JP2004137505A - Mesocarbon microbeads - Google Patents
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- JP2004137505A JP2004137505A JP2003388690A JP2003388690A JP2004137505A JP 2004137505 A JP2004137505 A JP 2004137505A JP 2003388690 A JP2003388690 A JP 2003388690A JP 2003388690 A JP2003388690 A JP 2003388690A JP 2004137505 A JP2004137505 A JP 2004137505A
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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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本発明は、高密度、高強度および耐薬品性、耐熱性等に優れた特殊炭素材やリチウム二次電池負極材料等の各用途に使用されるメソカーボンマイクロビーズに関する。 The present invention relates to mesocarbon microbeads used for various applications such as a special carbon material excellent in high density, high strength, chemical resistance, heat resistance and the like, and a negative electrode material for a lithium secondary battery.
コールタールやコールタールピッチを３００〜５００℃で加熱し、反応生成物を１５０〜４５０℃で高温遠心分離等を行うと、固形分、すなわち粗ＭＣＭＢ（以下、メソカーボンマイクロビーズとあるのは、ＭＣＭＢと略す。）が生成する。これらの製造方法を記載した文献として、例えば、特公平０１−２７９６８号公報、特開平０１−２４２６９１号公報などがある。反応タールやピッチマトリックスから生成したＭＣＭＢ生品を分離するに際しては、溶剤抽出法、希釈重力沈降法などの溶媒を用いる方法と高温遠心分離法などの溶媒を用いない方法の２つがある。後者の方法においても、得られた粗ＭＣＭＢを洗浄、精製するために溶剤が用いられる。ここで、キノリン等のように溶解力が強過ぎる溶剤を用いれば、ＭＣＭＢの球体の球体の周囲にはタールやピッチマトリックスに由来するピッチ成分が付着していない単離ＭＣＭＢ（この単離ＭＣＭＢは、キノリン不溶分リッチな成分から成る球体である。）となる。このような単離ＭＣＭＢから特殊炭素材の各用途に使用する場合、単離ＭＣＭＢとバインダーを混合した後、成型焼成していた。また、粗ＭＣＭＢは、タールやピッチマトリックスに由来するピッチ成分（以下、単に、ピッチ成分という。）がＭＣＭＢの球体の周囲を取り囲み、ピッチ成分が癒着することにより、図１３に示すように、ピッチ成分で覆われたＭＣＭＢ同士が癒着、凝集した状態となっているが、トルエン等のように溶解力が弱過ぎる溶剤を用いられば、ピッチ成分の癒着部分を溶解し、ＭＣＭＢの球体の周囲が、ピッチ成分で覆われたＭＣＭＢをピッチ成分から、独立に分離することが困難であった。
従来用いられたキノリン等とトルエン等の溶剤の溶解力が強過ぎ又は弱過ぎたため、溶解力が中程度の安価な溶剤によりタールやピッチマトリックスに由来するピッチ成分の癒着部分のみを溶解し、ＭＣＭＢの球体の周囲のピッチ成分はそのまま溶解させないで残し、ピッチ成分で覆われたＭＣＭＢを独立して分離精製することが大きな課題となっていた。さらに、このような単離ＭＣＭＢから特殊炭素材の各用途に使用する場合、単離ＭＣＭＢとバインダーを混合した後、成型焼成する必要があったが、このバインダーを混合する行程の省略化によるコストダウンを図ることも課題となっていた。そこで、本発明は、コールタールやコールタールピッチなどの石炭系重質油を原料として、独立分離精製された、ＭＣＭＢの球体の周囲を均一な膜厚のピッチ成分で覆われたＭＣＭＢを製造することを目的とする。また、従来用いられたキノリン等により独立して分離精製されたＭＣＭＢを製造することができるが、キノリン等は高価であり、安価な溶剤により、独立して分離精製されたＭＣＭＢを製造することをも目的とする。 Solvents such as conventionally used quinoline and toluene and the solvent such as toluene were too strong or too weak, so that only a coalescence portion of the pitch component derived from the tar or pitch matrix was dissolved with an inexpensive solvent having a medium solubility, and MCMB It has been a great problem to leave the pitch component around the sphere without dissolving it as it is, and to independently separate and purify the MCMB covered with the pitch component. Further, when such an isolated MCMB is used for each purpose as a special carbon material, it is necessary to mix the isolated MCMB and a binder and then form and bake. However, the cost due to the omission of the step of mixing the binder is required. It was also an issue to go down. Therefore, the present invention produces an MCMB in which the periphery of an MCMB sphere is covered with a pitch component having a uniform thickness by using a coal-based heavy oil such as coal tar or coal tar pitch as a raw material. The purpose is to: In addition, although it is possible to produce MCMB which is independently separated and purified by a conventionally used quinoline or the like, quinoline or the like is expensive, and it is necessary to produce MCMB which is independently separated and purified by an inexpensive solvent. Also aim.
