JP2008153694A - Electrode material for electric double layer capacitor, method of manufacturing the same, and electric double layer capacitor - Google Patents
Electrode material for electric double layer capacitor, method of manufacturing the same, and electric double layer capacitor Download PDFInfo
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- 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
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- Y02E60/13—Energy storage using capacitors
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Abstract
Description
本発明は、電気二重層キャパシタ用電極材、その製造方法及び電気二重層キャパシタに関する。 The present invention relates to an electrode material for an electric double layer capacitor, a manufacturing method thereof, and an electric double layer capacitor.
電気二重層キャパシタは、ファラッド級の大容量を有し、充放電サイクル特性にも優れることから、電気機器のバックアップ電源、車載バッテリー等の用途に使用されている。 Electric double layer capacitors have a farad-class large capacity and are excellent in charge / discharge cycle characteristics, and are therefore used in applications such as backup power supplies for electric devices and in-vehicle batteries.
電気二重層キャパシタは、その内部に２つの電極を備えている。これらの２つの電極がセパレータにより分離され、それぞれ陽極および陰極として作用するよう構成されている。このような電気二重層キャパシタの電極には、微細な細孔を有する活性炭が用いられている。活性炭からなる電気二重層キャパシタの電極には、溶媒と電解質とからなる電解液が含浸されている。電解液中で溶媒和している電解質イオンが活性炭の細孔中に吸着集合することにより、電気二重層キャパシタの陽極および陰極が構成される。 The electric double layer capacitor has two electrodes therein. These two electrodes are separated by a separator and are configured to function as an anode and a cathode, respectively. Activated carbon having fine pores is used for the electrode of such an electric double layer capacitor. An electrode of an electric double layer capacitor made of activated carbon is impregnated with an electrolytic solution made of a solvent and an electrolyte. The electrolyte ions solvated in the electrolytic solution are adsorbed and assembled in the pores of the activated carbon, thereby forming the anode and cathode of the electric double layer capacitor.
このような電気二重層キャパシタにおける活性炭は、溶媒や電解質イオンが電気化学的に作用するための場を提供するものであると考えることができる。したがって、その物性や微細構造によって、電気二重層キャパシタの性能が大きく左右される。 The activated carbon in such an electric double layer capacitor can be considered to provide a field for the solvent and electrolyte ions to act electrochemically. Therefore, the performance of the electric double layer capacitor greatly depends on its physical properties and fine structure.
電気二重層キャパシタの性能を向上させるためには、活性炭の微細構造を改良することが重要であるため、多くの試みがなされている。活性炭の比表面積を増加させることにより、吸着される電解質イオンの量を増加させ、これにより電極密度や静電容量を向上させようとする試みが主としてなされているが、近年、車載用等さまざまな分野で用いられるようになった電気二重層キャパシタには使用温度などの環境に左右されない、これまで以上の電極材高出力化が求められている。キャパシタ用電極材を高出力化するためには、用いられる活性炭のメソポアを発達させるなど、細孔径を拡大させる手法を用いるのが一般的である。しかしながら、細孔径を大きくすると必然的にかさ密度の低下を招き、結果的に体積容量が低下するという問題があった。 Many attempts have been made to improve the fine structure of the activated carbon in order to improve the performance of the electric double layer capacitor. Attempts have been mainly made to increase the amount of electrolyte ions adsorbed by increasing the specific surface area of the activated carbon, thereby improving the electrode density and capacitance. Electric double layer capacitors that have been used in the field are required to have higher electrode material output than ever before, regardless of the environment such as the operating temperature. In order to increase the output of the capacitor electrode material, it is common to use a technique for expanding the pore diameter, such as by developing a mesopore of the activated carbon used. However, when the pore diameter is increased, the bulk density is inevitably lowered, resulting in a problem that the volume capacity is lowered.
このように従来は活性炭の性能向上のため、賦活の条件を制御し、比表面積及び細孔径の最適化を図ることに主眼が置かれていた。しかしながら電気二重層キャパシタの設計には充放電前の電極材の設計のみでは、その性能発現は不十分である。キャパシタの電極材には充電時に構造変化を起こすものが存在し、それによって充電後の細孔構造が充電前のそれと変化するためである。これらの事実は、ソフト系カーボンを前駆体とする材料では起こることが知られおり、ソフト系カーボン電極材の充放電時の膨張収縮の問題点について検討されている（例えば特許文献１、特許文献２参照）。
Thus, conventionally, in order to improve the performance of activated carbon, the main focus has been on controlling the activation conditions and optimizing the specific surface area and pore diameter. However, in the design of the electric double layer capacitor, the performance expression is insufficient only by the design of the electrode material before charging and discharging. This is because some capacitor electrode materials undergo structural changes during charging, which causes the pore structure after charging to change from that before charging. These facts are known to occur in materials using soft carbon as a precursor, and problems of expansion and contraction during charging and discharging of the soft carbon electrode material have been studied (for example,
しかしながら、ハード系カーボンを前駆体とする電極材については、これまでこのような報告がなされた例はない。従来より、ハード系カーボンは炭素結晶子が等方的に並んでおり、十分な固さを持っているため充放電による構造変化は起こらないものと考えられていた。しかしながら発明者らは、このハード系カーボンを用いた電極材においても充放電時に構造変化を起こしており、これらがキャパシタの出力特性等に悪影響を与えることを突き止めた。 However, no report has been made on electrode materials having hard carbon as a precursor. Conventionally, it has been thought that hard carbon has isotropically aligned carbon crystallites and has sufficient hardness, so that structural change due to charge / discharge does not occur. However, the inventors have found that even in the electrode material using the hard carbon, structural changes occur during charging and discharging, and these adversely affect the output characteristics and the like of the capacitor.
本発明は、使用される温度領域によらず高い出力特性を有する電気二重層キャパシタ用電極材、その製造方法及び電気二重層キャパシタを提供する。 The present invention provides an electrode material for an electric double layer capacitor having a high output characteristic regardless of the temperature range to be used, a manufacturing method thereof, and an electric double layer capacitor.
発明者らは、鋭意検討の結果、電気二重層キャパシタ用として種々の電極材を作製し検討を行ってきた結果、充放電によって構造変化が起こりにくくすることで、使用される温度領域によらず高出力特性な電気二重層キャパシタに好適な電極材を得ることができることを見出し、本発明に至った。 As a result of intensive studies, the inventors have made and studied various electrode materials for electric double layer capacitors, and as a result, structural changes are less likely to occur due to charge / discharge, regardless of the temperature range used. The inventors have found that an electrode material suitable for an electric double layer capacitor having high output characteristics can be obtained, and have reached the present invention.
具体的には下記の［１］〜［３］に記載の事項を特徴とするものである。
［１］ 比表面積が１８００〜２６００ｍ２／ｇ、細孔容量０．７〜１．５ｍｌ／ｇ、平均細孔径が１．６０〜２．００ｎｍ、表面官能基濃度が０．１〜１．０ｍｍｏｌ／ｇ、平均粒径が１〜２０μｍであり、ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）が、６５〜８０ｃｍ−１である電気二重層キャパシタ用電極材。
［２］ 上記［１］に記載の電気二重層キャパシタ用電極材の製造方法であって、フェノール樹脂の炭化物をアルカリ化合物共存下で加熱して作製されることを特徴とする電気二重層キャパシタ用電極材の製造方法。
［３］ 上記［１］に記載の電気二重層キャパシタ用電極材又は上記［２］に記載の製造方法で得られる電気二重層キャパシタ用電極材を電極材として用いてなる電気二重層キャパシタ。
Specifically, the items described in [1] to [3] below are characterized.
[1] The specific surface area is 1800 to 2600 m 2 / g, the pore volume is 0.7 to 1.5 ml / g, the average pore diameter is 1.60 to 2.00 nm, and the surface functional group concentration is 0.1 to 1.0 mmol. / g, an average particle size of 1 to 20 [mu] m, the half-value width of the peak around 1580 cm -1 which is observed in the Raman spectrum (G1) (Δν1) is an electric double layer capacitor electrode member is 65～80Cm -1 .
[2] The method for producing an electrode material for an electric double layer capacitor according to [1], wherein the electrode material is produced by heating a phenol resin carbide in the presence of an alkali compound. Manufacturing method of electrode material.
[3] An electric double layer capacitor using the electrode material for an electric double layer capacitor according to [1] or the electrode material for an electric double layer capacitor obtained by the production method according to [2] as an electrode material.
本発明によれば、使用される温度領域によらず高い出力特性を有する電気二重層キャパシタ用電極材、その製造方法及び電気二重層キャパシタを得ることが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to obtain the electrode material for electric double layer capacitors which has a high output characteristic irrespective of the temperature range to be used, its manufacturing method, and an electric double layer capacitor.
以下、本発明を詳細に説明する。
本発明は、比表面積が１８００〜２６００ｍ２／ｇ、細孔容量０．７〜１．５ｍｌ／ｇ、平均細孔径が１．６０〜２．００ｎｍ、表面官能基濃度が０．１〜１．０ｍｍｏｌ／ｇ、平均粒径が１〜２０μｍであり、ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）が、６５〜８０ｃｍ−１である電気二重層キャパシタ用電極材である。
本発明における電気二重層キャパシタ用電極材は、比表面積が１８００〜２６００ｍ２／ｇであり、１９００〜２５５０ｍ２／ｇであることが好ましく、２０００〜２５００ｍ２／ｇであることがより好ましい。比表面積が１８００ｍ２／ｇ未満であると、十分な静電容量が得られない傾向があり、２６００ｍ２／ｇを超えるとかさ密度が低くなり、キャパシタの体積容量が低下する傾向がある。なお、本発明における比表面積は窒素ガス吸着測定によって測定することが可能である。
Hereinafter, the present invention will be described in detail.
The present invention has a specific surface area of 1800 to 2600 m 2 / g, a pore volume of 0.7 to 1.5 ml / g, an average pore diameter of 1.60 to 2.00 nm, and a surface functional group concentration of 0.1 to 1. An electrode for an electric double layer capacitor having a 0 mmol / g, an average particle diameter of 1 to 20 μm, and a half-width (Δν1) of a peak (G1) near 1580 cm −1 observed in a Raman spectrum of 65 to 80 cm −1 It is a material.
