JP2011195432A - Method for producing flaky graphite and flaky graphite - Google Patents
Method for producing flaky graphite and flaky graphite Download PDFInfo
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本発明は、薄片化黒鉛の製造方法及び薄片化黒鉛に関する。 The present invention relates to a method for producing exfoliated graphite and exfoliated graphite.
近年、炭素骨格を有し且つ形状異方性の高い物質として、黒鉛をその層面間で剥離し、層面（グラフェン）の重なりが数十層以下になるまで薄片化した薄片化黒鉛が注目されており、薄片化黒鉛は非常に大きな表面積を有するため、樹脂などと複合化すると、少量の薄片化黒鉛の添加で各種機能が発現すると期待されている。 In recent years, exfoliated graphite, which has a carbon skeleton and has high shape anisotropy, has been attracted attention by exfoliating graphite between its layer surfaces and exfoliating until the layer surface (graphene) overlaps to several tens of layers or less. Since exfoliated graphite has a very large surface area, it is expected that various functions will be manifested by adding a small amount of exfoliated graphite when combined with a resin or the like.
薄片化黒鉛の製造方法としては、例えば、特許文献１に、硫酸及び過マンガン酸カリウムを用いて酸化させた黒鉛層間化合物を精製し、遠心分離した後、上澄みを除去することによって薄片化黒鉛を製造する製造方法が開示されている。
As a method for producing exfoliated graphite, for example, in
特許文献２には、酸化グラファイトを急速加熱することにより酸化グラファイトを剥離する方法が提案されている。具体的な酸化方法として、濃硫酸、硝酸及び塩素酸カリウムを用いることが記載されている。 Patent Document 2 proposes a method of exfoliating graphite oxide by rapidly heating the graphite oxide. As a specific oxidation method, it is described that concentrated sulfuric acid, nitric acid and potassium chlorate are used.
しかしながら、特許文献１、２に記載の薄片化黒鉛の製造方法では、黒鉛が高度に剥離され且つ層面に沿った大きさが大きい薄片化黒鉛を製造することは困難であった。
However, in the method for producing exfoliated graphite described in
本発明は、層面同士の積層数の少なく且つ層面の面方向に沿った面積の大きい薄片化黒鉛を製造する薄片化黒鉛の製造方法及びこの製造方法によって得られた薄片化黒鉛を提供する。 The present invention provides a method for producing exfoliated graphite, which produces exfoliated graphite having a small number of laminated layer surfaces and a large area along the surface direction of the layer surfaces, and exfoliated graphite obtained by this production method.
本発明の薄片化黒鉛の製造方法は、黒鉛化合物を電気化学反応によって黒鉛層間化合物とし、この黒鉛層間化合物をその層面間において剥離することを特徴とする。 The method for producing exfoliated graphite of the present invention is characterized in that a graphite compound is converted into a graphite intercalation compound by an electrochemical reaction, and the graphite intercalation compound is peeled between the layer surfaces.
本発明において用いられる黒鉛化合物としては、黒鉛、膨張黒鉛の何れであってもよいが、層面間から剥離し易いので、膨張黒鉛が好ましい。なお、黒鉛に官能基が化学的に結合してしても、或いは、黒鉛に官能基が弱い相互作用により疑似的に結合していてもよい。 The graphite compound used in the present invention may be either graphite or expanded graphite, but expanded graphite is preferred because it is easily peeled from between the layer surfaces. Note that a functional group may be chemically bonded to graphite, or a functional group may be artificially bonded to graphite due to weak interaction.
黒鉛としては、粒子全体で単一の多層構造を有する黒鉛が好ましく、例えば、天然黒鉛、キッシュ黒鉛、高配向性熱分解黒鉛などが挙げられる。天然黒鉛とキッシュ黒鉛は、各層面（基本層）が略単一の方位を有する単独の結晶又はその集合体であり、高配向性熱分解黒鉛の各層面（基本層）は異なる方位を有する多数の小さな結晶の集合体である。 As the graphite, graphite having a single multilayer structure as a whole is preferable, and examples thereof include natural graphite, quiche graphite, and highly oriented pyrolytic graphite. Natural graphite and quiche graphite are single crystals or aggregates in which each layer surface (basic layer) has a substantially single orientation, and each layer surface (basic layer) of highly oriented pyrolytic graphite has many different orientations. It is an aggregate of small crystals.
膨張黒鉛としては従来公知のものが用いられる。膨張黒鉛の製造方法としては、公知の方法が用いられ、例えば、硫酸と硝酸との混合水溶液中に天然黒鉛を浸漬した後、天然黒鉛を混合水溶液から取り出して水洗して残余化合物とする。この残余化合物を急速加熱して、天然黒鉛の層面間に進入した化合物の分解によって天然黒鉛の層面間の間隔を拡げて天然黒鉛を膨張させる膨張黒鉛の製造方法などが挙げられる。なお、膨張黒鉛は圧延することによってシート状として用いてもよい。 Conventionally known expanded graphite is used. As a method for producing expanded graphite, a known method is used. For example, after immersing natural graphite in a mixed aqueous solution of sulfuric acid and nitric acid, the natural graphite is taken out from the mixed aqueous solution and washed with water to obtain a residual compound. Examples include a method for producing expanded graphite in which the residual compound is rapidly heated and the natural graphite is expanded by expanding the interval between the natural graphite layers by decomposing the compound that has entered between the natural graphite layers. The expanded graphite may be used as a sheet by rolling.