従来用いられたキノリン等とトルエン等の溶剤の溶解力が強過ぎ又は弱過ぎたため、溶解力が中程度の安価な溶剤としてタール中油を選定することにより、ピッチマトリックスに由来するピッチ成分の癒着部分のみを溶解して ピッチ成分の膜厚を制御して 球体の周囲を覆っているＭＣＭＢを発明した。
［請求項１］石炭系重質油を熱処理し、生成した粗メソカーボンマイクロビーズを遠心分離後、沸点範囲１００〜５００℃のタール中油を粗メソカーボンマイクロビーズ重量の０．１〜２０倍量加え、１０〜３００℃で０．１〜２０時間洗浄処理することにより得られる、メソカーボンマイクロビーズの球体の周囲が０．０１〜１μｍの厚さのピッチ成分で覆われており、しかも球体同士が癒着または凝集しないメソカーボンマイクロビーズ生品。
［請求項２］請求項１記載のメソカーボンマイクロビーズ生品を、粉体のまま炭化することによって得られ、表面に異方性組織を有するリチウム２次電池負極材料の用途に使用されるメソカーボンマイクロビーズ炭化品。
［請求項３］請求項１記載のメソカーボンマイクロビーズ生品を、粉体のまま炭化し、次に黒鉛化することによって得られ、表面に異方性組織を有するリチウム２次電池負極材料の用途に使用されるメソカーボンマイクロビーズ黒鉛化品。
［請求項４］請求項１記載のメソカーボンマイクロビーズ生品に酸化処理を行い、粉体のまま炭化することによって得られ、表面に等方性組織を有するリチウム２次電池負極材料の用途に使用されるメソカーボンマイクロビーズ炭化品。
［請求項５］請求項１記載のメソカーボンマイクロビーズ生品に酸化処理を行い、粉体のまま炭化し、次に黒鉛化することによって得られ、表面に等方性組織を有するリチウム２次電池負極材料の用途に使用されるメソカーボンマイクロビーズ黒鉛化品。
［請求項６］１〜１０μｍの厚さのピッチ成分で覆われた請求項１〜５記載のリチウム２次電池負極材料の用途に使用されるメソカーボンマイクロビーズ生品、メソカーボンマイクロビーズの黒鉛化品又はメソカーボンマイクロビーズの炭化品。
すなわち、コールタールやコールタールピッチなどの 石炭系重質油を熱処理し、生成した粗メソカーボンマイクロビーズを遠心分離後、沸点範囲１００〜５００℃のタール中油を粗メソカーボンマイクロビーズ重量の０．１〜２０倍量加え、１０〜３００℃で０．１〜２０時間洗浄処理することにより得られる０．０１〜１０μｍのピッチ成分で覆われており、しかも球体同士が癒着または凝集しないメソカーボンマイクロビーズ生品、を得る。この時洗浄処理することにより、ＭＣＭＢの球体の周囲を覆っているピッチ成分の膜厚を０．０１〜１０μｍに調製することができる。（溶剤分析におけるＴＩ〜ＱＩの値を０〜２０％に調製することができる。）
すなわち、タール中油の量と洗浄時間を洗浄温度を加減することにより、溶剤の洗浄力をコントロールすることによりピッチ成分に覆われたＭＣＭＢ生品を独立して分離精製することができ、さらにＭＣＭＢを覆ったピッチ成分の膜厚を均一かつ所定の厚さにすることが可能となった。タール中油の量が少なすぎると均一に洗浄することができず、多すぎるとタール中油がコスト高となる。洗浄時間は短か過ぎると、ピッチ成分に覆われたＭＣＭＢを独立して分離することができず、長すぎると、ピッチ成分に覆われていないＭＣＭＢを独立して分離することができるが、必要以上の時間をかけ過ぎ不経済となる。洗浄温度は、高くなる程、タール中油の溶解力が大となり、ＭＣＭＢを覆ったピッチ成分の膜厚を薄くまたはピッチ成分で覆われていないＭＣＭＢを製造することができる。ここに、洗浄は、機械攪拌等の攪拌下、ＭＣＭＢを覆っているピッチ成分の癒着部分のみを溶解させた後、各ピッチ成分で覆われたＭＣＭＢ同士を衝突させて、機械的な力によりピッチ成分の角部分が研磨されて球面状の均一な膜厚とすることができる。ＭＣＭＢの球体の周囲を覆っているピッチ成分は、ＭＣＭＢ生品を成型及び焼成して炭素製品を製造するに際し、焼成時に軟化溶融して収縮率を高め、炭素製品の密度及び強度を向上させる効果を有するため、非常に有用なものである。特に、ピッチ成分の膜厚が均一であることは、ＭＣＭＢ生品を成型及び焼成してできた炭素製品の密度及び強度等の品質が均一であるという利点がある。また、上記の方法で得られたＭＣＭＢの球体の周囲が均一にピッチ成分で覆われているＭＣＭＢ生品は、粉体のまま炭化さらには黒鉛化焼成を行ってもＭＣＭＢの球体の周囲のピッチ成分は異方性組織となって維持され、図１４に示すように、球体同士が癒着、凝集することはない。