JP2012166980A - Synthetic method of carbide-derived carbon - Google Patents

Synthetic method of carbide-derived carbon Download PDF

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JP2012166980A
JP2012166980A JP2011029140A JP2011029140A JP2012166980A JP 2012166980 A JP2012166980 A JP 2012166980A JP 2011029140 A JP2011029140 A JP 2011029140A JP 2011029140 A JP2011029140 A JP 2011029140A JP 2012166980 A JP2012166980 A JP 2012166980A
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carbide
solution
cdc
derived carbon
phase material
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Chunfeng Hu
ショーフェン フ
Yoshio Sakka
義雄 目
Mishra Mrinalini
ムリナリニ ミシュラ
Salvatore Grasso
サルバトーレ グラッソ
Hidehiko Tanaka
英彦 田中
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National Institute for Materials Science
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National Institute for Materials Science
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Abstract

PROBLEM TO BE SOLVED: To synthesize carbide-derived carbon (CDC) in an environment-friendly mode under a mild condition.SOLUTION: The CDC is produced by etching selectively M and A elements in Mn+1AXphase (n=1, 2 or 3), wherein M is a transition metal, A is a group A element, and X is carbon. A produced CDC has a turbostratic microstructure, or various kinds of barrel-shaped, ribbon-shaped, onion-shaped or bar-shaped forms. Since this process does not use chlorine gas, it is by far environment-friendly in comparison with a process depending on a conventional technology.

Description

本発明はカーバイド誘導炭素（ＣＤＣ）の合成方法に関し、特に液相中でカーバイドから他の元素を除去することによってＣＤＣを合成する方法に関する。   The present invention relates to a method for synthesizing carbide-derived carbon (CDC), and more particularly to a method for synthesizing CDC by removing other elements from carbide in a liquid phase.

大きな比表面積を持ち、またナノサイズの細孔を有することによって、ナノポーラス炭素には濾過、ガス分離、ガス蓄積、及び電気化学分野への応用の可能性が見出されている。カーバイド誘導炭素（ＣＤＣ）は、他の多孔質炭素材料に比較して、調節可能かつ狭い細孔サイズ分布を有することが確認されている。通常、ＣＤＣは４００℃〜１２００℃の高温での塩素化プロセスによって製造される。炭素以外の元素は塩素との反応によってカーバイドから選択的にエッチングされる。その結果、得られたＣＤＣは元のカーバイドの形態を保持している。今日まで、ＳｉＣ、ＴｉＣ等の二元系のカーバイドやＴｉ３ＳｉＣ２、Ｔｉ２ＡｌＣ等の三元系のカーバイドを使用して成功裏にＣＤＣを作成することができた。しかし、塩素ガスは有毒で環境を汚染しやすいことが知られている。従って、環境にやさしい条件下でＣＤＣを製造する新規な方法を見出すことが緊急に必要とされている。 By having a large specific surface area and nano-sized pores, nanoporous carbon has been found to have potential applications in the fields of filtration, gas separation, gas accumulation, and electrochemical. Carbide derived carbon (CDC) has been confirmed to have a tunable and narrow pore size distribution compared to other porous carbon materials. CDC is usually produced by a chlorination process at a high temperature of 400 ° C to 1200 ° C. Elements other than carbon are selectively etched from the carbide by reaction with chlorine. As a result, the obtained CDC retains its original carbide form. To date, CDCs have been successfully created using binary carbides such as SiC and TiC, and ternary carbides such as Ti 3 SiC 2 and Ti 2 AlC. However, it is known that chlorine gas is toxic and easily pollutes the environment. Accordingly, there is an urgent need to find a new method for producing CDC under environmentally friendly conditions.

本発明の課題は、穏やかな条件の下で環境にやさしい態様でＣＤＣを製造する方法を提供することである。      The object of the present invention is to provide a method for producing CDC in an environmentally friendly manner under mild conditions.