Electric double layer capacitor electrode material in the present invention has a specific surface area of 1800~2600m 2 / g, is preferably 1900~2550m 2 / g, more preferably 2000~2500m 2 / g. When the specific surface area is less than 1800 m 2 / g, there is a tendency that sufficient capacitance cannot be obtained, and when it exceeds 2600 m 2 / g, the bulk density tends to be low, and the volume capacity of the capacitor tends to decrease. The specific surface area in the present invention can be measured by nitrogen gas adsorption measurement.
また、本発明における電気二重層キャパシタ用電極材は、細孔容量が０．７〜１．５ｍｌ／ｇであり、０．８〜１．４ｍｌ／ｇであることが好ましく、０．９〜１．３ｍｌ／ｇであることがより好ましい。細孔容量が０．７ｍｌ／ｇ未満であると、レート特性及び出力特性が低下する傾向があり、１．５ｍｌ／ｇを超えると体積容量が低下する傾向がある。なお、本発明における細孔容量は窒素ガス吸着測定によって測定することが可能である。 The electrode material for electric double layer capacitors in the present invention has a pore capacity of 0.7 to 1.5 ml / g, preferably 0.8 to 1.4 ml / g, preferably 0.9 to 1 More preferably, it is 3 ml / g. If the pore volume is less than 0.7 ml / g, the rate characteristics and output characteristics tend to decrease, and if it exceeds 1.5 ml / g, the volume capacity tends to decrease. The pore volume in the present invention can be measured by nitrogen gas adsorption measurement.
また、本発明における電気二重層キャパシタ用電極材は、平均細孔径が１．６０〜２．００ｎｍであり、１．７０〜１．９０ｎｍであることが好ましく、１．７５〜１．８５ｎｍであることがより好ましい。平均細孔径が１．６０ｎｍ未満であると、細孔表面に吸着するイオンの拡散が不充分であるため、レート特性及び出力特性が低下する傾向があり、２．００ｎｍを超えると余分な細孔幅のため、体積容量が低下する傾向がある。なお、本発明における平均細孔径は窒素ガス吸着測定によって測定することが可能である。 Moreover, the electrode material for electric double layer capacitors in the present invention has an average pore diameter of 1.60 to 2.00 nm, preferably 1.70 to 1.90 nm, and preferably 1.75 to 1.85 nm. It is more preferable. If the average pore diameter is less than 1.60 nm, the diffusion of ions adsorbed on the pore surface is insufficient, so that the rate characteristics and output characteristics tend to decrease. Due to the width, the volume capacity tends to decrease. The average pore diameter in the present invention can be measured by nitrogen gas adsorption measurement.
また、本発明における電気二重層キャパシタ用電極材は、表面官能基濃度が０．１〜１．０ｍｍｏｌ／ｇであり、０．１〜０．８ｍｍｏｌ／ｇであることが好ましく、０．１〜０．６ｍｍｏｌ／ｇであることがより好ましい。表面官能基濃度が０．１ｍｍｏｌ／ｇ未満であると、水などの極性溶媒に対する濡れ性が著しく低下し、電極スラリの作製に支障をきたす傾向があり、１．０ｍｍｏｌ／ｇを超えると充放電時の分解反応により寿命特性に悪影響を及ぼす傾向がある。なお、本発明における表面官能基濃度は（Ｂｏｈｅｍ法）によって測定することが可能である。 The electrode material for electric double layer capacitors in the present invention has a surface functional group concentration of 0.1 to 1.0 mmol / g, preferably 0.1 to 0.8 mmol / g, More preferably, it is 0.6 mmol / g. When the surface functional group concentration is less than 0.1 mmol / g, the wettability with respect to polar solvents such as water is remarkably lowered, and there is a tendency that the production of the electrode slurry is disturbed. There is a tendency for the life characteristics to be adversely affected by the decomposition reaction of time. In addition, the surface functional group density | concentration in this invention can be measured by (Bohem method).
また、本発明における電気二重層キャパシタ用電極材は、平均粒径が１〜２０μｍであり、１〜１５μｍであることが好ましく、１〜１０μｍであることがより好ましい。平均粒径が１μｍ未満であると、電極材の取り扱い性が低下する傾向があり、自己放電特性が悪化する傾向があり、２０μｍを超えるとレート特性及び出力特性が低下する傾向がある。なお、本発明における平均粒径はレーザー回折粒度測定によって測定することが可能である。 Moreover, the electrode material for electric double layer capacitors in the present invention has an average particle diameter of 1 to 20 μm, preferably 1 to 15 μm, and more preferably 1 to 10 μm. When the average particle size is less than 1 μm, the handleability of the electrode material tends to decrease, the self-discharge characteristics tend to deteriorate, and when it exceeds 20 μm, the rate characteristics and output characteristics tend to decrease. The average particle size in the present invention can be measured by laser diffraction particle size measurement.
また、ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）が、６５〜８０ｃｍ−１であり、６５〜７８ｃｍ−１であることがより好ましく、６５〜７５ｃｍ−１であることがさらに好ましい。該半値幅（Δν１）が６５ｃｍ−１未満であると、静電容量が低下する傾向があり、８０ｃｍ−１を超えると出力特性が低下する傾向がある。なお、本発明におけるラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）はレーザーラマン分光光度計によって測定することが可能である。 The peak around 1580 cm -1 which is observed in the Raman spectrum (G1) half-width (Δν1) of a 65～80Cm -1, more preferably 65~78cm -1, 65~75cm -1 More preferably. When the half width (Δν1) is less than 65 cm −1 , the capacitance tends to decrease, and when it exceeds 80 cm −1 , the output characteristics tend to decrease. In addition, the half width (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum in the present invention can be measured by a laser Raman spectrophotometer.
本発明の電気二重層キャパシタ用電極材は、例えば、フェノール樹脂を原料として、不活性雰囲気下で炭化し、その後賦活することによって得ることが可能である。原料としてフェノール樹脂を用いる場合はノボラック型フェノール樹脂を用いることが好ましく、ノボラック型フェノール樹脂を、硬化剤によって硬化処理を施すことが好ましい。ノボラック樹脂を硬化させた原料は、充電時に構造変化をより抑制し、出力特性の悪化をも抑制することが可能である点で好ましい。 The electrode material for an electric double layer capacitor of the present invention can be obtained, for example, by using a phenol resin as a raw material, carbonizing in an inert atmosphere, and then activating. When a phenol resin is used as a raw material, it is preferable to use a novolac type phenol resin, and it is preferable to perform a curing treatment on the novolac type phenol resin with a curing agent. A raw material obtained by curing a novolac resin is preferable in that it can suppress structural changes during charging and can also suppress deterioration of output characteristics.
原料となるノボラック型フェノール樹脂の硬化剤としては特に制限はないが、具体的にはヘキサメチレンテトラミン、パラホルムアルデヒド等のホルムアルデヒド供給源が挙げられる。これらは、単独で又は２種以上を組み合わせて使用される。また、硬化の手法としてはノボラック型フェノール樹脂を溶融させ硬化剤と混合する溶融硬化が一般的であるが、ノボラック型フェノール樹脂を水溶液中に縣濁させた後、硬化剤を添加し、水溶液中で熱処理する縣濁硬化法、また、乾燥機等の加熱処理装置を用いた加熱硬化等が挙げられる。これらは、単独で又は２種以上を組み合わせて使用される。 Although there is no restriction | limiting in particular as a hardening | curing agent of the novolak-type phenol resin used as a raw material, Specifically, formaldehyde supply sources, such as hexamethylenetetramine and paraformaldehyde, are mentioned. These are used alone or in combination of two or more. As a curing method, melt curing in which a novolac type phenol resin is melted and mixed with a curing agent is generally used. After the novolac type phenol resin is suspended in an aqueous solution, a curing agent is added and the aqueous solution is added. Examples thereof include a suspension curing method in which heat treatment is performed with heat treatment, and heat curing using a heat treatment apparatus such as a dryer. These are used alone or in combination of two or more.
硬化した樹脂は粉砕して用いられることが好ましい。粉砕については、通常の粉砕機が用いられるが、具体的にはカッターミル、ピンミル、ジェットミル等によって粉砕することが挙げられる。これらは、単独で行ってもよく又は２種以上の方法を組み合わせて行ってもよい。 The cured resin is preferably used after being pulverized. For pulverization, a normal pulverizer is used, and specific examples include pulverization with a cutter mill, a pin mill, a jet mill or the like. These may be performed alone or in combination of two or more methods.
硬化し、粉砕処理を施した樹脂は熱処理によって炭化することが好ましい。炭化については、通常不活性雰囲気下５００〜１０００℃の範囲で行うのが好ましく、６００〜８００℃で行うのがより好ましく、６５０〜７５０℃で行うことがさらに好ましい。炭化温度が５００℃未満であると、炭素マトリクスの形成が不充分になり、後の賦活処理時の収率が低下する傾向がある。炭化温度が１０００℃を超えると、炭素マトリクスの形成が進行しすぎるため、後の賦活処理時に細孔形成が抑制される傾向があり、そのため、賦活の際、高い処理温度または多量のアルカリ化合物が必要となる傾向がある。 The cured and pulverized resin is preferably carbonized by heat treatment. About carbonization, it is preferable to carry out normally in the range of 500-1000 degreeC under inert atmosphere, it is more preferable to carry out at 600-800 degreeC, and it is more preferable to carry out at 650-750 degreeC. If the carbonization temperature is less than 500 ° C., the formation of the carbon matrix becomes insufficient, and the yield during the subsequent activation treatment tends to decrease. When the carbonization temperature exceeds 1000 ° C., the formation of the carbon matrix proceeds excessively, so that the formation of pores tends to be suppressed during the subsequent activation treatment. Therefore, during activation, a high treatment temperature or a large amount of alkaline compound is present. There is a tendency to be necessary.
