JP2021178772A - Porous carbon particle, porous carbon particle dispersion, and method for producing the same - Google Patents

Porous carbon particle, porous carbon particle dispersion, and method for producing the same Download PDF

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JP2021178772A
JP2021178772A JP2021107145A JP2021107145A JP2021178772A JP 2021178772 A JP2021178772 A JP 2021178772A JP 2021107145 A JP2021107145 A JP 2021107145A JP 2021107145 A JP2021107145 A JP 2021107145A JP 2021178772 A JP2021178772 A JP 2021178772A
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porous carbon
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拓磨 井元
Takuma Imoto
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Mikuni Color Ltd
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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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

To provide a porous carbon particle with many mesopore that can be effectively used.SOLUTION: Provided are (1) a porous carbon particle that has a pore diameter peak on adsorption side by the BJH method present between 2 nm to 50 nm, a specific surface area of 100 to 600 m2/g, and a 2.6nm to 200nm pore volume on adsorption side by BJH method of 0.4 ml/g or more, and (2) a porous carbon particle that has a pore diameter peak on adsorption side by the BJH method present between 2 nm to 50 nm, a specific surface area of 100 to 600 m2/g, and a total pore volume of 0.5 to 1.3 ml/g.

Description

本発明は、新規な多孔質炭素粒子、多孔質炭素粒子を含有する分散体及びこれらの製造方法並びにこれらの用途に関する。 The present invention relates to novel porous carbon particles, dispersions containing the porous carbon particles, methods for producing the same, and uses thereof.

従来より、多孔質炭素が様々な分野で注目されている。例えば、リチウム２次電池、燃料電池等の電池材料用途、細孔を利用したエネルギーや水素の貯蔵、その他各種の物質の吸着、触媒担体などである。他にも、触媒、吸着、ガス検知、イオン交換、キャパシタ、平板振動板、フィルター材、金属精錬の際のガス吹き込み管、フィルター、断熱材、着材、電極、空気中の液体資料中の吸着物質の濃度測定、高表面積電極材料や小型分離用途、生体分子に対する吸着・脱離に関する試料調整への適用可能性が検討されている。 Conventionally, porous carbon has been attracting attention in various fields. For example, it is used as a battery material such as a lithium secondary battery and a fuel cell, stores energy and hydrogen using pores, adsorbs various other substances, and is a catalyst carrier. In addition, catalysts, adsorption, gas detection, ion exchange, capacitors, flat plate vibration plates, filter materials, gas blow tubes for metal refining, filters, heat insulating materials, landing materials, electrodes, adsorption in liquid materials in the air. The applicability to the measurement of substance concentration, high surface area electrode materials and small separation applications, and sample preparation related to adsorption / desorption of biomolecules is being investigated.

このように細孔を利用した用途での多孔質炭素としては、従来は活性炭が代表的であったが、活性炭は細孔容量は大きいものの、細孔径の分布が広い。これに対して近年は特に、細孔のうち２〜５０ｎｍのいわゆるメソ孔の機能に注目し、メソ孔を多く付与した多孔質炭素（メソポーラスカーボン）の製造や細孔径のコントロール技術、用途開発の研究が活発に行われている。 As described above, activated carbon has been a typical example of porous carbon for applications using pores, but activated carbon has a large pore capacity but a wide distribution of pore diameters. On the other hand, in recent years, we have paid particular attention to the function of so-called mesopores of 2 to 50 nm among the pores, and have been developing porous carbon (mesoporous carbon) with many mesopores, pore diameter control technology, and application development. Research is being actively conducted.

メソ孔を多く有することにより、吸着しようとする物質の吸着や濃縮が高速で、電荷を貯めやすく、吸蔵がしやすい等の利点があるとされる。例えば高湿度における水蒸気吸着量はメソ孔容量に異存するとされるため、ヒートポンプ等への適用も検討されている。またタンパク質や酵素などの大きさにメソ孔が対応できるため、ライフサイエンス分野への適用も期待されている。
このようなメソ孔の多い多孔質炭素材料としては様々な形状のものが開発されている。例えば、フェルト状、膜状、シート状、板状、円筒状、スポンジ状、球状などがある。 It is said that having many mesopores has advantages such as high speed adsorption and concentration of the substance to be adsorbed, easy storage of electric charge, and easy storage. For example, since the amount of water vapor adsorbed at high humidity is considered to be different from the mesopore capacity, its application to heat pumps and the like is also being considered. It is also expected to be applied to the life science field because the mesopores can correspond to the size of proteins and enzymes.
As a porous carbon material having many mesopores, various shapes have been developed. For example, there are felt-like, film-like, sheet-like, plate-like, cylindrical, sponge-like, spherical and the like.

従来の代表的な多孔質炭素である活性炭は低結晶性であるのに対し、グラファイト化したメソポーラスカーボン、ナノ樹状体構造を有するもの、細孔壁が単層グラフェンからなるもの等もある。 Activated carbon, which is a typical porous carbon in the past, has low crystallinity, but there are also graphitized mesoporous carbon, those having a nanodendritic structure, and those having a pore wall made of single-layer graphene.

また、メソ孔を多く有する多孔質炭素では、孔同士が繋がり連通孔を形成することを特徴とするものもある。細孔のコントロールは一般に、大きさがコントロールされ鋳型となる物質（粘土鉱物、シリカや酸化マグネシウム等の酸化物や金属アルコキシドなど）を炭素源となる材料を混ぜあるいは鋳型と炭素源を兼ね備える材料から鋳型となる物質を用いて炭化処理して炭素を析出させ、さらに鋳型となる物質を除去する方法が一般的である（特許文献１〜７、非特許文献１）。 Further, some of the porous carbons having many mesopores are characterized in that the pores are connected to each other to form communication pores. Pore control is generally performed by mixing a substance that is controlled in size and serves as a template (clay minerals, oxides such as silica and magnesium oxide, metal alkoxide, etc.) with a material that is a carbon source, or from a material that has both a template and a carbon source. A general method is to carry out carbonization treatment using a template substance to precipitate carbon, and further remove the template substance (Patent Documents 1 to 7 and Non-Patent Document 1).

特許文献１ WO2015/137106
特許文献２ WO2010/104102
特許文献３ WO2012/029920
特許文献４ 特開2014-017230号公報
特許文献５ 特開2007-123284号公報
特許文献６ 特開2014-129597号公報
特許文献７ 特開2017-126514号公報 Patent Document 1 WO2015 / 137106
Patent Document 2 WO2010/104102
Patent Document 3 WO 2012/029920
Patent Document 4 Japanese Patent Application Laid-Open No. 2014-017230 Patent Document 5 Japanese Patent Application Laid-Open No. 2007-123284 Patent Document 6 Japanese Patent Application Laid-Open No. 2014-129597 Patent Document 7 Japanese Patent Application Laid-Open No. 2017-126514

非特許文献１ 京谷他 「炭素 TANSO 」2001(no.199)176-186 Non-Patent Document 1 Kyotani et al. "Carbon TANSO" 2001 (no.199) 176-186

ところが、これらメソポーラスカーボンのうち、直接シートや膜等の形成体を作成するのは物性のコントロールが難しく手間がかかると考えられる。そこで球状の多孔質炭素や多孔質炭素の破砕物を用い、樹脂や電極活物質等と混合して用いることが工程上有利である。しかし、既存の多孔質材料の粒子や破砕物を用いた場合、機能が十分に発揮できないことが分かった。多孔質炭素が十分に機能を発揮するには、たとえば電池材料として用いる場合には活物質や樹脂等他の電極構成成分と均一に混合される必要がある。と同時に、特徴である細孔が十分に維持されなければ機能は発揮できない。
メソポーラスカーボンには分散性に優れているとされる製品もあるが、やはりそのままでは粒径が２０μｍ以上もあり、メディアに十分均一に分散することができない。他方、粒子径を微細化すると、その過程でメソ孔も破壊され、十分に機能が発揮できないことが推測される。
また、多孔質炭素と他の成分との親和性が十分でなければ経時で不均一化するおそれもある。 However, among these mesoporous carbons, it is considered that it is difficult and time-consuming to directly produce a forming body such as a sheet or a film because it is difficult to control the physical properties. Therefore, it is advantageous in the process to use spherical porous carbon or a crushed product of porous carbon and mix it with a resin, an electrode active material, or the like. However, it was found that the function could not be fully exhibited when the particles and crushed materials of the existing porous material were used. In order for the porous carbon to fully exhibit its function, for example, when it is used as a battery material, it needs to be uniformly mixed with other electrode constituents such as an active material and a resin. At the same time, the function cannot be exhibited unless the characteristic pores are sufficiently maintained.
Some mesoporous carbon products are said to have excellent dispersibility, but as they are, they have a particle size of 20 μm or more and cannot be sufficiently uniformly dispersed in media. On the other hand, if the particle size is miniaturized, the mesopores are also destroyed in the process, and it is presumed that the function cannot be fully exerted.
In addition, if the affinity between the porous carbon and other components is not sufficient, it may become non-uniform over time.