本発明の一側面によれば、以下のステップを有するカーバイド誘導炭素の合成方法が与えられる：Ｍを早期遷移元素、ＡをＡ族元素、ＸをＣ、またｎ＝１〜３とするとき、組成式Ｍｎ＋１ＡＸｎで表されるＭＡＸ相材料を準備し、前記ＭＡＸ相材料を酸またはアルカリ溶液中に保持して、前記ＭＡＸ相材料から前記早期遷移元素及びＡ族元素を除去する。
前記早期遷移元素はＴｉ、Ｖ、Ｃｒ、Ｎｂ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｏ及びＳｃからなる群から選択してよい。
前記Ａ族元素はＡｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｐ、Ｓ、Ｇａ、Ａｓ、Ｃｄ、Ｉｎ、Ｔｌ及びＳｉからなる群から選択してよい。
前記ＭＡＸ相材料はＮｂ４ＡｌＣ３及びＴｉ３ＳｉＣ２からなる群から選択してよい。
前記ＭＡＸ相材料は０℃〜２００℃の範囲内で１〜６００時間、前記溶液中に保持してよい。
前記溶液はＮａＯＨ、ＫＯＨ、ＨＣｌ、Ｈ２ＳＯ４及びＨＮＯ３からなる群から選択された１つまたは複数の物質の溶液であってよい。
前記溶液の濃度は０．１〜２ｍｏｌ／Ｌの範囲であってよい。
前記ＭＡＸ相材料と前記溶液との質量比は１／５０〜１／５００の範囲であってよい。
前記方法は前記ＭＡＸ相材料を前記溶液中に保持する前記ステップの後に更に前記溶液のｐＨの値を７に変更するステップを含んでよい。
前記ＭＡＸ相材料はバルクまたは粉末の形態であってよい。 According to one aspect of the present invention, there is provided a method for synthesizing a carbide-derived carbon having the following steps: when M is an early transition element, A is a group A element, X is C, and n = 1-3, A MAX phase material represented by a composition formula M n + 1 AX n is prepared, and the MAX phase material is held in an acid or alkaline solution to remove the early transition element and the group A element from the MAX phase material.
The early transition element may be selected from the group consisting of Ti, V, Cr, Nb, Ta, Zr, Hf, Mo and Sc.
The group A element may be selected from the group consisting of Al, Ge, Sn, Pb, P, S, Ga, As, Cd, In, Tl, and Si.
The MAX phase material may be selected from the group consisting of Nb 4 AlC 3 and Ti 3 SiC 2 .
The MAX phase material may be kept in the solution for 1 to 600 hours in the range of 0 ° C to 200 ° C.
The solution may be a solution of one or more substances selected from the group consisting of NaOH, KOH, HCl, H 2 SO 4 and HNO 3 .
The concentration of the solution may be in the range of 0.1 to 2 mol / L.
The mass ratio between the MAX phase material and the solution may be in the range of 1/50 to 1/500.
The method may further include changing the pH value of the solution to 7 after the step of retaining the MAX phase material in the solution.
The MAX phase material may be in bulk or powder form.

本発明による方法は塩素ガスを使用せず、またその廃液は中性であるため、その環境負荷は上で説明した従来技術による方法よりもはるかに低い。   Since the method according to the invention does not use chlorine gas and its waste liquid is neutral, its environmental burden is much lower than the prior art methods described above.

