JP4696751B2 - Method for producing electrode using carbon nanotube - Google Patents
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Description
本発明は、カーボンナノチューブを用いた電極に関するものである。本発明による電極は、例えば、大容量の電気を蓄えることが可能な電気二重層キャパシタの素子として用いることができる。本発明はまたカーボンナノチューブを用いた電極の製造方法にも関する。 The present invention relates to an electrode using carbon nanotubes. The electrode according to the present invention can be used, for example, as an element of an electric double layer capacitor capable of storing a large amount of electricity. The present invention also relates to a method for producing an electrode using carbon nanotubes.
一般に、電気化学反応を利用した素子として、電池や電気二重層キャバシタといった素子が知られており、さまざまなタイプの電池やキャパシタが電子機器・電気自動車等、さまざまな用途に利用されている。最近は、ノートパソコン等の携帯端末や携帯電話等の機器の小型化が進み、これらに用いる電池やキャパシタも小型で大容量のものが望まれている。このため、リチウム二次電池や電気二重層キャパシタ等の電極のシート構造化や積層化等、さまざまな研究開発がされている。 In general, elements such as batteries and electric double layer capacitors are known as elements utilizing electrochemical reactions, and various types of batteries and capacitors are used in various applications such as electronic devices and electric vehicles. Recently, downsizing of devices such as notebook personal computers and mobile terminals and mobile phones has progressed, and batteries and capacitors used for these devices are desired to be small and have a large capacity. For this reason, various research and developments such as sheet structure and lamination of electrodes such as lithium secondary batteries and electric double layer capacitors have been conducted.
電池やキャパシタの大容量化については、電池やキャパシタの電極材料として、従来は、比表面積の高い活性炭が主として用いられてきたが、近年、活性炭より単位面積あたりの蓄電容量の高い電極材料としてカーボンナノチューブが注目され、鋭意研究開発がなされている。 For increasing the capacity of batteries and capacitors, activated carbon having a high specific surface area has been mainly used as an electrode material for batteries and capacitors, but in recent years, carbon has been used as an electrode material having a higher storage capacity per unit area than activated carbon. Nanotubes have been attracting attention and earnest research and development.
カーボンナノチューブを用いた電極の製造方法は、具体的には、カーボンナノチューブと樹脂の粉末を混合し、この混合物を所定圧力でペレット化する方法や、カーボンナノチューブと活性炭に樹脂を所定量混合し、この混合物をペースト化する方法がある。一般に、こうして得られた電極からなるキャパシタは、カーボンナノチューブへの活性炭等の添加により、大きい蓄電容量を有するようになる。 Specifically, the method of manufacturing an electrode using carbon nanotubes is a method of mixing carbon nanotubes and resin powder, pelletizing the mixture at a predetermined pressure, or mixing a predetermined amount of resin with carbon nanotubes and activated carbon, There is a method of pasting this mixture. In general, a capacitor composed of the electrode thus obtained has a large storage capacity by adding activated carbon or the like to the carbon nanotube.
また、上記のようなペレット化やペースト化をせず、垂直に配向させたカーボンナノチューブを用いた電極を製造する方法もある。この方法は、ペレット化やペースト化の工程を省くことができるとともに、キャパシタの充放電の際にイオンの出入りにより電極が膨張収縮して劣化するのを防ぎ、樹脂含有により内部抵抗が増加するのを防ぐことができるという利点がある。
カーボンナノチューブを用いた電極は上述のような利点を有するが、垂直に配向させた多数のカーボンナノチューブ間に隙間があるため、その分、蓄電容量が低下するという問題があった。このため、カーボンナノチューブ間の隙間に活性炭粉末等を充填することが考えられるが、カーボンナノチューブ間の隙間は、数十ｎｍ程度しかなく、それに対して、活性炭粉末の粒径は、最低でも４０ｎｍあるため、カーボンナノチューブ間の隙間を
活性炭粉末で埋めることは困難であった。
Although an electrode using carbon nanotubes has the above-described advantages, there is a problem in that the storage capacity is reduced correspondingly because there are gaps between a number of vertically aligned carbon nanotubes. For this reason, it is conceivable to fill the gap between the carbon nanotubes with activated carbon powder or the like, but the gap between the carbon nanotubes is only about several tens of nm, whereas the particle diameter of the activated carbon powder is at least 40 nm. Therefore, it was difficult to fill the gaps between the carbon nanotubes with activated carbon powder.