そこで、本発明者らは、上記の課題を解決するために、鋭意検討を行った。その結果、特定の粒径、細孔径及び最高分布を有する多孔質炭素を得ることができ、優れた機能が得られることを見出して、本発明を完成させた。
すなわち本発明は、
（１）BJH法による吸着側の細孔直径ピークが2.6nm〜200nmの間に存在し、比表面積が１００〜６００ｍ２／ｇであり、かつBJH法による吸着側の2.6nm〜200nmの細孔容積が０．４ｍｌ／ｇ以上である多孔質炭素粒子、
（２）BJH法による吸着側の細孔直径ピークが2.6nm〜200nmの間に存在し、比表面積が１００〜６００ｍ２／ｇであり、かつ全細孔容積が０．５〜１．３ｍｌ／ｇである多孔質炭素粒子、
（３）液中に上記（１）又は（２）記載の多孔質炭素粒子を１〜３５重量％含有する多孔質炭素粒子分散体、
（４）上記（３）記載の多孔質炭素粒子分散体を、バインダーと混合して、シート状に加工することを特徴とするフィルターの製造方法、
（５）上記（３）記載の多孔質炭素粒子分散体を、カーボンブラックと、バインダーと混錬・ペースト化して、シート状に加工することを特徴とする電気二重層キャパシタ電極の製造方法。
（６）上記（３）記載の多孔質炭素粒子分散体を、活物質、導電材、及びバインダーと混錬・ペースト化し、シート状に加工することを特徴とするリチウムイオン電池電極の製造方法、
にある。 Therefore, the present inventors have conducted diligent studies in order to solve the above-mentioned problems. As a result, it was found that porous carbon having a specific particle size, pore size and maximum distribution can be obtained, and excellent functions can be obtained, and the present invention has been completed.
That is, the present invention
(1) The pore diameter peak on the adsorption side by the BJH method exists between 2.6 nm and 200 nm, the specific surface area is 100 to 600 m 2 / g, and the pores on the adsorption side by the BJH method are 2.6 nm to 200 nm. Porous carbon particles with a volume of 0.4 ml / g or more,
(2) The pore diameter peak on the adsorption side by the BJH method exists between 2.6 nm and 200 nm, the specific surface area is 100 to 600 m 2 / g, and the total pore volume is 0.5 to 1.3 ml / g. Porous carbon particles that are g,
(3) A porous carbon particle dispersion containing 1 to 35% by weight of the porous carbon particles according to (1) or (2) above in a liquid.
(4) A method for producing a filter, which comprises mixing the porous carbon particle dispersion according to (3) above with a binder and processing the mixture into a sheet.
(5) A method for manufacturing an electric double layer capacitor electrode, which comprises kneading and pasting the porous carbon particle dispersion according to (3) above with carbon black and a binder to form a sheet.
(6) A method for producing a lithium ion battery electrode, which comprises kneading and pasting the porous carbon particle dispersion according to (3) above with an active material, a conductive material, and a binder, and processing the porous carbon particle dispersion into a sheet.
It is in.

本発明により、メソ孔領域の細孔を多く有し、このメソ孔領域の細孔が有効活用でき、かつ分散性に優れ各種の媒体への均一な混合が容易な多孔質炭素粒子及びこれを含有する分散体を提供でき、各種の用途への展開が可能である。 INDUSTRIAL APPLICABILITY According to the present invention, porous carbon particles having many pores in the mesopore region, the pores in the mesopore region can be effectively utilized, the dispersibility is excellent, and uniform mixing with various media is easy, and the porous carbon particles thereof. It is possible to provide a dispersion containing the mixture, and it is possible to develop it into various uses.

図１は、実施例１、２及び比較例１の分散体を用いてメチレンブルー吸着試験を行った結果を示す図である。FIG. 1 is a diagram showing the results of a methylene blue adsorption test using the dispersions of Examples 1 and 2 and Comparative Example 1. 図２は、実施例におけるメチレンブルー吸着テストでの吸光度の測定結果を示す図である。FIG. 2 is a diagram showing the measurement results of the absorbance in the methylene blue adsorption test in the examples. 図３は、実施例１及び２の分散液の原料として用いた市販の多孔質炭素材料のSEM写真を示す図である。FIG. 3 is a diagram showing SEM photographs of commercially available porous carbon materials used as raw materials for the dispersions of Examples 1 and 2. 図４は、実施例１の分散液中の多孔質炭素粒子のSEM写真を示す図である。FIG. 4 is a diagram showing an SEM photograph of the porous carbon particles in the dispersion liquid of Example 1. 図５は、実施例２の分散液中の多孔質炭素粒子のSEM写真を示す図である。FIG. 5 is a diagram showing an SEM photograph of the porous carbon particles in the dispersion liquid of Example 2. 図６は、実施例２の分散液中の多孔質炭素粒子のSEM写真を示す図である。FIG. 6 is a diagram showing an SEM photograph of the porous carbon particles in the dispersion liquid of Example 2.

<多孔質炭素材料の説明>
本発明における多孔質炭素材料とは、炭素を主体とし、細孔を有する材料である。
本発明においては細孔の大きさや量は、以下のとおりである。 <Explanation of porous carbon material>
The porous carbon material in the present invention is a material mainly composed of carbon and having pores.
In the present invention, the size and amount of the pores are as follows.

<出発原料>
出発原料として用いることのできる多孔性炭素材料は、好ましくは以下の細孔特性を有する。 <Starting raw material>
The porous carbon material that can be used as a starting material preferably has the following pore characteristics.

<比表面積>
比表面積は限定されないが、200m2/g以上が一般的である。好ましくは400m2/g以上、さらに好ましくは500m2/g、最も好ましくは600-2000m2/gである。ただし、用途に応じて選択すればよい。 <Specific surface area>
The specific surface area is not limited, but is generally 200 m 2 / g or more. It is preferably 400 m 2 / g or more, more preferably 500 m 2 / g, and most preferably 600-2000 m 2 / g. However, it may be selected according to the intended use.

<メソ孔容量>
メソ孔容積、いわゆるメソ孔領域（直径２〜５０ｎｍ）の細孔の容積も特に限定されないが、メソ孔の有する機能を発揮しうる用途のためには、通常0.2-1.5ml/gが好適である。
ただし、用途に応じて選択すればよい。
後述する方法で本発明の多孔質炭素粒子を製造すれば、メソ孔容量はほぼ維持できるため、目的とするメソ孔容量に応じて原料を選択すればよい。 <Meso hole capacity>
The volume of the mesopores, that is, the volume of the pores in the so-called mesopore region (diameter 2 to 50 nm) is not particularly limited, but 0.2-1.5 ml / g is usually preferable for applications in which the functions of the mesopores can be exhibited. be.
However, it may be selected according to the intended use.
If the porous carbon particles of the present invention are produced by the method described later, the mesopore capacity can be substantially maintained, so that the raw material may be selected according to the target mesopore capacity.

