JP2011213571A - Spherical carbon material, electricity storage device using the material, method for producing the material, spherical phenol resin, and method for producing the resin - Google Patents
Spherical carbon material, electricity storage device using the material, method for producing the material, spherical phenol resin, and method for producing the resin Download PDFInfo
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Abstract
Description
本発明は、球状炭素材、及び同材を用いた蓄電装置、並びに同材の製造方法、球状フェノール樹脂、同樹脂の製造方法に関する。 The present invention relates to a spherical carbon material, a power storage device using the material, a method for producing the material, a spherical phenol resin, and a method for producing the resin.
炭素材には、ガス成分や臭い成分の吸着材、有機合成品への添加剤、複写機のトナー材、蓄電装置の電極材など多種の用途があることが知られている。このうち、蓄電装置の電極用炭素材は、特定の層構造を有する黒鉛質（結晶質）のものと、特定の層構造を有しない活性炭質のものとに大別することができる。電解質イオンのインターカレーションを利用する場合には黒鉛質のものが用いられ、吸着を利用する場合には活性炭質のものが用いられる。 It is known that carbon materials have various uses such as adsorbents for gas components and odor components, additives for organic synthetic products, toner materials for copying machines, and electrode materials for power storage devices. Among these, carbon materials for electrodes of power storage devices can be broadly classified into graphite materials (crystalline) having a specific layer structure and activated carbon materials having no specific layer structure. Graphite is used when intercalation of electrolyte ions is used, and activated carbon is used when adsorption is used.
上記蓄電装置の電極用炭素材の一例が特許文献１に記載されている。それは、平均粒子径１〜１０μｍ、細孔容積１．５ｃｍ３／ｇ以下の球状活性炭を電気二重層キャパシタの電極に用いるというものである。その球状活性炭の製法としては、溶媒中で、フェノール類とアルデヒド類を、触媒及び懸濁安定剤の存在下、撹拌しながら加熱・硬化させることにより球状フェノール樹脂を得ること、この球状フェノール樹脂を炭化し賦活させることにより球状活性炭とすることが記載されている。撹拌条件や懸濁安定剤の濃度等の合成条件の変更により粒子径を制御できることも記載されている。 An example of the carbon material for an electrode of the power storage device is described in Patent Document 1. That is, spherical activated carbon having an average particle diameter of 1 to 10 μm and a pore volume of 1.5 cm 3 / g or less is used for an electrode of an electric double layer capacitor. The spherical activated carbon can be produced by heating and curing phenols and aldehydes in a solvent in the presence of a catalyst and a suspension stabilizer while stirring, to obtain a spherical phenol resin. It is described that a spherical activated carbon is obtained by carbonization and activation. It is also described that the particle size can be controlled by changing the synthesis conditions such as the stirring conditions and the concentration of the suspension stabilizer.
また、特許文献２には、レゾルシノール系ポリマー粒子を前駆体とした直径３０〜５００ｎｍの超微細球状炭素材について記載されている。また、この球状炭素材は、レゾルシノール／ホルムアルデヒド系共重合体を骨格成分とする層状構造を構成単位とする球状構造体の形態的特徴を有してなるものである。それは、層状構造を構成単位とすることから、黒鉛質の球状炭素材であると認められる。特許文献２に掲載された図１（ｂ）の写真によれば、その球状炭素材は、個々の粒子が分離独立しておらず、粒子同士が部分的に結合したものである。その製法は、塩基性縮合剤の存在下、アルキルアンモニウム塩、アルキルアミンよりなる群から選択された１種以上の界面活性剤と水を特定モル比で混合した溶液に、レゾルシノールモノマーとアルデヒド類の中から選択された１種以上のモノマーを加え、反応させることにより得られる球状の重合体生成物を不活性雰囲気下で焼成するというものである。 Patent Document 2 describes an ultrafine spherical carbon material having a diameter of 30 to 500 nm using resorcinol-based polymer particles as a precursor. The spherical carbon material has a morphological feature of a spherical structure having a layered structure having a resorcinol / formaldehyde copolymer as a skeleton component as a structural unit. Since it has a layered structure as a structural unit, it is recognized as a graphite-like spherical carbon material. According to the photograph of FIG. 1B published in Patent Document 2, the spherical carbon material is one in which individual particles are not separated and independent, but the particles are partially bonded. In the production method, a resorcinol monomer and an aldehyde are mixed with a solution in which one or more surfactants selected from the group consisting of alkylammonium salts and alkylamines and water are mixed at a specific molar ratio in the presence of a basic condensing agent. A spherical polymer product obtained by adding one or more monomers selected from the above and reacting them is baked in an inert atmosphere.
特許文献１に記載されている如く、活性炭質の球状炭素材は知られているが、その平均粒子径は１〜１０μｍであって比較的大きい。また、市販の活性炭は、炭素材を賦活し機械的に粉砕して微細化したものであるため、粒径が大きいだけでなく、不規則な破砕形状（不定形）になっている。そのため、これら従前の活性炭を蓄電装置の電極に用いても、性能の飛躍的な向上は望めない。 As described in Patent Document 1, an activated carbon spherical carbon material is known, but its average particle diameter is 1 to 10 μm, which is relatively large. In addition, since the activated carbon on the market is activated and mechanically pulverized and refined, it has not only a large particle size but also an irregularly crushed shape (indefinite shape). Therefore, even if these conventional activated carbons are used for the electrodes of the power storage device, a dramatic improvement in performance cannot be expected.
例えば、電気二重層キャパシタの場合、エネルギー密度の増大（蓄えることができるエネルギー量の増大）のためには、静電容量が大きな活性炭を所定容積内に高密度に充填することが必要になる。活性炭に対するイオンの吸着量で静電容量が決まることから、単位重量あたりの静電容量を増大するためには、有効な表面積を増加させること、並びにミクロポア内部へのイオンの拡散進入を容易にすべく拡散経路を短くすることが重要になる。しかし、活性炭の粒子径が大きいと、それだけ表面積の増大及び拡散経路の短縮に不利になる。また、活性炭が不規則な破砕形状であれば、所定容積に充填しても粒子間の空隙が大きくなり、充填密度は低くなる。つまり、単位体積あたりの静電容量の増大に不利になる。 For example, in the case of an electric double layer capacitor, in order to increase the energy density (increase in the amount of energy that can be stored), it is necessary to fill activated carbon with a large capacitance into a predetermined volume at a high density. Since the capacitance is determined by the amount of ions adsorbed on the activated carbon, in order to increase the capacitance per unit weight, it is necessary to increase the effective surface area and facilitate diffusion of ions into the micropore. It is important to shorten the diffusion path as much as possible. However, the larger the particle size of activated carbon, the more disadvantageous it is for increasing the surface area and shortening the diffusion path. Moreover, if activated carbon is an irregular crushing shape, even if it fills predetermined volume, the space | gap between particles will become large and a packing density will become low. That is, it is disadvantageous for an increase in capacitance per unit volume.