ＮａＯＨ溶液中でＮｂ４ＡｌＣ３粉末から合成されたカーバイド誘導炭素（ＣＤＣ）の高分解能透過型電子顕微鏡（ＨＲＴＥＭ）写真。（ａ）凝集したＣＤＣ、（ｂ）乱層構造ＣＤＣ、（ｃ）樽状ＣＤＣ、（ｄ）リボン状ＣＤＣ、（ｅ）玉葱状ＣＤＣ、（ｆ）棒状ＣＤＣ。High resolution transmission electron microscope (HRTEM) photograph of carbide derived carbon (CDC) synthesized from Nb 4 AlC 3 powder in NaOH solution. (A) Aggregated CDC, (b) Turbulent structure CDC, (c) Barrel-shaped CDC, (d) Ribbon-shaped CDC, (e) Onion-shaped CDC, (f) Rod-shaped CDC. ＮａＯＨ溶液中でＮｂ４ＡｌＣ３粒子を分解して得られたＣＤＣのＨＲＴＥＭ写真。（ａ）ＣＤＣ粒子とＮｂ４ＡｌＣ３粒子の共存状態、（ｂ）ＣＤＣ粒子とＮｂ４ＡｌＣ３粒子との間の境界の拡大写真。HRTEM photograph of CDC obtained by decomposing Nb 4 AlC 3 particles in NaOH solution. (A) Coexistence state of CDC particles and Nb 4 AlC 3 particles, (b) An enlarged photograph of the boundary between CDC particles and Nb 4 AlC 3 particles. ＨＣｌ溶液中でＮｂ４ＡｌＣ３粉末から製造されたＣＤＣのＨＲＴＥＭ写真。（ａ）乱層構造ＣＤＣ、（ｂ）樽状ＣＤＣ、（ｃ）リボン状ＣＤＣ、（ｄ）棒状ＣＤＣ。HRTEM photograph of CDC made from Nb 4 AlC 3 powder in HCl solution. (A) Turbulent structure CDC, (b) barrel-shaped CDC, (c) ribbon-shaped CDC, (d) rod-shaped CDC. ＮａＯＨ溶液中でＴｉ３ＳｉＣ２粉末から製造されたＣＤＣのＨＲＴＥＭ写真。（ａ）リボン状ＣＤＣ、（ｂ）樽状ＣＤＣ、（ｃ）チューブ状ＣＤＣ、（ｄ）針の孔状(needle eye-like)ＣＤＣ。HRTEM photograph of CDC made from Ti 3 SiC 2 powder in NaOH solution. (A) Ribbon-shaped CDC, (b) Barrel-shaped CDC, (c) Tube-shaped CDC, (d) Needle eye-like CDC. Ｎｂ４ＡｌＣ３前駆体及びＴｉ３ＳｉＣ２前駆体から得られたカーバイド誘導炭素についてのラマンスペクトル。Raman spectra for carbide-derived carbon obtained from Nb 4 AlC 3 precursor and Ti 3 SiC 2 precursor.

本発明の発明者は、ＭＡＸ相中のＭ元素及びＡ元素（Ｍは遷移金属、ＡはＡ族元素、Ｘは炭素）が化学反応により酸性溶液または塩基溶液中に溶け出し、残存した炭素がＣＤＣとして形成され得ることを見出した。この知見に基づき、本願発明者は以下に説明するように本発明を完成したものである。   The inventor of the present invention is that the M element and the A element in the MAX phase (M is a transition metal, A is a group A element, and X is carbon) are dissolved into an acidic solution or a base solution by a chemical reaction, and the remaining carbon is It has been found that it can be formed as a CDC. Based on this knowledge, the present inventor has completed the present invention as described below.

本発明は溶液中でカーバイド誘導炭素（ＣＤＣ）を製造する方法をサポートする。その出発物質は、Ｍを遷移金属、ＡをＡ族元素、Ｘを炭素とし、またｎを１〜３とするとき、組成式Ｍｎ＋１ＡＸｎで表されるＭＡＸ相材料である。本発明は以下の合成ステップを含む。 The present invention supports a method for producing carbide derived carbon (CDC) in solution. The starting material is a MAX phase material represented by a composition formula M n + 1 AX n where M is a transition metal, A is a group A element, X is carbon, and n is 1 to 3. The present invention includes the following synthesis steps.

（ａ）ＭＡＸ相材料を秤量する。ＭＡＸ相材料は大きな塊でもよいし、粉末でも良い。 (A) Weigh MAX phase material. The MAX phase material may be a large mass or a powder.

（ｂ）酸性溶液あるいは塩基溶液を準備する。溶液中の酸あるいはアルカリの好ましい濃度は０．１〜２ｍｏｌ／Ｌであり、より好ましくは０．１〜１ｍｏｌ／Ｌである。溶媒として脱イオン水を使用する。 (B) Prepare an acidic solution or a base solution. A preferred concentration of acid or alkali in the solution is 0.1 to 2 mol / L, more preferably 0.1 to 1 mol / L. Deionized water is used as the solvent.