<メソ孔径>
メソ孔領域の細孔の特性を示す指標の一つとしていわゆるメソ孔径がある。通常、ＢＪＨ法により求められる。原料となる多孔質炭素材料のメソ孔径は特に限定されないが、メソ孔の有する機能を発揮しうる用途のためには、通常0.3〜200ｍｌ／ｇが好適である。より好ましくは0.3〜150ｍｌ／ｇ、さらに好ましくは0.3〜50ｍｌ／ｇである。ただし、用途に応じて選択すればよい。
後述する方法で本発明の多孔質炭素粒子を製造すれば、メソ孔容量はほぼ維持又は増加できるため、目的とするメソ孔径に応じて原料を選択すればよい。 <Meso hole diameter>
The so-called mesopore diameter is one of the indexes showing the characteristics of the pores in the mesopore region. Usually, it is obtained by the BJH method. The mesopore diameter of the porous carbon material as a raw material is not particularly limited, but 0.3 to 200 ml / g is usually suitable for applications in which the functions of the mesopores can be exhibited. It is more preferably 0.3 to 150 ml / g, still more preferably 0.3 to 50 ml / g. However, it may be selected according to the intended use.
If the porous carbon particles of the present invention are produced by the method described later, the mesopore capacity can be substantially maintained or increased, so that the raw material may be selected according to the target mesopore diameter.

<ミクロ孔容積>
ミクロ孔容積も特に限定されない。通常は0.10ｍｌ／ｇ以上であるが、用途によってはより少なくてもよい。また原料となる多孔質炭素材料製造時にミクロ孔容積のコントロールをすることは容易ではなく、また後述する本発明の方法によりミクロ孔を減少できるので、あえて容積を制限する必要はないため、用途に応じて選択すればよい。
ガス補足用途等では、メソ孔が開気孔であって、気孔部分が連続するようなものが好ましい。開気孔とは、気孔の少なくとも一部分が粒子表面に出ていることをいう。開気孔であることからガスと接触し有効活用される細孔部分が多くなるためである。また、気孔部分が連続していれば、ガスの流れが円滑になりガスを補足しやすくなるとされるためである。また炭素質壁が３次元網目構造を形成しているものが強度の点からは望ましい。このような開気孔、連続した気孔部分、３次元網目構造の有無は、電子顕微鏡写真により確認できる。
このような開気孔、連続した気孔部分、３次元網目構造を有する多孔質炭素は、前述した公知の製造方法により得ることができ、また各種の市販品を使用することもできる。 <Micro pore volume>
The micropore volume is also not particularly limited. Normally, it is 0.10 ml / g or more, but it may be less depending on the application. In addition, it is not easy to control the micropore volume during the production of the porous carbon material as a raw material, and since the micropores can be reduced by the method of the present invention described later, it is not necessary to dare to limit the volume. You can select according to your needs.
For gas supplementing applications and the like, it is preferable that the mesopores are open pores and the pores are continuous. Open pores mean that at least a part of the pores is exposed on the surface of the particles. This is because since the pores are open, the number of pores that come into contact with the gas and are effectively utilized increases. Further, if the pores are continuous, the flow of gas becomes smooth and it becomes easy to capture the gas. Further, it is desirable from the viewpoint of strength that the carbonaceous wall forms a three-dimensional network structure. The presence or absence of such open pores, continuous pore portions, and a three-dimensional network structure can be confirmed by electron micrographs.
Porous carbon having such open pores, continuous pore portions, and a three-dimensional network structure can be obtained by the above-mentioned known production method, and various commercially available products can also be used.

<物性値の測定方法>
以上説明した原料となる多孔質炭素材料の各物性は以下の方法により求めることができる。
比表面積はBET比表面積であり、窒素吸着法で相対圧力とN2吸着量の関係（吸着等温線）を調べ吸着等温線の結果からBET法を用いて算出する。装置は特に限定されず各種の比表面積測定装置が使用できる。
一般には試料約０．1ｇをセルに採取し前処理として３００℃で約５時間程度脱ガス処理をした後に測定する。
メソ孔容積及びメソ孔径はBJH法、ミクロ孔容量及びミクロ孔径はHK法で求める。 <Measurement method of physical property value>
The physical characteristics of the porous carbon material as the raw material described above can be obtained by the following methods.
The specific surface area is the BET specific surface area, which is calculated using the BET method from the results of the adsorption isotherm by investigating the relationship between the relative pressure and the N 2 adsorption amount (adsorption isotherm) using the nitrogen adsorption method. The device is not particularly limited, and various specific surface area measuring devices can be used.
Generally, about 0.1 g of a sample is collected in a cell and degassed at 300 ° C. for about 5 hours as a pretreatment before measurement.
The mesopore volume and mesopore diameter are determined by the BJH method, and the micropore capacity and micropore diameter are determined by the HK method.

<作り方>
以上のような多孔質炭素材料の製造方法は、特に限定されず、前述した各種の公知の多孔質炭素材料の製造方法によるものが使用できる。 <How to make>
The method for producing the porous carbon material as described above is not particularly limited, and the above-mentioned various known methods for producing the porous carbon material can be used.

<市販品>
各種の市販品も使用できる。
例えば、「クノーベル」（東洋炭素株式会社製）、「エスカーボン」（新日鉄住金化学株式会社製）等が挙げられる。 <Commercial product>
Various commercial products can also be used.
For example, "Knobel" (manufactured by Toyo Tanso Co., Ltd.), "S Carbon" (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be mentioned.

<本発明の多孔質炭素粒子及び多孔質炭素分散体>
以上説明した多孔質炭素材料を、各種の液媒体に分散して本発明の多孔質炭素粒子分散体を得ることができる。本発明の多孔質炭素分散体中には、本発明の多孔質炭素粒子が含有されており、以下の物性を有する。 <Porous carbon particles and porous carbon dispersion of the present invention>
The porous carbon material described above can be dispersed in various liquid media to obtain the porous carbon particle dispersion of the present invention. The porous carbon particles of the present invention contain the porous carbon particles of the present invention, and have the following physical characteristics.

<本発明の多孔質炭素粒子の第一の形態>
本発明の多孔質炭素粒子の第二の形態は、BJH法による吸着側の細孔直径ピークが2.6nm〜200nmの間に存在し、比表面積が１００〜６００ｍ２／ｇであり、かつBJH法による吸着側の2.6nm〜200nmの細孔容積が０．４ｍｌ／ｇ以上のものである。 <First Form of Porous Carbon Particles of the Present Invention>
The second form of the porous carbon particles of the present invention has a pore diameter peak on the adsorption side between 2.6 nm and 200 nm by the BJH method, a specific surface area of 100 to 600 m 2 / g, and a BJH method. The pore volume of 2.6 nm to 200 nm on the adsorption side is 0.4 ml / g or more.

<本発明の多孔質炭素粒子の第二の形態>
本発明の多孔質炭素粒子の第一の形態は、BJH法による吸着側の細孔直径ピークが2.6nm〜200nmの間に存在し、比表面積が１００〜６００ｍ２／ｇであり、かつ全細孔容積が０．５〜１．３ｍｌ／ｇのものである。 <Second Form of Porous Carbon Particles of the Present Invention>
The first form of the porous carbon particles of the present invention has a pore diameter peak on the adsorption side between 2.6 nm and 200 nm by the BJH method, a specific surface area of 100 to 600 m 2 / g, and total fineness. The pore volume is 0.5 to 1.3 ml / g.

