JP4625950B2 - Activated carbon, manufacturing method thereof, and polarizable electrode for electric double layer capacitor - Google Patents
Activated carbon, manufacturing method thereof, and polarizable electrode for electric double layer capacitor Download PDFInfo
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Description
本発明は、活性炭、その製造方法、及びこの活性炭を用いて成形され、特に高電流充放電特性に優れた電気二重層キャパシタ用分極性電極に関する。 The present invention relates to activated carbon, a method for producing the same, and a polarizable electrode for an electric double layer capacitor that is molded using the activated carbon and that is particularly excellent in high-current charge / discharge characteristics.
電気二重層キャパシタを含む電気化学キャパシタ（以下キャパシタ）は、高出力密度と優れたサイクル特性を示すエネルギー貯蔵デバイスであり、ハイブリッド自動車・燃料電池自動車の補助電源や通電加熱触媒（ＥＨＣ）電源への応用にむけ高容量化が期待され、そのためには高充放電電流でのキャパシタ特性の向上が不可欠である。 Electrochemical capacitors (hereinafter referred to as “capacitors”) including electric double layer capacitors are energy storage devices that exhibit high power density and excellent cycle characteristics, and can be used for auxiliary power supplies and electrically heated catalyst (EHC) power supplies for hybrid and fuel cell vehicles. For applications, higher capacities are expected. For this purpose, improvement of capacitor characteristics at high charge / discharge current is indispensable.
キャパシタの高容量化に関する研究開発はこれまで様々行われているが（例えば，特許文献１）、高充放電電流に対応するハイパワーキャパシタ電極の技術開発はこれまで主に電流取出部の低抵抗化または電極の存在しないデスボリュームの低減（例えば、特許文献２）等のキャパシタユニットとしての技術開発が主流であり、電極材料である炭素組成物の技術開発による高充放電電流キャパシタ特性の向上は見られない。 Various researches and developments on increasing the capacitance of capacitors have been carried out so far (for example, Patent Document 1), but technological development of high-power capacitor electrodes corresponding to high charge / discharge currents has mainly been performed so far with a low resistance of the current extraction part. Technology development as a capacitor unit such as reduction of the death volume without electrode or reduction of the electrode (for example, Patent Document 2) is the mainstream, and improvement of high charge / discharge current capacitor characteristics by technical development of the carbon composition as the electrode material is can not see.
ハイブリッド自動車・燃料電池自動車の補助電源や通電加熱触媒（ＥＨＣ）電源へのキャパシタの適用には、高充放電電流、特に５０ｍＡ／平方センチメートル以上、好ましくは１００ｍＡ／平方センチメートル以上の高充放電電流におけるキャパシタ電極静電容量増大が必要である。 Capacitor electrodes for application of capacitors to auxiliary power supplies and energized heating catalyst (EHC) power supplies for hybrid vehicles and fuel cell vehicles, especially at high charge / discharge currents, particularly high charge / discharge currents of 50 mA / square centimeters or more, preferably 100 mA / square centimeters An increase in capacitance is necessary.
プラズマ処理を用いる類似技術としては、特許文献３、特許文献４等が挙げられるが、これらは窒素ガスもしくはフッ素化合物を用いたものである上、充放電電流密度５０ｍＡ
／平方センチメートル以上での高充放電電流特性の向上については触れられていない。
Similar techniques using plasma treatment include Patent Document 3, Patent Document 4, and the like, which use nitrogen gas or a fluorine compound and have a charge / discharge current density of 50 mA.
No mention is made of the improvement of the high charge / discharge current characteristics at / cm 2 or more.
従って本発明の目的は、５０ｍＡ／平方センチメートル以上、好ましくは１００ｍＡ／平方センチメートル以上の高充放電電流における静電容量が高い電気化学キャパシタ用分極性電極と、この電極用材料として好適な活性炭およびその製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a polarizable electrode for an electrochemical capacitor having a high capacitance at a high charge / discharge current of 50 mA / square centimeter or more, preferably 100 mA / square centimeter or more, activated carbon suitable as the electrode material, and a method for producing the same. Is to provide.