本発明は、上記の問題から、実質上垂直に配向させたカーボンナノチューブを用いる電極の利点を生かしつつ、さらに蓄電容量を増大させたカーボンナノチューブを用いた電極およびその製造方法を提供するものである。 In view of the above problems, the present invention provides an electrode using carbon nanotubes having a further increased storage capacity while taking advantage of electrodes using carbon nanotubes oriented substantially vertically, and a method for manufacturing the same. .
本発明により得られるカーボンナノチューブを用いた電極は、集電体と該集電体表面に実質上垂直に配向された複数本のカーボンナノチューブとからなる電極において、該カーボンナノチューブ間の隙間に炭化物が形成されて隙間を埋めていること特徴とするものである。 Electrodes using by Ri obtained that carbon nanotubes in the present invention, the electrode comprising a plurality of carbon nanotubes substantially oriented perpendicularly to the current collector and the current collector surface, the gaps between the carbon nanotubes It is characterized in that carbides are formed on the surface to fill the gaps.
カーボンナノチューブ間の隙間を埋める炭化物は、例えば、該隙間に含浸した樹脂を炭化させたもの、または、該カーボンナノチューブ間の隙間に含浸したモノマーを重合させ生じた重合物を炭化させたものである。炭化すべき樹脂の代表例としてはポリフッ化ビニリデン、フェノール樹脂、ポリテトラフルオロエチレン（ＰＴＦＥ）、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリビニルアルコール（ＰＶＡ）が挙げられる。カーボンナノチューブ間の隙間に含浸されるモノマーの代表例としては、フェノール、メタクリル酸メチルなどが挙げられる。 The carbide filling the gaps between the carbon nanotubes is, for example, carbonized resin impregnated in the gaps, or carbonized polymer obtained by polymerizing the monomer impregnated in the gaps between the carbon nanotubes. . Typical examples of the resin to be carbonized include polyvinylidene fluoride, phenol resin, polytetrafluoroethylene (PTFE), polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF), and polyvinyl alcohol (PVA). Typical examples of the monomer impregnated in the gaps between the carbon nanotubes include phenol and methyl methacrylate.
本発明による、カーボンナノチューブを用いた電極の製造方法は、集電体と該集電体表面に実質上垂直に配向された複数本のカーボンナノチューブを形成する工程と、モノマーを含む液をカーボンナノチューブ間の隙間に所定量滴下して乾燥させる工程と、該カーボンナノチューブを非酸化雰囲気下で加熱し、該モノマーを重合させ、得られた重合物を炭化し、カーボンナノチューブ間の隙間に炭化物を形成して隙間を埋める工程とからなることを特徴とする方法である。 According to the invention, a manufacturing method of an electrode using carbon nanotubes, carbon and forming a plurality of carbon nanotubes substantially oriented perpendicularly to the current collector and the current collector surface, a liquid containing a motor Nomar and drying dropwise a predetermined amount into the gap between the nanotubes, and heating the carbon nanotubes in a non-oxidizing atmosphere, thereby polymerizing the monomer, and carbonizing the resulting polymer, the carbide in the gap between the carbon nanotubes Forming a gap and filling the gap.
実質上垂直に配向されたブラシ毛状カーボンナノチューブは、公知の方法で作製できる。例えば、集電体となるシリコン基板の少なくとも片面上に、ニッケル、コバルト、鉄などの金属の錯体を含む溶液をスプレーや刷毛で塗布した後、加熱して形成した皮膜上に、あるいは、クラスター銃で打ち付けて形成した皮膜上に、アセチレン（Ｃ２Ｈ２）のような炭化水素ガスを用いて一般的な熱化学気相蒸着法を施すことにより、直径１２〜３８ｎｍのカーボンナノチューブが多層構造で基板上に垂直に起毛される。具体的には、まず、基板上に触媒微粒子を形成し、触媒微粒子を核として高温雰囲気で原料ガスからカーボンナノチューブを成長させる。基板は触媒微粒子を支持するものであればよく、触媒微粒子が濡れにくいものが好ましく、シリコン基板であってよい。触媒微粒子はニッケル、コバルト、鉄などの金属微粒子であってよい。これらの金属またはその錯体等の化合物の溶液をスプレーや刷毛で基板に塗布し、またはクラスター銃で基板に打ち付け、乾燥させ、必要であれば加熱し、皮膜を形成する。皮膜の形成は電子ビーム蒸着法によって行ってもよい。皮膜の厚みは、厚過ぎると加熱による微粒子化が困難になるので、好ましくは１〜１００ｎｍである。次いでこの皮膜を好ましくは減圧下または非酸化雰囲気中で好ましくは６５０〜８００℃に加熱すると、直径１〜５０ｎｍ程度の触媒微粒子が形成される。カーボンナノチューブの原料ガスとしては、アセチレン、メタン、エチレン等の脂肪族炭化水素が使用でき、とりわけアセチレンガスが好ましい。アセチレンの場合、多層構造で太さ１２〜３８nmのカーボンナノチューブが触媒微粒子を核として基板上にブラシ状に形成される。カーボンナノチューブの形成温度は、好ましくは６５０〜８００℃である。 