本発明の薄片化黒鉛の製造方法では、黒鉛化合物を電気化学反応によって黒鉛層間化合物とする。具体的には、図１に示したように、黒鉛化合物１を含む陽極２と、陰極３とを電解質水溶液４中に浸漬し、陽極と陰極との間に直流電源Ｖを用いて直流電圧を印加する。
In the method for producing exfoliated graphite of the present invention, the graphite compound is converted into a graphite intercalation compound by an electrochemical reaction. Specifically, as shown in FIG. 1, an anode 2 containing a
黒鉛化合物１を含む陽極としては、電極の一部に黒鉛化合物を用いた電極であっても、電極自体を黒鉛化合物から形成した電極であってもよいが、黒鉛化合物１を処理毎に交換する場合は、黒鉛化合物１の交換作業を効率良く行うことができるので、電極の一部に黒鉛化合物を用いた電極が好ましい。
The anode containing the
電極の一部に黒鉛化合物を用いた電極としては、電気分解の際に通常、陽極として用いられる電極の表面に黒鉛化合物のシートを接触させた状態に巻回し固定させてなる電極、電気分解の際に通常、陽極として用いられる電極の表面に黒鉛化合物を接触させた状態に電気絶縁性の粘着テープを用いて固着させてなる電極などが挙げられ、電極から黒鉛層間化合物を容易に離脱させることができるので、電気分解の際に通常、陽極として用いられる電極の表面に黒鉛化合物のシートを接触させた状態に巻回し固定させてなる電極が好ましい。なお、電気分解の際に陽極として用いられる電極としては、例えば、白金、ステンレスなどの金属が挙げられ、酸性電解質水溶液を用いる場合には、白金が好ましい。 As an electrode using a graphite compound as a part of an electrode, an electrode formed by winding and fixing a sheet of a graphite compound in contact with a surface of an electrode usually used as an anode during electrolysis, In general, an electrode that is fixed with an electrically insulating adhesive tape in a state in which the graphite compound is in contact with the surface of the electrode used as an anode, and the graphite intercalation compound can be easily detached from the electrode. Therefore, an electrode obtained by winding and fixing a sheet of a graphite compound in contact with the surface of an electrode used as an anode during electrolysis is preferable. In addition, as an electrode used as an anode in the case of electrolysis, metals, such as platinum and stainless steel, are mentioned, for example, When using acidic electrolyte aqueous solution, platinum is preferable.
なお、電極自体を黒鉛化合物から形成した電極は、黒鉛化合物のシート又は棒状体を電極として用いればよい。 In addition, the electrode which formed electrode itself from the graphite compound should just use the sheet | seat or rod-shaped body of a graphite compound as an electrode.
黒鉛化合物における層面の面方向に沿った面積は、小さいと、得られる薄片化黒鉛における層面の面方向に沿った大きさが小さくなることがあり、大きいと、黒鉛層間化合物をその層面間から剥離する際に、黒鉛層間化合物の層面が割れてしまい、得られる薄片化黒鉛の大きさがかえって小さくなることがあるので、５０〜２０００ｍｍ2が好ましい。 If the area along the surface direction of the layer surface in the graphite compound is small, the size along the surface direction of the layer surface in the exfoliated graphite obtained may be small. If it is large, the graphite intercalation compound will be peeled from between the layer surfaces. In doing so, the layer surface of the graphite intercalation compound is cracked, and the size of the exfoliated graphite obtained may be reduced, so 50 to 2000 mm 2 is preferable.
又、黒鉛化合物の厚みは、薄いと、黒鉛化合物の取扱性が低下することがあり、厚いと、黒鉛層間化合物の薄片化が困難となることがあるので、１０μｍ〜３ｍｍが好ましい。 Further, if the thickness of the graphite compound is thin, the handleability of the graphite compound may be lowered, and if it is thick, it may be difficult to make the graphite intercalation compound flakes, so 10 μm to 3 mm is preferable.
なお、黒鉛化合物における層面の面方向に沿った面積及び厚みとは、黒鉛化合物が粒子状である場合には、粒子状の黒鉛化合物における層面の面方向に沿った面積及び厚みをいい、黒鉛化合物がシート状である場合には、シートを構成している黒鉛化合物における層面の面方向に沿った面積及び厚みをいう。 In addition, the area and thickness along the surface direction of the layer surface in the graphite compound means the area and thickness along the surface direction of the layer surface in the particulate graphite compound when the graphite compound is in the form of particles. When is in the form of a sheet, it refers to the area and thickness along the plane direction of the layer surface in the graphite compound constituting the sheet.
又、黒鉛化合物における層面の面方向に沿った面積とは、黒鉛化合物の面積が最も大きくなる方向から見た時の黒鉛化合物の面積をいう。黒鉛化合物の厚みとは、黒鉛化合物の面積が最も大きくなる方向から見た時の黒鉛化合物の表面に対して直交する方向の黒鉛化合物の最大寸法をいう。 Moreover, the area along the surface direction of the layer surface in the graphite compound means the area of the graphite compound when viewed from the direction in which the area of the graphite compound becomes the largest. The thickness of the graphite compound refers to the maximum dimension of the graphite compound in a direction orthogonal to the surface of the graphite compound when viewed from the direction in which the area of the graphite compound is maximized.
なお、黒鉛化合物における層面の面方向に沿った面積は、ＦＥ−ＳＥＭを用いて測定することができ、ＳＥＭで観察した任意の１０視野に存在する全ての黒鉛化合物における層面の面方向に沿った面積を相加平均した値をいう。 In addition, the area along the surface direction of the layer surface in the graphite compound can be measured using the FE-SEM, and is along the surface direction of the layer surface in all the graphite compounds present in any 10 visual fields observed by the SEM. A value obtained by arithmetically averaging the areas.
又、黒鉛化合物の厚みは、ＦＥ−ＳＥＭ又はＡＦＭを用いて測定することができ、ＳＥＭ又はＡＦＭで観察した任意の１０視野に存在する全ての黒鉛化合物の厚みを相加平均した値をいう。 Moreover, the thickness of a graphite compound can be measured using FE-SEM or AFM, and means the value which carried out the arithmetic mean of the thickness of all the graphite compounds which exist in arbitrary 10 visual fields observed with SEM or AFM.
又、陰極としては、電気分解の際に陰極として用いられる電極であれば、特に限定されず、例えば、白金、ステンレスなどの金属が挙げられ、酸性電解質水溶液を用いる場合には、白金が好ましい。 Further, the cathode is not particularly limited as long as it is an electrode used as a cathode during electrolysis, and examples thereof include metals such as platinum and stainless steel, and platinum is preferable when an acidic electrolyte aqueous solution is used.
上記陽極及び上記陰極を浸漬させる電解質水溶液としては、特に限定されず、例えば、硝酸水溶液、硫酸水溶液、塩酸水溶液、酢酸水溶液、ホウ酸水溶液、蟻酸水溶液などの種々の無機酸及び有機酸が挙げられ、硝酸水溶液が好ましい。 The electrolyte aqueous solution in which the anode and the cathode are immersed is not particularly limited, and examples thereof include various inorganic acids and organic acids such as nitric acid aqueous solution, sulfuric acid aqueous solution, hydrochloric acid aqueous solution, acetic acid aqueous solution, boric acid aqueous solution, and formic acid aqueous solution. Nitric acid aqueous solution is preferable.