<BJH法による細孔直径ピーク>
本発明の多孔質炭素粒子は、BJH法による吸着側の細孔直径ピークが2.6nm〜200nmの間に存在することを特徴とする。特に好ましくは2〜100nm、最も好ましくは2〜50nmに存在するものである。ピークが2〜50nmに存在するということは、いわゆるメソ孔径の細孔を多く有することであるため、メソ孔に選択的に吸着される物質の吸脱着にはこの範囲の多孔質炭素粒子とすれば好適に使用できる。 <Pore diameter peak by BJH method>
The porous carbon particles of the present invention are characterized in that the pore diameter peak on the adsorption side by the BJH method exists between 2.6 nm and 200 nm. It is particularly preferably present at 2 to 100 nm, most preferably 2 to 50 nm. The fact that the peak is present at 2 to 50 nm means that it has many pores with so-called mesopore diameters. Can be preferably used.

本発明の多孔質炭素粒子は、原料とする多孔質炭素材料の有するメソ孔をほぼ維持できる上、後述するように分散工程によって原料の内部に存在していた細孔が表面に出てくる。また原料のミクロ孔が分散工程によって細孔径が広がり、メソ孔を増加させていると推測される。しかも、本発明の多孔質炭素粒子は、後述するように多孔質炭素材料の製造工程でメソ孔量を増大させる方法に比べて比表面積が抑えられる。このため、比表面積が大きすぎる場合のような粒子の凝集等の問題も防止できるという利点を有する。 The porous carbon particles of the present invention can substantially maintain the mesopores of the porous carbon material as a raw material, and as will be described later, the pores existing inside the raw material appear on the surface by the dispersion step. Further, it is presumed that the micropores of the raw material expand the pore diameter by the dispersion step and increase the mesopores. Moreover, the specific surface area of the porous carbon particles of the present invention can be suppressed as compared with the method of increasing the amount of mesopores in the manufacturing process of the porous carbon material as described later. Therefore, there is an advantage that problems such as agglutination of particles such as when the specific surface area is too large can be prevented.

なお、BJHプロットにおいて吸着側の細孔直径の極大値が複数ある場合、最も大きな極大値がここでいう最高直径ピークである。
BJH法による吸着側の細孔直径ピークは、以下のようにして求める。
まず、以下の条件で窒素吸着法による吸着等温線を求め、マイクロトラック・ベル（株）推奨のＦＨＨ基準曲線を用いてＢＪＨプロットを算出し、吸着側の細孔直径ピークを求める。 When there are a plurality of maximum values of the pore diameter on the adsorption side in the BJH plot, the largest maximum value is the maximum diameter peak referred to here.
The pore diameter peak on the adsorption side by the BJH method is obtained as follows.
First, the adsorption isotherm by the nitrogen adsorption method is obtained under the following conditions, the BJH plot is calculated using the FHH reference curve recommended by Microtrac Bell Co., Ltd., and the pore diameter peak on the adsorption side is obtained.

前処理方法
装置：BELPREP-vacII（マイクロトラック・ベル（株）製）
測定方法
装置：BELSORP-mini（マイクロトラック・ベル（株）製）
定容法を用いて、窒素による吸着脱離等温線を測定する。
吸着温度：７７Ｋ
吸着質断面積：０．１６２ｎｍ２
吸着質：窒素
平衡待ち時間（吸脱着の際の圧力変化が所定の値以下になる状態）に達してからの待ち時間：５００ｓｅｃ
なお、他の方法でも同等の値を求めることのできる方法であれば制限なく使用できる。 Pretreatment method Equipment: BELPREP-vacII (manufactured by Microtrack Bell Co., Ltd.)
Measurement method Equipment: BELSORP-mini (manufactured by Microtrack Bell Co., Ltd.)
Using the constant volume method, the adsorption / desorption isotherm with nitrogen is measured.
Adsorption temperature: 77K
Adsorbent cross-sectional area: 0.162 nm 2
Adsorbent: Nitrogen Waiting time after reaching equilibrium waiting time (state in which pressure change during adsorption / desorption becomes less than a predetermined value): 500 sec
It should be noted that any other method can be used without limitation as long as the equivalent value can be obtained.

<BJH法による吸着側の2.6nm〜200nmの細孔容積>
本発明の多孔質炭素粒子の第一の形態において、BJH法による吸着側の2.6nm〜200nmの細孔容積は、０．４ｍｌ／ｇ以上である。より好ましくは０．５ｍｌ／ｇ以上、最も好ましくは０．６ｍｌ／ｇ以上である。
BJH法による吸着側の2.6nm〜200nmの細孔容積は、メソ孔領域である２〜５０ｎｍの細孔を多く含む。つまり本発明の多孔質炭素粒子はメソ孔領域の細孔を多く含みメソ孔を有効に活用できる。 <Pore volume of 2.6 nm to 200 nm on the adsorption side by the BJH method>
In the first form of the porous carbon particles of the present invention, the pore volume of 2.6 nm to 200 nm on the adsorption side by the BJH method is 0.4 ml / g or more. It is more preferably 0.5 ml / g or more, and most preferably 0.6 ml / g or more.
The pore volume of 2.6 nm to 200 nm on the adsorption side by the BJH method includes many pores of 2 to 50 nm, which is a mesopore region. That is, the porous carbon particles of the present invention contain many pores in the mesopore region, and the mesopores can be effectively utilized.

特に、本発明の多孔質炭素粒子は後述のようにミクロ孔の量を抑えることができ、全細孔の平均細孔径をメソ孔領域に有することができるため、本発明の多孔質炭素粒子はメソ孔領域の細孔を極めて多く含むものとすることができる。
例えば、BJH法による吸着側の2.6nm〜200nmの細孔容積とｔ法によるミクロ細孔容積との比（BJH法による吸着側の2.6nm〜200nmの細孔容積）／（ｔ法によるミクロ細孔容積）は、５〜３０、さらに好ましくは７〜２０、より好ましくは９〜１５とすることもできる。 In particular, since the porous carbon particles of the present invention can suppress the amount of micropores and can have the average pore diameter of all pores in the mesopore region, the porous carbon particles of the present invention can be used. It can contain an extremely large number of pores in the mesopore region.
For example, the ratio of the pore volume of 2.6 nm to 200 nm on the adsorption side by the BJH method to the micropore volume by the t method (pore volume of 2.6 nm to 200 nm on the adsorption side by the BJH method) / (microfine by the t method). The pore volume) can be 5 to 30, more preferably 7 to 20, and even more preferably 9 to 15.

また、本発明の多孔質炭素粒子は、原料となる多孔質炭素材料に比較してもBJH法による吸着側の2.6nm〜200nmの細孔容積、ひいてはメソ孔領域の粒子の量を維持し、さらには増加させることもできている。
BJH法による吸着側の2.6nm〜200nmの細孔容積は、ＢＨＪプロットをマイクロトラック・ベル株式会社推奨のＦＨＨ基準曲線を用いて算出する。具体的にはマイクロトラック・ベル社のガス吸着装置に付属する専用ソフト「BELMaster」を使用すればよい。 In addition, the porous carbon particles of the present invention maintain a pore volume of 2.6 nm to 200 nm on the adsorption side by the BJH method, and thus the amount of particles in the mesopore region, even when compared with the porous carbon material used as a raw material. It can also be increased.
The pore volume of 2.6 nm to 200 nm on the adsorption side by the BJH method is calculated by using the FHH reference curve recommended by Microtrac Bell Co., Ltd. on the BHJ plot. Specifically, the dedicated software "BELMaster" attached to the gas adsorption device of Microtrac Bell Co., Ltd. may be used.

<全比表面積>
本発明の多孔質炭素粒子の第二の形態においては、BET法により求めた全比表面積（Ａ（ｍ２／ｇ））が通常、１００〜７００ｍ２／ｇである。より好ましくは、２００〜６００ｍ２／ｇである。この範囲で、ハンドリングに優れ、各種の分散媒に好適に分散する。
また、この範囲にすることによりメソ孔領域の細孔容積を特に有効に活用できる。 <Total specific surface area>
In a second embodiment of the porous carbon particles of the present invention, the total specific surface area determined by the BET method (A (m 2 / g) ) is usually, 100~700m 2 / g. More preferably, it is 200 to 600 m 2 / g. Within this range, it is excellent in handling and is suitably dispersed in various dispersion media.
Further, by setting this range, the pore volume in the mesopore region can be utilized particularly effectively.

