JPWO2016039268A1 - 多孔質黒鉛の製造方法および多孔質黒鉛 - Google Patents
多孔質黒鉛の製造方法および多孔質黒鉛 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 335
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 4
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- 238000004544 sputter deposition Methods 0.000 description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 229910001416 lithium ion Inorganic materials 0.000 description 2
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- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/336—Preparation characterised by gaseous activating agents
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
Description
本発明の実施の形態の多孔質黒鉛の製造方法は、前駆体の炭素含有材料に対して、脱成分工程、黒鉛化工程、賦活工程を行い、本発明の実施の形態の多孔質黒鉛を製造することができる。なお、脱成分工程により十分に黒鉛化されている場合には、黒鉛化工程を省略することもできる。
本発明の実施の形態の多孔質黒鉛の製造方法では、まず、炭素含有材料として、炭素と炭素以外の他の主成分とを含む化合物、合金または非平衡合金から成る前駆体を作製する。例えば、図1に示すMn−C系状態図を参考にして、炭素以外の他の成分をMnとした、Mn−C系の前駆合金を作製する。なお、Mnやその合金の溶融体は一般に酸化しやすいため、溶製の際は、アルゴン等の不活性雰囲気中で行うことが好ましい。
次に、図2(a)に示すように、作製された前駆体の炭素含有材料11を、反応性を向上させるために粉末状またはシート状にし、その炭素含有材料11の融点よりも低い凝固点を有する金属浴12の内部に、所定の時間浸漬する。このとき、金属浴12を、炭素含有材料11から炭素以外の他の主成分が減少して炭素に至るまでの組成変動範囲内における液相線温度の最小値よりも低い温度に制御する。例えば、炭素含有材料11としてMn−C系の前駆合金を使用した場合には、図1に示す状態図から、金属浴12を、Mnが減少してCに至るまでの組成変動範囲内における液相線温度の最小値1231℃よりも低い温度に制御する。なお、この場合、600℃以下では反応が起こりにくいため、金属浴12を600℃以上にすることが好ましい。
次に、得られた炭素部材を加熱して黒鉛化処理を行う。このとき、黒鉛化処理により結晶性を高め、電気抵抗率を下げて電気電導率を高めるために、加熱温度を2000℃以上、特に2400℃以上にすることが好ましい。黒鉛化処理前後の炭素部材の顕微鏡写真を、図6および図7に示す。また、黒鉛化処理前後の炭素部材のX線回折(XRD)パターンを、図8に示す。また、黒鉛化処理前後の炭素部材の細孔分布を、図9に示す。なお、図6乃至図9に示す炭素部材は、前駆体の炭素含有材料Mn80C20を、1200℃のAg溶湯の金属浴に5分間浸漬して得られた炭素部材を、2000℃で1時間加熱して黒鉛化処理したものである。
次に、黒鉛化処理により黒鉛化された炭素部材に対して、賦活処理を行う。賦活処理には、炭素部材にミクロ孔を形成できるものであれば、二酸化炭素や水蒸気、空気などを用いるガス賦活や、塩化亜鉛や硫酸塩、リン酸などを用いる薬品賦活など、いかなる方法を使用してもよい。
こうして得られた脱成分工程後の炭素部材について、それぞれ1500℃(1773K)、2000℃(2273K)、および2500℃(2773K)で2時間加熱して、黒鉛化処理を行った。2000℃で黒鉛化処理を行ったときの、黒鉛化処理前後の炭素部材の走査型電子顕微鏡写真を、図15に示す。図15に示すように、黒鉛化処理前後で、炭素部材の外観には、ほとんど変化が認められず、黒鉛化処理前後の炭素部材が高い熱的安定性を有していることが確認された。