電解質水溶液中における電解質の濃度は、その酸化度に依存するため、特に限定されないが、０．５〜２０モル／リットルが好ましい。酸化力の強い電解質の場合は、高い電解質濃度が好ましいが、酸化力の弱い電解質の場合は、低い電解質濃度が好ましい。硝酸水溶液の場合には、電解質の濃度は１０〜１３モル／リットルが好ましい。硫酸水溶液の場合には、電解質の濃度は０．５〜５モル／リットルが好ましい。蟻酸水溶液の場合には、電解質の濃度は０．５〜５モル／リットルが好ましい。 The concentration of the electrolyte in the electrolyte aqueous solution is not particularly limited because it depends on the degree of oxidation, but is preferably 0.5 to 20 mol / liter. In the case of an electrolyte having a strong oxidizing power, a high electrolyte concentration is preferable, but in the case of an electrolyte having a weak oxidizing power, a low electrolyte concentration is preferable. In the case of an aqueous nitric acid solution, the concentration of the electrolyte is preferably 10 to 13 mol / liter. In the case of an aqueous sulfuric acid solution, the concentration of the electrolyte is preferably 0.5 to 5 mol / liter. In the case of formic acid aqueous solution, the concentration of the electrolyte is preferably 0.5 to 5 mol / liter.
次に、上記電解質水溶液中に、陰極と、黒鉛化合物を一部に含む陽極とを浸漬し、陽極と陰極との間に直流電源（ポテンショスタット／ガルバノスタット）を用いて定電流条件で電気分解を行う。電気分解の開始直後に自然電位から電位が上昇し，初期の電位上昇において、電解質が電離して生成された陰イオンが、黒鉛化合物の層面間にインターカレーション（挿入）される（黒鉛層間化合物の形成）。その後、チャージ量の増加に伴い、陽極の黒鉛化合物の電気化学的な酸化が始まり、黒鉛化合物の表面又は黒鉛化合物の層面間に黒鉛酸が生成される。なお、陽極と陰極との間の電位の上昇は、黒鉛層間化合物の形成状態、黒鉛層間化合物の層面の酸化状態によって異なり、換言すれば、黒鉛層間化合物の形成又は黒鉛層間化合物の層面の酸化による抵抗の変化に依存する。陽極と陰極との間の電位は，黒鉛層間化合物の酸化が完了した時点で、ほぼ飽和に達する。 Next, the cathode and an anode containing a graphite compound are immersed in the electrolyte aqueous solution, and electrolysis is performed under a constant current condition using a DC power source (potentiostat / galvanostat) between the anode and the cathode. I do. Immediately after the start of electrolysis, the potential increases from the natural potential, and in the initial potential increase, the anion generated by ionization of the electrolyte is intercalated (inserted) between the graphite compound layers (graphite intercalation compound). Formation). Thereafter, as the charge amount increases, electrochemical oxidation of the graphite compound of the anode starts, and graphite acid is generated between the surface of the graphite compound or the layer surface of the graphite compound. The increase in potential between the anode and the cathode varies depending on the formation state of the graphite intercalation compound and the oxidation state of the layer surface of the graphite intercalation compound, in other words, due to the formation of the graphite intercalation compound or the oxidation of the layer surface of the graphite intercalation compound. Depends on resistance change. The potential between the anode and the cathode almost reaches saturation when the oxidation of the graphite intercalation compound is completed.
初期の電位上昇においては、陽極方向に移動した陰イオンが、陽極の表面に配設された黒鉛化合物又は陽極自体を形成している黒鉛化合物の層面間に挿入され黒鉛層間化合物を形成する。この際、電解質に由来する陰イオンは、黒鉛化合物の層面間の内部にまで充分に進入し、層面間にて剥離の容易な黒鉛層間化合物を形成する。 In the initial potential increase, the anion moved in the anode direction is inserted between the graphite compound disposed on the surface of the anode or the graphite compound forming the anode itself to form a graphite intercalation compound. At this time, the anion derived from the electrolyte sufficiently penetrates to the inside between the layer surfaces of the graphite compound to form a graphite intercalation compound that is easily peeled between the layer surfaces.
又、過マンガン酸カリウムなどの酸化剤を用いる場合と異なり、黒鉛化合物から黒鉛層間化合物を生成する過程において不純物が生成し難く、更に、酸化剤のような発熱反応を生じないため、黒鉛層間化合物の大量生産にも適している。 In addition, unlike the case of using an oxidizing agent such as potassium permanganate, impurities are not easily generated in the process of generating a graphite intercalation compound from a graphite compound, and further, an exothermic reaction such as an oxidizing agent does not occur. Suitable for mass production.
更に、上述のように、水の電解反応は生じていないので、水の電解反応に伴う酸素は発生しておらず、黒鉛層間化合物を構成している層面の酸化を概ね防止することができる。従って、黒鉛層間化合物をその層面間において剥離して得られる薄片化黒鉛は、その層面の酸化が極めて少なく、導電性に優れた薄片化黒鉛を製造することができる。 Furthermore, as described above, since no water electrolysis occurs, oxygen accompanying the water electrolysis is not generated, and oxidation of the layer surface constituting the graphite intercalation compound can be generally prevented. Therefore, exfoliated graphite obtained by exfoliating the graphite intercalation compound between the layer surfaces can produce exfoliated graphite having very little oxidation of the layer surface and excellent conductivity.
即ち、各層面が酸化の少ない黒鉛層間化合物を製造したい場合には、電気分解を開始後、印加チャージ量が少なく、電位上昇の小さい条件下にて、黒鉛化合物の層面間に、電解質が電離して生成される陰イオンを挿入させて黒鉛層間化合物を製造すればよい。 That is, when it is desired to produce a graphite intercalation compound with less oxidation on each layer surface, the electrolyte is ionized between the layer surfaces of the graphite compound under the conditions that the applied charge is small and the potential rise is small after electrolysis is started. The graphite intercalation compound may be produced by inserting the anions generated in this manner.
なお、チャージ量とは、陽極と陰極との間を流れる電流（Ａ）と時間（秒）との積であるクーロン量（Ｃ）を意味する。 The charge amount means a coulomb amount (C) that is a product of current (A) flowing between the anode and the cathode and time (seconds).