<全細孔容積>
本発明の多孔質炭素粒子は、全細孔容積は、０．４５ｍｌ以上、好ましくは０．５〜１．３ｍｌ／ｇとすることが好ましい。より好ましくは０．５〜２．０ｍｌ／ｇ、最も好ましくは０．５〜１．０ｍｌ／ｇである。
全細孔容積が多すぎると、ミクロ孔の割合が大きくなりやすく、他方メソ孔領域の細孔の割合を維持しつつ全細孔容積を増やすと炭素壁の強度が十分でなくなることもあるためである。 <Total pore volume>
The porous carbon particles of the present invention preferably have a total pore volume of 0.45 ml or more, preferably 0.5 to 1.3 ml / g. It is more preferably 0.5 to 2.0 ml / g, and most preferably 0.5 to 1.0 ml / g.
If the total pore volume is too large, the proportion of micropores tends to increase, while increasing the total pore volume while maintaining the proportion of pores in the mesopore region may result in insufficient strength of the carbon wall. Is.

全細孔容積は、相対圧（０．９９）までの全細孔容積であり、下記の式を用いて吸着等温線の相対圧（Ｐ／Ｐ０）の吸着量より算出する。
Ｖｐ＝（Ｖ／２２４１４）×Ｍｇ／ρｇ
Ｖｐ：相対圧（０．９９）までの全細孔容積
Ｖ：相対圧（０．９９）の吸着量
Ｍｇ：吸着質（Ｎ２）の分子量（２８．０１３）
Ρｇ：吸着質（Ｎ２）の密度（０．８０８） The total pore volume is the total pore volume up to the relative pressure (0.99), and is calculated from the adsorption amount of the relative pressure (P / P 0) of the adsorption isotherm using the following formula.
V p = (V / 22414) × M g / ρ g
V p: total pore volume of up to relative pressure (0.99) V: adsorption amount of relative pressure (0.99) M g: molecular weight of the adsorbate (N 2) (28.013)
Ρ g : Density of adsorbent (N 2 ) (0.808)

<平均細孔径>
本発明の多孔質炭素粒子の平均細孔径は、特に限定されないが、通常、４〜５０ｎｍ、より好ましくは５〜２０ｎｍ、さらに好ましくは７〜１５ｎｍである。
この範囲において特にメソ孔領域の細孔を多く含有させることができ、メソ孔を活用する用途に好適である。 <Average pore size>
The average pore diameter of the porous carbon particles of the present invention is not particularly limited, but is usually 4 to 50 nm, more preferably 5 to 20 nm, still more preferably 7 to 15 nm.
In this range, a large number of pores in the mesopore region can be contained, which is suitable for applications in which the mesopores are utilized.

平均細孔径は、比表面積及び全細孔容積より以下の式により求めることができる。
Ｄ＝４Ｖ／Ａ×１０００
Ｄ：平均細孔径（ｎｍ）
Ｖ：全細孔容積（ｃｍ３／ｇ）
Ａ：比表面積（ｍ２／ｇ） The average pore diameter can be calculated from the specific surface area and the total pore volume by the following formula.
D = 4V / A × 1000
D: Average pore diameter (nm)
V: Total pore volume (cm 3 / g)
A: Specific surface area (m 2 / g)

なお、平均細孔径は、原料とした多孔質炭素材料に比べて通常少し大きくなる。また、以下に説明するようにミクロ孔領域の細孔容積は少なくなる。これは、ミクロ孔領域の細孔が分散工程により広がり、メソ孔領域に移行したとも推測される。
このため、本発明の多孔質炭素粒子では、有効にメソ孔として機能する細孔が多く存在していると推測される。 The average pore diameter is usually slightly larger than that of the porous carbon material used as a raw material. Further, as described below, the pore volume in the micropore region is reduced. It is also presumed that the pores in the micropore region expanded due to the dispersion step and moved to the mesopore region.
Therefore, it is presumed that the porous carbon particles of the present invention have many pores that effectively function as mesopores.

<ミクロ細孔容積>
本発明の多孔質炭素粒子において、ミクロ細孔容積は特に限定されないが、通常、０．０５〜０．１５ｍｌ／ｇである。より好ましくは０．０７〜０．１０ｍｌである。
もっとも用途に応じて選択すればよく、ミクロ細孔はより少なくともよい。
本発明の多孔質炭素粒子のミクロ細孔容積は、原料となる多孔質炭素材料におけるミクロ細孔容積に対して減少させることができ、３分の２から３分の１程度にも減らすこともできる。ミクロ細孔容積減少の過程は完全には明らかではないが、分散工程により粒子表面のミクロ細孔の細孔径が大きくなりメソ孔領域に移行していることが推測される。 <Micropore volume>
In the porous carbon particles of the present invention, the micropore volume is not particularly limited, but is usually 0.05 to 0.15 ml / g. More preferably, it is 0.07 to 0.10 ml.
However, it may be selected according to the application, and the micropores are at least better.
The micropore volume of the porous carbon particles of the present invention can be reduced with respect to the micropore volume of the porous carbon material as a raw material, and can be reduced to about two-thirds to one-third. can. Although the process of reducing the volume of the micropores is not completely clear, it is presumed that the pore size of the micropores on the particle surface is increased by the dispersion step and the particles are transferred to the mesopore region.

上記のミクロ細孔容積は、ＭＰ法により細孔直径約０．４２ｎｍ〜約２ｎｍの解析を行うことにより求めることができる。ＭＰ−Ｐｌｏｔはマイクロトラック・ベル株式会社推奨のＨａｒｋｉｎｓ−Ｊｕｒａ基準曲線を用いて算出することができる。具体的にはマイクロトラック・ベル社のガス吸着装置に付属する専用ソフト「BELMaster」を使用すればよい。
ミクロ細孔容積はｔ法でも測定可能であるが、この場合の数値は好ましくは０．０４〜０．１ｍｌ、より好ましくは０．０５〜０．０９ｍｌである。
ミクロ孔も同様に「BELMaster」を使用して解析すればよい。 The above micropore volume can be determined by performing an analysis with a pore diameter of about 0.42 nm to about 2 nm by the MP method. MP-Plot can be calculated using the Harkins-Jura reference curve recommended by Microtrack Bell Co., Ltd. Specifically, the dedicated software "BELMaster" attached to the gas adsorption device of Microtrac Bell Co., Ltd. may be used.
The micropore volume can also be measured by the t method, but the numerical value in this case is preferably 0.04 to 0.1 ml, more preferably 0.05 to 0.09 ml.
Micropores may be analyzed using "BEL Master" in the same manner.

<粒径>
本発明の多孔質炭素粒子の粒径D50は一般には、０．５〜１０μm、好ましくは１．０〜５．０μm、さらに好ましくは１．５〜４．０μmである。
この範囲で分散性が良く安定な液として存在する上、各種の媒体への均一な混合が容易である。さらに、以上説明した細孔特性を得ることが容易である。 <particle size>
The particle size D50 of the porous carbon particles of the present invention is generally 0.5 to 10 μm, preferably 1.0 to 5.0 μm, and more preferably 1.5 to 4.0 μm.
In this range, it exists as a stable liquid with good dispersibility, and it is easy to uniformly mix it with various media. Furthermore, it is easy to obtain the pore characteristics described above.