さらに、生品の段階で酸化処理を行っておけば、焼成時に表面のピッチ成分は等方性組織となる。こうして得られたＭＣＭＢの球体の周囲がピッチ成分で覆われているＭＣＭＢの炭化品ならびに黒鉛化品はリチウム二次電池の負極材として用いた場合、電解液の有機溶媒と反応しにくいという利点を有している。この理由として、ＭＣＭＢは、活性な結晶子の端面（ｅｄｇｅ ｐｌａｎｅ）が、外側に配向しているため、電解液の有機溶媒と反応しやすい。これを炭素の縮合多環網目である基底面（ｂａｓａｌ ｐｌａｎｅ）が外側に配向しているピッチ成分で覆うことにより、電解液の有機溶媒との反応を防止できるからであると考えられる。ＭＣＭＢの球体の周囲がピッチ成分で覆われていないＭＣＭＢは、粉体のまま炭化さらには黒鉛化することにより、ＭＣＭＢ炭化品および黒鉛化品が得られる。こうして得られたＭＣＭＢの球体の周囲がピッチ成分で覆われていないＭＣＭＢの炭化品、黒鉛化品はリチウム二次電池の負極材として用いた場合、ピッチ成分で覆われていない効果として、リチウムイオンの吸蔵能力が向上するため、放電容量より充放電効率が高い値となる。この理由として、球体表面のピッチ成分は、炭素の縮合多環網目である基底面（ｂａｓａｌ ｐｌａｎｅ）が球面方向に配向しているので、リチウムイオンの出入りを阻害する。しかし、この表面層が除去されれば、精製ＭＣＭＢ内の結晶子の端面（ｅｄｇｅ ｐｌａｎｅ）が、球体表面に露出するため、この端面から出るためリチウムイオンが出入りしやすくなり精製ＭＣＭＢが本来有するリチウムイオン吸蔵能力を十分に発揮するからであると予想される。また、これらのＭＣＭＢを炭化、さらには、黒鉛化しても、表面のピッチ成分は維持され、異方性組織のままであることが実験的に確認された。また、生品の段階で酸化しておけば、ピッチ成分は等方性組織となることも実験的に確認された。なお、上記において、等方性組織からなるピッチ成分に覆われたＭＣＭＢの炭化品または黒鉛化品は、リチウム二次電池負極材料等の各用途に使用されると、異方性組織からなるピッチ成分に覆われたＭＣＭＢの炭化品または黒鉛化品に比較して、溶媒と反応しにくいという利点がある。すなわち、ＭＣＭＢ生品を粉体のまま、炭化および黒鉛化する前に、酸化雰囲気中、２０〜３００℃の温度範囲で酸化する行程を設ければ、ＭＣＭＢ生品をそのままで、粉体のまま、炭化および黒鉛化した場合に比較して、炭化品または黒鉛化品は、より溶媒と反応しにくくなる。
Solvents of conventionally used solvents such as quinoline etc. and toluene etc. were too strong or too weak, so by selecting tar medium oil as an inexpensive solvent with a medium solubility, the coalescence of pitch components derived from the pitch matrix Invented MCMB that covers the periphery of a sphere by dissolving only the pitch component and controlling the film thickness of the pitch component.
[Claim 1] Coal-based heavy oil is heat-treated, and the resulting crude mesocarbon microbeads are centrifuged, and then the tar-medium oil having a boiling range of 100 to 500 ° C is 0.1 to 20 times the weight of the crude mesocarbon microbeads. In addition, the periphery of the sphere of the mesocarbon microbeads obtained by performing the washing treatment at 10 to 300 ° C. for 0.1 to 20 hours is covered with a pitch component having a thickness of 0.01 to 1 μm. Mesocarbon microbeads that do not adhere or aggregate.