上記した課題は、以下の構成からなる活性炭、その製造方法、電気二重層キャパシタ用分極性電極によって解決される。
本発明の活性炭は、
（１） 活性炭材料を含ホウ酸水蒸気低温プラズマ処理してなることを特徴とする活性炭である。
（２） 活性炭材料が炭素質材料を炭化し賦活して得られた活性炭材料からなることを特徴とする前記（１）に記載の活性炭である。
（３） ＢＥＴ比表面積が１５００ｍ２／ｇ以上３３００ｍ２／ｇ以下の範囲であることを特徴とする前記（１）または前記（２）に記載の活性炭である。
（４） 活性炭が電気二重層キャパシタ用分極性電極用活性炭であることを特徴とする前記（１）ないし（３）のいずれかに記載の活性炭である。
本発明の活性炭の製造方法は
（５） 活性炭材料を含ホウ酸水蒸気低温プラズマ処理することを特徴とする活性炭の製造方法である。
（６） 活性炭材料が炭素質材料を炭化し賦活して得られた活性炭材料からなることを特徴とする前記（５）に記載の活性炭の製造方法である。
（７） 活性炭のＢＥＴ比表面積が１５００ｍ ２ ／ｇ以上３３００ｍ ２ ／ｇ以下の範囲であることを特徴とする前記（５）または前記（６）に記載の活性炭の製造方法である。
（８） 活性炭が電気二重層キャパシタ用分極性電極用活性炭であることを特徴とする前記（５）ないし（７）のいずれかに記載の活性炭の製造方法である。
（９） 前記（１）ないし（４）のいずれかに記載の活性炭を含む組成物を成形してなることを特徴とする電気二重層キャパシタ用分極性電極である。
The above-described problems are solved by activated carbon having the following configuration, a manufacturing method thereof, and a polarizable electrode for an electric double layer capacitor.
The activated carbon of the present invention is
(1) An activated carbon obtained by subjecting an activated carbon material to a boric acid water vapor low-temperature plasma treatment.
(2) The activated carbon according to (1), wherein the activated carbon material is an activated carbon material obtained by carbonizing and activating a carbonaceous material.
(3) The activated carbon according to (1) or (2) above, wherein the BET specific surface area is in a range of 1500 m 2 / g to 3300 m 2 / g.
(4) The activated carbon according to any one of (1) to (3), wherein the activated carbon is activated carbon for polarizable electrodes for electric double layer capacitors.
The method for producing activated carbon according to the present invention is (5) a method for producing activated carbon characterized by subjecting an activated carbon material to a low-temperature plasma treatment with boric acid water vapor.
(6) The method for producing activated carbon according to (5), wherein the activated carbon material is an activated carbon material obtained by carbonizing and activating a carbonaceous material.
(7) The method for producing activated carbon according to (5) or (6) above, wherein the activated carbon has a BET specific surface area of 1500 m 2 / g or more and 3300 m 2 / g or less.
( 8 ) The method for producing activated carbon according to any one of (5) to (7), wherein the activated carbon is activated carbon for polarizable electrodes for electric double layer capacitors.
( 9 ) A polarizable electrode for an electric double layer capacitor, which is formed by molding a composition containing activated carbon according to any one of (1) to (4).
本発明の活性炭を用いて成形される電気二重層キャパシタ用分極性電極は、５０ｍＡ／平方センチメートル以上、好ましくは１００ｍＡ／平方センチメートル以上の高充放電電流における静電容量が高い。 The polarizable electrode for an electric double layer capacitor formed using the activated carbon of the present invention has a high capacitance at a high charge / discharge current of 50 mA / square centimeter or more, preferably 100 mA / square centimeter or more.
本発明の活性炭は、活性炭材料を炭酸ガス又はホウ酸水蒸気存在下での低温プラズマ処理によって得られたものをいう。本発明において、活性炭材料とは、「炭酸ガス又はホウ酸水溶水蒸気の存在下での低温プラズマ処理が施される活性炭の材料」を意味し、「炭酸ガス又はホウ酸水蒸気存在下での低温プラズマ処理が施された活性炭」と区別している。 The activated carbon of the present invention refers to an activated carbon material obtained by low-temperature plasma treatment in the presence of carbon dioxide gas or boric acid water vapor. In the present invention, the activated carbon material means “a material of activated carbon that is subjected to low temperature plasma treatment in the presence of carbon dioxide gas or boric acid water-soluble water vapor”, and “low temperature plasma in the presence of carbon dioxide gas or boric acid water vapor” This is distinguished from “treated activated carbon”.