一方、黒鉛層間化合物の層面の酸化が多い黒鉛層間化合物を製造したい場合には、チャージ量の増加に伴い、陽極である黒鉛化合物の電気化学的な酸化が始まる急激な電位の上昇と、その後の電位変化が認められず、飽和状態に達した条件下にて、黒鉛層間化合物を製造すればよい。このようにして得られた黒鉛層間化合物は、その表面又は層面が酸化されている。 On the other hand, when it is desired to produce a graphite intercalation compound with a large amount of oxidation of the graphite intercalation compound layer, as the amount of charge increases, an abrupt increase in potential starts, and then the electrochemical oxidation of the graphite compound as the anode begins. What is necessary is just to manufacture a graphite intercalation compound on the conditions which an electric potential change is not recognized but reached the saturation state. The graphite intercalation compound thus obtained has its surface or layer surface oxidized.
このように、陽極と陰極との間に一定電流が流れるように、即ち、定電流電気分解を行い、初期の電位変化の小さいチャージ量では酸化の少ない黒鉛層間化合物が得られ、急激な電位上昇とその後の電位の飽和状態に達したチャージ量の領域では酸化が多い黒鉛層間化合物が得られる。この急激な電位上昇及び飽和に達するチャージ量は、電解質水溶液や陽極の重量などによって変化するために一概には決められないが、例えば、硝酸水溶液を電解質水溶液に用いた場合、陽極と陰極との間における計測電位が３Ｖ未満以下では酸化の少ない黒鉛層間化合物が得られ、陽極と陰極との間における計測電位が４Ｖ以上では酸化が多い黒鉛層間化合物が得られる。 In this way, constant current electrolysis is performed between the anode and the cathode, that is, constant current electrolysis is performed, and a graphite intercalation compound with little oxidation is obtained with a small charge amount with a small initial potential change, and the potential increases rapidly. Then, in the charge amount region where the potential saturation state is reached, a graphite intercalation compound with much oxidation is obtained. The amount of charge that reaches this sudden increase in potential and saturation cannot be determined unconditionally because it varies depending on the weight of the electrolyte aqueous solution or the anode. For example, when a nitric acid aqueous solution is used for the electrolyte aqueous solution, A graphite intercalation compound with little oxidation is obtained when the measured potential between the anode and the cathode is less than 3 V, and a graphite intercalation compound with much oxidation is obtained when the measured potential between the anode and the cathode is 4 V or more.
このように、黒鉛層間化合物の層面が酸化されることによって、各層面に酸化に起因した極性基（酸性官能基）が結合し、この極性基によっても黒鉛層間化合物の層面間が押し広げられ、この後に行われる黒鉛層間化合物の剥離をより容易に行うことができる。 Thus, by oxidizing the layer surface of the graphite intercalation compound, a polar group (acidic functional group) due to oxidation is bonded to each layer surface, and the layer surface of the graphite intercalation compound is also expanded by this polar group, Thereafter, the graphite intercalation compound can be peeled off more easily.
更に、このようにして得られた黒鉛層間化合物をその層面間において剥離して得られる薄片化黒鉛は、その層面の酸化によって層面の表面に極性基（酸性官能基）が結合した状態となっており、合成樹脂などと混合させて複合体とする場合には、合成樹脂の持つ極性基との間において相互作用を生じ、合成樹脂中に薄片化黒鉛を均一に且つ容易に混合することができる。 Further, exfoliated graphite obtained by exfoliating the graphite intercalation compound thus obtained between the layer surfaces is in a state in which polar groups (acidic functional groups) are bonded to the surface of the layer surface by oxidation of the layer surface. In the case of mixing with a synthetic resin or the like to form a composite, an interaction occurs with the polar group of the synthetic resin, and the exfoliated graphite can be uniformly and easily mixed in the synthetic resin. .
なお、上記合成樹脂としては、例えば、メタクリル系樹脂、アクリル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリエステル系樹脂、ポリアミド樹脂、スチレン−アクリロニトリル共重合体などのポリスチレン系樹脂、ポリカーボネート系樹脂、ポリカプロラクトン、ポリカプロラクタム、ポリフッ素化エチレン、ポリ酢酸ビニル樹脂、ポリ塩化ビニル系樹脂、ポリイミド系樹脂、エポキシ系樹脂、ポリウレタン系樹脂、ポリブタジエン、ブチルゴム、スチレン−ブタジエン共重合体、ポリイソプレン、ポリジメチルシロキサンなどが挙げられる。なお、合成樹脂は単独で用いられても二種以上が併用されてもよい。又、モノマーとしては、上述の合成樹脂を構成しているモノマーが挙げられ、例えば、アクリル酸、アクリル酸メチル、メタクリル酸、メタクリル酸メチル、エチレン、プロピレン、スチレン、α−メチルスチレン、アクリロニトリル、酢酸ビニル、塩化ビニル、ブタジエン、イソプレンなどが挙げられる Examples of the synthetic resin include methacrylic resins, acrylic resins, polyethylene resins, polypropylene resins, polyester resins, polyamide resins, polystyrene resins such as styrene-acrylonitrile copolymers, polycarbonate resins, and polyresins. Caprolactone, polycaprolactam, polyfluorinated ethylene, polyvinyl acetate resin, polyvinyl chloride resin, polyimide resin, epoxy resin, polyurethane resin, polybutadiene, butyl rubber, styrene-butadiene copolymer, polyisoprene, polydimethylsiloxane Etc. In addition, a synthetic resin may be used independently or 2 or more types may be used together. In addition, examples of the monomer include monomers constituting the above-described synthetic resin. For example, acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, ethylene, propylene, styrene, α-methylstyrene, acrylonitrile, acetic acid. Examples include vinyl, vinyl chloride, butadiene, and isoprene.
陽極と陰極との間に流れる電流密度は、小さいと、所定のクーロン量となるまでの処理時間が長くなることがあり、大きいと、電気的な衝撃によって電極や配線が破損することがあるので、０．３〜２０Ａ／ｇが好ましく、０．５〜１０Ａ／ｇがより好ましい。 If the current density flowing between the anode and the cathode is small, the processing time until the predetermined amount of coulomb is reached may be long, and if it is large, the electrode or wiring may be damaged by electrical shock. 0.3 to 20 A / g is preferable, and 0.5 to 10 A / g is more preferable.