[Claim 2] A mesocarbon microbead according to
[Claim 3] A negative electrode material for a lithium secondary battery, which is obtained by carbonizing the raw mesocarbon microbeads according to
[Claim 4] The raw mesocarbon microbeads according to
[5] A lithium secondary material obtained by subjecting the raw mesocarbon microbeads according to [1] to an oxidation treatment, carbonizing the powder as it is, and then graphitizing, and having an isotropic structure on the surface. Graphitized mesocarbon microbeads used for battery anode materials.
[Claim 6] Raw mesocarbon microbeads and graphite of mesocarbon microbeads used for a negative electrode material for a lithium secondary battery according to
That is, coal-based heavy oil such as coal tar or coal tar pitch is heat-treated, and the resulting crude mesocarbon microbeads are centrifuged. A mesocarbon microparticle covered with a pitch component of 0.01 to 10 μm obtained by washing at 0.1 to 20 hours at a temperature of 10 to 300 ° C. and not adhering or coagulating spheres. Get raw beads. At this time, by performing the washing treatment, the thickness of the pitch component covering the periphery of the sphere of MCMB can be adjusted to 0.01 to 10 μm. (The value of TI to QI in solvent analysis can be adjusted to 0 to 20%.)
That is, by controlling the washing power of the solvent by adjusting the amount of the oil in the tar and the washing time to the washing temperature, the MCMB raw product covered with the pitch component can be separated and purified independently by controlling the washing power of the solvent. The thickness of the covered pitch component can be made uniform and a predetermined thickness. If the amount of the oil in the tar is too small, it cannot be washed uniformly. If the amount is too large, the cost of the oil in the tar increases. If the cleaning time is too short, the MCMB covered with the pitch component cannot be separated independently, and if the cleaning time is too long, the MCMB not covered with the pitch component can be separated independently. It takes too much time and becomes uneconomical. The higher the washing temperature, the greater the dissolving power of the oil in the tar, and the smaller the thickness of the pitch component covering the MCMB, or the more the MCMB not covered with the pitch component can be produced. Here, the washing is performed by dissolving only the adhered portion of the pitch component covering the MCMB under stirring such as mechanical stirring, and then colliding the MCMB covered with each pitch component with each other, and the mechanical force is applied to the pitch. The corners of the components are polished to obtain a spherical uniform film thickness. The pitch component covering the periphery of the sphere of MCMB, when forming and firing a raw MCMB product to produce a carbon product, softens and melts during firing to increase the shrinkage and improve the density and strength of the carbon product. Is very useful. In particular, the uniform film thickness of the pitch component has the advantage that the quality, such as the density and strength, of the carbon product obtained by molding and firing the MCMB raw product is uniform. Further, the MCMB raw product obtained by the above method, in which the periphery of the MCMB sphere is uniformly covered with the pitch component, can be carbonized as it is as a powder, and even if the graphitization firing is performed, the pitch around the MCMB sphere can be reduced. The components are maintained in an anisotropic structure, and the spheres do not adhere or aggregate as shown in FIG. Furthermore, if the oxidation treatment is performed at the stage of the raw product, the pitch component on the surface becomes an isotropic structure during firing. The MCMB carbonized and graphitized products obtained by covering the periphery of the spheres of the MCMB thus obtained with the pitch component have an advantage that when used as a negative electrode material of a lithium secondary battery, they hardly react with an organic solvent of an electrolytic solution. Have. For this reason, MCMB easily reacts with the organic solvent of the electrolytic solution because the edge planes (edge planes) of active crystallites are oriented outward. It is considered that the reaction with the organic solvent of the electrolytic solution can be prevented by covering this with a pitch component whose basal plane, which is a carbon condensed polycyclic network, is oriented outward. MCMB in which the periphery of the sphere of MCMB is not covered with the pitch component is carbonized and graphitized in powder form to obtain carbonized MCMB and graphitized products. The MCMB carbonized and graphitized products in which the periphery of the spheres of the MCMB thus obtained are not covered with the pitch component are used as the negative electrode material of the lithium secondary battery. Is increased, so that the charge / discharge efficiency is higher than the discharge capacity. The reason for this is that the pitch component on the surface of the sphere impedes the entry and exit of lithium ions because the basal plane, which is a fused polycyclic network of carbon, is oriented in the spherical direction. However, if this surface layer is removed, the edge plane (edge plane) of the crystallite in the purified MCMB is exposed to the sphere surface, so that the lithium ion easily enters and exits from this edge face, and the lithium which the purified MCMB originally has It is expected that this is because the ion storage capacity is sufficiently exhibited. Further, it was experimentally confirmed that even if these MCMB were carbonized and further graphitized, the pitch component on the surface was maintained and remained anisotropic structure. It was also experimentally confirmed that the pitch component had an isotropic structure if oxidized at the stage of the raw product. In the above, the carbonized or graphitized MCMB covered with the pitch component composed of an isotropic structure, when used in various applications such as a negative electrode material for a lithium secondary battery, has a pitch composed of an anisotropic structure. There is an advantage that it is less likely to react with a solvent as compared to a carbonized or graphitized MCMB covered with a component. That is, if a step of oxidizing the raw MCMB in a temperature range of 20 to 300 ° C. in an oxidizing atmosphere before carbonizing and graphitizing the raw raw MCMB is provided, the raw raw MCMB is left in the powder state as it is. The carbonized product or the graphitized product is less likely to react with the solvent as compared with the case of carbonization and graphitization.