一方、特許文献２に記載されている球状炭素材は、活性炭ではないものの、その粒子径は小さい。しかし、上述の如く個々の粒子が分離独立しておらず、粒子同士が部分的に結合している。従って、これを電極材料として利用するとしても、当該球状炭素材を粉砕する必要がある。そして、粉砕しても、得られる粒子が必ずしも球状になるわけではなく、また、大径粒子も含まれることになるから、上記静電容量及び充填密度の大きな増加を望むことはできない。 On the other hand, the spherical carbon material described in Patent Document 2 is not activated carbon, but its particle size is small. However, as described above, the individual particles are not separated and independent, and the particles are partially bonded. Therefore, even if this is used as an electrode material, it is necessary to grind the spherical carbon material. And even if it grind | pulverizes, since the particle | grains obtained do not necessarily become spherical shape and large diameter particle | grains are contained, the big increase in the said electrostatic capacitance and packing density cannot be desired.
そこで、本発明は、吸着材、複写機のトナー材など種々の用途に供することができ、また、蓄電装置の電極材として供したときに上記エネルギー密度を増大させることができる炭素材を提供することを課題とする。 Therefore, the present invention provides a carbon material that can be used for various applications such as an adsorbent and a toner material for a copying machine, and that can increase the energy density when used as an electrode material for a power storage device. This is the issue.
本発明の観点の一つは、本発明を球状炭素材として具現化したものであり、それは、平均粒子径が１００ｎｍ以上８５０ｎｍ以下である球状の活性炭粒子よりなることを特徴とする。 One aspect of the present invention is that the present invention is embodied as a spherical carbon material, and is characterized by comprising spherical activated carbon particles having an average particle diameter of 100 nm or more and 850 nm or less.
すなわち、本発明に係る球状炭素材は、活性炭質であって、平均粒子径がサブミクロンオーダで非常に小さく且つ球状であるから、吸着材、複写機のトナー材、蓄電装置の電極材など種々の用途において、製品品質改善を図ることができる。 That is, since the spherical carbon material according to the present invention is activated carbon and has an average particle size on the order of submicron, which is very small and spherical, various materials such as an adsorbent, a copier toner material, a power storage device electrode material, etc. Product quality can be improved in the above applications.
また、本発明の好ましい態様では、上記活性炭粒子が個々に独立した球状粒子になっている。これにより、当該球状炭素材を、機械的粉砕を要することなく、利用することができ、破砕による不定形化を避けることができる。従って、球状炭素材を所定容積に充填して使用する場合の充填密度を高めることができ、製品品質の改善に有利になる。 Moreover, in the preferable aspect of this invention, the said activated carbon particle is an independent spherical particle. Thereby, the said spherical carbon material can be utilized without requiring a mechanical grinding | pulverization, and the amorphous form by crushing can be avoided. Therefore, it is possible to increase the packing density when the spherical carbon material is used in a predetermined volume, which is advantageous for improving the product quality.
例えば、上記球状炭素材を活物質として用いた蓄電装置にあっては、個々の活性炭粒子の平均粒子径が非常に小さいことから、表面積の増大及び拡散経路の短縮により単位重量当たりの静電容量が大きくなり、また、高密度充填が可能になり、エネルギー密度の増大に有利になる。 For example, in a power storage device using the spherical carbon material as an active material, since the average particle diameter of each activated carbon particle is very small, the capacitance per unit weight is increased by increasing the surface area and shortening the diffusion path. Becomes larger, and high-density filling becomes possible, which is advantageous for increasing the energy density.
本発明の別の観点は、上記球状炭素材の製造方法であって、フェノール類と、アルデヒド類と、界面活性剤と、硬化剤と、酸触媒とを混合してなる反応溶液を調製する工程と、上記反応溶液を加熱して重合反応を進めることにより、炭素材前駆体である平均粒子径１μｍ以下の球状フェノール樹脂を調製する工程と、上記炭素材前駆体を加熱硬化させる工程と、得られた硬化物を加熱して炭素化する工程と、得られた炭素化物を水蒸気賦活する工程とを備えていることを特徴とする。 Another aspect of the present invention is a method for producing the above spherical carbon material, which comprises a step of preparing a reaction solution obtained by mixing phenols, aldehydes, a surfactant, a curing agent, and an acid catalyst. And a step of preparing a spherical phenol resin having an average particle diameter of 1 μm or less, which is a carbon material precursor, by heating the reaction solution to advance a polymerization reaction, a step of heat curing the carbon material precursor, and obtaining It is characterized by comprising a step of heating and carbonizing the obtained cured product and a step of steam-activating the obtained carbonized product.
上記重合反応においては、上記反応溶液を例えば７５℃以上１１０℃以下で数時間ないし数十時間攪拌すればよい。上記加熱硬化においては、上記炭素材前駆体（球状フェノール樹脂）の該前駆体を不活性ガス雰囲気下で加熱して１１０℃以上３００℃以下の温度に０．５時間以上５時間以下保持すればよい。上記炭素化においては、上記硬化後の球状フェノール樹脂を不活性ガス雰囲気下で加熱して６００℃以上９００℃以下に１時間前後保持すればよい。さらに、上記水蒸気賦活においては、上記炭素化物を、飽和水蒸気を含む窒素ガス雰囲気下で加熱して９００℃前後の温度に１時間前後保持すればよい。 In the polymerization reaction, the reaction solution may be stirred, for example, at 75 ° C. or higher and 110 ° C. or lower for several hours to several tens of hours. In the heat curing, if the precursor of the carbon material precursor (spherical phenol resin) is heated in an inert gas atmosphere and maintained at a temperature of 110 ° C. or higher and 300 ° C. or lower for 0.5 hour or longer and 5 hours or shorter. Good. In the carbonization, the cured spherical phenol resin may be heated in an inert gas atmosphere and held at 600 ° C. or higher and 900 ° C. or lower for about 1 hour. Furthermore, in the steam activation, the carbonized material may be heated in a nitrogen gas atmosphere containing saturated steam and kept at a temperature of about 900 ° C. for about 1 hour.
この製造方法により、平均粒子径が１００ｎｍ以上８５０ｎｍ以下である球状の活性炭粒子よりなる球状炭素材を得ることができる。この製造方法の特徴は界面活性剤及び酸触媒をフェノール樹脂の球状化及び微細化に利用したことにある。 By this production method, a spherical carbon material made of spherical activated carbon particles having an average particle diameter of 100 nm or more and 850 nm or less can be obtained. This production method is characterized in that a surfactant and an acid catalyst are used for spheroidization and refinement of a phenol resin.