本発明において、活性炭材料は、炭素質材料を炭化、賦活して得られるものが望ましい。炭素質材料としては、木材、鋸屑，木炭、ヤシ殻等の果実殻、果実種等の植物系、泥炭、亜炭、褐炭、無煙炭等の石炭、石油ピッチ、石炭ピッチ等のピッチ、コークス、コールタール、石油タール等のタール、石油蒸留残渣等の鉱物、木綿、レーヨン等のセルロース系繊維、フェノール樹脂、ポリビニルアルコール等の合成ポリマー等の公知の材料が用いられ、これらの炭素質材料を炭化、賦活することによって活性炭材料が得られる。炭素質材料は加熱乾留により炭化され、その後、薬剤賦活、あるいは水蒸気、炭酸ガス、酸素ガス、燃焼排ガス、これらの混合ガスによるガス賦活法によって活性炭材料とすることができる。このようにして得られる活性炭材料の形状は、特に制限はなく任意の形態を採ることができる。 In the present invention, the activated carbon material is preferably obtained by carbonizing and activating a carbonaceous material. Carbonaceous materials include wood, sawdust, charcoal, palm shells and other fruit shells, plant types such as fruit seeds, peat, lignite, lignite, anthracite, etc. coal, petroleum pitch, coal pitch, etc., coke, coal tar Well-known materials such as tars such as petroleum tar, minerals such as petroleum distillation residues, cellulosic fibers such as cotton and rayon, synthetic polymers such as phenolic resins and polyvinyl alcohol, etc. are used to carbonize and activate these carbonaceous materials By doing so, an activated carbon material is obtained. The carbonaceous material is carbonized by heating carbonization, and then activated carbon material can be obtained by chemical activation or gas activation method using water vapor, carbon dioxide gas, oxygen gas, combustion exhaust gas, or mixed gas thereof. There is no restriction | limiting in particular in the shape of the activated carbon material obtained in this way, Arbitrary forms can be taken.
次に活性炭材料に低温プラズマ処理を施す。低温プラズマ処理には含炭酸ガス低温プラズマ処理または含ホウ酸水蒸気低温プラズマ処理があり、ここでいう「低温」とは、２０℃〜４５０℃、好ましくは５０〜３００℃の条件下で実施されることを意味する。含炭酸ガス低温プラズマ処理は、希釈剤としては不活性ガスやメタン等が用いられる。不活性ガスとしてはアルゴンガス、チッ素ガス等が好適に用いられる。炭酸ガス：希釈剤の混合比としては、容量比で１：９〜９：１が好ましく、より好ましくは５：５〜８：２である。ホウ酸水蒸気：希釈剤の混合比も炭酸ガスの場合と同様である。 Next, the activated carbon material is subjected to a low temperature plasma treatment. The low temperature plasma treatment includes carbon dioxide-containing gas low temperature plasma treatment or boric acid water vapor low temperature plasma treatment, and the term “low temperature” as used herein is carried out at 20 ° C. to 450 ° C., preferably 50 to 300 ° C. Means that. In the carbon-containing gas low-temperature plasma treatment, an inert gas, methane, or the like is used as a diluent. Argon gas, nitrogen gas or the like is preferably used as the inert gas. The mixing ratio of carbon dioxide gas: diluent is preferably 1: 9 to 9: 1 by volume, more preferably 5: 5 to 8: 2. The mixing ratio of boric acid steam: diluent is the same as that for carbon dioxide.
炭酸ガスまたはホウ酸水蒸気のプラズマ雰囲気に対する濃度は１０体積％〜９０体積％、好ましくは５０体積％〜８０体積％の範囲であることが望ましい。１０体積％以下では本発明の効果が充分に得られず、９０体積％以上では充分なプラズマ出力が得られず好ましくない。プラズマ印加電力は、５〜１００Ｗが好ましく、より好ましくは１０〜６０Ｗである。プラズマ印加電力が５Ｗより低いと本発明の効果が充分に得られず、一方、１００Ｗよりも高いと燃焼に近い反応が生じ好ましくない。 The concentration of carbon dioxide gas or boric acid water vapor in the plasma atmosphere is desirably 10 volume% to 90 volume%, preferably 50 volume% to 80 volume%. If it is 10 volume% or less, the effect of the present invention cannot be sufficiently obtained, and if it is 90 volume% or more, a sufficient plasma output cannot be obtained. The plasma applied power is preferably 5 to 100 W, more preferably 10 to 60 W. If the plasma applied power is lower than 5 W, the effect of the present invention cannot be sufficiently obtained. On the other hand, if it is higher than 100 W, a reaction close to combustion occurs, which is not preferable.