Brush hair-like carbon nanotubes oriented substantially vertically can be produced by a known method. For example, a solution containing a metal complex such as nickel, cobalt, or iron is applied to at least one surface of a silicon substrate serving as a current collector by spraying or brushing, and then heated on a coating film or a cluster gun By applying a general thermal chemical vapor deposition method using a hydrocarbon gas such as acetylene (C2H2) on the film formed by bombarding the carbon nanotubes, carbon nanotubes having a diameter of 12 to 38 nm have a multilayer structure on the substrate. Brushed vertically. Specifically, first, catalyst fine particles are formed on a substrate, and carbon nanotubes are grown from a raw material gas in a high temperature atmosphere using the catalyst fine particles as nuclei. The substrate is not particularly limited as long as it supports the catalyst fine particles, and is preferably one in which the catalyst fine particles are difficult to wet, and may be a silicon substrate. The catalyst fine particles may be metal fine particles such as nickel, cobalt, and iron. A solution of a compound such as a metal or a complex thereof is applied to the substrate with a spray or a brush, or is applied to the substrate with a cluster gun, dried, and heated if necessary to form a film. The film may be formed by electron beam evaporation. If the thickness of the film is too thick, it becomes difficult to make fine particles by heating, and therefore it is preferably 1 to 100 nm. Subsequently, when this film is heated preferably under reduced pressure or in a non-oxidizing atmosphere, preferably at 650 to 800 ° C., catalyst fine particles having a diameter of about 1 to 50 nm are formed. As a raw material gas for carbon nanotubes, aliphatic hydrocarbons such as acetylene, methane, and ethylene can be used, and acetylene gas is particularly preferable. In the case of acetylene, carbon nanotubes having a multilayer structure and a thickness of 12 to 38 nm are formed in a brush shape on a substrate with catalyst fine particles as nuclei. The formation temperature of the carbon nanotube is preferably 650 to 800 ° C.
モノマーの含浸工程において、モノマーの例は上述したものであってよい。モノマーを含む液は、モノマーの溶解液、懸濁液、分散液、乳化液等であってよい。これらの液の媒体としてはテトラヒドロフラン、水、Ｎ−メチル−２−ピロリドンなどが例示される。 In the impregnation step of the motor Nomar, examples of motor Nomar may be those described above. Liquid containing a motor Nomar is solution of Mo Nomar, suspensions, dispersions, may be emulsion or the like. Examples of the medium of these liquids include tetrahydrofuran, water, N-methyl-2-pyrrolidone and the like.
カーボンナノチューブを加熱する工程は、モノマーまたは重合物の燃焼を防ぐために非酸化雰囲気下で行う。非酸化雰囲気の代表例は窒素ガス雰囲気のような不活性ガス雰囲気である。重合物の炭化に必要な加熱温度は好ましくは４００〜１０００℃である。モノマーの重合と、得られた重合物の炭化とは段階的に行ってもよいし、一挙に行ってもよい。 Heating the carbon nanotubes is performed in a non-oxidizing atmosphere to prevent burning of the motor Nomar or polymer. A typical example of the non-oxidizing atmosphere is an inert gas atmosphere such as a nitrogen gas atmosphere. The heating temperature necessary for carbonization of the heavy compounds is preferably 400 to 1000 ° C.. The polymerization of the monomer and the carbonization of the obtained polymer may be performed stepwise or at once.
本発明によれば、集電体と該集電体表面に実質上垂直に配向された複数本のカーボンナノチューブとからなる電極において、該カーボンナノチューブ間の隙間に炭化物が形成されて隙間を埋めているものが得られるので、上記隙間がなくなり、その分、蓄電容量を増大することができる。 According to the present invention, in an electrode composed of a current collector and a plurality of carbon nanotubes oriented substantially perpendicular to the current collector surface, carbides are formed in the gaps between the carbon nanotubes to fill the gaps. since that there are obtained, it is not the gap, which makes it possible to increase the storage capacity.