すなわち、フェノール類とアルデヒド類とを酸触媒の存在下で縮合重合させると、ノボラックと呼ばれる熱可塑性樹脂が得られることは知られている。しかし、界面活性剤が添加されていない場合、得られるフェノール樹脂は不定形の塊状物となる。これに対して、本発明では、上記縮合重合反応が界面活性剤の各ミセル内で進む。そのために、互いに分離独立した多数の球状フェノール樹脂が得られる。その際、酸触媒の存在により、ミセルサイズが小さくなるため、得られる球状フェノール樹脂の粒子径が小さくなると考えられる。 That is, it is known that a thermoplastic resin called novolak can be obtained by condensation polymerization of phenols and aldehydes in the presence of an acid catalyst. However, when no surfactant is added, the resulting phenolic resin becomes an irregularly shaped lump. On the other hand, in the present invention, the condensation polymerization reaction proceeds in each micelle of the surfactant. Therefore, a large number of spherical phenol resins separated and independent from each other are obtained. At that time, the presence of the acid catalyst reduces the micelle size, so that the particle diameter of the resulting spherical phenol resin is considered to be small.
上記酸触媒としては、ハロゲン化水素、硝酸及び硫酸のうちから選ばれる少なくとも一種とすることができる。フェノール類に対する酸触媒の添加割合はモル比で０．０１以上０．１５以下とすることが好ましい。このモル比が０．０１未満になると、上記縮合重合反応が進み難くなり、また、０．１５を越えるモル比になると、球状フェノール樹脂を得ることが困難になる。 The acid catalyst may be at least one selected from hydrogen halide, nitric acid and sulfuric acid. The addition ratio of the acid catalyst to the phenol is preferably 0.01 or more and 0.15 or less in terms of molar ratio. When the molar ratio is less than 0.01, the condensation polymerization reaction is difficult to proceed, and when the molar ratio exceeds 0.15, it is difficult to obtain a spherical phenol resin.
また、上記界面活性剤として、陽イオン性界面活性剤及び陰イオン性界面活性剤の少なくとも一方を用いることが好ましい。 Moreover, it is preferable to use at least one of a cationic surfactant and an anionic surfactant as the surfactant.
本発明の別の観点は、新規な球状のフェノール樹脂であって、平均粒子径が３００ｎｍ以上１０００ｎｍ以下であることを特徴とする。この球状フェノール樹脂によれば、これを加熱硬化させ、得られた硬化物を加熱して炭素化し、さらに得られた炭素化物を水蒸気賦活することにより、平均粒子径が１００ｎｍ以上８５０ｎｍ以下である球状の活性炭粒子よりなる上記球状炭素材を得ることができる。また、この球状フェノール樹脂を電池電極、砥石、フィラー、成形材料等の原料として利用し、関連製品の品質改善を図ることができる。 Another aspect of the present invention is a novel spherical phenol resin having an average particle diameter of 300 nm to 1000 nm. According to this spherical phenol resin, this is cured by heating, the obtained cured product is heated and carbonized, and the resulting carbonized product is steam-activated, whereby a spherical particle having an average particle diameter of 100 nm or more and 850 nm or less is obtained. The above-mentioned spherical carbon material made of the activated carbon particles can be obtained. Moreover, this spherical phenol resin can be used as a raw material for battery electrodes, grindstones, fillers, molding materials, and the like, so that the quality of related products can be improved.
本発明のさらに別の観点は、上記平均粒子径が３００ｎｍ以上１０００ｎｍ以下である球状のフェノール樹脂の製造方法であって、フェノール類と、アルデヒド類と、界面活性剤と、硬化剤と、酸触媒との混合溶液を調製する工程と、上記混合溶液を７５℃以上１１０℃以下の熱処理温度に加熱して重合反応を進める工程とを備えていることを特徴とする。 Still another aspect of the present invention is a method for producing a spherical phenol resin having an average particle diameter of 300 nm or more and 1000 nm or less, comprising phenols, aldehydes, a surfactant, a curing agent, and an acid catalyst. And a step of proceeding a polymerization reaction by heating the mixed solution to a heat treatment temperature of 75 ° C. or higher and 110 ° C. or lower.
先に説明した球状炭素材の製造方法の説明から明らかなように、当該製造方法によれば、平均粒子径が３００ｎｍ以上１０００ｎｍ以下である球状のフェノール樹脂を得ることができる。上記重合反応においては、上記反応溶液を例えば７５℃以上１１０℃以下で数時間ないし数十時間攪拌すればよい。上記酸触媒としては、ハロゲン化水素、硝酸及び硫酸のうちから選ばれる少なくとも一種とすることができる。フェノール類に対する酸触媒の添加割合はモル比で０．０１以上０．１５以下とすることが好ましい。このモル比が０．０１未満になると、上記縮合重合反応が進み難くなり、また、０．１５を越えるモル比になると、球状フェノール樹脂を得ることが困難になる。また、上記界面活性剤として、陽イオン性界面活性剤及び陰イオン性界面活性剤の少なくとも一方を用いることが好ましい。 As is apparent from the explanation of the method for producing the spherical carbon material described above, according to the production method, a spherical phenol resin having an average particle diameter of 300 nm or more and 1000 nm or less can be obtained. In the polymerization reaction, the reaction solution may be stirred, for example, at 75 ° C. or higher and 110 ° C. or lower for several hours to several tens of hours. The acid catalyst may be at least one selected from hydrogen halide, nitric acid and sulfuric acid. The addition ratio of the acid catalyst to the phenol is preferably 0.01 or more and 0.15 or less in terms of molar ratio. When the molar ratio is less than 0.01, the condensation polymerization reaction is difficult to proceed, and when the molar ratio exceeds 0.15, it is difficult to obtain a spherical phenol resin. Moreover, it is preferable to use at least one of a cationic surfactant and an anionic surfactant as the surfactant.
以上のように本発明に係る球状炭素材によれば、平均粒子径が１００ｎｍ以上８５０ｎｍ以下である球状の活性炭粒子よりなるから、吸着材、複写機のトナー材、蓄電装置の電極材など種々の用途において、製品品質改善を図ることができ、特に上記球状炭素材を蓄電装置の活物質として用いると、エネルギー密度の増大に有利になる。 As described above, the spherical carbon material according to the present invention is composed of spherical activated carbon particles having an average particle diameter of 100 nm or more and 850 nm or less. Therefore, various materials such as an adsorbent, a copier toner material, and a power storage device electrode material are used. In use, product quality can be improved. In particular, when the spherical carbon material is used as an active material of a power storage device, it is advantageous to increase energy density.
また、本発明に係る球状炭素材の製造方法によれば、フェノール類、アルデヒド類、硬化剤及び酸触媒の混合溶液に界面活性剤を添加し、縮合重合反応によって炭素材前駆体である平均粒子径１μｍ以下の球状フェノール樹脂を調製し、これを加熱硬化させて炭素化及び水蒸気賦活を行なうようにしたから、平均粒子径が１００ｎｍ以上８５０ｎｍ以下である球状の活性炭粒子よりなる球状炭素材を得ることができる。 Further, according to the method for producing a spherical carbon material according to the present invention, an average particle which is a carbon material precursor is added by a condensation polymerization reaction by adding a surfactant to a mixed solution of phenols, aldehydes, a curing agent and an acid catalyst. A spherical phenol resin having a diameter of 1 μm or less was prepared, and this was heated and cured to perform carbonization and steam activation, so that a spherical carbon material composed of spherical activated carbon particles having an average particle diameter of 100 nm to 850 nm was obtained. be able to.