（ｃ）ＭＡＸ相材料を溶液中に入れる。ＭＡＸ相材料と溶液との質量比は、好ましくは１／５００〜１／５０の範囲であり、より好ましくは１／５００〜１／２００である。 (C) Place the MAX phase material into the solution. The mass ratio between the MAX phase material and the solution is preferably in the range of 1/500 to 1/50, more preferably 1/500 to 1/200.

（ｄ）温度を適切な値に設定してそれを好ましくは１〜６００時間、より好ましくは３００〜６００時間、一層好ましくは約３６０時間、保持する。使用する温度は好ましくは０℃〜２００℃、更に好ましくは２０℃〜１００℃、一層好ましくは２５℃である。 (D) Set the temperature to a suitable value and hold it preferably for 1 to 600 hours, more preferably 300 to 600 hours, more preferably about 360 hours. The temperature used is preferably 0 ° C to 200 ° C, more preferably 20 ° C to 100 ° C, and even more preferably 25 ° C.

（ｅ）溶液のｐＨ値を７に変化させてもよい。これは環境汚染を防止するためである。そして、処理されたＭＡＸ相材料を溶液から濾過により分離する。製造された直後の試料を脱イオン水にて例えば３〜５回洗浄する。 (E) The pH value of the solution may be changed to 7. This is to prevent environmental pollution. The treated MAX phase material is then separated from the solution by filtration. The sample immediately after being manufactured is washed with deionized water, for example, 3 to 5 times.

（ｆ）試料を空気中で乾燥してそれを清浄なガラス瓶中に入れる。 (F) Dry the sample in air and place it in a clean glass bottle.

上述のプロセスを用い、酸あるいは塩基溶液を使用してＭＡＸ相材料中のＭ元素及びＡ元素のエッチングによってＣＤＣを合成する。残留した炭素はＣＤＣを形成する。   Using the process described above, CDC is synthesized by etching of M element and A element in the MAX phase material using an acid or base solution. Residual carbon forms CDC.

以下の例はＭＡＸ相材料と溶液の各種の組合せによりカーバイド誘導炭素を製造することについて説明している。合成条件を変更してもＣＤＣの形成には影響しないと考えられる。   The following examples illustrate the production of carbide-derived carbon from various combinations of MAX phase materials and solutions. It is considered that changing the synthesis conditions does not affect the formation of CDC.

しかしながら、本発明は本明細書中で説明したものだけに限定されないことに注意しなければならない。本発明の技術的範囲は特許請求の範囲に基づいて定められる。   However, it should be noted that the present invention is not limited to what has been described herein. The technical scope of the present invention is defined based on the claims.

例えば、本発明に使用可能なＭＡＸ相材料は、早期遷移金属であるＴｉ、Ｖ、Ｃｒ、Ｎｂ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｏ及びＳｃから選択した少なくとも一つの元素を含むような多様なＭＡＸ相材料とすることができる。このようなＭＡＸ相材料としては例えばＮｂ４ＡｌＣ３及びＴｉ３ＳｉＣ２がある。酸性あるいはアルカリ性溶液に使用可能な酸及びアルカリとしては、これに限定するものではないが、ＮａＯＨ、ＫＯＨ、ＨＣｌ、Ｈ２ＳＯ４及びＨＮＯ３などが挙げられ、これらのうちでＮａＯＨ及びＨＣｌが好ましい。溶液を作成するため、これらの物質は単独であるいは組み合わせて使用される。 For example, the MAX phase material that can be used in the present invention includes various MAX phases including at least one element selected from Ti, V, Cr, Nb, Ta, Zr, Hf, Mo, and Sc, which are early transition metals. Can be a material. Examples of such a MAX phase material include Nb 4 AlC 3 and Ti 3 SiC 2 . Acids and alkalis that can be used in acidic or alkaline solutions include, but are not limited to, NaOH, KOH, HCl, H 2 SO 4 and HNO 3 , among which NaOH and HCl are preferred. . These materials are used alone or in combination to make a solution.

