gel precursor based on an ionic liquid.

イオン性液体とは、イオン性の物質でありながら、室温（１５〜２５℃程度）で無色透明の液体状態を示す塩類をいい、代表的な例として、
エチルメチルイミダゾリウムテトラフルオロボレート（ＥＭＩ・ＢＦ４）
エチルメチルイミダゾリウムパーフルオロスルホンイミド（ＥＭＩ・ＴＦＳＩ）
ブチルピリジウムテトラフルオロボレート（ＢＰ・ＢＦ４）
ブチルピリジウムパーフルオロスルホンイミド（ＢＰ・ＴＦＳＩ）
トリメチルプロピルアンモニウムテトラフルオロボレート（ＴＭＰＡ・ＢＦ４）
トリメチルプロピルアンモニウムパーフルオロスルホンイミド（ＴＭＰＡ・ＴＦＳＩ）
エチルメチルピロリジニウムテトラフルオロボレート（Ｐ１２・ＢＦ４）
エチルメチルピロリジニウムパーフルオロスルホンイミド（Ｐ１２・ＴＦＳＩ）
などが挙げられるが、イオン性液体はこれらに限定されるものではない。 An ionic liquid refers to a salt that shows a colorless and transparent liquid state at room temperature (about 15 to 25 ° C.) while being an ionic substance.
Ethylmethylimidazolium tetrafluoroborate (EMI / BF4)
Ethylmethylimidazolium perfluorosulfonimide (EMI / TFSI)
Butylpyridium tetrafluoroborate (BP / BF4)
Butylpyridium perfluorosulfonimide (BP / TFSI)
Trimethylpropylammonium tetrafluoroborate (TMPA / BF4)
Trimethylpropylammonium perfluorosulfonimide (TMPA / TFSI)
Ethylmethylpyrrolidinium tetrafluoroborate (P12 / BF4)
Ethylmethylpyrrolidinium perfluorosulfonimide (P12 / TFSI)
The ionic liquid is not limited to these.

この発明によるカーボンナノチューブを用いた電気二重層キャパシタの製造方法は、上記の電気二重層キャパシタを製造する方法であって、集電体上にカーボンナノチューブ群を設けることで電極を作成する工程と、カーボンナノチューブ付き集電体からなる電極をプレス装置にセットし、カーボンナノチューブを押さえ付けることで、カーボンナノチューブ群を集電体に対して傾斜させる工程と、ゲル前駆体をカーボンナノチューブ側の集電体表面に滴下することで、集電体上に設けられたカーボンナノチューブ群を覆うように集電体上にゲル前駆体膜を形成する工程と、ゲル前駆体をゲル化するために加熱処理する工程と、加熱処理によって得られたゲル状電解質膜を冷却する工程と、カーボンナノチューブ群を有する集電体からなる正負一対の電極を、正極のカーボンナノチューブ群と負極のカーボンナノチューブ群が互いに向き合うように容器内に配置する工程と、容器を密封する工程とを含んでいることを特徴とするものである。A method for producing an electric double layer capacitor using carbon nanotubes according to the present invention is a method for producing the above electric double layer capacitor, the step of creating an electrode by providing a carbon nanotube group on a current collector, A step of tilting the carbon nanotube group with respect to the current collector by setting the electrode made of the current collector with carbon nanotubes in the press device and pressing the carbon nanotube, and the current collector on the carbon nanotube side as the gel precursor A step of forming a gel precursor film on the current collector so as to cover a group of carbon nanotubes provided on the current collector by dropping onto the surface, and a step of heat-treating to gel the gel precursor A step of cooling the gel electrolyte membrane obtained by the heat treatment, and a positive electrode comprising a current collector having a group of carbon nanotubes. A pair of electrodes, is characterized in that it includes a step of carbon nanotube group and the carbon nanotube group negative of the positive electrode is placed in the container so as to face each other, and a step of sealing the container.

本発明では、従来の電極構成部材である有機系電解液を用いず、また、正極・負極を分離するためのセパレータも用いず、これらの代わりに、ゲル状電解質を用いる。カーボンナノチューブを用いた電極とゲル状電解質を組み合わせることにより、これまでにない薄いシート状の電気二重層キャパシタが作製できる。   In the present invention, an organic electrolytic solution that is a conventional electrode constituent member is not used, and a separator for separating the positive electrode and the negative electrode is not used. Instead, a gel electrolyte is used. By combining an electrode using carbon nanotubes with a gel electrolyte, an unprecedented thin sheet-shaped electric double layer capacitor can be produced.