また、本発明に係る平均粒子径が３００ｎｍ以上１０００ｎｍ以下である球状フェノール樹脂によれば、これを上記球状炭素材の原料とすることができ、或いは電池電極、砥石、フィラー、成形材料等の原料として利用し、関連製品の品質改善を図ることができる。 Further, according to the spherical phenol resin having an average particle diameter of 300 nm or more and 1000 nm or less according to the present invention, this can be used as a raw material for the spherical carbon material, or a raw material for battery electrodes, grindstones, fillers, molding materials, etc. To improve the quality of related products.
また、本発明に係る球状のフェノール樹脂の製造方法によれば、フェノール類と、アルデヒド類と、界面活性剤と、硬化剤と、酸触媒との混合溶液を調製する工程と、上記混合溶液を７５℃以上１１０℃以下の熱処理温度に加熱して重合反応を進める工程とを備えているから、平均粒子径が３００ｎｍ以上１０００ｎｍ以下である球状のフェノール樹脂を得ることができる。 According to the method for producing a spherical phenol resin according to the present invention, a step of preparing a mixed solution of phenols, aldehydes, a surfactant, a curing agent, and an acid catalyst, And a step of proceeding the polymerization reaction by heating to a heat treatment temperature of 75 ° C. or higher and 110 ° C. or lower, and thus a spherical phenol resin having an average particle size of 300 nm or more and 1000 nm or less can be obtained.
以下、本発明を実施するための形態を図面に基づいて説明する。尚、以下の好ましい実施形態の説明は、本質的に例示に過ぎず、本発明、その適用物或いはその用途を制限することを意図するものではない。 Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. It should be noted that the following description of the preferred embodiment is merely illustrative in nature, and is not intended to limit the present invention, its application, or its use.
＜球状フェノール樹脂の調製＞
図１に調製方法を概略的に示す。すなわち、界面活性剤と硬化剤とを水中で混合し、これに、フェノール、ホルムアルデヒド及び酸触媒を加えて混合することにより、反応溶液（混合溶液）を調製する。この反応溶液を９５℃の温度になるように加熱しながら２４時間攪拌する（重合反応）。その後、反応溶液を遠心分離し、得られた生成物を水及びメタノールで洗浄することにより、球状炭素材の前駆体である球状フェノール樹脂を得る。得られた球状フェノール樹脂は、アルゴンガス雰囲気下で加熱して２７０℃の温度に２時間保持して硬化させる。
<Preparation of spherical phenol resin>
FIG. 1 schematically shows the preparation method. That is, a surfactant and a curing agent are mixed in water, and a reaction solution (mixed solution) is prepared by adding and mixing phenol, formaldehyde, and an acid catalyst. The reaction solution is stirred for 24 hours while being heated to a temperature of 95 ° C. (polymerization reaction). Thereafter, the reaction solution is centrifuged, and the resulting product is washed with water and methanol to obtain a spherical phenol resin which is a precursor of the spherical carbon material. The obtained spherical phenol resin is heated under an argon gas atmosphere and kept at a temperature of 270 ° C. for 2 hours to be cured.
この場合、図２に示すように、水相において界面活性剤のミセルが形成され、そのミセル内にフェノールが導入され、酸触媒の存在下、縮合重合反応が進行する。このミセル内での重合反応の進行により、球状フェノール樹脂が得られる。また、酸触媒によって、界面活性剤の分散が図れ、その結果、ミセルサイズが小さくなるため、得られる球状フェノール樹脂は粒子径が小さくなる。すなわち、平均粒子径が３００ｎｍ以上１０００ｎｍ以下である球状フェノール樹脂を得ることができる。 In this case, as shown in FIG. 2, surfactant micelles are formed in the aqueous phase, phenol is introduced into the micelles, and the condensation polymerization reaction proceeds in the presence of an acid catalyst. A spherical phenol resin is obtained by the progress of the polymerization reaction in the micelle. In addition, the surfactant can be dispersed by the acid catalyst, and as a result, the micelle size becomes small, so that the resulting spherical phenol resin has a small particle size. That is, a spherical phenol resin having an average particle diameter of 300 nm or more and 1000 nm or less can be obtained.
図３は得られた球状フェノール樹脂のＳＥＭ（走査型電子顕微鏡）像である。これは、界面活性剤としてＣＴＡＢ（臭化セチルトリメチルアンモニウム；陽イオン界面活性剤）を用い、酸触媒として塩酸を用い、硬化剤としてヘキサメチレンテトラミンを用いたものである。フェノール１モル当たりの添加量は、ＣＴＡＢが０．２８モル、塩酸が０．０２モル、硬化剤が０．０３４モルである。図３により、得られる球状フェノール樹脂は高い真球度を有することがわかる。その平均粒子径は０．８２μｍであった。 FIG. 3 is an SEM (scanning electron microscope) image of the obtained spherical phenol resin. This uses CTAB (cetyltrimethylammonium bromide; cationic surfactant) as a surfactant, hydrochloric acid as an acid catalyst, and hexamethylenetetramine as a curing agent. The addition amount per mole of phenol is 0.28 mole of CTAB, 0.02 mole of hydrochloric acid, and 0.034 mole of curing agent. FIG. 3 shows that the obtained spherical phenol resin has high sphericity. The average particle diameter was 0.82 μm.
−酸触媒の添加量の影響−
上記球状フェノール樹脂の調製において、酸触媒（塩酸）の添加量が、得られる球状フェノール樹脂の粒径に与える影響を調べた。原料添加割合は表１に示すとおりである。図４に得られた球状フェノール樹脂の粒度分布（頻度分布）を示す。
-Effect of addition amount of acid catalyst-
In the preparation of the spherical phenol resin, the influence of the amount of acid catalyst (hydrochloric acid) added on the particle size of the resulting spherical phenol resin was examined. The raw material addition ratio is as shown in Table 1. FIG. 4 shows the particle size distribution (frequency distribution) of the obtained spherical phenol resin.