また、本発明方法によれば、モノマーもしくはこれを含む液をカーボンナノチューブ間の隙間に含浸させるので、カーボンナノチューブ間の隙間に支障なく、モノマーもしくはこれを含む液を浸透させることができ、次いで該カーボンナノチューブを非酸化雰囲気下で加熱し、これにより該モノマーを重合させ、得られた重合物を炭化するので、カーボンナノチューブ間の隙間にむらなく炭化物を形成して隙間を埋めることができる。 Further, according to the present invention, since the impregnating motor Nomar or liquid containing the same into the gap between the carbon nanotubes, without any trouble to the gaps between the carbon nanotubes, it is possible to infiltrate motor Nomar or liquid containing the same, then heating the carbon nanotubes in a non-oxidizing atmosphere, thereby to polymerize the 該Mo Nomar, since the obtained polymer is carbonized, can fill a gap to form a uniformly carbide in the gap between the carbon nanotubes it can.
こうして、本発明によれば、実質上垂直に配向させたカーボンナノチューブを用いる電極の利点を生かしつつ、さらに蓄電容量を増大させたカーボンナノチューブを用いた電極を提供することができる。 Thus, according to the present invention, it is possible to provide an electrode using carbon nanotubes having an increased storage capacity while taking advantage of the electrodes using carbon nanotubes oriented substantially vertically.
つぎに、本発明を具体的に説明するために、本発明の実施例およびこれとの比較を示すための比較例をいくつか挙げる。 Next, in order to specifically explain the present invention, some examples of the present invention and comparative examples for showing comparison with the examples will be given.
実施例１
〔工程１〕
５０ｍｍ×５０ｍｍのシリコン基板上に電子ビーム蒸着法により厚さ５ｎｍの鉄薄膜を生成させた。
Example 1
[Step 1]
An iron thin film having a thickness of 5 nm was formed on a 50 mm × 50 mm silicon substrate by electron beam evaporation.
〔工程２〕
内径５０ｍｍの石英反応管の内部に、工程１により鉄薄膜を被覆したシリコン基板を設置した。
[Step 2]
A silicon substrate coated with an iron thin film in
〔工程３〕
石英反応管に、ヘリウムガスを２００ｍｌ／分で流し、内部温度を７００℃まで昇温した。
[Step 3]
Helium gas was passed through the quartz reaction tube at 200 ml / min, and the internal temperature was raised to 700 ° C.
〔工程４〕
温度が７００℃になった後、工程３のヘリウムガス中にアセチレンガスを８０ｍｌ／分導入し、この混合ガスを反応管に１０分流した。
[Step 4]
After the temperature reached 700 ° C., acetylene gas was introduced into the helium gas in
〔工程５〕
アセチレンガスの導入を止めて、その後常温まで反応管内を冷却した。以上の操作により、シリコン基板上に垂直配向したカーボンナノチューブ（高さ約４７μｍ）が生成した。
[Step 5]
The introduction of acetylene gas was stopped, and then the reaction tube was cooled to room temperature. By the above operation, vertically aligned carbon nanotubes (about 47 μm in height) were generated on the silicon substrate.
〔工程６〕
ポリ塩化ビニリデンをテトラヒドロフランに溶解させた。
[Step 6]
Polyvinylidene chloride was dissolved in tetrahydrofuran.
〔工程７〕
工程５において得た、シリコン基板上に垂直配向したカーボンナノチューブに、工程６において得たポリ塩化ビニリデンのテトラヒドロフラン溶液を所定量滴下し、約８０℃でカーボンナノチューブを乾燥させた。
[Step 7]
A predetermined amount of the polyvinylidene chloride tetrahydrofuran solution obtained in
〔工程８〕
工程７において、ポリ塩化ビニリデンのテトラヒドロフラン溶液を含ませたカーボンナノチューブを窒素雰囲気下、８００〜９００℃で焼成した。これによりカーボンナノテューブとポリ塩化ビニリデン由来の炭化物の複合体を得た（カーボンナノチューブ：ポリ塩化ビニリデン由来の炭化物＝１：ｌ．３、重量比）。
[Step 8]
In
〔工程９〕
工程８において得た、固定化した複合体を片面に有する一対のシリコン基板を電極として、図１、図２に示すように、容器(6) 内で、露点下（温度−６０℃、水分なし）の窒素雰囲気で、セパレータ(5) を介して、互いに対向するように配置し、サンドイッチ体(17)を作製した。その後、これを１５０〜２００℃で２４時間乾燥させた。
[Step 9]
As shown in FIGS. 1 and 2, using the pair of silicon substrates having the immobilized composite on one side obtained in step 8 as electrodes, in the container (6), below the dew point (temperature −60 ° C., no moisture) ) In a nitrogen atmosphere through the separator (5) so as to face each other to produce a sandwich body (17). Then, this was dried at 150-200 degreeC for 24 hours.