上述のようにして得られた黒鉛層間化合物は、電解質水溶液中から取り出されて常温、常圧下にて乾燥される。乾燥温度は、黒鉛層間化合物の層面間に挿入された陰イオン又は黒鉛層間化合物の表面若しくは層面に形成された酸性官能基が分解する温度未満であることが好ましい。なお、電解質水溶液を用いた場合は、黒鉛層間化合物を室温にて１日風乾させればよい。 The graphite intercalation compound obtained as described above is taken out from the aqueous electrolyte solution and dried at room temperature and normal pressure. The drying temperature is preferably lower than the temperature at which the anion inserted between the layer surfaces of the graphite intercalation compound or the acidic functional group formed on the surface or layer surface of the graphite intercalation compound is decomposed. When an aqueous electrolyte solution is used, the graphite intercalation compound may be air-dried at room temperature for 1 day.
上述のようにして得られた黒鉛層間化合物は上述のように乾燥されるものの、層面間の間隔は極めて狭いため、層面間は完全に乾燥しておらず、黒鉛層間化合物の層面間には陰イオンが保持されていると推定される。 Although the graphite intercalation compound obtained as described above is dried as described above, the distance between the layer surfaces is extremely narrow, so that the layer surface is not completely dried, and the graphite intercalation compound is not exposed between the layer surfaces. It is presumed that ions are retained.
そして、黒鉛層間化合物は後述する剥離工程の前に急速加熱によって膨張させておくことが好ましい。黒鉛層間化合物を急速加熱する方法としては、特に限定されず、例えば、電気炉、好ましくは電気管状炉を用いて黒鉛層間化合物を急速加熱する方法、黒鉛層間化合物を集光加熱する方法などが挙げられ、電気炉を用いて黒鉛層間化合物を急速加熱する方法が好ましい。なお、黒鉛層間化合物の層面の酸化を防止するために、黒鉛層間化合物を窒素、ヘリウム、アルゴンなどの不活性ガス中にて急速加熱してもよい。 And it is preferable to expand the graphite intercalation compound by rapid heating before the peeling process mentioned later. The method for rapidly heating the graphite intercalation compound is not particularly limited, and examples thereof include a method for rapidly heating the graphite intercalation compound using an electric furnace, preferably an electric tubular furnace, and a method for concentrating and heating the graphite intercalation compound. The method of rapidly heating the graphite intercalation compound using an electric furnace is preferred. In order to prevent oxidation of the layer surface of the graphite intercalation compound, the graphite intercalation compound may be rapidly heated in an inert gas such as nitrogen, helium, or argon.
黒鉛層間化合物の急速加熱時の加熱温度は、低いと、黒鉛層間化合物の層面間に挿入させた陰イオンが分解せず、黒鉛層間化合物の層面間の間隔を押し広げる効果が低いことがあり、高いと、押し広げられた黒鉛層間化合物の層面間の距離がかえって狭くなることがあるので、３００〜１１００℃が好ましい。 When the heating temperature at the time of rapid heating of the graphite intercalation compound is low, the anion inserted between the layer surfaces of the graphite intercalation compound is not decomposed, and the effect of pushing the gap between the layer surfaces of the graphite intercalation compound may be low, If it is high, the distance between the layer surfaces of the expanded graphite intercalation compound may become narrower, so 300 to 1100 ° C. is preferable.
黒鉛層間化合物の急速加熱時の加熱時間は、短いと、黒鉛層間化合物の層面間に挿入させた陰イオンが分解せず、黒鉛層間化合物の層面間の間隔を押し広げる効果が低いことがあり、長いと、黒鉛層間化合物の層面の酸化が進みすぎて燃焼してしまうことがあるので、５〜１００秒が好ましい。 When the heating time at the time of rapid heating of the graphite intercalation compound is short, the anion inserted between the layer surfaces of the graphite intercalation compound is not decomposed, and the effect of pushing the interval between the layer surfaces of the graphite intercalation compound may be low, If it is long, the oxidation of the layer surface of the graphite intercalation compound may progress too much and burn, so 5 to 100 seconds is preferable.
次に、黒鉛層間化合物をその層面間において剥離して黒鉛層間化合物を薄片化して薄片化黒鉛を製造する。黒鉛層間化合物をその層面間において剥離する方法としては、特に限定されず、例えば、黒鉛層間化合物に超音波、ラジオ波などを照射する方法、黒鉛層間化合物に物理的に応力を加える方法などが挙げられ、黒鉛層間化合物を媒体中に分散させた状態で行うことができることから、黒鉛層間化合物に超音波を照射する方法が好ましい。なお、黒鉛層間化合物を分散させる媒体としては、例えば、メタノール、エタノールなどのアルコール、水などが挙げられる。 Next, the graphite intercalation compound is peeled between the layer surfaces, and the graphite intercalation compound is exfoliated to produce exfoliated graphite. The method for peeling the graphite intercalation compound between the layer surfaces is not particularly limited, and examples thereof include a method of irradiating the graphite intercalation compound with ultrasonic waves and radio waves, and a method of physically applying stress to the graphite intercalation compound. Since the graphite intercalation compound can be dispersed in the medium, a method of irradiating the graphite intercalation compound with ultrasonic waves is preferable. Examples of the medium for dispersing the graphite intercalation compound include alcohols such as methanol and ethanol, and water.
黒鉛層間化合物に超音波を照射する照射条件としては、２０〜１００ｋＨｚの超音波を１〜６０分間に亘って黒鉛層間化合物に照射することが好ましい。黒鉛層間化合物に超音波を照射する際における超音波の電気エネルギーは、１００〜５００Ｗが好ましい。 As irradiation conditions for irradiating the graphite intercalation compound with ultrasonic waves, it is preferable to irradiate the graphite intercalation compound with ultrasonic waves of 20 to 100 kHz for 1 to 60 minutes. The electrical energy of the ultrasonic waves when irradiating the graphite intercalation compound with ultrasonic waves is preferably 100 to 500W.
このようにして薄片化黒鉛を製造することができるが、上述のように、印加するチャージ量によっては、薄片化黒鉛の各層面が酸化されている場合があり、各層面は酸化グラフェンと呼ばれる。 In this way, exfoliated graphite can be produced. As described above, depending on the amount of charge applied, each layer surface of exfoliated graphite may be oxidized, and each layer surface is called graphene oxide.
この酸化グラフェンからなる薄片化黒鉛を導電膜などの用途に用いる場合には、高い導電性を得るために、酸化グラフェンを還元・脱酸素することが好ましい。薄片化黒鉛を構成している酸化グラフェンを還元・脱酸素する方法としては、特に限定されず、例えば、薄片化黒鉛を構成している酸化グラフェンに還元剤を接触させる方法が挙げられる。 When exfoliated graphite made of graphene oxide is used for applications such as a conductive film, it is preferable to reduce and deoxygenate graphene oxide in order to obtain high conductivity. The method for reducing and deoxygenating graphene oxide constituting exfoliated graphite is not particularly limited, and examples thereof include a method of bringing a reducing agent into contact with graphene oxide constituting exfoliated graphite.