塩酸の添加量が多くなるほど、得られる球状フェノール樹脂の粒子径が小さくなっている。また、図４に示すように、塩酸の添加量が多くなるほど、粒子径の分散度が小さくなっている。一方、表１に示すように、塩酸の添加量が多い（モル比で０．１８）サンプル５では、球状フェノール樹脂が得られなかった。これは、塩酸の添加量が多くなり過ぎると、界面活性剤（ＣＴＡＢ）の多くがプロトンと結合し、ミセルを形成できなくなるためと考えられる。以上から、酸触媒の添加量によって球状フェノール樹脂の粒子径を制御できることがわかる。 The larger the amount of hydrochloric acid added, the smaller the particle size of the resulting spherical phenol resin. Moreover, as shown in FIG. 4, the dispersion degree of the particle diameter decreases as the amount of hydrochloric acid added increases. On the other hand, as shown in Table 1, in the sample 5 having a large amount of hydrochloric acid added (0.18 in molar ratio), the spherical phenol resin was not obtained. This is presumably because if the amount of hydrochloric acid added is too large, most of the surfactant (CTAB) binds to protons and cannot form micelles. From the above, it can be seen that the particle size of the spherical phenol resin can be controlled by the addition amount of the acid catalyst.
−酸触媒の種類の影響−
上記球状フェノール樹脂の調製において、酸触媒の種類が、得られる球状フェノール樹脂の粒径に与える影響を調べた。酸触媒としては、ＨＢｒ、ＨＩ、ＨＮＯ３及びＨ２ＳＯ４の各無機酸を準備した。原料添加割合は表１のサンプル２と同じである。すなわち、いずれの無機酸も、フェノールに対するモル比は０．０２モル％とした。いずれの無機酸を採用した場合でも球状フェノール樹脂を得ることができた。それら球状フェノール樹脂の粒度分布（頻度分布）を、先のサンプル２（酸触媒；塩酸ＨＣｌ）の結果と共に図５に示す。ＨＢｒ、ＨＩ、ＨＮＯ３及びＨ２ＳＯ４のいずれにおいても、ＨＣｌの場合よりも、球状フェノール樹脂の平均粒子径の小さく、また、粒子径の分散度が小さくなっている。以上から、酸触媒の種類で球状フェノール樹脂の粒子径を制御できることがわかる。
-Influence of the type of acid catalyst-
In the preparation of the spherical phenol resin, the effect of the type of acid catalyst on the particle size of the obtained spherical phenol resin was examined. As the acid catalyst, inorganic acids of HBr, HI, HNO 3 and H 2 SO 4 were prepared. The raw material addition ratio is the same as Sample 2 in Table 1. That is, in any inorganic acid, the molar ratio to phenol was 0.02 mol%. Even when any inorganic acid was used, a spherical phenol resin could be obtained. The particle size distribution (frequency distribution) of these spherical phenol resins is shown in FIG. 5 together with the result of the previous sample 2 (acid catalyst; hydrochloric acid HCl). In any of HBr, HI, HNO 3 and H 2 SO 4 , the average particle diameter of the spherical phenol resin is smaller than that of HCl, and the degree of dispersion of the particle diameter is small. From the above, it can be seen that the particle size of the spherical phenol resin can be controlled by the type of the acid catalyst.
−界面活性剤の種類の影響−
上記球状フェノール樹脂の調製において、界面活性剤の種類が、得られる球状フェノール樹脂の粒径に与える影響を調べた。すなわち、陰イオン性界面活性剤として、ＳＤＳ（ドデシル硫酸ナトリウム）を準備した。原料添加割合は表１のサンプル２と同じにした。得られた球状フェノール樹脂の粒度分布（頻度分布）を、先のサンプル２（陽イオン性界面活性剤；ＣＴＡＢ）の結果と共に図６に示す。ＳＤＳの場合、粒子径はサンプル２のＣＴＡＢより少し大きくなり、粒子径の分散度も少し大きくなっているものの、陰イオン性界面活性剤でも陽イオン性界面活性剤の場合と同じく、粒子径が比較的小さな球状フェノール樹脂が得られることがわかる。
-Effect of surfactant type-
In the preparation of the spherical phenol resin, the effect of the type of surfactant on the particle size of the obtained spherical phenol resin was examined. That is, SDS (sodium dodecyl sulfate) was prepared as an anionic surfactant. The raw material addition ratio was the same as Sample 2 in Table 1. The particle size distribution (frequency distribution) of the obtained spherical phenol resin is shown in FIG. 6 together with the result of the previous sample 2 (cationic surfactant; CTAB). In the case of SDS, the particle size is a little larger than the CTAB of sample 2 and the dispersion of the particle size is also a little larger, but the anionic surfactant has the same particle size as in the case of the cationic surfactant. It turns out that a comparatively small spherical phenol resin is obtained.
＜球状炭素材の調製＞
図７は上記調製法で得られた球状フェノール樹脂から球状炭素材を得る調製法を概略的に示す。すなわち、上述の硬化させた球状フェノール樹脂をアルゴンガス雰囲気下で加熱して８００℃の温度に１時間保持する。これは球状フェノール樹脂の炭素化処理である。次いで当該炭素化物を飽和水蒸気を含む窒素ガス雰囲気下で加熱して９００℃の温度に５５分間保持する。これは水蒸気賦活処理である。
<Preparation of spherical carbon material>
FIG. 7 schematically shows a preparation method for obtaining a spherical carbon material from the spherical phenol resin obtained by the above preparation method. That is, the above-described cured spherical phenol resin is heated in an argon gas atmosphere and held at a temperature of 800 ° C. for 1 hour. This is a carbonization treatment of a spherical phenol resin. Next, the carbonized product is heated in a nitrogen gas atmosphere containing saturated water vapor and held at a temperature of 900 ° C. for 55 minutes. This is a steam activation treatment.
図８は表１のサンプル２の球状フェノール樹脂に上記炭素化処理及び水蒸気賦活処理を施して得た多数の球状活性炭粒子よりなる球状炭素材のＳＥＭ像である。図９は界面活性剤を添加せずに調製した塊状フェノール樹脂に上記炭素化処理及び水蒸気賦活処理を施し、粉砕して得た粉末炭素材のＳＥＭ像である。 FIG. 8 is an SEM image of a spherical carbon material composed of a number of spherical activated carbon particles obtained by subjecting the spherical phenol resin of Sample 2 in Table 1 to the carbonization treatment and the steam activation treatment. FIG. 9 is an SEM image of a powdered carbon material obtained by subjecting the bulk phenol resin prepared without adding a surfactant to the carbonization treatment and the steam activation treatment and pulverization.
サンプル２の球状フェノール樹脂の場合、炭素化及び水蒸気賦活後も粒子の球形は保持されている。すなわち、個々の活性炭粒子は、互いに分離独立した球状になっている。図１０はサンプル２の炭素化前及び炭素化・水蒸気賦活後の粒度分布（頻度分布）である。球状フェノール樹脂は、炭素化・水蒸気賦活によってその粒子径が小さくなり、粒子径の分散度も小さくなっている。炭素化・水蒸気賦活後の平均粒子径は０．３３μｍ（３３０ｎｍ）である。 In the case of the spherical phenol resin of sample 2, the spherical shape of the particles is maintained even after carbonization and steam activation. That is, each activated carbon particle has a spherical shape that is separated and independent from each other. FIG. 10 shows the particle size distribution (frequency distribution) of sample 2 before carbonization and after carbonization / steam activation. The spherical phenol resin has a reduced particle size due to carbonization and steam activation, and the degree of dispersion of the particle size is also reduced. The average particle diameter after carbonization and steam activation is 0.33 μm (330 nm).