本発明は、精製ＭＣＭＢの球体の周囲を覆っているピッチ成分の膜厚を０．０１〜１０μｍとくに０．０１から１μｍの薄さに制御できるため、ＭＣＭＢの球体の周囲がピッチ成分で均一に覆われたＭＣＭＢ、及び、ＭＣＭＢの球体の周囲がピッチ成分で覆われていないＭＣＭＢを製造することができる。タール中油による洗浄条件をコントロールすることにより、電解液の有機溶媒と反応しにくいという性質を有するＭＣＭＢの球体の周囲が厚いピッチ成分で均一に覆われたＭＣＭＢ、あるいは、充放電効率が高いという性質を有するＭＣＭＢの球体の周囲が薄いピッチ成分で均一に覆われたＭＣＭＢの両方を適宜選択的に製造することができる。
したがって、ピッチ成分の膜厚を制御することによりピッチ成分で均一に覆われたＭＣＭＢの性質を予測してピッチ成分で覆われたＭＣＭＢを製造することができる。さらに、ＭＣＭＢの球体の周囲がピッチ成分で均一に覆われたＭＣＭＢは、成型する場合、従来であれば、単離ＭＣＭＢを接着するために、用いるバインダーの役割をＭＣＭＢの球体の周囲を覆っているピッチ成分に負わせるためにバインダーとＭＣＭＢを混合する行程を省略できるという効果がある。そして、従来は、単離ＭＣＭＢとバインダーを混合して成型されたものを炭化または黒鉛化する場合、バインダーの量が少な過ぎると、単離ＭＣＭＢの隙間をピッチ成分が十分に埋めることができず局部的に強度が弱い部分を生じ、全体の製品としても強度が不十分となる。また、逆に、バインダーの量が多過ぎると、焼成時に膨張して、成型時に割れてしまうという不都合があり、単離ＭＣＭＢとバインダーを混合割合に留意する必要があった。ここに、本発明では、バインダーの役割をするピッチ成分の膜厚を適当な厚さに制御することにより従来の上記の様な不都合を回避できるという効果を有する。
The present invention can control the thickness of the pitch component covering the periphery of the purified MCMB sphere to a thickness of 0.01 to 10 μm, particularly 0.01 to 1 μm. A covered MCMB and an MCMB in which the periphery of the sphere of the MCMB is not covered with the pitch component can be manufactured. By controlling the washing conditions with oil in tar, it is difficult to react with the organic solvent of the electrolytic solution. MCMB in which the circumference of the sphere of MCMB is uniformly covered with a thick pitch component, or high charge / discharge efficiency Both MCMBs in which the periphery of a sphere of MCMB having a uniform pitch is uniformly covered with a thin pitch component can be appropriately and selectively manufactured.
Therefore, by controlling the film thickness of the pitch component, the properties of the MCMB uniformly covered with the pitch component can be predicted, and the MCMB covered with the pitch component can be manufactured. Furthermore, when molding the MCMB in which the periphery of the sphere of the MCMB is uniformly covered with the pitch component, conventionally, in order to bond the isolated MCMB, the role of the binder used is to cover the periphery of the sphere of the MCMB. There is an effect that the process of mixing the binder and the MCMB in order to impose a certain pitch component can be omitted. Conventionally, when carbonizing or graphitizing a molded product obtained by mixing an isolated MCMB and a binder, if the amount of the binder is too small, the pitch component cannot sufficiently fill the gaps of the isolated MCMB. A locally weak part is generated, and the strength is insufficient as a whole product. Conversely, if the amount of the binder is too large, there is a disadvantage that the binder expands during firing and breaks during molding, so that attention has to be paid to the mixing ratio of the isolated MCMB and the binder. Here, in the present invention, by controlling the thickness of the pitch component serving as a binder to an appropriate thickness, there is an effect that the above-described disadvantages of the related art can be avoided.