また、ゲル状電解質を用いた電気二重層キャパシタでは、電解質成分は高分子マトリクス中に保持されており、外装材に何らかの破壊が生じた場合においても、液成分が外へ漏出することがない。さらに、ゲル状電解質は多孔性のセパレータでは困難であるような薄い膜を容易に作製できる。このような理由から、ゲル状電解質を用いた電気二重層キャパシタは極めて安全であり、かつ製品の厚さを極めて薄くすることができる。   In the electric double layer capacitor using the gel electrolyte, the electrolyte component is held in the polymer matrix, and the liquid component does not leak to the outside even when some destruction occurs in the exterior material. Furthermore, the gel electrolyte can easily produce a thin film which is difficult with a porous separator. For this reason, the electric double layer capacitor using the gel electrolyte is extremely safe and the thickness of the product can be extremely reduced.

さらに本発明によれば、カーボンナノチューブ電極構造とゲル状電解質の相乗効果が得られる。すなわち、通常の活性炭を使用した電極では、表面積が大きく、細孔径が２ｎｍ以下の細孔が非常に沢山炭素表面に存在する。このような細孔には、ゲル電解質はもちろんのこと、電解質のイオンですら染込まない。つまりゲル電解質はこの細孔に染込まず、利用できない細孔になってしまう。   Furthermore, according to the present invention, a synergistic effect of the carbon nanotube electrode structure and the gel electrolyte can be obtained. That is, an electrode using normal activated carbon has a large surface area and a large number of pores having a pore diameter of 2 nm or less on the carbon surface. Such pores are not infused with electrolyte ions as well as gel electrolytes. In other words, the gel electrolyte does not penetrate into the pores, resulting in pores that cannot be used.

カーボンナノチューブは、細孔構造を有しているのではなく、ブラシ状であるがために２ｎｍより小さなスペースは存在せず、むしろ１０ｎｍ以上の間隔でカーボンナノチューブは存在している。これによって、ゲル電解質のゲル前駆体はカーボンナノチューブ間に含浸することが可能となりうる。   Since the carbon nanotubes are not having a pore structure but are brush-like, there are no spaces smaller than 2 nm. Rather, carbon nanotubes exist at intervals of 10 nm or more. This may allow the gel precursor of the gel electrolyte to be impregnated between the carbon nanotubes.

通常、ゲル状電解質は、溶液を使用した電解液と比較して、イオン伝導性が低くなる。このような電解質を用いると、活性炭を用いた通常の電極では、大きい電流に対する容量の発現が悪くなる（高レート特性時に容量が出ない）。ゲル状電解質である限り同じ現象がカーボンナノチューブ電極においても起こるが、本発明のようにブラシ毛状のカーボンナノチューブ電極とすることで、カーボンナノチューブの構造が略垂直状になり、低いイオン導電性であっても、その移動方向が揃う、もしくは乱れないため、大きい電流に対する容量が活性炭よりも優れている。   Usually, the gel electrolyte has lower ionic conductivity as compared with an electrolytic solution using a solution. When such an electrolyte is used, in a normal electrode using activated carbon, the development of capacity with respect to a large current is deteriorated (capacity is not output during high rate characteristics). As long as it is a gel electrolyte, the same phenomenon occurs in a carbon nanotube electrode. However, by using a brush-like carbon nanotube electrode as in the present invention, the structure of the carbon nanotube becomes substantially vertical, and the ionic conductivity is low. Even if it exists, since the moving direction is aligned or not disturbed, the capacity for a large current is superior to activated carbon.

（１）キャパシタ電極の作成は例えばつぎのように行われる。 (1) The capacitor electrode is produced, for example, as follows.

１）ブラシ毛状カーボンナノチューブ群は化学蒸着法などの公知の方法で基板上に成長させられ、基板から集電体に転写されて電極が作成される（例えばＷＯ０３／０７３４４０参照）。   1) A group of brush-like carbon nanotubes is grown on a substrate by a known method such as chemical vapor deposition, and transferred from the substrate to a current collector to produce an electrode (see, for example, WO03 / 073440).