薄片化黒鉛を構成している酸化グラフェンに還元剤を接触させる方法としては、例えば、薄片化黒鉛を含有する薄膜を形成し、この薄膜に還元剤を接触させることによって酸化グラフェンを還元・脱酸素させる方法、薄片化黒鉛を不活性ガス雰囲気下で加熱する方法などが挙げられる。 As a method of bringing a reducing agent into contact with graphene oxide constituting exfoliated graphite, for example, a thin film containing exfoliated graphite is formed, and graphene oxide is reduced and deoxygenated by bringing the reducing agent into contact with this thin film. And a method of heating exfoliated graphite in an inert gas atmosphere.
上述のようにして得られた薄片化黒鉛は、その層面の面方向に沿った面積が５０〜１０００μｍ2で且つ厚みが５０ｎｍ未満であることが好ましく、層面の面方向に沿った面積が１００〜１０００μｍ2で且つ厚みが１０ｎｍ未満であることがより好ましい。 The exfoliated graphite obtained as described above preferably has an area along the surface direction of the layer surface of 50 to 1000 μm 2 and a thickness of less than 50 nm, and has an area along the surface direction of the layer surface of 100 to 100 μm. More preferably, the thickness is 1000 μm 2 and the thickness is less than 10 nm.
本発明で得られる薄片化黒鉛は、その層面の面方向に沿って大きな面積を有し且つ厚みが極めて薄いので、機能性フィラーとして様々な用途に用いることができる。 The exfoliated graphite obtained in the present invention has a large area along the surface direction of the layer surface and is extremely thin, and can be used for various applications as a functional filler.
又、薄片化黒鉛における層面の面方向に沿った面積とは、薄片化黒鉛の面積が最も大きくなる方向から見た時の薄片化黒鉛の面積をいう。薄片化黒鉛の厚みとは、薄片化黒鉛の面積が最も大きくなる方向から見た時の薄片化黒鉛の表面に対して直交する方向の薄片化黒鉛の最大寸法をいう。 Moreover, the area along the surface direction of the layer surface in exfoliated graphite means the area of exfoliated graphite when viewed from the direction in which the area of exfoliated graphite becomes the largest. The thickness of exfoliated graphite refers to the maximum dimension of exfoliated graphite in the direction orthogonal to the surface of exfoliated graphite when viewed from the direction in which the area of exfoliated graphite is the largest.
なお、薄片化黒鉛における層面の面方向に沿った面積は、ＦＥ−ＳＥＭを用いて測定することができ、ＳＥＭで観察した任意の１０視野に存在する全ての薄片化黒鉛における層面の面方向に沿った面積を相加平均した値をいう。 In addition, the area along the surface direction of the layer surface in exfoliated graphite can be measured using FE-SEM, and in the surface direction of the layer surface in all exfoliated graphite existing in any 10 visual fields observed by SEM. The value obtained by arithmetically averaging the areas along the line.
又、薄片化黒鉛の厚みは、ＦＥ−ＳＥＭ又はＡＦＭを用いて測定することができ、ＳＥＭ又はＡＦＭで観察した任意の１０視野に存在する全ての薄片化黒鉛の厚みを相加平均した値をいう。 Moreover, the thickness of exfoliated graphite can be measured using FE-SEM or AFM, and the value obtained by arithmetically averaging the thicknesses of all exfoliated graphite existing in any 10 visual fields observed by SEM or AFM. Say.
そして、薄片化黒鉛において、元素分析によるＣの元素量は６５ａｔｍ％以上であることが好ましい。なお、薄片化黒鉛における元素分析によるＣの元素量は、ＥＳＣＡによって測定することができる。 And in exfoliated graphite, it is preferable that the elemental amount of C by elemental analysis is 65 atm% or more. In addition, the elemental amount of C by elemental analysis in exfoliated graphite can be measured by ESCA.
本発明の薄片化黒鉛の製造方法は、黒鉛化合物を電気化学反応によって黒鉛層間化合物とし、この黒鉛層間化合物をその層面間において剥離して薄片化することを特徴とするので、層面の面方向に沿って大きな面積を有し且つ厚みが極めて薄い薄片化黒鉛を容易に製造することができ、機能性フィラーとして様々な用途に用いることができる。 The method for producing exfoliated graphite according to the present invention is characterized in that a graphite compound is converted into a graphite intercalation compound by an electrochemical reaction, and the graphite intercalation compound is exfoliated between the layer surfaces so as to be exfoliated. The exfoliated graphite having a large area along the line and extremely thin can be easily produced, and can be used for various applications as a functional filler.
そして、上記薄片化黒鉛の製造方法において、黒鉛化合物を含む陽極と、陰極とを電解質水溶液中に浸漬し、上記陽極と上記陰極との間に直流電圧を印加し、上記黒鉛化合物の層面間に電解質に由来する陰イオンを挿入させて黒鉛層間化合物を製造する場合には、陽極の黒鉛層間化合物の層面間に陰イオンを充分に挿入することができ、その後の黒鉛層間化合物の層面間における剥離を円滑に行って、層面の面方向に沿って大きな面積を有し且つ厚みが極めて薄い薄片化黒鉛をより容易に製造することができる。 Then, in the method for producing exfoliated graphite, an anode containing a graphite compound and a cathode are immersed in an aqueous electrolyte solution, a DC voltage is applied between the anode and the cathode, and a layer surface of the graphite compound is applied. When an anion derived from an electrolyte is inserted to produce a graphite intercalation compound, the anion can be sufficiently inserted between the layer surfaces of the graphite intercalation compound of the anode, and the subsequent exfoliation between the layer surfaces of the graphite intercalation compound Thus, exfoliated graphite having a large area along the surface direction of the layer surface and an extremely thin thickness can be more easily produced.
次に本発明の実施例を説明するが、本発明は下記実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to the following examples.
（実施例１）
厚みが０．６ｍｍの黒鉛化合物のシート（エアウォーター社製 商品名「ＰＦ‐６０ＵＨＰ」）から縦１ｃｍ×横２ｃｍの平面長方形状の黒鉛化合物シート片を切り出した。
Example 1
From a graphite compound sheet having a thickness of 0.6 mm (trade name “PF-60UHP” manufactured by Air Water), a piece of a flat rectangular graphite compound sheet having a length of 1 cm and a width of 2 cm was cut out.