［実験１］
Ｎｂ４ＡｌＣ３を出発材料として使用し、カーバイド誘導炭素を製造した。０．１ｇのＮｂ４ＡｌＣ３粉末を秤量して２０ｍｌのＮａＯＨ溶液（１．０ｍｏｌ／Ｌ）に投入した。平均粒子サイズは０．９１μｍであった。１００ｍｌのプラスチック瓶を容器として使用した。粉末と溶液の入った瓶を２５℃で３６０時間保持した。溶液のｐＨ値を７に変更したあと、粉末を濾過によって分離し、脱イオン水で３回洗浄した。その後、粉末を空気中で乾燥して透過型電子顕微鏡（ＴＥＭ）により調べた。図１は製造されたカーバイド誘導炭素の高分解能透過型電子顕微鏡（ＨＲＴＥＭ）写真を示す。Ｎｂ４ＡｌＣ３粒子はエッチングされ、凝集したＣＤＣを形成したことがわかる（図１（ａ））。出来上がったＣＤＣの拡大像である図１（ｂ）〜（ｆ）は、上のようにして合成されたＣＤＣの各所に観察することができる乱層構造、樽状、リボン状、玉葱状及び棒状の微細構造等の形態を示している。これらの黒鉛状炭素の構造は多壁ナノチューブと同様に粒子の縁でねじれている。原子層同士の間隔は約０．３４ｎｍであった。また、エッチング過程は、図２に示すように外側から内側へ進行することがわかる。図２（ａ）では、外側の層は規則的な炭素であり、中間層はアモルファス炭素、つまり規則性のない炭素であるのに対して、中心部はＮｂ４ＡｌＣ３粒からできている。Ｎｂ４ＡｌＣ３粒子は最初エッチングされて規則性のない炭素（図２（ｂ））となり、次にこのアモルファス炭素が変化して規則性のある炭素になったと結論付けられる。更に、ラマン解析（図５中のカーブ（ａ））によれば、得られたままの状態のＣＤＣは１３５０ｃｍ−１（Ｄバンド）及び１５９０ｃｍ−１（Ｇバンド）の２つのバンドを示すが、これは欠陥のある不規則な微細構造を表している。 [Experiment 1]
Nb 4 AlC 3 was used as a starting material to produce carbide derived carbon. 0.1 g of Nb 4 AlC 3 powder was weighed and put into 20 ml of NaOH solution (1.0 mol / L). The average particle size was 0.91 μm. A 100 ml plastic bottle was used as the container. The bottle containing the powder and solution was held at 25 ° C. for 360 hours. After changing the pH value of the solution to 7, the powder was separated by filtration and washed 3 times with deionized water. Thereafter, the powder was dried in air and examined with a transmission electron microscope (TEM). FIG. 1 shows a high-resolution transmission electron microscope (HRTEM) photograph of the manufactured carbide-derived carbon. It can be seen that the Nb 4 AlC 3 particles were etched to form aggregated CDC (FIG. 1 (a)). FIGS. 1B to 1F, which are enlarged images of the completed CDC, are a turbulent layer structure, barrel shape, ribbon shape, onion shape, and rod shape that can be observed in various places of the CDC synthesized as described above. The form of the fine structure etc. is shown. These graphitic carbon structures are twisted at the edges of the particles, similar to multi-walled nanotubes. The distance between the atomic layers was about 0.34 nm. It can also be seen that the etching process proceeds from the outside to the inside as shown in FIG. In FIG. 2A, the outer layer is regular carbon, and the intermediate layer is amorphous carbon, that is, non-regular carbon, whereas the central portion is made of Nb 4 AlC 3 grains. It can be concluded that the Nb 4 AlC 3 particles were first etched to become non-ordered carbon (FIG. 2 (b)), and then this amorphous carbon changed to become regular carbon. Furthermore, according to the Raman analysis (curve in FIG. 5 (a)), but the CDC state as obtained shows two bands of 1350 cm -1 (D band) and 1590 cm -1 (G band), This represents a defective irregular microstructure.