２）カーボンナノチューブ群の厚み調整のために、ブラシ毛状カーボンナノチューブ群を集電体に対して傾斜させる。具体的には、ブラシ毛状カーボンナノチューブ付き集電体からなる電極をプレス装置にセットし、２枚のステンレス鋼板で挟み、圧力：４００〜１０００ｋｇ／ｃｍ２、保持時間：０．５〜２分程度でブラシ毛状カーボンナノチューブを押さえ付ける。 2) In order to adjust the thickness of the carbon nanotube group, the brush-like carbon nanotube group is inclined with respect to the current collector. Specifically, an electrode made of a current collector with brush-like carbon nanotubes is set in a press device and sandwiched between two stainless steel plates, pressure: 400 to 1000 kg / cm 2 , holding time: 0.5 to 2 minutes Press the brush-like carbon nanotubes to the extent.

傾斜角度については、垂直配向している状態を９０°とするとき、傾斜角度は９０°未満であればよいが、最小傾斜角度は
Sinθ ＞１０／Ｌ１ ……（Ｉ）
を満たす角度θである（図１参照）。 As for the tilt angle, when the vertically aligned state is 90 °, the tilt angle may be less than 90 °, but the minimum tilt angle is
Sinθ> 10 / L 1 (I)
Is an angle θ satisfying (see FIG. 1).

ここで、Sinθ ＝ Ｘ／Ｌ１
θ：傾斜角度
Ｘ：カーボンナノチューブ間距離
Ｌ１：集電体(1) 上の隣接カーボンナノチューブ(2) の中心間距離（ピッチ）
上記式（Ｉ）の導入はつぎのようになされる。 Here, Sinθ = X / L 1
θ: Inclination angle X: Distance between carbon nanotubes L 1 : Distance (pitch) between centers of adjacent carbon nanotubes (2) on the current collector (1)
The above formula (I) is introduced as follows.

前提条件として、Ｘは最低でも１０ｎｍ必要である。電気二重層の距離を考慮するとカーボンナノチューブ(2) 間距離は１０ｎｍ離れる必要があるからである。   As a prerequisite, X must be at least 10 nm. This is because the distance between the carbon nanotubes (2) needs to be 10 nm apart from the distance of the electric double layer.

よって、Ｘ ＝Ｌ１×Sinθ＞１０
すなわち、 Sinθ ＞１０／Ｌ１
となる。 Therefore, X = L 1 × Sinθ> 10
That is, Sinθ> 10 / L 1
It becomes.

ブラシ毛状カーボンナノチューブ群の傾斜化は省略してもよい（図３参照）。   The inclination of the bristle-like carbon nanotube group may be omitted (see FIG. 3).

３）ゲル状電解質膜の作製は下記の工程にしたがって行われる。 3) Production of the gel electrolyte membrane is performed according to the following steps.

ゲル前駆体の調製 →カーボンナノチューブ(2) 群上へのゲル前駆体の流し込み→加熱によるゲル化→冷却。   Preparation of gel precursor → Pour of gel precursor onto carbon nanotube (2) group → Gelation by heating → Cooling.

ゲル前駆体は、イオン性液体とゲル化剤を撹拌下に混合して得られる。イオン性液体とゲル化剤の割合はゲル化剤の高分子重合度により異なるが、好ましくは前者：後者＝５０〜９５：５０〜５（重量比）である。ゲル化剤は５０重量％もあれば十分であり、多すぎるとイオン性液体の濃度が低下しキャパシタの静電容量が低下する。ゲル化剤が５重量％未満であるとイオン性液体がゲル化しないことがある。   The gel precursor is obtained by mixing an ionic liquid and a gelling agent with stirring. The ratio of the ionic liquid and the gelling agent varies depending on the degree of polymer polymerization of the gelling agent, but the former: the latter = 50 to 95:50 to 5 (weight ratio) is preferable. A gelling agent of 50% by weight is sufficient, and if it is too much, the concentration of the ionic liquid is lowered and the capacitance of the capacitor is lowered. If the gelling agent is less than 5% by weight, the ionic liquid may not gel.