<粘度>
本発明の多孔質炭素粒子を含有する多孔質炭素粒子分散体は、特に限定されないが、粘度が5〜30000 mPa・sとすることができる。より好ましくは６〜２５０００ mPa・s、さらに好ましくは6〜10000 mPa・s 、さらに好ましくは6〜1000 mPa・s、さらに好ましくは６〜１００mPa・s、さらに好ましくは６〜３０mPa・sである。
この範囲において、特にハンドリング性に優れ、各種の材料と良好に混合することができる。また、本発明の多孔質炭素粒子分散体は、多孔質炭素粒子の含有量を1〜40重量％近くとすることもでき、このように高濃度で上記の粘度範囲に調整することができるため実用上も非常に有用である。 <Viscosity>
The porous carbon particle dispersion containing the porous carbon particles of the present invention is not particularly limited, but has a viscosity of 5 to 30,000 mPa · s. It is more preferably 6 to 25,000 mPa · s, still more preferably 6 to 10000 mPa · s, still more preferably 6 to 1000 mPa · s, still more preferably 6 to 100 mPa · s, still more preferably 6 to 30 mPa · s.
In this range, it is particularly excellent in handleability and can be mixed well with various materials. Further, the porous carbon particle dispersion of the present invention can have the content of the porous carbon particles close to 1 to 40% by weight, and can be adjusted to the above viscosity range at such a high concentration. It is also very useful in practice.

<製造方法>
本発明の多孔質炭素粒子は、例えば以下の方法で作製することができる。
まず、前述した出発原料となる多孔質炭素材料を液体中で分散して所望の粒子径にするのが効率的である。
ここで分散とは、材料を、より細かくするつまり微粒化を意味する。分散方法としては、湿式分散、乾式分散のいずれでもよいが、特に液体中で分散する湿式分散が、装置が簡便で均一な分散ができる。湿式分散の方法は、液体中で材料である多孔質炭素にシェアをかけて微粒化することのできる方法であれば、特に制限されない。例えば、メディア分散、メディアレス分散等各種の公知の方法を採用できる。 <Manufacturing method>
The porous carbon particles of the present invention can be produced, for example, by the following method.
First, it is efficient to disperse the above-mentioned porous carbon material as a starting material in a liquid to obtain a desired particle size.
Dispersion here means making the material finer, that is, atomizing. As the dispersion method, either wet dispersion or dry dispersion may be used, but in particular, wet dispersion in which the dispersion is carried out in a liquid can be easily and uniformly dispersed by the apparatus. The wet dispersion method is not particularly limited as long as it can be atomized by applying a share to the porous carbon which is a material in a liquid. For example, various known methods such as media dispersion and medialess dispersion can be adopted.

これらのうち特に、メディア分散が好ましい。メディア分散とは、材料である多孔質炭素を分散する過程で、いわゆるメディアすなわちビーズ等の固体が材料である多孔質炭素に衝突することによって微細化するものである。例えばビーズミル、ボールミル等が代表的である。
メディア分散において、メディアの粒径と分散時間を調整して、求める粒子径まで分散することができるので、所望の粒子径に応じて適宜分散を行えばよい。 Of these, media dispersion is particularly preferable. Media dispersion is a process of dispersing porous carbon as a material, in which a solid such as so-called media, that is, beads, collides with the porous carbon as a material to make the material finer. For example, bead mills, ball mills and the like are typical.
In the media dispersion, the particle size and the dispersion time of the media can be adjusted to disperse to the desired particle size, and therefore the dispersion may be appropriately performed according to the desired particle size.

また、メソ孔を多く残しつつ分散性の良い粒径まで到達させるために必要な分散強度は材料の量によっても異なるため、メソ孔の容量の代表値として前述したBJH法による吸着側の2.6nm〜200nmの細孔容積、BJH法による吸着側の2.6nm〜200nmの細孔径、又は比表面積の変化をチェックしながら分散工程を行い、所望の細孔特性を有する条件を求め、これを生産工程に採用すればよい。 In addition, the dispersion strength required to reach a particle size with good dispersibility while leaving a large number of mesopores varies depending on the amount of material. The dispersion step was performed while checking the change in the pore volume of ~ 200 nm, the pore diameter of 2.6 nm ~ 200 nm on the adsorption side by the BJH method, or the specific surface area, and the conditions having the desired pore characteristics were obtained. It should be adopted for.

<他に入れる材料の説明>
分散時には、各種の液媒体を使用できる。多孔質炭素の用途に応じて溶剤を選択すればよい。
一般には、水、アルコール、NMPその他ごく一般的な溶媒を使用できる。 <Explanation of other materials to put in>
Various liquid media can be used at the time of dispersion. The solvent may be selected according to the use of the porous carbon.
In general, water, alcohol, NMP and other very common solvents can be used.

固体粒子を液体中に分散させるための分散剤を使用することが好適である。分散剤の種類も特に制限されない。例えば、セルロース系ポリマー、ブチラール系ポリマー、ポリビニルピロリドン系、ポリエーテル系（、ポリエーテルアミン）、ポリエステル系、ポリウレタン系、スチレンアクリル系ポリマー、高級脂肪酸エステル系がある。ポリビニルピロリドンとしてはＩＳＰ社製のＫ１５、Ｋ３０がある。
その他一般に分散助剤として知られている銅フタロシアニン誘導体等を使用してもよい。
これら分散剤は一種又は二種以上を併用できる。 It is preferable to use a dispersant for dispersing the solid particles in the liquid. The type of dispersant is also not particularly limited. For example, there are cellulose-based polymers, butyral-based polymers, polyvinylpyrrolidone-based, polyether-based (, polyetheramine), polyester-based, polyurethane-based, styrene acrylic-based polymers, and higher fatty acid ester-based polymers. Examples of polyvinylpyrrolidone include K15 and K30 manufactured by ISP.
In addition, a copper phthalocyanine derivative generally known as a dispersion aid may be used.
These dispersants may be used alone or in combination of two or more.

正極用材料、負極用材料等の電池材料、キャパシタ等の電材用途では、導電材料として知られているカーボンブラックその他の固体微粒子の分散体と混合あるいはこれらの固体微粒子と前述した本発明の多孔質炭素粒子の原料となる多孔質炭素材料とを共に液媒体に配合して分散処理を行ってもよい。 In applications such as battery materials such as positive electrode materials and negative electrode materials, and electrical materials such as capacitors, it is mixed with a dispersion of carbon black or other solid fine particles known as a conductive material, or these solid fine particles and the above-mentioned porous of the present invention. A porous carbon material as a raw material for carbon particles may be blended together with a liquid medium for dispersion treatment.

<配合量>
各成分の配合量も特に制限されない。
一般には、多孔質炭素粒子１００重量部に対して、液媒体を１８５〜９９００重量部、好ましくは２００〜４０００重量部、さらに好ましくは３００〜２０００重量部である。液又はスラリー状の本願の多孔質炭素粒子分散体中の多孔質炭素粒子は1〜35重量％が好適である。
分散剤の量は、１００重量部に対して、１〜２００重量部、好ましくは５〜１５０重量部、さらに好ましくは１０〜１００重量部である。なお複数の分散剤を用いる場合は分散剤の合計量である。 <Mixing amount>
The blending amount of each component is not particularly limited.
Generally, the liquid medium is 185 to 9900 parts by weight, preferably 200 to 4000 parts by weight, and more preferably 300 to 2000 parts by weight with respect to 100 parts by weight of the porous carbon particles. The porous carbon particles in the porous carbon particle dispersion of the present application in the form of a liquid or a slurry are preferably 1 to 35% by weight.
The amount of the dispersant is 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight. When a plurality of dispersants are used, it is the total amount of the dispersants.

<<用途、使い方>>
こうして得られる本発明の多孔質炭素粒子及び多孔質炭素粒子分散体は、メソ孔を多く有する炭素質材料であることから、メソ孔を使用する用途に好適である。
しかも、そのまま使うのではなく、好ましい粒径に分散してあるため、均一であったり塗工性が良好である。
また、微細化してあるため、表面にメソ孔が多く有効活用できる。 << Usage and usage >>
Since the porous carbon particles and the porous carbon particle dispersion of the present invention thus obtained are carbonaceous materials having many mesopores, they are suitable for applications using mesopores.
Moreover, since it is not used as it is but dispersed in a preferable particle size, it is uniform and has good coatability.
Moreover, since it is miniaturized, many mesopores can be effectively used on the surface.