また、得られた炭化物はさらに目的平均粒径まで粉砕することが好ましい。粉砕機はピンミル、ジェットミル、ボールミル、ビーズミル等挙げられる。これらは、単独で行ってもよく又は２種以上の方法を組み合わせて行ってもよい。 Moreover, it is preferable to grind | pulverize the obtained carbide | carbonized_material to the target average particle diameter further. Examples of the pulverizer include a pin mill, a jet mill, a ball mill, and a bead mill. These may be performed alone or in combination of two or more methods.
樹脂の炭化後、アルカリ賦活を行うことが好ましい。アルカリ賦活は、通常の方法により行うことができる。アルカリ賦活は下記のようにして行うことが好ましい。炭化物と水酸化カリウムをプラネタリミキサ等の混合機を用い混合する。この混合物をＮｉ製容器に入れ、不活性雰囲気下で７００〜９００℃の範囲で０．５〜３時間熱処理を行う。この際の賦活温度は７５０〜８５０℃がより好ましく、７７０〜８３０℃がさらに好ましい。また、賦活時間は１〜２時間がより好ましい。賦活温度が７００℃未満であると賦活が進みにくく、所望の比表面積を持つ活性炭が得られない傾向があり、賦活温度が９００℃を超えると、Ｎｉ製容器中のアルカリ化合物が容器を腐食する傾向がある。また、賦活時間が０．５時間未満であると賦活が充分にいきわたらない傾向があり、所望の比表面積を持つ電極材が得られない傾向がある。賦活時間が３時間を超えて行っても細孔形成にほとんど変化はない傾向がある。 It is preferable to perform alkali activation after carbonization of the resin. The alkali activation can be performed by a usual method. The alkali activation is preferably performed as follows. Carbide and potassium hydroxide are mixed using a mixer such as a planetary mixer. This mixture is put in a Ni container and heat-treated at 700 to 900 ° C. in an inert atmosphere for 0.5 to 3 hours. The activation temperature at this time is more preferably 750 to 850 ° C, and further preferably 770 to 830 ° C. The activation time is more preferably 1 to 2 hours. If the activation temperature is less than 700 ° C., activation is difficult to proceed, and activated carbon having a desired specific surface area tends not to be obtained. If the activation temperature exceeds 900 ° C., the alkali compound in the Ni-made container corrodes the container. Tend. In addition, if the activation time is less than 0.5 hours, activation tends to be insufficient, and an electrode material having a desired specific surface area tends not to be obtained. Even if the activation time exceeds 3 hours, there is a tendency that the pore formation hardly changes.
賦活後は、アルカリ化合物またはＮｉ容器から混入した金属不純物を、酸により溶解抽出する。この方法については特に限定されるものではないが、例えば、賦活後の炭素・アルカリ混合物を４重量％の塩酸中で８０℃以上に加熱しながら攪拌し、金属不純物を溶解させる。その後酸溶液をろ過し、再度、同濃度塩酸を用いて前記工程を３〜４回繰り返す。次いで純水を用いて前記同様の工程を３回以上行い、電極材に付着した塩酸を除去することにより、高純度な電極材が得られる。 After activation, the metal impurities mixed from the alkali compound or Ni container are dissolved and extracted with an acid. The method is not particularly limited. For example, the activated carbon / alkali mixture is stirred in 4% by weight of hydrochloric acid while heating to 80 ° C. or more to dissolve metal impurities. Thereafter, the acid solution is filtered, and the above steps are repeated 3 to 4 times using the same concentration of hydrochloric acid again. Subsequently, the same process as described above is performed three times or more using pure water to remove hydrochloric acid adhering to the electrode material, thereby obtaining a high-purity electrode material.
精製した電極材は表面の酸性官能基を低減させるため、不活性雰囲気下で熱処理を行うことが好ましい。該熱処理温度は５００〜１０００℃が好ましく、６００〜９００℃がより好ましい。５００℃未満の温度では表面官能基が充分低減できない傾向があり、寿命特性が低下する傾向があり、また、不要なガス発生がしやすい傾向がある。また、熱処理温度が１０００℃を超えると、比表面積や細孔容量などが低下する傾向があり、静電容量が低下する傾向がある。 The purified electrode material is preferably subjected to a heat treatment in an inert atmosphere in order to reduce acidic functional groups on the surface. The heat treatment temperature is preferably 500 to 1000 ° C, more preferably 600 to 900 ° C. When the temperature is less than 500 ° C., the surface functional groups tend not to be sufficiently reduced, the life characteristics tend to be lowered, and unnecessary gas tends to be easily generated. On the other hand, when the heat treatment temperature exceeds 1000 ° C., the specific surface area and pore volume tend to decrease, and the capacitance tends to decrease.
本発明の電気二重層キャパシタ用電極材は、ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の充電前後の変化率が５％以下であることが好ましい。ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）は、炭素結晶子の結晶構造をあらわしており、充電前後でのこの値の変化率を見ることで、充電の前後で炭素の微細構造がどの程度変化しているのかを判断することが可能である。 In the electrode material for an electric double layer capacitor of the present invention, it is preferable that the rate of change before and after charging of the full width at half maximum (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum is 5% or less. The full width at half maximum (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum represents the crystal structure of the carbon crystallite. By looking at the rate of change of this value before and after charging, It is possible to judge how much the microstructure of carbon has changed before and after.
ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の充電前後の変化率は２％以下であることが好ましく、１％以下であることがさらに好ましい。該変化率が５％を超えると、充電による電極材の構造変化が大きくなり、低温での出力特性が低下する傾向にある。該変化率が小さくなるほど、電極材の構造変化が少ないものとなる。 The rate of change before and after charging of the full width at half maximum (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum is preferably 2% or less, and more preferably 1% or less. If the rate of change exceeds 5%, the structural change of the electrode material due to charging becomes large, and the output characteristics at low temperatures tend to deteriorate. The smaller the rate of change, the less the structural change of the electrode material.
なお、本発明におけるラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の変化率は、通常、下記の方法で測定するものとする。
［ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の充電前後の変化率の測定方法］
（ａ）電気二重層キャパシタ用電極材、ＣＭＣ（カルボキシメチルセルロース）及びＰＴＦＥ（ポリテトラフルオロエチレン）を１００：４：３の割合で混合し、電気二重層キャパシタ用電極材と等量の水を加えスラリを作製する。
（ｂ）膜厚２０μｍのアルミエッチング箔にアプリケーターによってスラリを塗布し、塗布電極を作製する。
（ｃ）この塗布電極を乾燥機にて５０℃、１時間、８０℃、１時間、１００℃、１時間で乾燥する。
（ｄ）乾燥した塗布電極を直径１５ｍｍの大きさに打ち抜き測定用電極を作製する。
（ｅ）測定用電極は正極用及び負極用２枚用意するが、正極及び負極とも同じ電極材を使用し、正極における電極材と負極における電極材の重量比（正極電極材／負極電極材）が１．４、正極の膜厚（乾燥後の塗布層の厚さ、アルミエッチング箔の厚みは含む）が１００μｍ、負極の膜厚（乾燥後の塗布層の厚さ、アルミ箔の厚みは含む）が７０μｍになるようにする。また、作製する電極のプレス処理はしないものとする。
（ｆ）正極、負極、紙セパレータ（例えば、宝泉製 ＴＦ４０５０（１９φ））、コインセル上下蓋（例えば、宝泉製 ２０１６型コインセル）、厚さ４００μｍアルミスペーサーを真空乾燥機にて１２０℃３時間の条件で真空乾燥する。
（ｇ）乾燥後、アルゴン置換グローブボックス内で、上記（ｆ）の材料を用いてコイン型電気二重層キャパシタを作製する。この際、乾燥した電極（正極、負極）及び紙セパレータはサイドボックス内で１０ｔｏｒｒ以下の減圧度で１０分間減圧脱気処理を行うものとする。電解液としては、テトラエチルメチルアンモニウムテトラフルオロボレートの１．４Ｍプロピオンカーボネート溶液を１コイン当たり０．５ｍｌ使用する。このようにして作製した電気二重層キャパシタの電極を充電前の電極とする。
（ｈ）作製した電気二重層キャパシタを、負極電極材基準で４０ｍＡ／ｇの充電電流、３．０Ｖの印加電圧を充電条件ＣＣ／ＣＶ（定電流／定電圧）で２４時間充電する。この状態の電気二重層キャパシタの電極を充電後の電極とする。
（ｉ）上記に従い作製した充電前の電極及び充電後の電極（ここで測定する電極は負極）をコインセル（キャパシタ）から取り出し、電解液を充分に洗い流し洗浄し、室温で乾燥させる。ここで、洗浄はプロピレンカーボネートで２回、アセトンで１回行う。
（ｊ）レーザーラマン分光光度計（励起光：アルゴンレーザ５１４．５ｎｍ）によって電極材のラマンスペクトルを波長範囲８３０ｃｍ−１〜１９４０ｃｍ−１で測定する。電極材はアルミエッチング箔からははずさず、電極のまま測定する。
（ｋ）得られたスペクトルについて解析ソフト（例えばｓｐｅｃｔｒａ ｍａｎａｇｅｒ（日本分光製））でフィッティングを行い、成分（ａ）（ピーク：１５９５ｃｍ−１ 半値幅７５ｃｍ−１）、成分（ｂ）（ピーク：１５１０ｃｍ−１ 半値幅：６５ｃｍ−１）、成分（ｃ）（ピーク：１３５５ｃｍ−１ 半値幅：１７５ｃｍ−１）、成分（ｄ）（ピーク：１２００ｃｍ−１ 半値幅：２００ｃｍ−１）の４成分を仮設定し、４成分フィッティングを行い、１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）を算出する。
（ｌ）同様の測定を３回繰り返しその平均値をラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）とし、充電前後での半値幅（Δν１）の変化率を下記式より算出し、ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の充電前後の変化率とする。
In addition, the change rate of the half width (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum in the present invention is usually measured by the following method.