プラズマ処理装置は、ガス供給口とガス排出口とを有する反応容器内に高周波電源と接続する電源と、この電極に対向して用けられた支持台上に活性炭材料がセットされる。このプラズマ処理装置において、含炭酸ガス低温プラズマ処理の場合、ガス供給口から希釈剤によって希釈された炭酸ガスが導入され、含ホウ酸水蒸気低温プラズマ処理の場合、ガス供給口から希釈剤によって希釈されたホウ酸水蒸気が導入される。低温プラズマ処理時において反応容器内は、１〜１４０Ｐａが好ましく、より好ましくは１０〜１２０Ｐａ、さらに好ましくは２０〜１００Ｐａである。反応容器内の減圧条件が１Ｐａよりも低いと反応容器内の気体分子存在数が少なく、プラズマ発生効率が低下するおそれがあり、一方、１４０Ｐａよりも高いと電子の平均自由行程が小さくなり、プラズマ発生効率が低下するおそれがある。 In the plasma processing apparatus, an activated carbon material is set on a power source connected to a high frequency power source in a reaction vessel having a gas supply port and a gas discharge port, and on a support table used facing the electrode. In this plasma treatment apparatus, in the case of carbon dioxide-containing low temperature plasma treatment, carbon dioxide gas diluted with a diluent is introduced from the gas supply port, and in the case of boric acid water vapor low-temperature plasma treatment, it is diluted with diluent from the gas supply port. Boric water vapor is introduced. During the low temperature plasma treatment, the inside of the reaction vessel is preferably 1 to 140 Pa, more preferably 10 to 120 Pa, and still more preferably 20 to 100 Pa. If the depressurization condition in the reaction vessel is lower than 1 Pa, the number of gas molecules in the reaction vessel is small and the plasma generation efficiency may be reduced. On the other hand, if it is higher than 140 Pa, the mean free path of electrons becomes small, and the plasma The generation efficiency may be reduced.
炭酸ガス存在下における熱賦活処理では７００℃以上の高温が必要であるが、本発明では５０℃〜３００℃低温で実施するのが望ましく、炭素材料の高温燃焼による重量減少を抑制できる。プラズマ処理時間は５分以上２００分以下か好ましく、１０分以上１８０分以下がより好ましく、６０分以上１２０分以下の範囲であることが特に好ましい。５分未満では本発明の効果が十分に得られず、２００分以上では過剰のプラズマ処理により活性炭伝導度が低下し、活性炭の強度も低下し好ましくない。 In the heat activation treatment in the presence of carbon dioxide gas, a high temperature of 700 ° C. or higher is necessary, but in the present invention, it is desirable to carry out at a low temperature of 50 ° C. to 300 ° C., and weight loss due to high temperature combustion of the carbon material can be suppressed. The plasma treatment time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 180 minutes, and particularly preferably from 60 minutes to 120 minutes. If it is less than 5 minutes, the effect of the present invention cannot be sufficiently obtained, and if it is 200 minutes or more, the activated carbon conductivity is lowered by excessive plasma treatment, and the strength of the activated carbon is also lowered.
上記したプラズマ処理によって得られる活性炭は、炭酸ガス又はホウ酸水蒸気存在下でのプラズマ処理の実施により含酸素官能基が活性炭表面に導入され、比表面積が増大する。得られる活性炭のＢＥＴ比表面積は１５００ｍ2／ｇ以上３３００ｍ2／ｇ以下、より好ましくは２０００ｍ2／ｇ以上３３００ｍ2／ｇ以下の範囲であることが望ましい。ＢＥＴ比表面積に関しては１５００ｍ2／ｇ未満ではプラズマ処理によって得られる活性炭を用いて成形されるキャパシタ電極が充分な静電容量を得ることが出来ず、ＢＥＴ比表面積が３３００ｍ2／ｇを超えると活性炭そのものの密度が低下し、相対的に電極材の密度低下からキャパシタの単位体積あたりの静電容量が低下する問題があるため好ましくない。 In the activated carbon obtained by the above plasma treatment, oxygen-containing functional groups are introduced to the activated carbon surface by performing the plasma treatment in the presence of carbon dioxide gas or boric acid water vapor, and the specific surface area is increased. The obtained activated carbon has a BET specific surface area of 1500 m 2 / g or more and 3300 m 2 / g or less, and more preferably 2000 m 2 / g or more and 3300 m 2 / g or less. When the BET specific surface area is less than 1500 m 2 / g, the capacitor electrode formed using the activated carbon obtained by plasma treatment cannot obtain a sufficient capacitance, and when the BET specific surface area exceeds 3300 m 2 / g, the activated carbon This is not preferable because the density of the electrode itself decreases and the capacitance per unit volume of the capacitor decreases relatively due to the decrease in density of the electrode material.