ゲル前駆体内に混合している気泡を取り除くためにこれを真空下で静置して脱泡処理する。イオン性液体としては上述したものを１種または２種の組み合わせて用いる。ゲル化剤としては高分子材料が適しており、加熱や架橋反応によって高分子ネットワークを形成するような材料が用いられる。ゲル化剤の代表例としては、ポリアクリロニトリル（ＰＡＮ）、ポリフッ化ビニリデン−六フッ化プロピレン共重合体（ＰＶｄＦ−ＨＦＰ）などが挙げられるが、ゲル化剤はこれらの高分子材料に限定されるものではない。   In order to remove bubbles mixed in the gel precursor, this is left to stand under vacuum and defoamed. As the ionic liquid, those described above are used alone or in combination of two. A polymer material is suitable as the gelling agent, and a material that forms a polymer network by heating or a crosslinking reaction is used. Typical examples of the gelling agent include polyacrylonitrile (PAN), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP) and the like, but the gelling agent is limited to these polymer materials. It is not a thing.

ゲル前駆体調製工程は、露点温度が−６０℃以下の環境、例えばドライルーム内もしくはグローブボックス内で行う。   The gel precursor preparation step is performed in an environment having a dew point temperature of −60 ° C. or lower, for example, in a dry room or a glove box.

ゲル状電解質中の電解質濃度は、液状の溶媒を用いた有機系電解液の濃度よりはるかに高くなり、電気二重層の容量増加に対する寄与が大きい。このため、ゲル状電解質を用いた電気二重層キャパシタでは、有機系電解液を用いた電気二重層キャパシタよりも、大きい容量が得られる。   The electrolyte concentration in the gel electrolyte is much higher than the concentration of the organic electrolyte solution using a liquid solvent, and contributes greatly to the increase in capacity of the electric double layer. For this reason, the electric double layer capacitor using the gel electrolyte can provide a larger capacity than the electric double layer capacitor using the organic electrolyte.

カーボンナノチューブ(2) 群上へのゲル前駆体の流し込み工程も、露点温度が−６０℃以下の環境、例えばドライルーム内もしくはグローブボックス内で行う。まず、ゲル前駆体をカーボンナノチューブ(2) 側の集電体表面に滴下し、カーボンナノチューブ(2) 群をゲル前駆体で覆う。次いで、これを真空下で６０分間静置して脱泡処理する。こうして、集電体上に設けられたカーボンナノチューブ(2) 群を覆うように集電体上にゲル前駆体膜(3) を形成し、ベーカーアプリケーターなどでゲル前駆体膜(3) の厚みを調整する。   The step of pouring the gel precursor onto the carbon nanotube (2) group is also performed in an environment having a dew point temperature of −60 ° C. or lower, for example, in a dry room or glove box. First, the gel precursor is dropped on the surface of the current collector on the carbon nanotube (2) side, and the carbon nanotube (2) group is covered with the gel precursor. Next, this is left to stand for 60 minutes under vacuum to be defoamed. In this way, the gel precursor film (3) is formed on the current collector so as to cover the carbon nanotubes (2) provided on the current collector, and the thickness of the gel precursor film (3) is reduced by a baker applicator or the like. adjust.

その後、ゲル前駆体をゲル化するために、これを加熱処理する。好ましい処理条件は１００〜２００℃、０．５〜１０時間である。加熱温度はゲル化剤の種類によって適宜決められるが、１００℃未満であると、ゲル前駆体のゲル化が生じない。加熱温度が２００℃を越えるとゲル化剤が分解等により変質する恐れがある。   Then, in order to gelatinize a gel precursor, this is heat-processed. Preferred treatment conditions are 100 to 200 ° C. and 0.5 to 10 hours. The heating temperature is appropriately determined depending on the type of the gelling agent, but if it is less than 100 ° C., gelation of the gel precursor does not occur. If the heating temperature exceeds 200 ° C, the gelling agent may be deteriorated due to decomposition or the like.

次いで、得られたゲル状電解質膜(3) を冷却する。こうして、集電体上に設けられたカーボンナノチューブ(2) 群を覆うように集電体上にゲル状電解質膜(3) を形成する。   Next, the obtained gel electrolyte membrane (3) is cooled. In this way, the gel electrolyte membrane (3) is formed on the current collector so as to cover the carbon nanotubes (2) provided on the current collector.