[Measurement method of rate of change before and after charging of half width (Δν1) of peak (G1) near 1580 cm −1 observed in Raman spectrum]
(A) Electroelectric double layer capacitor electrode material, CMC (carboxymethylcellulose) and PTFE (polytetrafluoroethylene) are mixed at a ratio of 100: 4: 3, and the same amount of water as the electric double layer capacitor electrode material is added. Make a slurry.
(B) A slurry is applied to an aluminum etching foil having a film thickness of 20 μm by an applicator to produce a coated electrode.
(C) The coated electrode is dried in a dryer at 50 ° C., 1 hour, 80 ° C., 1 hour, 100 ° C., 1 hour.
(D) The dried coating electrode is punched into a diameter of 15 mm to produce a measurement electrode.
(E) Two electrodes for positive electrode and negative electrode are prepared. The same electrode material is used for both the positive electrode and the negative electrode, and the weight ratio of the electrode material in the positive electrode to the electrode material in the negative electrode (positive electrode material / negative electrode material). 1.4, the thickness of the positive electrode (including the thickness of the coating layer after drying and the thickness of the aluminum etching foil) is 100 μm, and the thickness of the negative electrode (including the thickness of the coating layer after drying and the thickness of the aluminum foil) ) To be 70 μm. In addition, the electrode to be manufactured is not pressed.
(F) Positive electrode, negative electrode, paper separator (for example, TF4050 (19φ) manufactured by Hosen), coin cell upper and lower lids (for example, 2016-type coin cell manufactured by Hosen), and a 400 μm thick aluminum spacer at 120 ° C. for 3 hours in a vacuum dryer. Vacuum dry under the conditions of
(G) After drying, a coin-type electric double layer capacitor is produced using the material (f) in an argon-substituted glove box. At this time, the dried electrode (positive electrode, negative electrode) and paper separator are subjected to a vacuum degassing treatment for 10 minutes in a side box at a vacuum degree of 10 torr or less. As the electrolytic solution, 0.5 ml of a 1.4M propionate carbonate solution of tetraethylmethylammonium tetrafluoroborate is used per coin. The electrode of the electric double layer capacitor thus produced is used as an electrode before charging.
(H) The produced electric double layer capacitor is charged with a charging current of 40 mA / g on the basis of the negative electrode material and an applied voltage of 3.0 V for 24 hours under a charging condition CC / CV (constant current / constant voltage). Let the electrode of the electric double layer capacitor in this state be the electrode after charging.
(I) The pre-charged electrode and the post-charged electrode (the electrode to be measured here is the negative electrode) prepared according to the above are taken out from the coin cell (capacitor), and the electrolytic solution is thoroughly washed away and dried at room temperature. Here, washing is performed twice with propylene carbonate and once with acetone.
(J) The Raman spectrum of the electrode material is measured in a wavelength range of 830 cm −1 to 1940 cm −1 with a laser Raman spectrophotometer (excitation light: argon laser 514.5 nm). The electrode material is not removed from the aluminum etching foil, and the electrode material is measured as it is.
Performs fitting with (k) obtained analysis software for spectra (e.g. spectra manager (manufactured by JASCO)), component (a) (peak: 1595cm -1 half width 75 cm -1), the component (b) (peak: 1510 cm -1 half width: 65cm -1), component (c) (peak: 1355 cm -1 half width: 175cm -1), the component (d) (peak: 1200 cm -1 half width: provisionally the four components of the 200 cm -1) Setting is performed, four-component fitting is performed, and the half width (Δν1) of the peak (G1) near 1580 cm −1 is calculated.
(L) The same measurement is repeated three times, and the average value is defined as the half width (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum, and the rate of change of the half width (Δν1) before and after charging is It is calculated from the following formula and is defined as the rate of change before and after charging of the full width at half maximum (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum.
本発明の電気二重層キャパシタ用電極材は、２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率が５％以下であることが好ましく、４％で以下あることがより好ましく、３％であることがさらに好ましい。２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率は、充電電圧の変化による電極材の構造変化を示すと考えられ、該静電容量の変化率が５％を超えると、低温での出力特性が低下する傾向にある。 In the electrode material for an electric double layer capacitor of the present invention, the change rate of the capacitance at the time of 3.0 V charging with respect to the capacitance at the time of charging 2.7 V is preferably 5% or less, and preferably 4% or less. Is more preferable, and it is further more preferable that it is 3%. The change rate of the capacitance at the time of 3.0V charge with respect to the capacitance at the time of the charge of 2.7V is considered to indicate the structural change of the electrode material due to the change of the charge voltage, and the change rate of the capacitance is 5%. When the value exceeds, the output characteristics at low temperatures tend to deteriorate.
なお、本発明における２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率は、通常、下記の測定条件及び測定方法で測定するものとする。
［２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率の測定方法］
（ａ）電気二重層キャパシタ用電極材、導電助剤（カーボンブラック）、ＣＭＣ（カルボキシメチルセルロース）及びＰＴＦＥ（ポリテトラフルオロエチレン）を１００：１０：４：３の割合で混合し、電気二重層キャパシタ用電極材と等量の水を加えスラリを作製する。
（ｂ）膜厚２０μｍのアルミエッチング箔にアプリケーターによってスラリを塗布し、塗布電極を作製する。
（ｃ）この塗布電極を乾燥機にて５０℃、１時間、８０℃、１時間、１００℃、１時間で乾燥する。
（ｄ）乾燥した塗布電極を直径１５ｍｍの大きさに打ち抜き測定用電極を作製する。
（ｅ）測定用電極は正極用及び負極用２枚用意するが、正極及び負極とも同じ電極材を使用し、正極における電極材と負極における電極材の重量比（正極電極材／負極電極材）が１．４、正極の膜厚（乾燥後の塗布層の厚さ、アルミ箔の厚みは含む）が１００μｍ、負極の膜厚（乾燥後の塗布層の厚さ、アルミ箔の厚みは含む）が７０μｍになるようにする。また、作製する電極のプレス処理はしないものとする。
（ｆ）正極、負極、紙セパレータ（例えば、宝泉製 ＴＦ４０５０（１９φ））、コインセル上下蓋（例えば、宝泉製 ２０１６型コインセル）、厚さ４００μｍアルミスペーサーを真空乾燥機にて１２０℃、３時間の条件で真空乾燥する。
（ｇ）乾燥後、アルゴン置換グローブボックス内で、上記（ｆ）の材料を用いてコイン型電気二重層キャパシタを作製する。この際、乾燥した電極（正極、負極）及び紙セパレータはサイドボックス内で１０ｔｏｒｒ以下の減圧度で１０分間減圧脱気処理を行うものとする。電解液としては、テトラエチルメチルアンモニウムテトラフルオロボレートの１．４Ｍプロピオンカーボネート溶液を１コイン当たり０．５ｍｌ使用する。
（ｈ）作製した電気二重層キャパシタを、負極電極材基準で４０ｍＡ／ｇの充電電流、２．７Ｖ又は３．０Ｖの印加電圧を充電条件ＣＣ／ＣＶ（定電流／定電圧）で２４時間充電する。
（ｉ）その後、負極電極材基準で４０ｍＡ／ｇの放電電流、放電条件ＣＣ（定電流）で放電する。
（ｊ）静電容量は、前記記載の充放電試験で得られた放電曲線の２．３Ｖ（電圧：Ｖ１、時間：Ｔ１（秒））から１．７Ｖ（電圧：Ｖ２、時間：Ｔ２（秒））の傾きから下記式に従い算出する。
In addition, the change rate of the electrostatic capacity at the time of 3.0V charging with respect to the electrostatic capacity at the time of 2.7V charging in the present invention is usually measured under the following measurement conditions and measuring method.
[Measurement method of change rate of capacitance at 3.0V charge to capacitance at 2.7V charge]
(A) Electric double layer capacitor by mixing electrode material for electric double layer capacitor, conductive additive (carbon black), CMC (carboxymethylcellulose) and PTFE (polytetrafluoroethylene) in a ratio of 100: 10: 4: 3 A slurry is prepared by adding the same amount of water as the electrode material.
(B) A slurry is applied to an aluminum etching foil having a film thickness of 20 μm by an applicator to produce a coated electrode.
(C) The coated electrode is dried in a dryer at 50 ° C., 1 hour, 80 ° C., 1 hour, 100 ° C., 1 hour.
(D) The dried coating electrode is punched into a diameter of 15 mm to produce a measurement electrode.
(E) Two electrodes for positive electrode and negative electrode are prepared. The same electrode material is used for both the positive electrode and the negative electrode, and the weight ratio of the electrode material in the positive electrode to the electrode material in the negative electrode (positive electrode material / negative electrode material). 1.4, film thickness of the positive electrode (including the thickness of the coating layer after drying and the thickness of the aluminum foil) is 100 μm, film thickness of the negative electrode (including the thickness of the coating layer after drying and the thickness of the aluminum foil) To be 70 μm. In addition, the electrode to be manufactured is not pressed.
(F) Positive electrode, negative electrode, paper separator (for example, TF4050 (19φ) manufactured by Hosen), coin cell upper and lower lids (for example, 2016-type coin cell manufactured by Hosen), and a 400 μm thick aluminum spacer at 120 ° C. in a vacuum dryer. Vacuum dry under conditions of time.
(G) After drying, a coin-type electric double layer capacitor is produced using the material (f) in an argon-substituted glove box. At this time, the dried electrode (positive electrode, negative electrode) and paper separator are subjected to a vacuum degassing treatment for 10 minutes in a side box at a vacuum degree of 10 torr or less. As the electrolytic solution, 0.5 ml of a 1.4M propionate carbonate solution of tetraethylmethylammonium tetrafluoroborate is used per coin.
(H) Charging the produced electric double layer capacitor with a charging current of 40 mA / g on the basis of the negative electrode material, an applied voltage of 2.7 V or 3.0 V for 24 hours under a charging condition CC / CV (constant current / constant voltage) To do.
(I) Thereafter, discharging is performed with a discharge current of 40 mA / g on the basis of the negative electrode material and a discharge condition CC (constant current).