脱成分工程後の炭素部材(黒鉛化処理を行っていないもの)について、賦活処理を行った。賦活処理は、二酸化炭素を用いたもの、および塩化亜鉛を用いたものの2つの方法で行った。まず、二酸化炭素を用いた賦活処理では、窒素に二酸化炭素を約10%含有した混合ガスを用いて、それぞれ700℃、800℃、850℃、900℃、および950℃で処理を行った。各温度までの昇温速度を10℃/分とし、各温度になってから2時間維持した。また、混合ガスの流量は、1リットル/分とした。
12 金属浴
13 炭素部材
14 未反応の前駆体
15 水溶液
Claims (13)
- 炭素を含む化合物、合金または非平衡合金から成る炭素含有材料を、この炭素含有材料の融点よりも低い凝固点を有し、前記炭素含有材料から前記炭素以外の他の主成分が減少して前記炭素に至るまでの組成変動範囲内における液相線温度の最小値よりも低い温度に制御された溶融金属に接触させることにより、前記他の主成分を選択的に前記溶融金属に溶出させて、微小間隙を有する炭素部材を得る脱成分工程と、
前記脱成分工程で得られた前記炭素部材に対して賦活処理を行う賦活工程とを、
有することを特徴とする多孔質黒鉛の製造方法。 - 前記脱成分工程で得られた前記炭素部材を加熱して黒鉛化する黒鉛化工程を有し、
前記賦活工程は、前記黒鉛化工程で黒鉛化された前記炭素部材に対して賦活処理を行うことを
特徴とする請求項1記載の多孔質黒鉛の製造方法。 - 前記黒鉛化工程は、前記炭素部材を2000℃以上に加熱することを特徴とする請求項2記載の多孔質黒鉛の製造方法。
- 前記脱成分工程は、前記炭素含有材料を前記溶融金属から成る金属浴に浸すことにより、前記他の主成分を選択的に前記金属浴内に溶出させて、前記炭素部材を得ることを特徴とする請求項1乃至3のいずれか1項に記載の多孔質黒鉛の製造方法。
- 前記炭素含有材料の融点よりも低い凝固点を有する固体金属を、あらかじめ前記炭素含有材料に接触するよう配置しておく前処理工程を有し、
前記脱成分工程は、前記固体金属を加熱して前記溶融金属にすることにより、前記他の主成分を選択的に前記溶融金属に溶出させて、前記炭素部材を得ることを
特徴とする請求項1乃至3のいずれか1項に記載の多孔質黒鉛の製造方法。 - 前記脱成分工程は、前記炭素部材を前記溶融金属から離した後、酸またはアルカリ水溶液により、周囲または前記微小間隙の内部に付着した、前記溶融金属の成分および/または前記他の主成分を含む付着混和体のみを選択的に溶出して除去することを、特徴とする請求項1乃至5のいずれか1項に記載の多孔質黒鉛の製造方法。
- 前記溶融金属は、Ag,Bi,Cu,Ga,Ge,Hg,In,Ir,Pb,Pt,Rh,Sb,Sn,Zn、または、これらのうちの少なくとも一つを主成分とする合金である混和体から成り、
前記他の主成分は、Al,B,Be,Ca,Ce,Cr,Dy,Er,Eu,Fe,Gd,Hf,Ho,K,La,Li,Lu,Mg,Mn,Mo,Na,Nb,Nd,Pr,Sc,Se,Si,Sm,Sr,Ta,Ti,V,W,Zrのいずれか一つ、もしくは、その複数を含む混和体から成ることを
特徴とする請求項1乃至6のいずれか1項に記載の多孔質黒鉛の製造方法。 - 前記脱成分工程は、不活性雰囲気中もしくは真空雰囲気中で行われる、または、前記溶融金属にフラックスを添加して大気中で行われることを特徴とする請求項1乃至7のいずれか1項に記載の多孔質黒鉛の製造方法。
- バルク状で、黒鉛の(002)回折線より導出される(002)面平均間隔の値が0.342以下であり、かつ、全気孔体積中、2乃至100nmの大きさの気孔を80%以上含み、BET比表面積が100m2/g以上であることを特徴とする多孔質黒鉛。
- 黒鉛の(002)回折線のピーク半値幅が1.02°以下であり、結晶サイズが9nm以上であることを特徴とする請求項9記載の多孔質黒鉛。
- ラマンスペクトルのDバンドのピーク強度(ID)とGバンドのピーク強度(IG)の比ID/IGが0.5以下であり、前記Gバンドでのピーク半値幅が45cm−1以下であることを特徴とする請求項9または10記載の多孔質黒鉛。
- BET比表面積が2400m2/g以上であることを特徴とする請求項9乃至11のいずれか1項に記載の多孔質黒鉛。
- シート状であることを特徴とする請求項9乃至12のいずれか1項に記載の多孔質黒鉛。
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