上記のようにして得られる活性炭と、導電材、結合材から電気化学キャパシタ用分極性電極が得られる。該分極性電極は、例えば、前記活性炭と導電材とポリテトラフルオロエチレン等の結合材とをアルコールの存在下で混練してシート状に成形し、乾燥した後導電性接着剤等を介して集電体と接合させることによって得られる。また、該活性炭と導電材と結合材と溶媒を混合してスラリーとし、集電体金属箔の上にコートし、乾燥して集電体と一体化された電極を得ることもできる。 A polarizable electrode for an electrochemical capacitor is obtained from the activated carbon obtained as described above, a conductive material, and a binder. For example, the polarizable electrode is obtained by kneading the activated carbon, a conductive material, and a binder such as polytetrafluoroethylene in the presence of alcohol to form a sheet, drying it, and then collecting it through a conductive adhesive. It is obtained by bonding with an electric body. Alternatively, the activated carbon, the conductive material, the binder, and the solvent are mixed to form a slurry, which is coated on the current collector metal foil and dried to obtain an electrode integrated with the current collector.
導電材としては、カーボンブラック、天然黒鉛、人造黒鉛、酸化チタン、酸化ルテニウム等の粉末が用いられる。これらのうち、少量でも導電性を向上させる効果が大きいことから、カーボンブラックの１種であるケッチェンブラック又はアセチレンブラックを使用するのが好ましい。 As the conductive material, powder of carbon black, natural graphite, artificial graphite, titanium oxide, ruthenium oxide or the like is used. Of these, ketjen black or acetylene black, which is a kind of carbon black, is preferably used since the effect of improving conductivity is large even in a small amount.
分極性電極中のカーボンブラック等の導電材の配合量は、導電性を向上させられるように、該活性炭との合計量中５質量％以上、特には１０質量％以上配合するのが好ましい。また、該活性炭の配合割合が減ると分極性電極の容量が減るため分極性電極中の導電材の配合量は５〜４０質量％，特に１０〜３０質量％とするのが好ましい。 The blending amount of the conductive material such as carbon black in the polarizable electrode is preferably 5% by mass or more, particularly 10% by mass or more in the total amount with the activated carbon so as to improve the conductivity. Moreover, since the capacity | capacitance of a polarizable electrode will reduce if the mixture ratio of this activated carbon reduces, it is preferable that the compounding quantity of the electrically conductive material in a polarizable electrode shall be 5-40 mass%, especially 10-30 mass%.
スラリーに混合する結合材は、例えばポリテトラフルオロエチレン、ポリフッ化ビニリデン、フルオロオレフィン／ビニルエーテル共重合体架橋ポリマー、カルボキシメチルセルロース、ポリビニルピロリドン、ポリビニルアルコール、又はポリアクリル酸等が使用できる。分極性電極中の結合材の含有量は、活性炭、カーボンブラック等の炭素材料と結合材との合計量中０．５〜２０質量％とするのが好ましい。結合材の量が０．５質量％未満であると電極の強度が不足し、２０質量％超であると電気抵抗の増大や容量の低下が起きるためである。電極の容量と強度のバランスから、結合材の配合量は０．５〜１０質量％とするのがより好ましい。 For example, polytetrafluoroethylene, polyvinylidene fluoride, fluoroolefin / vinyl ether copolymer cross-linked polymer, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol, or polyacrylic acid can be used as the binder to be mixed with the slurry. The content of the binder in the polarizable electrode is preferably 0.5 to 20% by mass in the total amount of the carbon material such as activated carbon and carbon black and the binder. This is because if the amount of the binder is less than 0.5% by mass, the strength of the electrode is insufficient, and if it exceeds 20% by mass, the electrical resistance increases and the capacity decreases. From the balance of electrode capacity and strength, the blending amount of the binder is more preferably 0.5 to 10% by mass.