［実験２］
Ｎｂ４ＡｌＣ３を出発材料として使用し、カーバイド誘導炭素を製造した。０．１ｇのＮｂ４ＡｌＣ３粉末を秤量して４０ｍｌのＨＣｌ溶液（０．１ｍｏｌ／Ｌ）に投入した。平均粒子サイズは０．９１μｍであった。１００ｍｌのプラスチック瓶を容器として使用した。粉末と溶液の入った瓶を２５℃で３６０時間保持した。溶液のｐＨ値を７に変更した後、粉末を濾過によって分離し、脱イオン水で３回洗浄した。処理された粉末をＨＲＴＥＭを使用して調べることで、乱層構造、樽状、リボン状及び棒状のＣＤＣが存在することが観察された（図３（ａ）〜（ｄ））。原子層同士の間隔は約０．３４ｎｍであった。ラマン解析に基づいて、Ｄバンド（１３５０ｃｍ−１）及びＧバンド（１５９０ｃｍ−１）が確認された（図５中のカーブ（ｂ））。この結果はＣＤＣの欠陥のある不規則な微細構造を示している。 [Experiment 2]
Nb 4 AlC 3 was used as a starting material to produce carbide derived carbon. 0.1 g of Nb 4 AlC 3 powder was weighed and put into 40 ml of HCl solution (0.1 mol / L). The average particle size was 0.91 μm. A 100 ml plastic bottle was used as the container. The bottle containing the powder and solution was held at 25 ° C. for 360 hours. After changing the pH value of the solution to 7, the powder was separated by filtration and washed 3 times with deionized water. By examining the treated powder using HRTEM, it was observed that a CDC in a turbulent structure, barrel shape, ribbon shape and rod shape was present (FIGS. 3A to 3D). The distance between the atomic layers was about 0.34 nm. Based on the Raman analysis, D-band (1350 cm -1) and G band (1590 cm -1) was confirmed (the curve in Figure 5 (b)). This result shows an irregular microstructure with CDC defects.

［実験３］
Ｔｉ３ＳｉＣ２を出発材料として使用し、カーバイド誘導炭素を合成した。０．１ｇのＴｉ３ＳｉＣ２を秤量して２０ｍｌのＮａＯＨ溶液（１．０ｍｏｌ／Ｌ）に投入した。平均粒子サイズは０．３６μｍであった。１００ｍｌのプラスチック瓶を容器として使用した。粉末と溶液の入った瓶を２５℃で３６０時間保持した。溶液のｐＨ値を７に変更して濾過した後、処理された粉末を脱イオン水を使って３回洗浄した。この粉末をＨＲＴＥＭによって調べた。図４（ａ）〜（ｄ）はＣＤＣの顕微鏡写真を示す。明らかに、ナノ構造の炭素が見出され、このカーボンはリボン状、樽状、チューブ状及び針の孔状の形態を示している。２つの原子層同士の距離は約０．３４ｎｍであった。更に、ラマン解析により、図５のカーブ（ｃ）が示すようにＤバンド（１３５０ｃｍ−１）及びＧバンド（１５６７ｃｍ−１）が確認されたことで、ＣＤＣの欠陥のある不規則な微細構造の存在が示される。 [Experiment 3]
Carbide-derived carbon was synthesized using Ti 3 SiC 2 as a starting material. 0.1 g of Ti 3 SiC 2 was weighed and put into 20 ml of NaOH solution (1.0 mol / L). The average particle size was 0.36 μm. A 100 ml plastic bottle was used as the container. The bottle containing the powder and solution was held at 25 ° C. for 360 hours. After changing the pH value of the solution to 7 and filtering, the treated powder was washed 3 times with deionized water. This powder was examined by HRTEM. 4 (a) to 4 (d) show photomicrographs of CDC. Clearly, nanostructured carbon is found, which shows ribbon, barrel, tube and needle hole morphology. The distance between the two atomic layers was about 0.34 nm. Further, the Raman analysis, that D band (1350 cm -1) and G band (1567cm -1) was observed as shown by curve (c) in FIG. 5, the irregular microstructure with defects of CDC Existence is indicated.