(J) The capacitance is from 2.3 V (voltage: V1, time: T1 (seconds)) to 1.7 V (voltage: V2, time: T2 (seconds) of the discharge curve obtained in the charge / discharge test described above. )) Is calculated according to the following formula.
（ｋ）上記により算出された２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率を下記式により算出する。 (K) The change rate of the capacitance at the time of 3.0 V charging with respect to the capacitance at the time of 2.7 V charging calculated as described above is calculated by the following formula.
また、本発明の電気二重層キャパシタ用電極材は、充電前後での電極材層の厚さの変化率が５％以下であることが好ましく、４％以下であることがより好ましく、３％以下であることがさらに好ましい。該変化率が大きくなると電極材が大きく構造変化していると考えられ、該変化率が５％を超えると、低温時の出力特性の悪化を招く傾向があり、セルに余分な圧力がかかり、圧力に耐えうるセル設計を必要とする等、コスト上昇等の要因となる傾向がある。 In the electrode material for electric double layer capacitors of the present invention, the rate of change of the thickness of the electrode material layer before and after charging is preferably 5% or less, more preferably 4% or less, and more preferably 3% or less. More preferably. When the rate of change increases, it is considered that the electrode material has undergone a large structural change. When the rate of change exceeds 5%, the output characteristics at low temperatures tend to be deteriorated, and excessive pressure is applied to the cell. There is a tendency to increase costs such as requiring a cell design that can withstand pressure.
なお、本発明における充電前後での電極材層の厚さの変化率は、通常、下記の測定条件及び測定方法で測定するものとする。
［充電前後での電極材層の厚さの変化率の測定方法］
（ａ）電気二重層キャパシタ用電極材、ＣＭＣ（カルボキシメチルセルロース）及びＰＴＦＥ（ポリテトラフルオロエチレン）を１００：４：３の割合で混合し、電気二重層キャパシタ用電極材と等量の水を加えスラリを作製する。
（ｂ）膜厚２０μｍのアルミエッチング箔にアプリケーターによってスラリを塗布し、塗布電極を作製する。
（ｃ）この塗布電極を乾燥機にて５０℃、１時間、８０℃、１時間、１００℃、１時間で乾燥する。
（ｄ）乾燥した塗布電極を直径１５ｍｍの大きさに打ち抜き測定用電極を作製する。
（ｅ）測定用電極は正極用及び負極用２枚用意するが、正極及び負極とも同じ電極材を使用し、正極における電極材と負極における電極材の重量比（正極電極材／負極電極材）が１．４、正極の膜厚（乾燥後の塗布層の厚さ、アルミ箔の厚みは含む）が１００μｍ、負極の膜厚（乾燥後の塗布層の厚さ、アルミ箔の厚みは含む）が７０μｍになるようにする。また、作製する電極のプレス処理はしないものとする。
（ｆ）正極、負極、紙セパレータ（例えば、宝泉製 ＴＦ４０５０（１９φ））、コインセル上下蓋（例えば、宝泉製 ２０１６型コインセル）、厚さ４００μｍアルミスペーサーを真空乾燥機にて１２０℃、３時間の条件で真空乾燥する。
（ｇ）乾燥後、アルゴン置換グローブボックス内で、上記（ｆ）の材料を用いてコイン型電気二重層キャパシタを作製する。この際、乾燥した電極（正極、負極）及び紙セパレータはサイドボックス内で１０ｔｏｒｒ以下の減圧度で１０分間減圧脱気処理を行うものとする。電解液としては、テトラエチルメチルアンモニウムテトラフルオロボレートの１．４Ｍプロピオンカーボネート溶液を１コイン当たり０．５ｍｌ使用する。このようにして作製した電気二重層キャパシタの電極を充電前の電極とする。
（ｈ）作製した電気二重層キャパシタを、負極電極材基準で４０ｍＡ／ｇの充電電流、３．０Ｖの印加電圧を充電条件ＣＣ／ＣＶ（定電流／定電圧）で２４時間充電する。この状態の電気二重層キャパシタの電極を充電後の電極とする。
（ｉ）マイクロメータ（例えば、Ｍｉｔｕｔｏｙｏ製 ＣＬＭ１−１５ＱＭ）を用いて、充電前の電極及び充電後の電極の厚さを測定する。二回測定の平均値を用い下記式より電極厚さの変化率を算出する。
In addition, the change rate of the thickness of the electrode material layer before and after charging in the present invention is usually measured under the following measurement conditions and measurement methods.
[Measurement method of change rate of thickness of electrode material layer before and after charging]
(A) Electroelectric double layer capacitor electrode material, CMC (carboxymethylcellulose) and PTFE (polytetrafluoroethylene) are mixed at a ratio of 100: 4: 3, and the same amount of water as the electric double layer capacitor electrode material is added. Make a slurry.
(B) A slurry is applied to an aluminum etching foil having a film thickness of 20 μm by an applicator to produce a coated electrode.
(C) The coated electrode is dried in a dryer at 50 ° C., 1 hour, 80 ° C., 1 hour, 100 ° C., 1 hour.
(D) The dried coating electrode is punched into a diameter of 15 mm to produce a measurement electrode.
(E) Two electrodes for positive electrode and negative electrode are prepared. The same electrode material is used for both the positive electrode and the negative electrode, and the weight ratio of the electrode material in the positive electrode to the electrode material in the negative electrode (positive electrode material / negative electrode material). 1.4, film thickness of the positive electrode (including the thickness of the coating layer after drying and the thickness of the aluminum foil) is 100 μm, film thickness of the negative electrode (including the thickness of the coating layer after drying and the thickness of the aluminum foil) To be 70 μm. In addition, the electrode to be manufactured is not pressed.
(F) Positive electrode, negative electrode, paper separator (for example, TF4050 (19φ) manufactured by Hosen), coin cell upper and lower lids (for example, 2016-type coin cell manufactured by Hosen), and a 400 μm thick aluminum spacer at 120 ° C. in a vacuum dryer. Vacuum dry under conditions of time.
(G) After drying, a coin-type electric double layer capacitor is produced using the material (f) in an argon-substituted glove box. At this time, the dried electrode (positive electrode, negative electrode) and paper separator are subjected to a vacuum degassing treatment for 10 minutes in a side box at a vacuum degree of 10 torr or less. As an electrolytic solution, 0.5 ml of a 1.4M propionate carbonate solution of tetraethylmethylammonium tetrafluoroborate is used per coin. The electrode of the electric double layer capacitor thus produced is used as an electrode before charging.
(H) The produced electric double layer capacitor is charged with a charging current of 40 mA / g on the basis of the negative electrode material and an applied voltage of 3.0 V for 24 hours under a charging condition CC / CV (constant current / constant voltage). Let the electrode of the electric double layer capacitor in this state be the electrode after charging.
(I) Using a micrometer (for example, CLM1-15QM manufactured by Mitutoyo), the thickness of the electrode before charging and the electrode after charging are measured. The change rate of the electrode thickness is calculated from the following formula using the average value of the two measurements.
以下に実施例により本発明を更に具体的に説明するが、本発明は以下の実施例に限定されるものではない。
（実施例１）
攪拌装置、還流冷却器、及び温度系を備えた３Ｌの三口フラスコ中にフェノール２８２ｇ、３８％ホルムアルデヒド水溶液１４６ｇ、１Ｍ塩酸３０ｇを入れ、１００℃まで加熱し、一時間保持した。その後１５０℃で４時間加熱還流し、１８０℃で系内の残存モノマと水を除去した。残存モノマは３％以下となることをＧＰＣで確認した。得られたノボラック樹脂を１００ｇ秤量しヘキサミン１０ｇとともに粉砕・混合した。混合物をホットプレート上のポリテトラフルオロエチレンバットで溶融混合し、フェノール樹脂の半硬化物を得た。得られたフェノール樹脂半硬化物を熱風乾燥機で１８０℃、４ｈアフターキュアを行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から７００℃まで昇温した。７００℃で２時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は４μｍまで粉砕し、これと炭化物の重量に対し２．５倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温から８００℃まで昇温し、２時間保持し賦活を行った。温度が室温（２５℃）に戻ったらサンプルを取り出し、前述の方法で金属不純物を除去し、再び熱処理を８００℃、１時間不活性雰囲気下で行い活性炭を得た。
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.
(Example 1)
In a 3 L three-necked flask equipped with a stirrer, a reflux condenser, and a temperature system, 282 g of phenol, 146 g of 38% formaldehyde aqueous solution, and 30 g of 1M hydrochloric acid were placed, heated to 100 ° C., and held for 1 hour. Thereafter, the mixture was heated to reflux at 150 ° C. for 4 hours, and residual monomers and water in the system were removed at 180 ° C. It was confirmed by GPC that the residual monomer was 3% or less. 100 g of the obtained novolak resin was weighed and pulverized and mixed with 10 g of hexamine. The mixture was melt-mixed with a polytetrafluoroethylene vat on a hot plate to obtain a semi-cured product of a phenol resin. The obtained phenol resin semi-cured product was subjected to after-curing at 180 ° C. for 4 hours with a hot air dryer to obtain a cured resin product. The obtained cured resin was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min at room temperature (25 ° C.) to 700 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by maintaining at 700 ° C. for 2 hours. The obtained carbide was pulverized to 4 μm, mixed with 2.5 times the amount of potassium hydroxide with respect to the weight of the carbide, and the temperature was raised from room temperature to 800 ° C. at a flow rate of 300 ml / min in a nitrogen stream in a box furnace. Warm and hold for 2 hours to activate. When the temperature returned to room temperature (25 ° C.), a sample was taken out, metal impurities were removed by the method described above, and heat treatment was performed again at 800 ° C. for 1 hour under an inert atmosphere to obtain activated carbon.