以下に実施例および比較例を示し、本発明の特徴とするところをより一層明確にする。 Examples and comparative examples are shown below to further clarify features of the present invention.
〔偏光顕微鏡観察〕ＭＣＭＢを樹脂と混合して、成型、研磨を行ない、光源にハロゲン白熱灯を用いたＺｅｉｓｓ社製オルソルックス反射偏光顕微鏡により、直交ニコル下で石こう検板を入れて組織を観察した。 [Polarization microscope observation] MCMB was mixed with resin, molded and polished, and a gypsum test plate was inserted under orthogonal Nicols using a Zeiss Ortholux reflection polarization microscope using a halogen incandescent lamp as a light source to observe the tissue. did.
実施例１
１００℃以下の沸点留分を除去したコールタール（一次ＱＩ含有率２．０％）を高温遠心分離し、清澄液（一次ＱＩ含有率トレース）を得た。遠心分離機としては、保有容積４０リットル遠心力分離機を使用し、回転数３０００ｒｐｍ、遠心力２２８０Ｇ、温度２００℃、処理量１ｔｏｎ／ｈｒの条件下に操作した。次いで、清澄液を温度３９５℃、圧力０．４ＭＰａに１６時間熱処理することにより、反応生成物（二次ＱＩ分４．４重量％）を得た後、上記と同様の第二の遠心分離機を使用して、回転数６０００ｒｐｍ、遠心力３０００Ｇ、温度２７０℃、処理量１ｔｏｎ／ｈｒの条件下に再度遠心分離に供し、粗ＭＣＭＢを収得した。次いで、上記のようにして得た粗ＭＣＭＢ１部に対し、１部のタール中油（沸点範囲２３０〜３３０℃）を加え、攪拌下に１５０℃で１時間洗浄処理した後、遠心分離して一次洗浄したＭＣＭＢを得た。次いで、上記で得た一次洗浄後のＭＣＭＢ１部に対し、トルエン１部を加え、攪拌下に２０℃で１時間洗浄処理をした後、遠心分離して二次洗浄を行い、精製ＭＣＭＢを得た。図７に一次洗浄ＭＣＭＢと生成ＭＣＭＢの性状を示す。この精製ＭＣＭＢの偏光顕微鏡での観察結果を図１（ａ）に示す。図１（ａ）においてＭＣＭＢ球体の粒径は１０μｍ、ＭＣＭＢの球体の周囲を覆っているピッチ成分の膜厚は０．１μｍである。しかも球体同士が癒着または凝集していないことがわかる。以下、この精製ＭＣＭＢをＭＣＭＢ生品と呼ぶことにする。このＭＣＭＢ生品を粉体のまま、窒素雰囲気中、１０００℃で１時間焼成し、炭化した。この炭化ＭＣＭＢの偏光顕微鏡での観察結果を図１（ｂ）に示す。図１（ｂ）において炭化ＭＣＭＢの球体の周囲が異方性組織からなるピッチ成分で均一に覆われており、しかも球体同士が癒着または凝集していないことがわかる。以下、この炭化ＭＣＭＢをＭＣＭＢ炭化品と呼ぶことにする。このＭＣＭＢ炭化品を粉体のまま、窒素雰囲気中、２８００℃で１時間焼成し、黒鉛化した。この黒鉛化ＭＣＭＢの偏光顕微鏡での観察結果を図１（ｃ）に示す。図１（ｃ）において黒鉛化ＭＣＭＢの球体の周囲が異方性組織からなるピッチ成分で均一に覆われていることがわかる。
Example 1
Coal tar (primary QI content: 2.0%) from which a boiling point fraction of 100 ° C. or less was removed was centrifuged at high temperature to obtain a clear liquid (primary QI content trace). The centrifugal separator used was a 40-liter centrifugal force separator having a rotation speed of 3000 rpm, a centrifugal force of 2280 G, a temperature of 200 ° C., and a throughput of 1 ton / hr. Then, the clarified liquid is heat-treated at a temperature of 395 ° C. and a pressure of 0.4 MPa for 16 hours to obtain a reaction product (secondary QI content: 4.4% by weight). The mixture was centrifuged again under the conditions of a rotation speed of 6000 rpm, a centrifugal force of 3000 G, a temperature of 270 ° C., and a processing amount of 1 ton / hr to obtain crude MCMB. Next, 1 part of the crude MCMB obtained above was added with 1 part of a medium in tar (boiling point range of 230 to 330 ° C.), washed at 150 ° C. for 1 hour with stirring, and then centrifuged to perform primary washing. MCMB was obtained. Next, 1 part of toluene was added to 1 part of the MCMB after the primary washing obtained above, and the mixture was subjected to a washing treatment at 20 ° C. for 1 hour with stirring, followed by centrifugal separation and secondary washing to obtain purified MCMB. . FIG. 7 shows the properties of the primary washed MCMB and the generated MCMB. FIG. 1 (a) shows the results of observation of the purified MCMB with a polarizing microscope. In FIG. 1A, the particle size of the MCMB sphere is 10 μm, and the thickness of the pitch component covering the periphery of the MCMB sphere is 0.1 μm. Moreover, it can be seen that the spheres do not adhere or aggregate. Hereinafter, this purified MCMB is referred to as a raw MCMB product. The raw MCMB was calcined in a nitrogen atmosphere at 1000 ° C. for 1 hour