４）電気二重層キャパシタの作製
カーボンナノチューブ(2) 群を有する集電体からなる正負一対の電極を、例えばパッケージング容器内に、正極のカーボンナノチューブ(2) 群と負極のカーボンナノチューブ(2) 群が互いに向き合うように配置する。正極のカーボンナノチューブ(2) 群と負極のカーボンナノチューブ(2) 群はいずれもゲル状電解質膜(3) で覆われているので、接触することはない。容器は次いで密封され、電気二重層キャパシタが得られる。 4) Fabrication of an electric double layer capacitor A pair of positive and negative electrodes made of a current collector having a carbon nanotube (2) group are placed in, for example, a packaging container, and the positive carbon nanotube (2) group and the negative carbon nanotube (2) Arrange so that the groups face each other. Since the carbon nanotube (2) group of the positive electrode and the carbon nanotube (2) group of the negative electrode are both covered with the gel electrolyte membrane (3), they do not contact each other. The container is then sealed to obtain an electric double layer capacitor.

つぎに、本発明を具体的に説明するために、本発明の実施例を挙げる。   Next, in order to describe the present invention specifically, examples of the present invention will be given.

実施例１
図２において、公知の方法でシリコン基板上に垂直に成長させたブラシ毛状カーボンナノチューブ(2) をアルミニウム箔からなる集電体(1) に転写して電極を作成した。このときのブラシ毛状カーボンナノチューブの長さは、６０μｍであった。 Example 1
In FIG. 2, brush-like carbon nanotubes (2) grown vertically on a silicon substrate by a known method were transferred to a current collector (1) made of aluminum foil to produce an electrode. At this time, the length of the bristle-like carbon nanotube was 60 μm.

転写後のブラシ毛状カーボンナノチューブ(2) 付き集電体(1) を油圧式プレス装置にセットし、２枚のステンレス鋼板で挟み、圧力：５００ｋｇ／ｃｍ２、保持時間：１．５分程度でブラシ毛状カーボンナノチューブ(2) を押さえ付け、集電体(1) に対し傾斜させた。このときアルミニウム箔にしわが入らないようにした。傾斜状カーボンナノチューブ(2) 群からなる層の厚さは３０μｍであった。 The transferred current collector (1) with brush-like carbon nanotubes (2) is set in a hydraulic press and sandwiched between two stainless steel plates, pressure: 500 kg / cm 2 , holding time: about 1.5 minutes Then, the brush-like carbon nanotube (2) was pressed and inclined with respect to the current collector (1). At this time, the aluminum foil was not wrinkled. The thickness of the layer made of the inclined carbon nanotube (2) group was 30 μm.

露点温度−６０℃以下の環境（具体的には、ドライルーム内もしくはグローブボックス内）で、１２ｇのエチルメチルイミダゾリウムテトラフルオロボレート（ＥＭＩ・ＢＦ４）と３ｇのポリフッ化ビニリデン−六フッ化プロピレン共重合体（ＰＶｄＦ−ＨＦＰ）を容器内で攪拌下に３時間混合し、ゲル前駆体を得た。   In an environment with a dew point of −60 ° C. or lower (specifically, in a dry room or glove box), 12 g of ethylmethylimidazolium tetrafluoroborate (EMI • BF4) and 3 g of polyvinylidene fluoride-hexafluoropropylene The polymer (PVdF-HFP) was mixed for 3 hours with stirring in a container to obtain a gel precursor.

ついで、ゲル前駆体内に混入している気泡を取り除くために、これを真空下で６０分静置して、脱泡処理を行った。   Next, in order to remove bubbles mixed in the gel precursor, this was left to stand for 60 minutes under vacuum to perform defoaming treatment.