（実施例２）
攪拌装置、還流冷却器、及び温度系を備えた２Ｌの三口フラスコ中にフェノール１９８ｇ、ｐ−ｔ−ブチルフェノール１３５ｇ、３８％ホルムアルデヒド水溶液１４６ｇ、１Ｍ塩酸３０ｇを入れ、１００℃まで加熱し、一時間保持した。その後１５０℃で４時間加熱還流し、１８０℃で系内の残存モノマと水を除去した。残存モノマは３％以下となることをＧＰＣで確認した。得られたノボラック樹脂を１００ｇ秤量しヘキサミン１０ｇとともに粉砕・混合した。混合物をホットプレート上のポリテトラフルオロエチレンバットで溶融混合し、フェノール樹脂の半硬化物を得た。得られたフェノール樹脂半硬化物を熱風乾燥機で１８０℃、４ｈアフターキュアを行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から７００℃まで昇温した。７００℃で２時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は４μｍまで粉砕し、これと炭化物の重量に対し２．４倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から８００℃まで昇温し、２時間保持し賦活を行った。温度が室温（２５℃）に戻ったらサンプルを取り出し金属不純物を除去し、再び熱処理を８００℃、１時間不活性雰囲気下で行い活性炭を得た。
(Example 2)
In a 2 L three-necked flask equipped with a stirrer, reflux condenser, and temperature system, 198 g of phenol, 135 g of pt-butylphenol, 146 g of 38% formaldehyde aqueous solution, and 30 g of 1M hydrochloric acid were heated to 100 ° C. and held for 1 hour. did. Thereafter, the mixture was heated to reflux at 150 ° C. for 4 hours, and residual monomers and water in the system were removed at 180 ° C. It was confirmed by GPC that the residual monomer was 3% or less. 100 g of the obtained novolak resin was weighed and pulverized and mixed with 10 g of hexamine. The mixture was melt-mixed with a polytetrafluoroethylene vat on a hot plate to obtain a semi-cured product of a phenol resin. The obtained phenol resin semi-cured product was subjected to after-curing at 180 ° C. for 4 hours with a hot air dryer to obtain a cured resin product. The obtained cured resin was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min at room temperature (25 ° C.) to 700 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by maintaining at 700 ° C. for 2 hours. The obtained carbide was pulverized to 4 μm, mixed with 2.4 times the amount of potassium hydroxide with respect to the weight of the carbide, and flowed from a flow rate of 300 ml / min at room temperature (25 ° C.) in a nitrogen stream in a box furnace. The temperature was raised to 800 ° C., and the activation was carried out by maintaining for 2 hours. When the temperature returned to room temperature (25 ° C.), the sample was taken out, metal impurities were removed, and heat treatment was performed again at 800 ° C. for 1 hour in an inert atmosphere to obtain activated carbon.
（実施例３）
攪拌装置、還流冷却器、及び温度系を備えた２Ｌの三口フラスコ中にｍ−クレゾール３２４ｇ、３８％ホルムアルデヒド水溶液１４６ｇ、１Ｍ塩酸３０ｇを入れ、１００℃まで加熱し、一時間保持した。その後１５０℃で４時間加熱還流し、１８０℃で系内の残存モノマと水を除去した。残存モノマは３％以下となることをＧＰＣで確認した。得られたノボラック樹脂を１００ｇ秤量しヘキサミン１０ｇとともに粉砕・混合した。混合物をホットプレート上のポリテトラフルオロエチレンバットで溶融混合し、フェノール樹脂の半硬化物を得た。得られたフェノール樹脂半硬化物を熱風乾燥機で１８０℃、４ｈアフターキュアを行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から７００℃まで昇温した。７００℃で２時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は６μｍまで粉砕し、これと炭化物の重量に対し２．８倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から８００℃まで昇温し、２時間保持し賦活を行った。温度が室温に戻ったらサンプルを取り出し金属不純物を除去し、再び熱処理を８００℃１時間不活性雰囲気下で行い活性炭を得た。
(Example 3)
In a 2 L three-necked flask equipped with a stirrer, a reflux condenser, and a temperature system, 324 g of m-cresol, 146 g of 38% formaldehyde aqueous solution, and 30 g of 1M hydrochloric acid were placed, heated to 100 ° C., and held for 1 hour. Thereafter, the mixture was heated to reflux at 150 ° C. for 4 hours, and residual monomers and water in the system were removed at 180 ° C. It was confirmed by GPC that the residual monomer was 3% or less. 100 g of the obtained novolak resin was weighed and pulverized and mixed with 10 g of hexamine. The mixture was melt-mixed with a polytetrafluoroethylene vat on a hot plate to obtain a semi-cured product of a phenol resin. The obtained phenol resin semi-cured product was subjected to after-curing at 180 ° C. for 4 hours with a hot air dryer to obtain a cured resin product. The obtained cured resin was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min at room temperature (25 ° C.) to 700 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by maintaining at 700 ° C. for 2 hours. The obtained carbide was pulverized to 6 μm, mixed with 2.8 times the amount of potassium hydroxide with respect to the weight of the carbide, and flowed at a flow rate of 300 ml / min from room temperature (25 ° C.) in a nitrogen stream in a box furnace. The temperature was raised to 800 ° C., and the activation was carried out by maintaining for 2 hours. When the temperature returned to room temperature, the sample was taken out to remove metal impurities, and heat treatment was performed again at 800 ° C. for 1 hour in an inert atmosphere to obtain activated carbon.
（実施例４）
フェノール樹脂（日立化成工業株式会社製ノボラック型フェノール樹脂Ｊ３）を１００ｇ秤量しヘキサミン１０ｇとともに粉砕・混合した。混合物をホットプレート上のポリテトラフルオロエチレンバットで溶融混合し、フェノール樹脂の半硬化物を得た。得られたフェノール樹脂半硬化物を熱風乾燥機で１８０℃、４ｈアフターキュアを行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から７００℃まで昇温した。７００℃で２時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は６μｍまで粉砕し、これと炭化物の重量に対し２．５倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から８００℃まで昇温し、１時間保持し賦活を行った。温度が室温（２５℃）に戻ったらサンプルを取り出し金属不純物を除去し再び熱処理を８００℃、１時間不活性雰囲気下で行い活性炭を得た。
Example 4
100 g of phenolic resin (Novolac type phenolic resin J3 manufactured by Hitachi Chemical Co., Ltd.) was weighed and ground and mixed with 10 g of hexamine. The mixture was melt-mixed with a polytetrafluoroethylene vat on a hot plate to obtain a semi-cured product of a phenol resin. The obtained phenol resin semi-cured product was subjected to after-curing at 180 ° C. for 4 hours with a hot air dryer to obtain a cured resin product. The obtained cured resin was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min at room temperature (25 ° C.) to 700 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by maintaining at 700 ° C. for 2 hours. The obtained carbide is pulverized to 6 μm, mixed with 2.5 times the amount of potassium hydroxide with respect to the weight of the carbide, and in a nitrogen flow in a box furnace, from a flow rate of 300 ml / min, from room temperature (25 ° C.) The temperature was raised to 800 ° C., and the activation was carried out by maintaining for 1 hour. When the temperature returned to room temperature (25 ° C.), a sample was taken out, metal impurities were removed, and heat treatment was performed again at 800 ° C. for 1 hour in an inert atmosphere to obtain activated carbon.
（比較例１）
フェノール樹脂溶液（日立化成工業株式会社製レゾール型フェノール樹脂ＶＰ８０１）を熱風乾燥機で１８０℃、４ｈで硬化処理を行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から６００℃まで昇温した。６００℃で５時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は５μｍまで粉砕し、これと炭化物の重量に対し２．１５倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温から８００℃まで昇温し、１時間保持し賦活を行った。温度が室温（２５℃）に戻ったらサンプルを取り出し金属不純物を除去し再び熱処理を８００℃１時間不活性雰囲気下で行い活性炭を得た。
(Comparative Example 1)
A phenol resin solution (Resol type phenol resin VP801 manufactured by Hitachi Chemical Co., Ltd.) was cured with a hot air dryer at 180 ° C. for 4 hours to obtain a cured resin. The obtained resin cured product was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min, room temperature (25 ° C.) to 600 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by holding at 600 ° C. for 5 hours. The obtained carbide is pulverized to 5 μm, mixed with 2.15 times the amount of potassium hydroxide with respect to the weight of the carbide, and the temperature is raised from room temperature to 800 ° C. at a flow rate of 300 ml / min in a nitrogen stream in a box furnace. Warm and hold for 1 hour to activate. When the temperature returned to room temperature (25 ° C.), a sample was taken out, metal impurities were removed, and heat treatment was performed again at 800 ° C. for 1 hour in an inert atmosphere to obtain activated carbon.
（比較例２）
攪拌装置、還流冷却器、及び温度系を備えた３Ｌの三口フラスコ中にフェノール２８２ｇ、３８％ホルムアルデヒド水溶液１４６ｇ、１Ｍ塩酸３０ｇを入れ、１００℃まで加熱し、１時間保持した。その後１５０℃で４時間加熱還流し、１８０℃で系内の残存モノマと水を除去した。残存モノマは３％以下となることをＧＰＣで確認した。得られたノボラック樹脂を１００ｇ秤量しヘキサミン１０ｇとともに粉砕・混合した。混合物をホットプレート上のポリテトラフルオロエチレンバットで溶融混合し、フェノール樹脂の半硬化物を得た。得られたフェノール樹脂半硬化物を熱風乾燥機で１８０℃、４ｈアフターキュアを行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から６００℃まで昇温した。６００℃で５時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は５μｍまで粉砕し、これと炭化物の重量に対し２．１５倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から８００℃まで昇温し、１時間保持し賦活を行った。温度が室温（２５℃）に戻ったらサンプルを取り出し金属不純物を除去し再び熱処理を８００℃、１時間不活性雰囲気下で行い活性炭を得た。
(Comparative Example 2)
In a 3 L three-necked flask equipped with a stirrer, a reflux condenser, and a temperature system, 282 g of phenol, 146 g of 38% formaldehyde aqueous solution, and 30 g of 1M hydrochloric acid were placed, heated to 100 ° C. and held for 1 hour. Thereafter, the mixture was heated to reflux at 150 ° C. for 4 hours, and residual monomers and water in the system were removed at 180 ° C. It was confirmed by GPC that the residual monomer was 3% or less. 100 g of the obtained novolak resin was weighed and pulverized and mixed with 10 g of hexamine. The mixture was melt-mixed with a polytetrafluoroethylene vat on a hot plate to obtain a semi-cured product of a phenol resin. The obtained phenol resin semi-cured product was subjected to after-curing at 180 ° C. for 4 hours with a hot air dryer to obtain a cured resin product. The obtained resin cured product was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min, room temperature (25 ° C.) to 600 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by holding at 600 ° C. for 5 hours. The obtained carbide was pulverized to 5 μm, mixed with 2.15 times the amount of potassium hydroxide with respect to the weight of the carbide, and flowed from a flow rate of 300 ml / min at room temperature (25 ° C.) in a nitrogen stream in a box furnace. The temperature was raised to 800 ° C., and the activation was carried out by maintaining for 1 hour. When the temperature returned to room temperature (25 ° C.), a sample was taken out, metal impurities were removed, and heat treatment was performed again at 800 ° C. for 1 hour in an inert atmosphere to obtain activated carbon.