上記サンプル１〜４の球状フェノール樹脂の他に、塩酸のモル比を０．１３として上記球状フェノール樹脂の調製法により、平均粒子径０．３２μｍの球状フェノール樹脂を調製した。そして、サンプル１〜４の球状フェノール樹脂及び平均粒子径０．３２μｍの球状フェノール樹脂各々から上記調製法によって球状炭素材を得た。それらの炭素化前及び炭素化・水蒸気賦活後の平均粒子径を図１１に示す。平均粒子径３２０ｎｍ〜９３０ｎｍの球状フェノール樹脂から平均粒子径１００ｎｍ〜４００ｎｍの球状炭素材が得られている。なお、図１１の各サンプルは上述した条件によって得られた一実施例であり、調製条件が異なる場合（但し、本願請求項４で特定する範囲内）には比較的大きな平均粒子径を有する球状炭素材が得られる。具体的には、図１１の各サンプルは最も小さい平均粒子径のものであり、条件によって、図１１で示すバーの範囲のものが得られる。最大で８５０ｎｍであった。以上から、平均粒子径３００ｎｍ〜１０００ｎｍの球状フェノール樹脂から平均粒子径１００ｎｍ〜８５０ｎｍの球状炭素材を得ることができることがわかる。 In addition to the spherical phenol resins of Samples 1 to 4, a spherical phenol resin having an average particle diameter of 0.32 μm was prepared by a method for preparing the spherical phenol resin with a molar ratio of hydrochloric acid of 0.13. And the spherical carbon material was obtained by the said preparation method from each of the spherical phenol resin of samples 1-4, and the spherical phenol resin with an average particle diameter of 0.32 micrometer. The average particle diameters before carbonization and after carbonization / steam activation are shown in FIG. A spherical carbon material having an average particle diameter of 100 nm to 400 nm is obtained from a spherical phenol resin having an average particle diameter of 320 nm to 930 nm. In addition, each sample of FIG. 11 is one Example obtained by the above-mentioned conditions, and when the preparation conditions are different (however, within the range specified in claim 4 of the present application), a spherical shape having a relatively large average particle diameter. Carbon material is obtained. Specifically, each sample in FIG. 11 has the smallest average particle diameter, and a sample in the bar range shown in FIG. 11 is obtained depending on the conditions. The maximum was 850 nm. From the above, it can be seen that a spherical carbon material having an average particle size of 100 nm to 850 nm can be obtained from a spherical phenol resin having an average particle size of 300 nm to 1000 nm.
−細孔特性−
図８の球状炭素材ＳＡＣ及び図９の粉末炭素材ＡＣ各々について、７７．４Ｋ（窒素の沸点）に冷却し、窒素ガスを導入して窒素ガスの吸着量を測定した。このとき、導入する窒素ガスの圧力Ｐを徐々に上げ、窒素ガスの飽和蒸気圧Ｐ０で除した値を相対圧Ｐ／Ｐ０として、各相対圧に対する吸着量をプロットすることにより図１２に示す窒素吸着等温線を得た。そして、ＢＥＴ法により各炭素材の比表面積を求め、上記窒素ガス吸着量の測定結果に基いて全細孔容積を求め、ＢＪＨ法によりメゾポア容積率（全細孔容積に対する細孔径２ｎｍ以上５０ｎｍ未満のメゾポアの容積の割合）を求め、さらに、比表面積および全細孔容積を用いて平均細孔径を求めた。結果を表２に示す。
-Pore properties-
Each of the spherical carbon material SAC in FIG. 8 and the powder carbon material AC in FIG. 9 was cooled to 77.4 K (the boiling point of nitrogen), nitrogen gas was introduced, and the adsorption amount of nitrogen gas was measured. At this time, the pressure P of the nitrogen gas to be introduced is gradually increased, and the value obtained by dividing by the saturated vapor pressure P 0 of the nitrogen gas is set as the relative pressure P / P 0 , and the amount of adsorption with respect to each relative pressure is plotted in FIG. The indicated nitrogen adsorption isotherm was obtained. Then, the specific surface area of each carbon material is obtained by the BET method, the total pore volume is obtained based on the measurement result of the nitrogen gas adsorption amount, and the mesopore volume ratio (pore diameter relative to the total pore volume is 2 nm or more and less than 50 nm by the BJH method. The ratio of mesopore volume) was determined, and the average pore diameter was determined using the specific surface area and the total pore volume. The results are shown in Table 2.
実施形態に係る球状炭素材ＳＡＣは、従前の破砕によって得られる粉末炭素材ＡＣと略同等の細孔特性を有する。実施形態に係る球状炭素材ＳＡＣは、球状であるにも拘わらず、その平均粒子径が非常に小さいためと考えられる。 The spherical carbon material SAC according to the embodiment has substantially the same pore characteristics as the powder carbon material AC obtained by conventional crushing. The spherical carbon material SAC according to the embodiment is considered to have a very small average particle diameter despite being spherical.
＜電気二重層キャパシタへの適用＞
表２に示すサンプルＳＡＣ及びＡＣ各々を電気二重層キャパシタの活物質として用いたときの特性を調べた。図１３はコイン型電気二重層キャパシタの構造を示す。同図において、１は集電体、２は電極、３はセパレータ、４は電解液である。集電体１としては白金を用い、セパレータ３としてはＰＶＤＦ（ポリフッ化ビニリデン）を用い、電解液４としては1モル濃度のＥｔ４ＮＢＦ４／ＰＣ（テトラエチルアンモニウムテトラフルオロブロマイド）を用いた。そして、電極２は、炭素材（ＳＡＣ又はＡＣ）９５質量％とＰＴＦＥ（ポリテトラフルオロエチレン）５質量％との混合体で構成した。
<Application to electric double layer capacitors>
The characteristics when each of the samples SAC and AC shown in Table 2 was used as the active material of the electric double layer capacitor were examined. FIG. 13 shows the structure of a coin-type electric double layer capacitor. In the figure, 1 is a current collector, 2 is an electrode, 3 is a separator, and 4 is an electrolytic solution. Platinum was used as the current collector 1, PVDF (polyvinylidene fluoride) was used as the separator 3, and 1 molar Et 4 NBF 4 / PC (tetraethylammonium tetrafluorobromide) was used as the electrolytic solution 4. The electrode 2 was composed of a mixture of 95% by mass of a carbon material (SAC or AC) and 5% by mass of PTFE (polytetrafluoroethylene).