ついで、露点温度が−６０℃以下の環境、例えばドライルーム内もしくはグローブボックス内で、まずゲル前駆体をカーボンナノチューブ(2) 側の集電体(1) 表面に滴下し、カーボンナノチューブ(2) 群に含浸し、さらにカーボンナノチューブ(2) 群をゲル前駆体で覆った。次いで、これを真空下で６０分間静置して脱泡処理した。こうして、集電体(1) 上のカーボンナノチューブ(2) 群を覆うように集電体(1) 上にゲル前駆体膜(3) を形成した。ベーカーアプリケーターでゲル前駆体膜(3) の厚みを３５μｍに調整した。   Next, in an environment having a dew point temperature of −60 ° C. or lower, for example, in a dry room or a glove box, first, a gel precursor is dropped on the surface of the current collector (1) on the carbon nanotube (2) side, and the carbon nanotube (2) The group was impregnated and the group of carbon nanotubes (2) was covered with a gel precursor. Subsequently, this was left to stand for 60 minutes under vacuum to perform defoaming treatment. Thus, the gel precursor film (3) was formed on the current collector (1) so as to cover the carbon nanotubes (2) group on the current collector (1). The thickness of the gel precursor film (3) was adjusted to 35 μm with a Baker applicator.

その後、ゲル前駆体をゲル化するために、これを約１２０℃で１時間加熱処理した。   Then, in order to gelatinize a gel precursor, this was heat-processed at about 120 degreeC for 1 hour.

次いで、得られたゲル状電解質膜(3) を冷却した。   Next, the obtained gel electrolyte membrane (3) was cooled.

こうして、集電体(1) 上のカーボンナノチューブ(2) 群を覆うように集電体(1) 上にゲル状電解質膜(3) を形成した。   Thus, the gel electrolyte membrane (3) was formed on the current collector (1) so as to cover the carbon nanotubes (2) group on the current collector (1).

ゲル状電解質膜(3) 被覆カーボンナノチューブ(2) 群を有する集電体(1) からなる正負一対の電極を、アルミニウムラミネートからなるパッケージング容器内に、正極のカーボンナノチューブ(2) 群と負極のカーボンナノチューブ(2) 群が互いに向き合うように配置した。   Gel electrolyte membrane (3) Coated carbon nanotube (2) A pair of positive and negative electrodes made of a current collector (1) group is placed in a packaging container made of an aluminum laminate and the positive electrode carbon nanotube (2) group and the negative electrode The carbon nanotubes (2) were arranged so as to face each other.

その後、パッケージング容器をインパルスシーラーなどのシール機で封止した。   Thereafter, the packaging container was sealed with a sealing machine such as an impulse sealer.

実施例２
９．５ｇのエチルメチルイミダゾリウムテトラフルオロボレート（ＥＭＩ・ＢＦ４）と０．５ｇのポリフッ化ビニリデン−六フッ化プロピレン共重合体（ＰＶｄＦ−ＨＦＰ）を混合してゲル前駆体を得た以外、実施例１と同様の操作を行い、電気二重層キャパシタを作製した。 Example 2
9.5 g of ethylmethylimidazolium tetrafluoroborate (EMI • BF4) and 0.5 g of polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP) were mixed to obtain a gel precursor. The same operation as in Example 1 was performed to produce an electric double layer capacitor.

このようにイオン性液体の割合を増加させることで、有効なイオン量を増やすことができ、また抵抗成分（ＰＶｄＦ−ＨＦＰは絶縁体）を減少させることができた。   Thus, by increasing the proportion of the ionic liquid, the amount of effective ions can be increased, and the resistance component (PVdF-HFP is an insulator) can be decreased.

比較例
図３において、ブラシ毛状カーボンナノチューブ(2) 群を集電体(1) に対し傾斜させる工程を省いた以外、実施例１と同様の操作を行い、電気二重層キャパシタを作製した。ブラシ毛状カーボンナノチューブ(2) 群からなる層の厚さは６０μｍ、これを覆うゲル状電解質膜(3) の厚さは６５μｍであった。 Comparative Example An electric double layer capacitor was produced in the same manner as in Example 1 except that the step of tilting the bristle-like carbon nanotubes (2) group with respect to the current collector (1) was omitted in FIG. The thickness of the layer composed of the group of brush-like carbon nanotubes (2) was 60 μm, and the thickness of the gel electrolyte membrane (3) covering the layer was 65 μm.

集電体に垂直に設けられたカーボンナノチューブを傾斜させる状態を示す垂直断面図である。It is a vertical sectional view showing a state in which carbon nanotubes provided perpendicular to the current collector are inclined. 集電体に対し傾斜したカーボンナノチューブがゲル状電解質で覆われてなる電極を示す垂直断面図である。It is a vertical sectional view showing an electrode in which carbon nanotubes inclined with respect to a current collector are covered with a gel electrolyte. 集電体に垂直に設けられたブラシ毛状カーボンナノチューブがゲル状電解質で覆われてなる電極を示す垂直断面図である。It is a vertical sectional view showing an electrode in which brush-like carbon nanotubes provided perpendicular to the current collector are covered with a gel electrolyte.