各種の用途に使用できる。例えば、本発明の分散体を、電極活物資、バインダーと混合して電極を形成する。あるいは、本発明の粒子を、ヒートポンプの吸着器に収容し、気相の熱媒を吸着及び脱着する吸着剤として用いる。あるいは各種の乾燥装置に充填して吸着剤として用いる。あるいは、生化学解析用ユニットの吸着性領域に充填してタンパク質分離に用いる等、様々な用途に有用である。より具体的には、例えば本発明の多孔質炭素粒子分散体を、バインダーと混合して、シート状に加工してフィルターを製造する、本発明の多孔質炭素粒子分散体を、カーボンブラックと、バインダー(ポリテトラフルオロエチレン粉末等)と混錬・ペースト化して、シート状に加工して電気二重層キャパシタ電極を製造する、本発明の多孔質炭素粒子分散体を、活物質、導電材、及びバインダー(ポリフッ化ビニリデン等)と混錬・ペースト化し、シート状に加工してリチウムイオン電池電極を製造する等である。 Can be used for various purposes. For example, the dispersion of the present invention is mixed with an electrode active material and a binder to form an electrode. Alternatively, the particles of the present invention are housed in an adsorber of a heat pump and used as an adsorbent for adsorbing and desorbing the heat medium of the gas phase. Alternatively, it is filled in various drying devices and used as an adsorbent. Alternatively, it is useful for various purposes such as filling the adsorptive region of a biochemical analysis unit and using it for protein separation. More specifically, for example, the porous carbon particle dispersion of the present invention is mixed with a binder and processed into a sheet to produce a filter. The porous carbon particle dispersion of the present invention, which is kneaded and pasted with a binder (polytetrafluoroethylene powder, etc.) and processed into a sheet to produce an electric double-layer capacitor electrode, is used as an active material, a conductive material, and a conductive material. It is kneaded and pasted with a binder (polyfluoride vinylidene, etc.) and processed into a sheet to manufacture a lithium ion battery electrode.

実施例１
市販の多孔質炭素材料（平均細孔径３．６９２ｎｍ、全細孔容積０．６０ｍｌ／ｇ、比表面積６５０ｍ２／ｇ）を５．０重量部、市販のポリビニルピロリドンを１．０重量部、市販の銅フタロシアニン誘導体を０．２重量部、イソプロピルアルコールを９３．８重量部添加し、ビーズミルを用いて分散処理して分散液を得た。
分散処理方法は、処理中の液を取り出し、平均細孔径を測定して８．８２ｎｍになった所で、分散処理を終了した。
得られた分散液中の多孔質炭素粒子の物性値を測定し、結果を表１に示す。 Example 1
5.0 parts by weight of a commercially available porous carbon material (average pore diameter 3.692 nm, total pore volume 0.60 ml / g, specific surface area 650 m 2 / g), 1.0 part by weight of commercially available polyvinylpyrrolidone, commercially available 0.2 parts by weight of the copper phthalocyanine derivative and 93.8 parts by weight of isopropyl alcohol were added, and the dispersion treatment was carried out using a bead mill to obtain a dispersion liquid.
In the dispersion treatment method, the liquid being treated was taken out, the average pore diameter was measured, and the dispersion treatment was completed when the average pore size was 8.82 nm.
The physical characteristics of the porous carbon particles in the obtained dispersion were measured, and the results are shown in Table 1.

実施例２
平均粒子径が８．８２ｎｍになったところで分散処理を終了せず、１１．０ｎｍになったところまで継続し、そこで分散処理を終了した以外は、実施例１と同様の操作を行い、分散液を得た。 Example 2
The dispersion treatment was not completed when the average particle size reached 8.82 nm, but continued until the average particle size reached 11.0 nm, and the same operation as in Example 1 was performed except that the dispersion treatment was completed there. Got

比較例１
実施例１及び２で用いた市販の多孔質炭素材料５．０重量部を分散処理混合撹拌することなく、イソプロピルアルコール９３．８重量部に配合し、軽く手で振って混合した。 Comparative Example 1
5.0 parts by weight of the commercially available porous carbon material used in Examples 1 and 2 was added to 93.8 parts by weight of isopropyl alcohol without dispersion treatment, mixing and stirring, and lightly shaken by hand to mix.

［表１］
原料多孔質炭素材料 実施例１ 実施例２
<粒子の細孔特性>
(1) 2.6-200nmピーク 31 24.3 91.0
(2) メソ孔細孔容積 - 0.67 1.17
(3) 比表面積 650 315 440
(4) 平均細孔径 3.692 8.82 11.0
(5) 全細孔容積 0.60 0.69 1.21
(6) T法マイクロ孔容積 - 0.066 0.071
(7) MP法マイクロ孔容積 - 0.090 0.086
(8) DA法細孔容積 0.25 0.12 0.16
(2)／(6) - 10.15 17.73
<液物性>
D10 1.23 0.33
D50 2.84 0.86
D90 5.99 1.36
粘度 11.136 249.6 [Table 1]
Raw Material Porous Carbon Material Example 1 Example 2
<Pore characteristics of particles>
(1) 2.6-200nm peak 31 24.3 91.0
(2) Mesopore pore volume --0.67 1.17
(3) Specific surface area 650 315 440
(4) Average pore diameter 3.692 8.82 11.0
(5) Total pore volume 0.60 0.69 1.21
(6) T method micropore volume --0.066 0.071
(7) MP method micropore volume --0.090 0.086
(8) DA method Pore volume 0.25 0.12 0.16
(2) / (6) --10.15 17.73
<Liquid characteristics>
D10 1.23 0.33
D50 2.84 0.86
D90 5.99 1.36
Viscosity 11.136 249.6

表中、粘度の測定はコーンプレート型粘度計（東機産業社製 RE-115R）を用いて行った。
分散粒径（D10、D50及びD90）の測定はレーザー回折・散乱法（日機装社製 マイクロトラックBlueraytrac）を用いて行った。 In the table, the viscosity was measured using a cone plate type viscometer (RE-115R manufactured by Toki Sangyo Co., Ltd.).
The dispersed particle size (D10, D50 and D90) was measured by the laser diffraction / scattering method (Microtrac Blueraytrac manufactured by Nikkiso Co., Ltd.).

実施例１の粒子は、原料多孔質炭素材料に比べ、比表面積は半分以下に抑えられているにもかかわらず、全細孔容積は維持され若干増加している。また2.6-200nmピークはメソ孔領域に保たれかつマイクロ孔領域の細孔の容積が減少していることからメソ孔領域の細孔が増加していることがわかる。
また、実施例２の粒子は実施例１の粒子よりも比表面積が増加しているが、原料多孔質炭素材料に比べれば３分の２弱である。また液物性は粘度が低く扱いやすく、粒径が揃っていて安定であることがわかる。 Although the specific surface area of the particles of Example 1 is suppressed to less than half as compared with the raw material porous carbon material, the total pore volume is maintained and slightly increased. In addition, the 2.6-200 nm peak is maintained in the mesopore region and the volume of the pores in the micropore region is decreasing, indicating that the pores in the mesopore region are increasing.
The specific surface area of the particles of Example 2 is larger than that of the particles of Example 1, but it is less than two-thirds of that of the raw material porous carbon material. In addition, it can be seen that the liquid properties are low in viscosity and easy to handle, and the particle size is uniform and stable.