そうして、活物質として球状炭素材ＳＡＣを用いたケース及び粉末炭素材ＡＣを用いたケース各々について、１０ｍＡの定電流で電圧３Ｖまで充電し、次に１〜５０ｍＡの定電流下、０Ｖまで放電し、次式により単位重量当たり電極容量（静電容量）Ｃ(ｇ)及び単位体積当たりの電極容量Ｃ(ｖ)を求めた。なお、Ｉは電流値、Δｔは電圧降下時間、ΔＶは電圧降下値、(Ｍ１＋Ｍ２)は電極２枚分の活物質質量（ｇ）、(Ｖ１＋Ｖ２)は電極２枚分の活物質体積（ｃｍ３）である。 Thus, each of the case using the spherical carbon material SAC and the case using the powder carbon material AC as the active material is charged to a voltage of 3V with a constant current of 10 mA, and then to 0 V under a constant current of 1 to 50 mA. After discharging, the electrode capacity (capacitance) C (g) per unit weight and the electrode capacity C (v) per unit volume were determined by the following equations. Here, I is a current value, Δt is a voltage drop time, ΔV is a voltage drop value, (M 1 + M 2 ) is an active material mass (g) for two electrodes, and (V 1 + V 2 ) is for two electrodes. It is an active material volume (cm 3 ).
Ｃ(ｇ)＝Ｉ×Δｔ／（ΔＶ×(Ｍ１＋Ｍ２)）
Ｃ(ｖ)＝Ｉ×Δｔ／（ΔＶ×(Ｖ１＋Ｖ２)）
C (g) = I × Δt / (ΔV × (M 1 + M 2 ))
C (v) = I × Δt / (ΔV × (V 1 + V 2 ))
まず、電極密度及び電気伝導率は表３に示すとおりである。球状炭素材ＳＡＣの場合は、電極密度が粉末炭素材ＡＣの場合の約２倍、電気伝導率が粉末炭素材ＡＣの場合の約５０倍になっている。 First, the electrode density and electrical conductivity are as shown in Table 3. In the case of the spherical carbon material SAC, the electrode density is about twice that of the powder carbon material AC, and the electric conductivity is about 50 times that of the powder carbon material AC.
図１４は放電電流密度に対する単位重量当たり電極容量を示し、図１４は放電電流密度に対する単位体積当たり電極容量を示す。いずれも、球状炭素材ＳＡＣの方が高い値を示している。特に、図１５の単位体積当たり電極容量に関しては、球状炭素材ＳＡＣは粉末炭素材ＡＣの２倍以上になっている。これは、球状炭素材ＳＡＣが粉末炭素材ＡＣに比べ、より高密度に充填されたことによるものと認められる。 FIG. 14 shows the electrode capacity per unit weight with respect to the discharge current density, and FIG. 14 shows the electrode capacity per unit volume with respect to the discharge current density. In any case, the spherical carbon material SAC shows a higher value. In particular, regarding the electrode capacity per unit volume in FIG. 15, the spherical carbon material SAC is more than twice the powder carbon material AC. This is considered to be due to the spherical carbon material SAC being filled at a higher density than the powder carbon material AC.
＜電池への適用＞
図１１に示す酸触媒モル比０．０４、０．０９及び０．１３各々の球状炭素材ＳＡＣ３種（それらのおよその平均粒子径は３００ｎｍ、２００ｎｍ、１００ｎｍである）と、従前の粉末炭素材ＡＣ（平均粒子径５０００ｎｍ）とについて、各々を負極材料とするコイン電池（ＣＲ２０３２）を作製し、特性を比較した。
<Application to batteries>
Spherical carbon material SAC3 types (their average particle diameters are 300 nm, 200 nm, and 100 nm) of the acid catalyst molar ratios 0.04, 0.09, and 0.13 shown in FIG. For AC (average particle diameter 5000 nm), coin batteries (CR2032) each having a negative electrode material were prepared and the characteristics were compared.
コイン電池の正極材料はリチウム金属とし、電解液には、プロピレンカーボネート及びジメチルカーボネートの混合溶媒にＬｉ電解質ＬｉＰＦ６を混合した溶液を採用した。そして、１ｍＡの定電流、−３．０〜−０．０１Ｖの電圧範囲で充放電サイクル試験（室温２５℃）を行なった。結果を図１６に示す。初期充放電効率（＝（放電容量／充電容量）×１００）を表４に示す。 The positive electrode material of the coin battery was lithium metal, and a solution obtained by mixing Li electrolyte LiPF 6 in a mixed solvent of propylene carbonate and dimethyl carbonate was used as the electrolyte. And the charge / discharge cycle test (room temperature 25 degreeC) was done in the constant current of 1 mA and the voltage range of -3.0--0.01V. The results are shown in FIG. Table 4 shows the initial charge / discharge efficiency (= (discharge capacity / charge capacity) × 100).
本発明に係る球状炭素材ＳＡＣの場合、従前の炭素材ＡＣに比べて初期充放電効率が高い。また、充放電サイクルの場合、サイクル数が多くなると、放電容量が小さくなるが、その放電容量の低下をみると、本発明に係る球状炭素材ＳＡＣは、従前の炭素材ＡＣに比べその低下度が小さい。図１７は２０サイクル後の放電容量を比較したものであり、本発明に係る球状炭素材ＳＡＣでは、２０サイクル後でも大きな放電容量が維持されていることがわかる。また、表４及び図１６，１７から、球状炭素材ＳＡＣの平均粒子径が小さくなるほど放電容量が増加することがわかる。 In the case of the spherical carbon material SAC according to the present invention, the initial charge / discharge efficiency is higher than that of the conventional carbon material AC. In the case of the charge / discharge cycle, the discharge capacity decreases as the number of cycles increases. However, when the discharge capacity decreases, the spherical carbon material SAC according to the present invention has a decrease degree compared to the conventional carbon material AC. Is small. FIG. 17 compares the discharge capacities after 20 cycles. It can be seen that the spherical carbon material SAC according to the present invention maintains a large discharge capacity even after 20 cycles. Moreover, it can be seen from Table 4 and FIGS. 16 and 17 that the discharge capacity increases as the average particle diameter of the spherical carbon material SAC decreases.
−レート特性−
上記本発明に係る３種の球状炭素材ＳＡＣ及び従前の炭素材ＡＣによる各コイン電池（ＣＲ２０３２）について、１ｍＡの定電流、−３．０〜−０．０１Ｖの電圧範囲でレート（印加電流変更）試験（室温２５℃）を行なった。すなわち、放電レート０．５Ｃ（２時間率）での放電容量を１００％としたときの、放電レートの増大による放電容量維持率の変化を測定した。結果を図１８に示す。いずれも、放電レートの増大（印加電流の増大）に伴って放電容量維持率が低下しているものの、本発明に係る３種の球状炭素材ＳＡＣは従前の炭素材ＡＣに比べて、その放電容量維持率が高い。また、球状炭素材ＳＡＣの平均粒子径が小さくなるほど放電容量維持率が高くなっている。
-Rate characteristics-
For each coin battery (CR2032) using the above-mentioned three types of spherical carbon material SAC and the conventional carbon material AC according to the present invention, the rate (applied current change) at a constant current of 1 mA and a voltage range of -3.0 to -0.01V. ) Test (room temperature 25 ° C.) was conducted. That is, the change in the discharge capacity retention rate due to the increase in the discharge rate was measured when the discharge capacity at a discharge rate of 0.5 C (2 hour rate) was 100%. The results are shown in FIG. In any case, although the discharge capacity maintenance rate decreases with an increase in discharge rate (increase in applied current), the three types of spherical carbon materials SAC according to the present invention have a higher discharge than the conventional carbon materials AC. Capacity maintenance rate is high. In addition, the discharge capacity retention rate increases as the average particle diameter of the spherical carbon material SAC decreases.