陽極及び陰極として白金電極を用意し、陽極の表面に黒鉛化合物シート片を巻回し、黒鉛化合物シート片を電気絶縁性の粘着テープを用いて陽極の表面に固定した。なお、参照極として銀・塩化銀電極を用意した。なお、電気絶縁性の粘着テープは、ポリテトラフルオロエチレン製の基材フィルム上にアクリル系粘着剤が積層一体化されてなるものであった。 Platinum electrodes were prepared as an anode and a cathode, a graphite compound sheet piece was wound around the surface of the anode, and the graphite compound sheet piece was fixed to the surface of the anode using an electrically insulating adhesive tape. A silver / silver chloride electrode was prepared as a reference electrode. The electrically insulating pressure-sensitive adhesive tape was obtained by laminating and integrating an acrylic pressure-sensitive adhesive on a base film made of polytetrafluoroethylene.
図１に示したように、電解質水溶液として濃度が１３モル／リットルの硝酸水溶液３００ミリリットルを用意し、この電解質水溶液４中に上記陽極２及び陰極３を浸漬した。なお、陽極２の表面に巻回した黒鉛化合物シート片１が電解質水溶液４中に完全に浸漬した状態とした。
As shown in FIG. 1, 300 ml of an aqueous nitric acid solution having a concentration of 13 mol / liter was prepared as an aqueous electrolyte solution, and the anode 2 and the
しかる後、電気化学反応による処理は、ポテンショスタット／ガルバノスタット（北斗電工社製 商品名「ＨＢＡ−１５１」）を用いて陽極２と陰極３との間に一定電流が流れるように設定し、電流密度０．５Ａ／ｇにてチャージ量が２０００Ｃとなるまで電気化学反応を行って、黒鉛化合物の層面間に硝酸イオンを水と共に挿入させて黒鉛層間化合物を製造すると共に、黒鉛層間化合物の層面を酸化した。
Thereafter, the treatment by electrochemical reaction is set so that a constant current flows between the anode 2 and the
次に、得られた黒鉛層間化合物のシート片を電解質溶液から取り出し、黒鉛層間化合物のシート片をドラフト内で室温、常圧下にて２４時間に亘って風乾した。次に、黒鉛層間化合物のシート片を１０００℃に保持された電気管状炉に供給して５秒間に亘って急速加熱して膨張させた後、黒鉛層間化合物のシート片を電気管状炉から取り出した。 Next, the obtained sheet piece of graphite intercalation compound was taken out from the electrolyte solution, and the sheet piece of graphite intercalation compound was air-dried in a draft at room temperature and normal pressure for 24 hours. Next, the graphite intercalation compound sheet piece was supplied to an electric tubular furnace maintained at 1000 ° C. and rapidly heated for 5 seconds to expand, and then the graphite intercalation compound sheet piece was taken out of the electric tubular furnace. .
続いて、黒鉛層間化合物のシート片をメチルアルコール中に浸漬し、黒鉛層間化合物に２０ｋＨｚの超音波を３分間に亘って２００Ｗ照射して黒鉛層間化合物をその層面間において剥離することによって薄片化し、薄片化黒鉛を得た。 Subsequently, the graphite intercalation compound sheet piece was immersed in methyl alcohol, and the graphite intercalation compound was exfoliated between the layer surfaces by irradiating the graphite intercalation compound with 200 W of ultrasonic waves at a frequency of 200 W for 3 minutes. Exfoliated graphite was obtained.
得られた薄片化黒鉛をメチルアルコール中から取り出して乾燥させた後、薄片化黒鉛を炭素製のるつぼに入れた上で小型超高温炉（倉田技研社製 商品名「ＳＣＣ−３０／２２０」）の炉内に供給し、小型超高温炉の炉内を１８００℃まで１．５時間かけて真空加熱した。 The obtained exfoliated graphite was taken out of methyl alcohol and dried, and then the exfoliated graphite was put in a carbon crucible and then a small ultra high temperature furnace (trade name “SCC-30 / 220” manufactured by Kurata Giken Co., Ltd.) The inside of the small ultra-high temperature furnace was heated in a vacuum to 1800 ° C. over 1.5 hours.
しかる後、小型超高温炉の炉内に高純度アルゴンガスを導入した上で、炉内を２８００℃まで１時間かけて加熱し、アルゴンガス雰囲気下で炉内を２８００℃にて３０分間に亘って保持することによって薄片化黒鉛の還元・脱酸素を行った。 After that, after introducing high purity argon gas into the furnace of the small ultra high temperature furnace, the inside of the furnace is heated to 2800 ° C. over 1 hour, and the inside of the furnace is kept at 2800 ° C. for 30 minutes under an argon gas atmosphere. The exfoliated graphite was reduced and deoxygenated.
（実施例２）
電解質水溶液として１モル／リットルの蟻酸水溶液を用いたこと、電流密度を０．５Ａ／ｇの代わりに２Ａ／ｇとし２４００Ｃとなるまで電気化学反応を行ったこと以外は実施例１と同様の要領で黒鉛層間化合物を製造すると共に、黒鉛層間化合物の層面を酸化した。
(Example 2)
The same procedure as in Example 1 except that a 1 mol / liter formic acid aqueous solution was used as the electrolyte aqueous solution and the electrochemical reaction was carried out until the current density was 2 A / g instead of 0.5 A / g until 2400 C was reached. While producing the graphite intercalation compound, the layer surface of the graphite intercalation compound was oxidized.
次に、得られた黒鉛層間化合物のシート片を電解質溶液から取り出し、黒鉛層間化合物のシート片をドラフト内で室温、常圧下にて２４時間に亘って風乾した。次に、黒鉛層間化合物のシート片を実施例１と同様の要領で膨張させた後、黒鉛層間化合物のシート片を電気管状炉から取り出した。 Next, the obtained sheet piece of graphite intercalation compound was taken out from the electrolyte solution, and the sheet piece of graphite intercalation compound was air-dried in a draft at room temperature and normal pressure for 24 hours. Next, the sheet piece of graphite intercalation compound was expanded in the same manner as in Example 1, and then the sheet piece of graphite intercalation compound was taken out from the electric tubular furnace.