（比較例３）
フェノール樹脂（日立化成工業株式会社製ノボラック型フェノール樹脂ＨＰ１９０Ｒ）を１００ｇ秤量し、熱風乾燥機で１８０℃、４ｈアフターキュアを行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から６００℃まで昇温した。６００℃で５時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は５μｍまで粉砕し、これと炭化物の重量に対し２．１５倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から８００℃まで昇温し、１時間保持し賦活を行った。温度が室温（２５℃）に戻ったらサンプルを取り出し金属不純物を除去し再び熱処理を８００℃、１時間不活性雰囲気下で行い活性炭を得た。
(Comparative Example 3)
100 g of phenol resin (Hitachi Kasei Kogyo novolak type phenolic resin HP190R) was weighed and aftercured at 180 ° C. for 4 hours with a hot air dryer to obtain a cured resin. The obtained resin cured product was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min, room temperature (25 ° C.) to 600 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by holding at 600 ° C. for 5 hours. The obtained carbide was pulverized to 5 μm, mixed with 2.15 times the amount of potassium hydroxide with respect to the weight of the carbide, and flowed from a flow rate of 300 ml / min at room temperature (25 ° C.) in a nitrogen stream in a box furnace. The temperature was raised to 800 ° C., and the activation was carried out by maintaining for 1 hour. When the temperature returned to room temperature (25 ° C.), a sample was taken out, metal impurities were removed, and heat treatment was performed again at 800 ° C. for 1 hour in an inert atmosphere to obtain activated carbon.
（比較例４）
フェノール樹脂溶液（日立化成工業株式会社製レゾール型フェノール樹脂ＶＰ８０１）を熱風乾燥機で１８０℃４ｈで硬化処理を行い樹脂硬化物を得た。得られた樹脂硬化物をカッターミルで１００μｍ程度に粉砕し、雰囲気焼成炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から７００℃まで昇温した。７００℃で２時間保持しフェノール樹脂炭化物を作製した。得られた炭化物は５μｍまで粉砕し、これと炭化物の重量に対し２．２倍量の水酸化カリウムと混合し、ボックス炉にて窒素気流中、３００ｍｌ／ｍｉｎの流量、室温（２５℃）から８００℃まで昇温し、１時間保持し賦活を行った。温度が室温（２５℃）に戻ったらサンプルを取り出し金属不純物を水洗し再び加熱処理を８００℃、１時間不活性雰囲気下で行い活性炭を得た。
(Comparative Example 4)
A phenol resin solution (Resol type phenol resin VP801 manufactured by Hitachi Chemical Co., Ltd.) was cured with a hot air dryer at 180 ° C. for 4 hours to obtain a cured resin. The obtained cured resin was pulverized to about 100 μm with a cutter mill, and heated from a flow rate of 300 ml / min at room temperature (25 ° C.) to 700 ° C. in a nitrogen stream in an atmosphere firing furnace. The phenol resin carbide was produced by maintaining at 700 ° C. for 2 hours. The obtained carbide is pulverized to 5 μm and mixed with 2.2 times the amount of potassium hydroxide with respect to the weight of the carbide. In a nitrogen flow in a box furnace, the flow rate is 300 ml / min, from room temperature (25 ° C.). The temperature was raised to 800 ° C., and the activation was carried out by maintaining for 1 hour. When the temperature returned to room temperature (25 ° C.), the sample was taken out, washed with metal impurities, and heat-treated again at 800 ° C. for 1 hour under an inert atmosphere to obtain activated carbon.
以上、実施例１〜４及び比較例１〜４で得られた電気二重層キャパシタ用電極材の比表面積、平均細孔径、細孔容積、平均粒径、電気二重層キャパシタ用電極材のラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）を下記の方法により測定した。その結果を表１に示す。 As mentioned above, the specific surface area, average pore diameter, pore volume, average particle diameter of the electrode material for electric double layer capacitors obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the Raman spectrum of the electrode material for electric double layer capacitors The full width at half maximum (Δν1) of the peak (G1) near 1580 cm −1 observed in 1 was measured by the following method. The results are shown in Table 1.
［比表面積の測定］
活性炭の細孔特性は、ガス吸着測定装置（島津製作所製 ＡＳＡＰ２０１０）を用いて評価した。所定のサンプルチューブに電気二重層キャパシタ用電極材を０．１ｇ秤量し、ガス吸着測定装置の乾燥ポートにセットし、２００℃２時間減圧乾燥を行った。乾燥したサンプルチューブを測定ポートにセットし、窒素ガスを吸着質として用い、７７Ｋにおいて相対圧０．００００１〜１．０の範囲で窒素吸脱着測定を行う。測定プログラムの所定の場所に電気二重層キャパシタ用電極材秤量値を入力し、得られた吸着等温線から、相対圧０．００１〜０．１の範囲でＢＥＴ法を用いて解析し、得られた値を比表面積として算出した。
[Specific surface area measurement]
The pore characteristics of the activated carbon were evaluated using a gas adsorption measuring device (ASAP2010 manufactured by Shimadzu Corporation). 0.1 g of the electrode material for an electric double layer capacitor was weighed into a predetermined sample tube, set in a drying port of a gas adsorption measuring device, and dried under reduced pressure at 200 ° C. for 2 hours. The dried sample tube is set in a measurement port, and nitrogen adsorption / desorption measurement is performed at 77K in a relative pressure range of 0.00001 to 1.0 using nitrogen gas as an adsorbate. Enter the measured value of the electrode material for the electric double layer capacitor at the predetermined place of the measurement program, and analyze it using the BET method in the range of relative pressure 0.001 to 0.1 from the obtained adsorption isotherm. The value was calculated as the specific surface area.
［細孔容積の測定］
前述の比表面積測定で得られた吸着等温線において、相対圧が最も１．０に近い測定点の吸着量を細孔容積として算出した。
[Measurement of pore volume]
In the adsorption isotherm obtained by the specific surface area measurement described above, the adsorption amount at the measurement point where the relative pressure was closest to 1.0 was calculated as the pore volume.
［平均細孔径の測定］
平均細孔径は、比表面積と細孔容量から算出した。関係式は以下の通りである。
[Measurement of average pore diameter]
The average pore diameter was calculated from the specific surface area and pore volume. The relational expression is as follows.
［平均粒径の測定］
平均粒子径はレーザー回折粒度測定装置（島津製作所製ＳＡＬＤ−３０００Ｊ）を用いて測定した。測定サンプルを０．１ｇ秤量し、粒度測定装置のサンプル測定部に投入した。手順に従い測定を行い、得られた粒度分布の５０％Ｄ値を平均粒子径とした。
[Measurement of average particle size]
The average particle diameter was measured using a laser diffraction particle size measuring device (SALD-3000J manufactured by Shimadzu Corporation). 0.1 g of a measurement sample was weighed and put into a sample measurement unit of a particle size measurement apparatus. Measurement was performed according to the procedure, and the 50% D value of the obtained particle size distribution was defined as the average particle size.
［電気二重層キャパシタ用電極材のラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）］
レーザーラマン分光光度計（日本分光製ＮＲＳ−１０００型 励起光：アルゴンレーザ５１４．５ｎｍ）によって電気二重層キャパシタ用電極材のラマンスペクトルを波長範囲８３０ｃｍ−１〜１９４０ｃｍ−１で測定した。得られたスペクトルについて解析ソフト（日本分光製 ｓｐｅｃｔｒａ ｍａｎａｇｅｒ）でフィッティングを行い、成分（ａ）（ピーク：１５９５ｃｍ−１ 半値幅７５ｃｍ−１）、成分（ｂ）（ピーク：１５１０ｃｍ−１ 半値幅：６５ｃｍ−１）、成分（ｃ）（ピーク：１３５５ｃｍ−１ 半値幅：１７５ｃｍ−１）、成分（ｄ）（ピーク：１２００ｃｍ−１ 半値幅：２００ｃｍ−１）の４成分を仮設定し、４成分フィッティングを行い、１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）を算出した。同様の測定を３回繰り返しその平均値を目的の値とした。
[Half width (Δν1) of peak (G1) near 1580 cm −1 observed in Raman spectrum of electrode material for electric double layer capacitor]
The Raman spectrum of the electrode material for an electric double layer capacitor was measured in a wavelength range of 830 cm −1 to 1940 cm −1 with a laser Raman spectrophotometer (NRS-1000 type excitation light manufactured by JASCO Corporation: argon laser 514.5 nm). The obtained spectra performs fitting with analysis software (manufactured by Japan Spectroscopy spectra manager), component (a) (peak: 1595cm -1 half width 75 cm -1), the component (b) (peak: 1510 cm -1 half width: 65cm −1 ), component (c) (peak: 1355 cm −1 half width: 175 cm −1 ), component (d) (peak: 1200 cm −1 half width: 200 cm −1 ) are temporarily set, and four component fitting The half width (Δν1) of the peak (G1) near 1580 cm −1 was calculated. The same measurement was repeated three times, and the average value was set as the target value.