すなわち、リチウム電池は大電流に弱いとされているところ、本発明に係る球状炭素材ＳＡＣの場合、その粒子径が小さく、ミクロポア内部へのＬｉイオンの拡散進入が容易である（拡散経路が短い）ために、大電流になっても、放電容量の維持率が高くなったものと認められる。換言すれば、従前の炭素材ＡＣの場合は、その粒子径が大きいことから、ミクロポア内部へのＬｉイオンの拡散に時間がかかり、大電流に対応できない、つまり、使用されない炭素材が多くなったものと認められる。 That is, the lithium battery is considered to be vulnerable to a large current. However, in the case of the spherical carbon material SAC according to the present invention, the particle diameter is small, and the diffusion and entry of Li ions into the micropores is easy (the diffusion path is short). Therefore, even when the current becomes large, it is recognized that the maintenance rate of the discharge capacity is increased. In other words, in the case of the conventional carbon material AC, since the particle diameter is large, it takes time to diffuse Li ions inside the micropore, and it is not possible to cope with a large current, that is, the carbon material that is not used has increased. It is accepted.
球状炭素材は、吸着材、複写機のトナー材、蓄電装置の電極材など種々の用途がある。また、球状フェノール樹脂は、粒状活性炭、電池電極、砥石、フィラー、成形材料等の原料とすることができる。 The spherical carbon material has various uses such as an adsorbing material, a toner material of a copying machine, and an electrode material of a power storage device. The spherical phenol resin can be used as a raw material for granular activated carbon, battery electrodes, grindstones, fillers, molding materials and the like.
１ 集電体
２ 電極
３ セパレータ
４ 電解液
DESCRIPTION OF SYMBOLS 1 Current collector 2 Electrode 3 Separator 4 Electrolyte
Claims (12)
上記活性炭粒子が個々に独立した球状粒子になっていることを特徴とする球状炭素材。 In claim 1,
A spherical carbon material, wherein the activated carbon particles are individually independent spherical particles.
フェノール類と、アルデヒド類と、界面活性剤と、硬化剤と、酸触媒との混合溶液を調製する工程と、
上記混合溶液を７５℃以上１１０℃以下の熱処理温度で反応させることにより、炭素材前駆体である平均粒子径１μｍ以下の球状フェノール樹脂を調製する工程と、
上記炭素材前駆体を１１０℃以上３００℃以下の温度雰囲気で硬化させる工程と、
得られた硬化物を６００℃以上８００℃以下の温度雰囲気で炭素化する工程と、
得られた炭素化物を水蒸気賦活する工程とを備えていることを特徴とする球状炭素材の製造方法。 A method for producing a spherical carbon material comprising spherical activated carbon particles having an average particle diameter of 100 nm or more and 850 nm or less,
Preparing a mixed solution of a phenol, an aldehyde, a surfactant, a curing agent, and an acid catalyst;
A step of preparing a spherical phenol resin having an average particle diameter of 1 μm or less, which is a carbon material precursor, by reacting the mixed solution at a heat treatment temperature of 75 ° C. or higher and 110 ° C. or lower;
Curing the carbon material precursor in a temperature atmosphere of 110 ° C. or higher and 300 ° C. or lower;
A step of carbonizing the obtained cured product in a temperature atmosphere of 600 ° C. or higher and 800 ° C. or lower;
And a step of steam activation of the obtained carbonized product. A method for producing a spherical carbon material.
上記酸触媒が、ハロゲン化水素、硝酸及び硫酸のうちから選ばれる少なくとも一種であることを特徴とする球状炭素材の製造方法。 In claim 4,
The method for producing a spherical carbon material, wherein the acid catalyst is at least one selected from hydrogen halide, nitric acid and sulfuric acid.
上記フェノール類に対する上記酸触媒の添加割合をモル比で０．０１以上０．１５以下とすることを特徴とする球状炭素材の製造方法。 In claim 4 or claim 5,
A method for producing a spherical carbon material, wherein the addition ratio of the acid catalyst to the phenols is 0.01 to 0.15 in molar ratio.
上記界面活性剤として、陽イオン性界面活性剤及び陰イオン性界面活性剤の少なくとも一方を用いることを特徴とする球状炭素材の製造方法。 In any one of Claims 4 thru | or 6,
A method for producing a spherical carbon material, wherein at least one of a cationic surfactant and an anionic surfactant is used as the surfactant.
フェノール類と、アルデヒド類と、界面活性剤と、硬化剤と、酸触媒との混合溶液を調製する工程と、
上記混合溶液を７５℃以上１１０℃以下の熱処理温度に加熱して重合反応を進める工程とを備えていることを特徴とする球状のフェノール樹脂の製造方法。 A method for producing a spherical phenol resin having an average particle size of 300 nm or more and 1000 nm or less,
Preparing a mixed solution of a phenol, an aldehyde, a surfactant, a curing agent, and an acid catalyst;
And a step of heating the mixed solution to a heat treatment temperature of 75 ° C. or higher and 110 ° C. or lower to advance a polymerization reaction.
上記酸触媒が、ハロゲン化水素、硝酸及び硫酸のうちから選ばれる少なくとも一種であることを特徴とする球状のフェノール樹脂の製造方法。 In claim 9,
The method for producing a spherical phenol resin, wherein the acid catalyst is at least one selected from hydrogen halide, nitric acid and sulfuric acid.
上記フェノール類に対する上記酸触媒の添加割合をモル比で０．０１以上０．１５以下とすることを特徴とする球状のフェノール樹脂の製造方法。 In claim 9 or claim 10,
A method for producing a spherical phenol resin, wherein the addition ratio of the acid catalyst to the phenols is 0.01 to 0.15 in terms of molar ratio.
上記界面活性剤として、陽イオン性界面活性剤及び陰イオン性界面活性剤の少なくとも一方を用いることを特徴とする球状のフェノール樹脂の製造方法。 In any one of Claims 9 to 11,
A method for producing a spherical phenol resin, wherein at least one of a cationic surfactant and an anionic surfactant is used as the surfactant.
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| CN113471419A (en) * | 2021-06-09 | 2021-10-01 | 济南精智方正新材料有限公司 | Silicon-carbon composite material and preparation method and application thereof |
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