カーバイド誘導炭素合成方法には実施に当たって多様な変更及び修正を行うことが可能となることを指摘しなければならない。このような変更及び修正は本発明の精神及び範囲を超えるものではなく、またそれに伴う効果を失わせるものでもない。従って、そのような全ての変更及び修正は添付の特許請求の範囲に包含される。   It should be pointed out that various changes and modifications can be made in the implementation of the carbide-derived carbon synthesis method. Such changes and modifications do not depart from the spirit and scope of the present invention and do not impair the attendant effects. Accordingly, all such changes and modifications are included within the scope of the appended claims.

上で説明したように、本発明は穏やかな条件下で塩素ガスなしでＣＤＣを合成する方法を提供するので、従来技術の方法によるＣＤＣの製造が引き起こす環境負荷を低減することができる。   As explained above, the present invention provides a method for synthesizing CDC under mild conditions and without chlorine gas, thus reducing the environmental burden caused by the production of CDC by prior art methods.

米国公開特許２００９／０２５８７８２Ａ１US Published Patent Application 2009 / 0258782A1 米国公開特許２００９／０３０１９０２Ａ１US Published Patent 2009 / 0301902A1 米国特許７，７４４，８４３US Patent 7,744,843

Y. Gogotsi et al., “Nanoporous Carbide-derived Carbon with Tunable Pore Size”, Nature Mater., 2: 591-4 (2003).Y. Gogotsi et al., “Nanoporous Carbide-derived Carbon with Tunable Pore Size”, Nature Mater., 2: 591-4 (2003). J. Chmiola et al., “Monolithic Carbide-derived Carbon Films for Micro-supercapacitors”, Science, 328: 480-3 (2010).J. Chmiola et al., “Monolithic Carbide-derived Carbon Films for Micro-supercapacitors”, Science, 328: 480-3 (2010). E. Urones-Garrote et al., “Electron Microscopy Study of Porous Carbide-derived Carbons Obtained from B4C”, J. Argentine Chem. Soc., 97: 13-24 (2009).E. Urones-Garrote et al., “Electron Microscopy Study of Porous Carbide-derived Carbons Obtained from B4C”, J. Argentine Chem. Soc., 97: 13-24 (2009). E. N. Hoffman et al., “Synthesis of Carbide-derived Carbon by Chlorination of Ti2AlC”, Chem. Mater., 17: 2317-22 (2005).E. N. Hoffman et al., “Synthesis of Carbide-derived Carbon by Chlorination of Ti2AlC”, Chem. Mater., 17: 2317-22 (2005). S. -H. Yeon et al., “Enhanced Volumetric Hydrogen and Methane Storage Capacity of Monolithic Carbide-derived Carbon”, Microporous and Mesoporous Mater., 131: 423-8 (2010).S. -H. Yeon et al., “Enhanced Volumetric Hydrogen and Methane Storage Capacity of Monolithic Carbide-derived Carbon”, Microporous and Mesoporous Mater., 131: 423-8 (2010). M. Kormann et al., “Processing of Carbide-derived Carbon (CDC) using Biomorphic Porous Titanium Carbide Ceramics”, J. Eur. Ceram. Soc., 28: 1297-1303 (2008).M. Kormann et al., “Processing of Carbide-derived Carbon (CDC) using Biomorphic Porous Titanium Carbide Ceramics”, J. Eur. Ceram. Soc., 28: 1297-1303 (2008).