(1) ：集電体
(2) ：カーボンナノチューブ
(3) ：ゲル前駆体膜（ゲル状電解質膜） (1): Current collector
(2): Carbon nanotube
(3): Gel precursor membrane (gel electrolyte membrane)

Claims (3)

平板状集電体上に設けられたブラシ毛状カーボンナノチューブ群を覆うように集電体上にゲル状電解質膜を形成してなる正負一対の電極を、容器内に、正極のカーボンナノチューブ群と負極のカーボンナノチューブ群が互いに向き合うようにかつ非接触状に配置するものであり、前記カーボンナノチューブ群は、集電体の平坦な表面に対して同じ方向に傾斜しており、各カーボンナノチューブと集電体とがなす傾斜角度をθ、集電体上の隣接カーボンナノチューブの中心間距離をＬ １ として、θ＜９０かつSinθ＞１０／Ｌ １ が満たされていることを特徴とする、カーボンナノチューブを用いた電気二重層キャパシタ。 A pair of positive and negative electrodes formed by forming a gel electrolyte membrane on the current collector so as to cover the bristle-like carbon nanotube group provided on the flat plate current collector, and the positive carbon nanotube group in the container The carbon nanotube groups of the negative electrode are arranged so as to face each other and in a non-contact manner, and the carbon nanotube groups are inclined in the same direction with respect to the flat surface of the current collector, and are collected from each carbon nanotube. A carbon nanotube characterized in that θ <90 and Sinθ> 10 / L 1 are satisfied, where θ is an inclination angle formed by the electric body, and L 1 is a distance between centers of adjacent carbon nanotubes on the current collector. Electric double layer capacitor using 前記ゲル状電解質がイオン性液体をベースとするゲル前駆体のゲル化により得られることを特徴とする、請求項１に記載のカーボンナノチューブを用いた電気二重層キャパシタ。   The electric double layer capacitor using carbon nanotubes according to claim 1, wherein the gel electrolyte is obtained by gelation of a gel precursor based on an ionic liquid. 請求項１または２のカーボンナノチューブを用いた電気二重層キャパシタを製造する方法であって、A method for producing an electric double layer capacitor using the carbon nanotubes according to claim 1 or 2,
集電体上にカーボンナノチューブ群を設けることで電極を作成する工程と、カーボンナノチューブ付き集電体からなる電極をプレス装置にセットし、カーボンナノチューブを押さえ付けることで、カーボンナノチューブ群を集電体に対して傾斜させる工程と、ゲル前駆体をカーボンナノチューブ側の集電体表面に滴下することで、集電体上に設けられたカーボンナノチューブ群を覆うように集電体上にゲル前駆体膜を形成する工程と、ゲル前駆体をゲル化するために加熱処理する工程と、加熱処理によって得られたゲル状電解質膜を冷却する工程と、カーボンナノチューブ群を有する集電体からなる正負一対の電極を、正極のカーボンナノチューブ群と負極のカーボンナノチューブ群が互いに向き合うように容器内に配置する工程と、容器を密封する工程とを含んでいることを特徴とする、カーボンナノチューブを用いた電気二重層キャパシタの製造方法。  A process of creating an electrode by providing a group of carbon nanotubes on a current collector, and an electrode made of a current collector with carbon nanotubes is set in a press device, and the carbon nanotube group is pressed by pressing the carbon nanotubes. And a gel precursor film on the current collector so as to cover the carbon nanotube group provided on the current collector by dropping the gel precursor onto the surface of the current collector on the carbon nanotube side. A step of forming a gel precursor, a step of heat-treating to gel the gel precursor, a step of cooling the gel electrolyte membrane obtained by the heat-treatment, and a pair of positive and negative consisting of a current collector having a carbon nanotube group Arranging the electrode in the container so that the carbon nanotube group of the positive electrode and the carbon nanotube group of the negative electrode face each other; Characterized in that it includes the step of sealing method of an electric double layer capacitor using a carbon nanotube.
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