本発明において、上述の分極性電極を正極、負極の両極に用いて電気二重層キャパシタを構成することができるが、負極のみを分極性電極とし正極として金属酸化物等の電池活物質を主体とする非分極性電極を用いたり、正極のみを非分極性電極とし負極にリチウム金属、リチウム合金、又はリチウムイオンを可逆的に吸蔵、放出しうる炭素材料を主成分とする非分極性電極を用いることもできる。 In the present invention, an electric double layer capacitor can be formed by using the above polarizable electrode as both a positive electrode and a negative electrode. However, only the negative electrode is a polarizable electrode and the positive electrode is used mainly as a battery active material such as a metal oxide. A non-polarizable electrode that uses only a positive electrode as a non-polarizable electrode and a negative electrode that contains lithium metal, a lithium alloy, or a carbon material capable of reversibly occluding and releasing lithium ions as a negative electrode. You can also.
これらの電気二重層キャパシタのうち、負極にリチウムイオンを可逆的に吸蔵、放出しうる炭素材料を用い、正極に上述の分極性電極を用いた電気二重層キャパシタは、充放電サイクル耐久性と安全性に優れており、作動電圧を高くでき、かつ容量が大きいという特徴があり特に好ましい。 Among these electric double layer capacitors, electric double layer capacitors using a carbon material capable of reversibly occluding and releasing lithium ions for the negative electrode and the polarizable electrode described above for the positive electrode are charge / discharge cycle durability and safety. It is particularly preferable because of its excellent characteristics, high operating voltage and large capacity.
非分極性電極の主材料である、リチウムイオンを吸蔵、放出しうる炭素材料としては、天然黒鉛、人造黒鉛、黒鉛化メソカーボン小球体、黒鉛化ウィスカー、気相成長させた黒鉛化炭素繊維、フルフリルアルコール樹脂の焼成品、ノボラック樹脂の焼成品が好ましく使用できる。 Carbon materials that can occlude and release lithium ions, the main material of non-polarizable electrodes, include natural graphite, artificial graphite, graphitized mesocarbon spherules, graphitized whiskers, vapor-grown graphitized carbon fibers, A fired product of furfuryl alcohol resin and a fired product of novolak resin can be preferably used.
電極の集電体は電気化学的、化学的に耐食性のある導電体であればよい。低温プラズマ処理によって得られる活性炭を主成分とする電極の集電体としては、ステンレス鋼、アルミニウム、チタン、タンタル、ニッケル等が用いられる。なかでも、ステンレス鋼とアルミニウムが性能と価格の両面で好ましい集電体である。リチウムイオンを吸蔵させた炭素材料を主成分とする非分極性電極の集電体としては、ステンレス鋼、銅又はニッケルが好ましく使用できる。 The current collector of the electrode may be a conductor that is electrochemically and chemically corrosion resistant. Stainless steel, aluminum, titanium, tantalum, nickel, etc. are used as the current collector of the electrode mainly composed of activated carbon obtained by low-temperature plasma treatment. Of these, stainless steel and aluminum are preferred current collectors in terms of both performance and cost. Stainless steel, copper or nickel can be preferably used as the current collector of the nonpolarizable electrode mainly composed of a carbon material occluded with lithium ions.
また、集電体の形状は箔でもよいし、二次元構造を有するニッケルやアルミニウムの発泡金属やステンレス鋼のネットやウールでもよい。 The shape of the current collector may be a foil, a nickel or aluminum foam metal having a two-dimensional structure, a stainless steel net, or wool.
本発明の電気化学キャパシタの電解液は特に限定されるものでなく、従来公知あるいは周知の非水系電解液を使用できる。溶媒としては、電気化学的に安定なプロピレンカーボネート、エチレンカーボネート、γ―ブチロラクトン、スルホラン、３−メチルスルホラン、１，２−ジメトキシエタン、アセトニトリル、ジメチルホルムアミド、ジエチルカーボネート、エチルメチルカーボネート、又はジメチルカーボネートから選ばれる１種以上からなる溶媒が好ましい。 The electrolytic solution of the electrochemical capacitor of the present invention is not particularly limited, and a conventionally known or well-known non-aqueous electrolytic solution can be used. Solvents include electrochemically stable propylene carbonate, ethylene carbonate, γ-butyrolactone, sulfolane, 3-methylsulfolane, 1,2-dimethoxyethane, acetonitrile, dimethylformamide, diethyl carbonate, ethyl methyl carbonate, or dimethyl carbonate. The solvent which consists of 1 or more types chosen is preferable.