また、ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の充電前後の変化率、２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率、充電前後での電極材層の厚さの変化率を測定した。その結果を、表２に示した。 Also, the rate of change before and after charging of the full width at half maximum (Δν1) of the peak (G1) near 1580 cm −1 observed in the Raman spectrum, and the capacitance at the time of 3.0 V charging relative to the capacitance at the time of 2.7 V charging. The rate of change and the rate of change of the thickness of the electrode material layer before and after charging were measured. The results are shown in Table 2.
［ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の充電前後の変化率］
上述の、［ラマンスペクトルに観察される１５８０ｃｍ−１付近のピーク（Ｇ１）の半値幅（Δν１）の充電前後の変化率の測定方法］に記載の事項に従い測定を行った。その際、紙セパレータは宝泉製 ＴＦ４０５０（１９φ）を、コインセル上下蓋は宝泉製 ２０１６型コインセルを用いた。また、レーザーラマン分光光度計は日本分光製ＮＲＳ−１０００型を用い、得られたスペクトルの解析は日本分光製ｓｐｅｃｔｒａ ｍａｎａｇｅｒで行った。
[Change rate before and after charging of half width (Δν1) of peak (G1) near 1580 cm −1 observed in Raman spectrum]
The measurement was performed according to the above-described items described in [Method of measuring change rate before and after charging of half-value width (Δν1) of peak (G1) near 1580 cm −1 observed in Raman spectrum]. At that time, TF4050 (19φ) manufactured by Hosen was used as the paper separator, and 2016 type coin cell manufactured by Hosen was used as the coin cell upper and lower lids. The laser Raman spectrophotometer used was NRS-1000 model manufactured by JASCO Corporation, and the obtained spectrum was analyzed by a spectro manager manufactured by JASCO Corporation.
［２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率］
上述の、［２．７Ｖ充電時の静電容量に対する３．０Ｖ充電時の静電容量の変化率の測定方法］に記載の事項に従い測定を行った。その際、紙セパレータは宝泉製 ＴＦ４０５０（１９φ）を、コインセル上下蓋は宝泉製 ２０１６型コインセルを用いた。
[Change rate of capacitance at 3.0V charge to capacitance at 2.7V charge]
The measurement was performed according to the above-mentioned items described in [Method of measuring rate of change of capacitance at 3.0 V charge to capacitance at 2.7 V charge]. At that time, TF4050 (19φ) manufactured by Hosen was used as the paper separator, and 2016 type coin cell manufactured by Hosen was used as the coin cell upper and lower lids.
［充電前後での電極材層の厚さの変化率］
上述の、［充電前後での電極材層の厚さの変化率の測定方法］に記載の事項に従い測定を行った。その際、紙セパレータは宝泉製 ＴＦ４０５０（１９φ）を、コインセル上下蓋は宝泉製 ２０１６型コインセルを用いた。
[Change rate of thickness of electrode material layer before and after charging]
The measurement was performed in accordance with the item described in [Method for measuring rate of change in thickness of electrode material layer before and after charging]. At that time, TF4050 (19φ) manufactured by Hosen was used as the paper separator, and 2016 type coin cell manufactured by Hosen was used as the coin cell upper and lower lids.
［表面官能基濃度の測定］
Ｂｏｈｅｍ法によって測定した。
[Measurement of surface functional group concentration]
It was measured by the Bohem method.
また、実施例１〜４及び比較例１〜４で得られた電気二重層キャパシタ用電極材を用いて下記の方法により電気二重層キャパシタを作製し、２５℃および−３０℃における内部抵抗を測定し出力特性の評価を行った。結果を表３に示す。 Moreover, the electric double layer capacitor was produced by the following method using the electrode material for electric double layer capacitors obtained in Examples 1 to 4 and Comparative Examples 1 to 4, and the internal resistance at 25 ° C. and −30 ° C. was measured. The output characteristics were evaluated. The results are shown in Table 3.
［電気二重層キャパシタの製造］
（ａ）電気二重層キャパシタ用電極材、導電助剤（カーボンブラック）、ＣＭＣ（カルボキシメチルセルロース）及びＰＴＦＥ（ポリテトラフルオロエチレン）を１００：１０：４：３の割合で混合し、電気二重層キャパシタ用電極材と等量の水を加えスラリを作製した。
（ｂ）膜厚２０μｍのアルミエッチング箔にアプリケーターによってスラリを塗布し、塗布電極を作製した。
（ｃ）この塗布電極を乾燥機にて５０℃１時間、８０℃１時間、１００℃１時間で乾燥した。
（ｄ）乾燥した塗布電極を直径１５ｍｍの大きさに打ち抜き測定用電極を作製した。
（ｅ）正極用及び負極用２枚用意したが、正極及び負極とも同じ電極材を使用し、正極における電極材と負極における電極材の重量比（正極電極材／負極電極材）が１、正極の膜厚（乾燥後の塗布層の厚さ、アルミ箔の厚みは含む）が７０μｍ、負極の膜厚（乾燥後の塗布層の厚さ、アルミ箔の厚みは含む）が７０μｍになるようにした。また、作製する電極のプレス処理はしなかった。
（ｆ）正極、負極、紙セパレータ（宝泉製 ＴＦ４０５０（１９φ））、コインセル上下蓋（宝泉製 ２０１６型コインセル）、厚さ４００μｍアルミスペーサーを真空乾燥機にて１２０℃３時間の条件で真空乾燥した。
（ｇ）乾燥後、アルゴン置換グローブボックス内で、上記（ｆ）の材料を用いてコイン型電気二重層キャパシタを作製した。この際、乾燥した電極（正極、負極）及び紙セパレータはサイドボックス内で１０ｔｏｒｒ以下の減圧度で１０分間減圧脱気処理を行った。電解液としては、テトラエチルメチルアンモニウムテトラフルオロボレートの１．４Ｍプロピオンカーボネート溶液を１コインセル当たり０．５ｍｌ使用した。
[Manufacture of electric double layer capacitors]
(A) Electric double layer capacitor by mixing electrode material for electric double layer capacitor, conductive additive (carbon black), CMC (carboxymethylcellulose) and PTFE (polytetrafluoroethylene) in a ratio of 100: 10: 4: 3 A slurry was prepared by adding the same amount of water as the electrode material.
(B) Slurry was applied to an aluminum etching foil having a thickness of 20 μm with an applicator to produce a coated electrode.
(C) The coated electrode was dried in a dryer at 50 ° C. for 1 hour, 80 ° C. for 1 hour, and 100 ° C. for 1 hour.
(D) The dried coating electrode was punched into a diameter of 15 mm to produce a measurement electrode.
(E) Two sheets for the positive electrode and the negative electrode were prepared. The same electrode material was used for both the positive electrode and the negative electrode, and the weight ratio of the electrode material in the positive electrode to the electrode material in the negative electrode (positive electrode material / negative electrode material) was 1. The film thickness (including the thickness of the coating layer after drying and the thickness of the aluminum foil) is 70 μm, and the film thickness of the negative electrode (including the thickness of the coating layer after drying and the thickness of the aluminum foil) is 70 μm. did. In addition, the electrode to be produced was not pressed.
(F) Positive electrode, negative electrode, paper separator (TF4050 (19φ) manufactured by Hosen), coin cell upper and lower lid (2016 type coin cell manufactured by Hosen), 400μm thick aluminum spacer, vacuumed at 120 ° C for 3 hours in a vacuum dryer. Dried.
(G) After drying, a coin-type electric double layer capacitor was produced using the material (f) in an argon-substituted glove box. At this time, the dried electrodes (positive electrode and negative electrode) and the paper separator were subjected to vacuum degassing treatment for 10 minutes at a reduced pressure of 10 torr or less in the side box. As the electrolytic solution, 0.5 ml of a 1.4M propionate carbonate solution of tetraethylmethylammonium tetrafluoroborate was used per coin cell.
［２５℃、−３０℃出力特性の評価］
上記で作製した電気二重層キャパシタを用いて、２５℃、−３０℃における出力特性を下記のように測定した。
（ａ）作製した電気二重層キャパシタを、負極電極材基準で４０ｍＡ／ｇの充電電流、２．７Ｖの印加電圧を充電条件ＣＣ／ＣＶ（定電流／定電圧）で２４時間充電した。
（ｂ）その後、負極電極材基準で４０ｍＡ／ｇの放電電流、放電条件ＣＣ（定電流）で放電した。
（ｃ）放電開始後１０〜４０秒の放電カーブについて近似直線を引き、その切片値と満充電電圧の差分を直流抵抗による電圧降下として見積り、直流抵抗値を算出した。同サンプルにつき２回の測定を行い、平均値を目的の値とした。
[Evaluation of output characteristics at 25 ° C and -30 ° C]
Using the electric double layer capacitor produced above, the output characteristics at 25 ° C. and −30 ° C. were measured as follows.
(A) The produced electric double layer capacitor was charged with a charging current of 40 mA / g on the basis of the negative electrode material and an applied voltage of 2.7 V for 24 hours under a charging condition CC / CV (constant current / constant voltage).
(B) Thereafter, the battery was discharged at a discharge current of 40 mA / g on the basis of the negative electrode material and discharge conditions CC (constant current).
(C) An approximate straight line was drawn for the discharge curve 10 to 40 seconds after the start of discharge, the difference between the intercept value and the full charge voltage was estimated as a voltage drop due to DC resistance, and the DC resistance value was calculated. The same sample was measured twice, and the average value was the target value.
以上より、実施例１〜４は、比較例１〜４と比較して、特に低温時（−３０℃）での抵抗値に優れ、使用される温度領域によらず高い出力特性を有し、かつ、高い体積当りの静電容量が得られることがわかる。 From the above, Examples 1 to 4 are excellent in resistance value particularly at a low temperature (−30 ° C.) as compared with Comparative Examples 1 to 4, and have high output characteristics regardless of the temperature range to be used. And it turns out that the electrostatic capacitance per high volume is obtained.
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