〔工程１０〕
乾燥窒素雰囲気下にグローブボックス内で電解液（テトラエチルアンモニウムテトラフルオロボレートのプロピレンカーボネート溶液（濃度＝１ｍｏｌ／ｌ））を容器(6) 内に注入し、カーボンナノチューブ(3) (4) に含浸させた。電解液の量は１ｃｍ２当たり１〜３ｃｃとした。
[Step 10]
In a glove box under a dry nitrogen atmosphere, an electrolytic solution (tetraethylammonium tetrafluoroborate propylene carbonate solution (concentration = 1 mol / l)) is injected into the container (6) and impregnated into the carbon nanotubes (3) (4). It was. The amount of the electrolyte was 1 to 3 cc per 1 cm2.
その後、ポリプロピレン製ガスケットを用いて容器(6) の口部をステンレス鋼製の蓋材(7) でかしめ封口した。こうして、上側電極(1) が陽極で下側電極(2) が陰極である電気二重層キャパシタ(Ａ)を作製した。 Thereafter, the mouth of the container (6) was caulked with a stainless steel lid (7) using a polypropylene gasket. Thus, an electric double layer capacitor (A) in which the upper electrode (1) was an anode and the lower electrode (2) was a cathode was produced.
実施例２
実施例１の〔工程１〕から〔工程５〕までを繰り返し、シリコン基板上に垂直配向したカーボンナノチューブ（高さ約４７μｍ）を生成させた。
Example 2
By repeating [Step 1] to [Step 5] of Example 1, carbon nanotubes (height of about 47 μm) vertically aligned on the silicon substrate were generated.
〔工程６〕
フェノール５ｃｃにホルマリン５ｃｃを加え、モノマーを得た。
[Step 6]
〔工程７〕
工程５において得た、シリコン基板上に垂直配向したカーボンナノチューブに、工程６において得たモノマーを所定量滴下し、約３００℃でカーボンナノチューブを乾燥させた。
[Step 7]
A predetermined amount of the monomer obtained in
〔工程８〕
工程７において、モノマーを含ませたカーボンナノチューブを窒素雰囲気下、８００〜９００℃で焼成した。これによりカーボンナノテューブと上記モノマー由来の炭化物の複合体を得た（カーボンナノチューブ：モノマー由来の炭化物＝１：２．４、重量比）。
[Step 8]
In
〔工程９〕
実施例１の〔工程９〕から〔工程１０〕までを繰り返し、電気二重層キャバシタ(Ｂ)を作製した。
[Step 9]
By repeating [Step 9] to [Step 10] of Example 1, an electric double layer capacitor (B) was produced.
比較例１
実施例１の〔工程１〕から〔工程５〕までを繰り返し、シリコン基板上に垂直配向したカーボンナノチューブ（高さ約４７μｍ）を生成させた。
Comparative Example 1
By repeating [Step 1] to [Step 5] of Example 1, carbon nanotubes (height of about 47 μm) vertically aligned on the silicon substrate were generated.
〔工程６〕
工程５において得た、シリコン基板上に垂直配向したカーボンナノチューブに対し、実施例１の〔工程９〕から〔工程１０〕までを繰り返し、電気二重層キャバシタ(Ｃ)を作製した。
[Step 6]
With respect to the carbon nanotubes vertically aligned on the silicon substrate obtained in
性能試験
実施例および比較例で作製した試料について、それぞれ静電容量を測定した。その結果を表１に示す。
表１から明らかなように、複合体によって得られた実施例のキャパシタの静電容量はカーボンナノチューブのみで作製した比較例のキャパシタの静電容量の１．８〜２．３倍である。 As is clear from Table 1, the capacitance of the capacitor of the example obtained by the composite is 1.8 to 2.3 times the capacitance of the capacitor of the comparative example made of only carbon nanotubes.
以上、本発明の実施の形態について説明したが、本発明はこのような実施の形態に何等限定されるものではなく、本発明の要旨を逸脱しない範囲内において、種々なる形態で実施し得る。さらに、本発明を基板上に成長したカーボンナノファイバーなど他のナノ材料にも適用できる。 The embodiment of the present invention has been described above, but the present invention is not limited to such an embodiment, and can be implemented in various forms without departing from the gist of the present invention. Furthermore, the present invention can be applied to other nanomaterials such as carbon nanofibers grown on a substrate.
(1) (2) ：電極
(3) (4) ：カーボンナノチューブ
(5) ：セパレータ
(6) ：容器
(7) ：蓋材
(8) ：電気二重層キャパシタ
(17)：サンドイッチ体
(1) (2): Electrode
(3) (4): Carbon nanotube
(5): Separator
(6): Container
(7): Cover material
(8): Electric double layer capacitor
(17): Sandwich body
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