本発明において正極と負極の間に介装されるセパレータとしては、例えばポリプロピレン繊維不織布、ガラス繊維不織布等が好適に使用できる。 In the present invention, as the separator interposed between the positive electrode and the negative electrode, for example, a polypropylene fiber nonwoven fabric and a glass fiber nonwoven fabric can be preferably used.
本発明の電気化学キャパシタは、一対のシート状電極の間にセパレータを介して電解液とともに金属ケースに収容したコイン型、一対の正極と負極を間にセパレータを介して巻回してなる巻回型、多数の電極をセパレータを介して積み重ねた積層型等いずれの構成もとることができる。 The electrochemical capacitor of the present invention includes a coin type housed in a metal case together with an electrolyte solution via a separator between a pair of sheet-like electrodes, and a winding type obtained by winding a pair of positive and negative electrodes via a separator. Any configuration such as a stacked type in which a large number of electrodes are stacked via a separator can be used.
本発明に低温プラズマ処理によって得られる活性炭を用いて成形されるキャパシタ電極は、高充放電電流、特に５０ｍＡ／平方センチメートル以上、好ましくは１００ｍＡ／平方センチメートル以上の高充放電電流におけるキャパシタ電極静電容量を大幅に向上させることができる。 The capacitor electrode formed by using the activated carbon obtained by the low-temperature plasma treatment in the present invention greatly increases the capacitance of the capacitor electrode at a high charge / discharge current, particularly at a high charge / discharge current of 50 mA / square centimeter or more, preferably 100 mA / square centimeter or more. Can be improved.
以下、本発明を実施例によってさらに詳細に説明する。
本発明において、静電容量は次の方法により測定した。到達電圧１．０Ｖまで電極表面積あたり５０ｍＡ／平方センチメートル、１００ｍＡ／平方センチメートル及び１５０ｍＡ／平方センチメートルでそれぞれ定電流充電し、１．０Ｖで３０分間定電圧下補充電する。補充電完了後、充電電流と同じ電流値で定電流放電する。その際０．６Ｖから０．５Ｖまでの放電傾きより静電容量を求めた。
［実施例１］
Hereinafter, the present invention will be described in more detail by way of examples.
In the present invention, the capacitance was measured by the following method. Constant current charging is performed at an electrode surface area of 50 mA / square centimeter, 100 mA / square centimeter, and 150 mA / square centimeter up to an ultimate voltage of 1.0 V, and supplementary charging is performed at a constant voltage of 1.0 V for 30 minutes. After completion of auxiliary charging, constant current discharge is performed at the same current value as the charging current. At that time, the capacitance was determined from the discharge slope from 0.6V to 0.5V.
[Example 1]
活性炭粉末（関西熱化学、商品名ＭＳＰ−２０）をプラズマＣＶＤ装置（Ｓａｍｃｏ製、商品名ＢＰ−１）にて処理をした。炭酸ガス及びアルゴンガスを総流量５０ｍｌ／分で流し、６７Ｐａに減圧後、室温にて低温プラズマ処理を１０分間施した。炭酸ガス濃度は８０体積％とした。プラズマ印加電力を１０Ｗとした。
プラズマ処理を施した活性炭粉末およびカーボンブラック（電気化学工業、商品名ＡＢ−３）、ポリテトラフルオロエチレン粉末（ダイキン、商品名Ｆ−１０４）を重量比８：１：１で取り、エタノール０．３ｍｌを加えながら混練した。混練物を０．１ｇ採り、直径１６ｍｍのペレット形成器を用いて１０メガパスカルで圧縮成型し、３３０℃で５時間真空焼成し、成形電極を作製した。
成形電極およびセパレーターを電解液中にて４０分間脱気した後、コイン型２端子セルにて定電流充放電試験測定を行った。セパレーターにはガラス繊維濾紙（ＡＤＶＡＮＴＥＣ、商品名ＧＡ−５５）、電解液には濃度０．５モル／Ｌの硫酸水溶液を用いた。ＢＥＴ比表面積の結果を表１に示し、静電容量の結果を表２に示す。
［実施例２］
Activated carbon powder (Kansai thermochemical, trade name MSP-20) was processed with a plasma CVD apparatus (Samco, trade name BP-1). Carbon dioxide gas and argon gas were allowed to flow at a total flow rate of 50 ml / min, and after reducing the pressure to 67 Pa, low-temperature plasma treatment was performed at room temperature for 10 minutes. The carbon dioxide gas concentration was 80% by volume. The plasma applied power was 10W.