Claims (10)

以下のステップ（ａ）及び（ｂ）を設けたカーバイド誘導炭素の合成方法。
（ａ）組成式Ｍｎ＋１ＡＸｎで表されるＭＡＸ相材料を準備する。ここでＭは早期遷移元素、ＡはＡ族元素、ＸはＣ、ｎ＝１〜３である。
（ｂ）前記ＭＡＸ相材料を酸またはアルカリ溶液中に保持して、前記ＭＡＸ相材料から前記早期遷移元素及びＡ族元素を除去する。 A method for synthesizing carbide-derived carbon provided with the following steps (a) and (b).
(A) A MAX phase material represented by a composition formula M n + 1 AX n is prepared. Here, M is an early transition element, A is a group A element, X is C, and n = 1 to 3.
(B) The MAX phase material is held in an acid or alkali solution to remove the early transition element and group A element from the MAX phase material. 前記早期遷移元素はＴｉ、Ｖ、Ｃｒ、Ｎｂ、Ｔａ、Ｚｒ、Ｈｆ、Ｍｏ及びＳｃからなる群から選択される、請求項１に記載のカーバイド誘導炭素の合成方法。   The method for synthesizing carbide-derived carbon according to claim 1, wherein the early transition element is selected from the group consisting of Ti, V, Cr, Nb, Ta, Zr, Hf, Mo, and Sc. 前記Ａ族元素はＡｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｐ、Ｓ、Ｇａ、Ａｓ、Ｃｄ、Ｉｎ、Ｔｌ及びＳｉからなる群から選択される、請求項１または２に記載のカーバイド誘導炭素の合成方法。   The method for synthesizing carbide-derived carbon according to claim 1 or 2, wherein the group A element is selected from the group consisting of Al, Ge, Sn, Pb, P, S, Ga, As, Cd, In, Tl, and Si. . 前記ＭＡＸ相材料はＮｂ４ＡｌＣ３及びＴｉ３ＳｉＣ２からなる群から選択される、請求項２または３に記載のカーバイド誘導炭素の合成方法。 The method for synthesizing carbide-derived carbon according to claim 2 or 3, wherein the MAX phase material is selected from the group consisting of Nb 4 AlC 3 and Ti 3 SiC 2 . 前記ＭＡＸ相材料を０℃〜２００℃の範囲内で１〜６００時間、前記溶液中に保持する、請求項１から４の何れかに記載のカーバイド誘導炭素の合成方法。   The method for synthesizing carbide-derived carbon according to any one of claims 1 to 4, wherein the MAX phase material is held in the solution within a range of 0 ° C to 200 ° C for 1 to 600 hours. 前記溶液はＮａＯＨ、ＫＯＨ、ＨＣｌ、Ｈ２ＳＯ４及びＨＮＯ３からなる群から選択された１つまたは複数の物質の溶液である、請求項１から５の何れかに記載のカーバイド誘導炭素の合成方法。 The synthesis of carbide-derived carbon according to any one of claims 1 to 5, wherein the solution is a solution of one or more substances selected from the group consisting of NaOH, KOH, HCl, H 2 SO 4 and HNO 3. Method. 前記溶液の濃度は０．１〜２ｍｏｌ／Ｌの範囲である、請求項１から６の何れかに記載のカーバイド誘導炭素の合成方法。   The method for synthesizing carbide-derived carbon according to any one of claims 1 to 6, wherein the concentration of the solution is in a range of 0.1 to 2 mol / L. 前記ＭＡＸ相材料と前記溶液との質量比は１／５０〜１／５００の範囲である、請求項１から７の何れかに記載のカーバイド誘導炭素の合成方法。   The method for synthesizing carbide-derived carbon according to any one of claims 1 to 7, wherein a mass ratio between the MAX phase material and the solution is in a range of 1/50 to 1/500. 前記ＭＡＸ相材料を前記溶液中に保持する前記ステップの後に更に前記溶液のｐＨの値を７に変更するステップを含む、請求項１から８の何れかに記載のカーバイド誘導炭素の合成方法。   The method for synthesizing a carbide-derived carbon according to any one of claims 1 to 8, further comprising a step of changing the pH value of the solution to 7 after the step of holding the MAX phase material in the solution. 前記ＭＡＸ相材料はバルクまたは粉末の形態である、請求項１から９の何れかに記載のカーバイド誘導炭素の合成方法。   The method for synthesizing carbide-derived carbon according to claim 1, wherein the MAX phase material is in a bulk or powder form.
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