in the form of powder, and carbonized. The observation result of the carbonized MCMB by a polarizing microscope is shown in FIG. In FIG. 1 (b), it can be seen that the periphery of the carbonized MCMB spheres is uniformly covered with the pitch component composed of an anisotropic structure, and that the spheres do not adhere or aggregate. Hereinafter, this carbonized MCMB will be referred to as MCMB carbonized product. This MCMB carbonized product was calcined in a nitrogen atmosphere at 2800 ° C. for 1 hour in the form of a powder to be graphitized. FIG. 1 (c) shows the results of observation of the graphitized MCMB with a polarizing microscope. In FIG. 1C, it can be seen that the periphery of the sphere of the graphitized MCMB is uniformly covered with a pitch component composed of an anisotropic structure.
実施例２
実施例１と同様にして得られた粗ＭＣＭＢ１部に対し、１部のタール中油（沸点範囲２３０〜３３０℃）を加え、攪拌下に１００℃で１時間洗浄処理した後、遠心分離して一次洗浄したＭＣＭＢを得た。次いで、上記で得た一次洗浄後のＭＣＭＢ１部に対し、トルエン１部を加え、攪拌下に２０℃で１時間洗浄処理した後、遠心分離して二次洗浄を行い、精製ＭＣＭＢを得た。図８に一次洗浄ＭＣＭＢと精製ＭＣＭＢの性状を示す。この精製ＭＣＭＢの偏光顕微鏡での観察結果を図２（ａ）に示す。図２（ａ）においてＭＣＭＢ球体の粒径は１０μｍ、ＭＣＭＢの球体の周囲を覆っているピッチ成分の膜厚は０．２μｍである。しかも球体同士が癒着または凝集していないことがわかる。このＭＣＭＢ生品を空気雰囲気中、１２０℃で３時間酸化処理した後、粉体のまま、窒素雰囲気中、１０００℃で１時間焼成し、炭化した。この炭化ＭＣＭＢの偏光顕微鏡での観察結果を図２（ｂ）に示す。図２（ｂ）において球体の周りが、等方性組織からなるピッチ成分で均一に覆われており、しかも球体同士が癒着または凝集していないことがわかる。このＭＣＭＢ炭化品を粉体のまま、窒素雰囲気中、２８００℃で１時間焼成し、黒鉛化した。黒鉛化ＭＣＭＢの偏光顕微鏡での観察結果を図２（ｃ）に示す。図２（ｃ）において球体の周りが等方性組織からなるピッチ成分で均一に覆われており、しかも球体同士が癒着または凝集していないことがわかる。
Example 2
To 1 part of the crude MCMB obtained in the same manner as in Example 1, 1 part of a medium in tar (boiling range: 230 to 330 ° C.) was added, and the mixture was washed at 100 ° C. for 1 hour with stirring, and then centrifuged to separate the primary liquid. A washed MCMB was obtained. Next, 1 part of toluene was added to 1 part of the MCMB obtained above after the primary washing, and the mixture was subjected to a washing treatment at 20 ° C. for 1 hour with stirring, followed by centrifugal separation for secondary washing to obtain purified MCMB. FIG. 8 shows the properties of the primary washed MCMB and the purified MCMB. FIG. 2 (a) shows the result of observation of the purified MCMB with a polarizing microscope. In FIG. 2A, the particle size of the MCMB sphere is 10 μm, and the film thickness of the pitch component covering the periphery of the MCMB sphere is 0.2 μm. Moreover, it can be seen that the spheres do not adhere or aggregate. The MCMB raw product was oxidized in an air atmosphere at 120 ° C. for 3 hours, and then calcined in a nitrogen atmosphere at 1000 ° C. for 1 hour in a nitrogen atmosphere to carbonize. FIG. 2 (b) shows the results of observation of the carbonized MCMB with a polarizing microscope. In FIG. 2B, it can be seen that the periphery of the sphere is uniformly covered with the pitch component composed of an isotropic tissue, and that the spheres do not adhere or aggregate. This MCMB carbonized product was calcined in a nitrogen atmosphere at 2800 ° C. for 1 hour in the form of a powder to be graphitized. FIG. 2 (c) shows the results of observation of the graphitized MCMB with a polarizing microscope. In FIG. 2 (c), it can be seen that the periphery of the sphere is uniformly covered with the pitch component composed of an isotropic tissue, and that the spheres do not adhere or aggregate.