<メチレンブルー吸着テスト>
以上の実施例１、２及び比較例１の分散液を用い、以下の方法で細孔に染料(メチレンブルー)を吸着させ、脱色具合で有効な細孔の量を確認した。
(1) 分散液をバットに投入し、100℃で乾燥させ、多孔質炭素粉を準備した。
(2) MB(メチレンブルー)0.1%aqを調製し、20mLサンプラに10.00g入れた。
(3) (2)に(1)で用意した多孔質炭素粉を0.1000g入れ、超音波洗浄機にて手でふりながら30秒混ぜた。
(4) (3)を注射器で全量吸い、5μmのコマフィルターで多孔質炭素粉を除去した。
(5) (4)の除去後の液と(2)の外観を写真に撮った結果を図１に示す。
(6) 各々の液を１００倍希釈に調整して、紫外可視分光光度計UV-1850（島津製作所社製）を用いて波長が500〜800nmにおいての吸光度を測定した。セルは光路長10mmの角形セルを使用した。
(7) (6)の測定結果を表２に示す。(6)の測定結果のグラフを図２に示す。 <Methylene blue adsorption test>
Using the dispersions of Examples 1 and 2 and Comparative Example 1 above, the dye (methylene blue) was adsorbed on the pores by the following method, and the amount of effective pores was confirmed by the degree of decolorization.
(1) The dispersion was put into a vat and dried at 100 ° C to prepare a porous carbon powder.
(2) MB (methylene blue) 0.1% aq was prepared and 10.00 g was placed in a 20 mL sampler.
(3) In (2), 0.1000 g of the porous carbon powder prepared in (1) was added, and the mixture was mixed for 30 seconds while shaking by hand with an ultrasonic cleaner.
(4) The whole amount of (3) was sucked with a syringe, and the porous carbon powder was removed with a 5 μm coma filter.
(5) Fig. 1 shows the results of taking photographs of the liquid after removal of (4) and the appearance of (2).
(6) Each solution was adjusted to 100-fold dilution, and the absorbance at a wavelength of 500 to 800 nm was measured using an ultraviolet-visible spectrophotometer UV-1850 (manufactured by Shimadzu Corporation). The cell used was a square cell with an optical path length of 10 mm.
(7) Table 2 shows the measurement results of (6). The graph of the measurement result of (6) is shown in FIG.

[表２]
MB 比較例１ 実施例１ 実施例２
＠670nm" Abs 2.1321 0.0544 0.0038 1.787
x/MB 100.00% 2.55% 0.18% 83.81%
＠620nm" Abs 1.3084 0.0245 0.0018 1.0431
x/MB 100.00% 1.87% 0.14% 79.72%

図１からは実施例１の分散液は色素を良く吸着していることがわかる。また図２〜４からも、実施例１の分散液はメチレンブルーが示す６７０ｎｍ及び６２０ｎｍにおいて比較例１よりも吸光度が大幅に減少しており、色素を良く吸着していることがわかる。 [Table 2]
MB Comparative Example 1 Example 1 Example 2
@ 670nm "Abs 2.1321 0.0544 0.0038 1.787
x / MB 100.00% 2.55% 0.18% 83.81%
@ 620nm "Abs 1.3084 0.0245 0.0018 1.0431
x / MB 100.00% 1.87% 0.14% 79.72%

From FIG. 1, it can be seen that the dispersion liquid of Example 1 adsorbs the dye well. Further, from FIGS. 2 to 4, it can be seen that the dispersion liquid of Example 1 has a significantly reduced absorbance at 670 nm and 620 nm indicated by methylene blue as compared with Comparative Example 1, and adsorbs the dye well.

<SEM観察>
実施例１の分散液中の多孔質炭素粒子のSEM写真を図４に示す。実施例２の分散液中の多孔質炭素粒子のSEM写真を図５及び６に示す。これらの分散液の原料として用いた市販の多孔質炭素材料のSEM写真を図３に示す。
図５により多孔質炭素材料に細孔径１５〜４０nm程度の細孔が存在していることがわかる。
図６により実施例１の分散液では原料とした多孔質炭素材料中に存在していた細孔径１５〜４０nm程度の細孔がたくさん残っていることがわかる。これに対し図７及び８により実施例２の分散液では細孔径１５〜４０nm程度の細孔は全く残っていないことはないが、これらの細孔が分散工程により破砕された痕跡と思われる凹凸の存在が確認できる。このことから、実施例１の分散液は細孔径１５〜４０nm程度の細孔を活用する用途ではより好適であることが推測され、これがメチレンブルー吸着テストの結果にも表れていると推測される。 <SEM observation>
FIG. 4 shows an SEM photograph of the porous carbon particles in the dispersion liquid of Example 1. SEM photographs of the porous carbon particles in the dispersion liquid of Example 2 are shown in FIGS. 5 and 6. FIG. 3 shows an SEM photograph of a commercially available porous carbon material used as a raw material for these dispersions.
From FIG. 5, it can be seen that the porous carbon material has pores having a pore diameter of about 15 to 40 nm.
From FIG. 6, it can be seen that in the dispersion liquid of Example 1, many pores having a pore diameter of about 15 to 40 nm, which were present in the porous carbon material used as a raw material, remain. On the other hand, according to FIGS. 7 and 8, in the dispersion liquid of Example 2, pores having a pore diameter of about 15 to 40 nm did not remain at all, but irregularities that seemed to be traces of these pores being crushed by the dispersion step. The existence of can be confirmed. From this, it is presumed that the dispersion liquid of Example 1 is more suitable for applications utilizing pores having a pore diameter of about 15 to 40 nm, and it is presumed that this is also reflected in the results of the methylene blue adsorption test.

Claims (7)

BJH法による吸着側の細孔直径ピークが2nm〜50nmの間に存在し、比表面積が１００〜６００ｍ２／ｇであり、かつBJH法による吸着側の2.6nm〜200nmの細孔容積が０．４ｍｌ／ｇ以上である多孔質炭素粒子。 The pore diameter peak on the adsorption side by the BJH method exists between 2 nm and 50 nm, the specific surface area is 100 to 600 m 2 / g, and the pore volume on the adsorption side by the BJH method is 2.6 nm to 200 nm. Porous carbon particles of 4 ml / g or more. BJH法による吸着側の細孔直径ピークが2nm〜50nmの間に存在し、比表面積が１００〜６００ｍ２／ｇであり、かつ全細孔容積が０．５〜１．３ｍｌ／ｇである多孔質炭素粒子。 Porousness with a pore diameter peak on the adsorption side between 2 nm and 50 nm by the BJH method, a specific surface area of 100 to 600 m 2 / g, and a total pore volume of 0.5 to 1.3 ml / g. Quality carbon particles. ｔ法によるミクロ細孔容積が０．０４〜０．１ｍｌである請求項１又は２記載の多孔質炭素粒子。 The porous carbon particles according to claim 1 or 2, wherein the micropore volume by the t method is 0.04 to 0.1 ml. 液中に請求項１〜３のいずれかに記載の多孔質炭素粒子を１〜３５重量％含有する多孔質炭素粒子分散体。 A porous carbon particle dispersion containing 1 to 35% by weight of the porous carbon particles according to any one of claims 1 to 3 in a liquid. 請求項４記載の多孔質炭素粒子分散体をバインダーと混合して、シート状に加工することを特徴とするフィルターの製造方法。 A method for producing a filter, which comprises mixing the porous carbon particle dispersion according to claim 4 with a binder and processing the mixture into a sheet. 請求項４記載の多孔質炭素粒子分散体を、カーボンブラックと、バインダーと混錬・ペースト化して、シート状に加工することを特徴とする電気二重層キャパシタ電極の製造方法。 A method for producing an electric double layer capacitor electrode, which comprises kneading / pasting the porous carbon particle dispersion according to claim 4 with carbon black and a binder to form a sheet. 請求項４記載の多孔質炭素粒子分散体を、活物質、導電材、及びバインダーと混錬・ペースト化して、シート状に加工することを特徴とするリチウムイオン電池電極の製造方法。 A method for producing a lithium ion battery electrode, which comprises kneading / pasting the porous carbon particle dispersion according to claim 4 with an active material, a conductive material, and a binder to form a sheet.
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