続いて、黒鉛層間化合物のシート片を実施例１と同様の要領で薄片化し、薄片化黒鉛を得た。薄片化黒鉛から充分に薄片化されていない黒鉛層間化合物を除去するために、薄片化黒鉛を遠心分離機に供給して３０００ｒｐｍの回転速度にて遠心分離して薄片化が不充分な黒鉛層間化合物を除去した。 Subsequently, a sheet piece of the graphite intercalation compound was exfoliated in the same manner as in Example 1 to obtain exfoliated graphite. In order to remove the graphite intercalation compound that has not been exfoliated sufficiently from the exfoliated graphite, the exfoliated graphite is supplied to a centrifuge and centrifuged at a rotational speed of 3000 rpm, and the graphite intercalation compound is insufficiently exfoliated. Was removed.
得られた薄片化黒鉛をメチルアルコール中から取り出して乾燥させた。次に、小型超高温炉の炉内に薄片化黒鉛を供給した後に炉内に高純度アルゴンガスを導入し、炉内を１０００℃まで１時間かけて加熱し、アルゴンガス雰囲気下で炉内を１０００℃にて２０分間に亘って保持することによって薄片化黒鉛の還元・脱酸素を行った。 The obtained exfoliated graphite was taken out from methyl alcohol and dried. Next, after supplying exfoliated graphite into the furnace of a small ultra-high temperature furnace, high purity argon gas is introduced into the furnace, the inside of the furnace is heated to 1000 ° C. over 1 hour, and the inside of the furnace is kept under an argon gas atmosphere. The exfoliated graphite was reduced and deoxygenated by holding at 1000 ° C. for 20 minutes.
（実施例３）
電解質水溶液として２モル／リットルの硫酸を用いたこと以外は実施例２と同様にして薄片化黒鉛を得た。
(Example 3)
Exfoliated graphite was obtained in the same manner as in Example 2 except that 2 mol / liter sulfuric acid was used as the aqueous electrolyte solution.
（実施例４）
チャージ量を３００Ｃとしたこと以外は実施例１と同様にして薄片化黒鉛を得た。
Example 4
Exfoliated graphite was obtained in the same manner as in Example 1 except that the charge amount was 300C.
（実施例５）
薄片化黒鉛の還元・脱酸素を行わなかったこと以外は実施例２と同様にして薄片化黒鉛を得た。
(Example 5)
Exfoliated graphite was obtained in the same manner as in Example 2 except that exfoliated graphite was not reduced or deoxygenated.
（比較例１）
天然黒鉛粉末０．２５ｇを濃硫酸水溶液１１．５ミリリットル中に供給し、硫酸水溶液を氷で冷却しつつ硫酸水溶液を攪拌しながら、硫酸水溶液中に過マンガン酸カリウム１．５ｇをゆっくり加えて、硫酸水溶液中の黒鉛単結晶粉末と過マンガン酸カリウムとを約３５℃にて３０分間に亘って反応させた。
(Comparative Example 1)
While supplying 0.25 g of natural graphite powder into 11.5 ml of concentrated sulfuric acid aqueous solution and stirring the sulfuric acid aqueous solution while cooling the sulfuric acid aqueous solution with ice, 1.5 g of potassium permanganate was slowly added to the sulfuric acid aqueous solution, The graphite single crystal powder and the potassium permanganate in the sulfuric acid aqueous solution were reacted at about 35 ° C. for 30 minutes.
硫酸水溶液中に水２３ミリリットルをゆっくり加えて９８℃にて１５分間に亘って放置した後、硫酸水溶液中に純水７０ミリリットルと３０重量％の過酸化水素水４．５ミリリットルを加えて反応を停止させた。 After slowly adding 23 ml of water to the sulfuric acid aqueous solution and leaving it at 98 ° C. for 15 minutes, 70 ml of pure water and 4.5 ml of 30% by weight hydrogen peroxide solution were added to the sulfuric acid aqueous solution to react. Stopped.
しかる後、硫酸水溶液を回転速度１４０００ｒｐｍにて３０分間に亘って遠心分離して硫酸水溶液中から沈殿物を分離し、沈殿物を希塩酸及び水で洗浄して、薄片化黒鉛が水中に分散してなる薄片化黒鉛の分散液を得た。 Thereafter, the sulfuric acid aqueous solution is centrifuged at a rotational speed of 14,000 rpm for 30 minutes to separate the precipitate from the sulfuric acid aqueous solution, the precipitate is washed with dilute hydrochloric acid and water, and the exfoliated graphite is dispersed in water. A dispersion of exfoliated graphite was obtained.
（比較例２）
比較例１で得られた薄片化黒鉛の分散液を石英ガラス上で乾燥させた後、薄片化黒鉛にヒドラジン１水和物を添加して、薄片化黒鉛を９０℃にて３０分間に亘って加熱することによって薄片化黒鉛の薄膜を得た。
(Comparative Example 2)
After the exfoliated graphite dispersion obtained in Comparative Example 1 was dried on quartz glass, hydrazine monohydrate was added to the exfoliated graphite, and the exfoliated graphite was kept at 90 ° C. for 30 minutes. By heating, a thin film of exfoliated graphite was obtained.
得られた薄片化黒鉛について、層面の面方向の面積及び厚み、並びに、元素分析によるＣの元素量を測定し、その結果を表１に示した。表１において「層面の面方向の面積」は単に「面積」と、「元素分析によるＣの元素量」は単に「Ｃ元素量」と表記した。なお、薄片化黒鉛における層面の面方向の面積及び厚みは、ＦＥ−−ＳＥＭ（日本電子株式会社製 商品名「ＪＥＭ−２０１０ＦＥＦ」）を用いて測定した。薄片化黒鉛における元素分析によるＣの元素量は、ＥＳＣＡ（ＫＲＡＴＯＳ社製 商品名「ＡＸＩＳ−１６５」）を用いて測定した。 About the obtained exfoliated graphite, the area and thickness of the layer surface in the plane direction, and the elemental amount of C by elemental analysis were measured, and the results are shown in Table 1. In Table 1, “area in the plane direction of the layer surface” is simply expressed as “area”, and “element amount of C by elemental analysis” is simply expressed as “C element amount”. In addition, the area and thickness of the layer surface in the exfoliated graphite were measured using FE--SEM (trade name “JEM-2010FEF” manufactured by JEOL Ltd.). The elemental amount of C by elemental analysis in exfoliated graphite was measured using ESCA (trade name “AXIS-165” manufactured by KRATOS).
１ 黒鉛化合物
２ 陽極
３ 陰極
４ 電解質水溶液
Ｖ 直流電源
1 Graphite Compound 2
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