Activated carbon powder and carbon black (Electrochemical Industry, trade name AB-3) and polytetrafluoroethylene powder (Daikin, trade name F-104) subjected to plasma treatment were taken at a weight ratio of 8: 1: 1, and ethanol was added in an amount of 0. The mixture was kneaded while adding 3 ml. 0.1 g of the kneaded product was taken, compression-molded with 10 megapascals using a pellet former having a diameter of 16 mm, and baked in vacuum at 330 ° C. for 5 hours to produce a molded electrode.
The molded electrode and the separator were deaerated in the electrolytic solution for 40 minutes, and then a constant current charge / discharge test measurement was performed using a coin-type two-terminal cell. Glass fiber filter paper (ADVANTEC, trade name GA-55) was used as the separator, and an aqueous sulfuric acid solution having a concentration of 0.5 mol / L was used as the electrolyte. The results of BET specific surface area are shown in Table 1, and the results of capacitance are shown in Table 2.
[Example 2]
実施例１においてプラズマ処理を６０分施した以外は実施例１と同様に行った。ＢＥＴ比表面積の結果を表１に示し、静電容量の結果を表２に示す。
［実施例３］
Example 1 was performed in the same manner as Example 1 except that plasma treatment was performed for 60 minutes. The results of BET specific surface area are shown in Table 1, and the results of capacitance are shown in Table 2.
[Example 3]
実施例１においてプラズマ処理を１２０分施した以外は実施例１と同様に行った。ＢＥＴ比表面積の結果を表１に示し、静電容量の結果を表２に示す。
［実施例４］
Example 1 was performed in the same manner as Example 1 except that plasma treatment was performed for 120 minutes. The results of BET specific surface area are shown in Table 1, and the results of capacitance are shown in Table 2.
[Example 4]
実施例１においてプラズマ処理を１８０分施した以外は実施例１と同様に行った。ＢＥＴ比表面積の結果を表１に示し、静電容量の結果を表２に示す。
［実施例５］
Example 1 was performed in the same manner as Example 1 except that plasma treatment was performed for 180 minutes. The results of BET specific surface area are shown in Table 1, and the results of capacitance are shown in Table 2.
[Example 5]
実施例１において、炭酸ガス濃度を５０体積％とした以外は実施例１と同様に行った。ＢＥＴ比表面積の結果を表１に示し、静電容量の結果を表２に示す。
［実施例６］
In Example 1, it carried out like Example 1 except having made carbon dioxide gas concentration into 50 volume%. The results of BET specific surface area are shown in Table 1, and the results of capacitance are shown in Table 2.
[Example 6]
実施例１において、濃度０．５モル／Ｌのホウ酸水蒸気を含むアルゴン希釈メタン雰囲気下においてプラズマ処理を施した以外は実施例１と同様に行った。ＢＥＴ比表面積の結果を表１に示し、静電容量の結果を表２に示す。
［比較例１］
In Example 1, it carried out like Example 1 except having performed plasma processing in the argon dilution methane atmosphere containing 0.5 mol / L boric-acid water vapor | steam. The results of BET specific surface area are shown in Table 1, and the results of capacitance are shown in Table 2.
[Comparative Example 1]
実施例１において、プラズマ処理を施していない活性炭粉末を使用した以外は、実施例１と同様に行った。ＢＥＴ比表面積の結果を表１に示し、静電容量の結果を表２に示す。表２中、増大率とはプラズマ処理していない活性炭を基準にしてその増大率を示している。 In Example 1, it carried out like Example 1 except having used the activated carbon powder which has not performed plasma treatment. The results of BET specific surface area are shown in Table 1, and the results of capacitance are shown in Table 2. In Table 2, the rate of increase indicates the rate of increase based on activated carbon that has not been plasma-treated.
表１，２から本発明の実施例６にかかる成形電極は、５０ｍＡ／平方センチメートル、１００ｍＡ／平方センチメートル及び１５０ｍＡ／平方センチメートルのいずれの高充放電電流の場合にもプラズマ処理しない活性炭を用いて成形された電極に比べて静電容量が大幅に向上していることがわかる。 From Tables 1 and 2, the molded electrode according to Example 6 of the present invention is an electrode molded using activated carbon that is not plasma-treated in any of the high charge / discharge currents of 50 mA / square centimeter, 100 mA / square centimeter, and 150 mA / square centimeter. It can be seen that the capacitance is greatly improved as compared with FIG.
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