実施例３
実施例１と同様にして得られて粗ＭＣＭＢ１部に対し、１部のタール中油（沸点範囲２３０〜３３０℃）を加え、攪拌下に２０℃で１時間洗浄処理した後、遠心分離して一次洗浄したＭＣＭＢを得た。次いで、上記で得た一次洗浄後のＭＣＭＢ１部に対し、トルエン１部を加え、攪拌下に２０℃で１時間洗浄処理をした後、遠心分離して二次洗浄を行い、図９に一次洗浄ＭＣＭＢと精製ＭＣＭＢの性状を示す。この精製ＭＣＭＢ生品の偏光顕微鏡での観察結果を図３に示す。図３においてＭＣＭＢ球体の粒径は１０μｍ、ＭＣＭＢの球体の周囲を覆っているピッチ成分の膜厚は０．３μｍである。しかも球体同士が癒着または凝集していないことがわかる。
Example 3
To 1 part of the crude MCMB obtained in the same manner as in Example 1, 1 part of a medium in tar (boiling point range of 230 to 330 ° C.) was added, washed with stirring at 20 ° C. for 1 hour, and then centrifuged to separate the primary A washed MCMB was obtained. Next, 1 part of toluene was added to 1 part of the MCMB after the primary washing obtained above, a washing treatment was performed at 20 ° C. for 1 hour with stirring, and then a secondary washing was performed by centrifugation. The properties of MCMB and purified MCMB are shown. FIG. 3 shows the results of observation of the purified MCMB raw product under a polarizing microscope. In FIG. 3, the particle size of the MCMB sphere is 10 μm, and the film thickness of the pitch component covering the periphery of the MCMB sphere is 0.3 μm. Moreover, it can be seen that the spheres do not adhere or aggregate.
実施例４
実施例１と同様にして得られた粗ＭＣＭＢ１部に対し、１部のタール中油（沸点範囲２３０〜３３０℃）を加え、攪拌下に２００℃で１時間洗浄処理した後、遠心分離して一次洗浄したＭＣＭＢを得た。次いで、上記で得た一次洗浄後のＭＣＭＢ１部に対し、トルエン１部を加え、攪拌下に２０℃で１時間洗浄処理をした後、遠心分離して二次洗浄を行い、精製ＭＣＭＢを得た。図１０に一次洗浄ＭＣＭＢと精製ＭＣＭＢの性状を示す。このＭＣＭＢ生品の偏光顕微鏡での観察結果を図４（ａ）に示す。図４（ａ）において球体の周りのピッチ成分が完全に取り除かれていることがわかる。この精製ＭＣＭＢ生品を粉体もまま、窒素雰囲気中、１０００℃で１時間焼成し、炭化した。この炭化ＭＣＭＢの偏光顕微鏡での観察結果を図４（ｂ）に示す。このＭＣＭＢ炭化品を粉体のまま、窒素雰囲気中、２８００℃で１時間焼成し、黒鉛化した。この黒鉛化ＭＣＭＢの偏光顕微鏡での観察結果を図４（ｃ）に示す。
Example 4
1 part of crude MCMB obtained in the same manner as in Example 1 was added with 1 part of oil in tar (boiling point range of 230 to 330 ° C.), washed at 200 ° C. for 1 hour with stirring, and then centrifuged to separate primary oil. A washed MCMB was obtained. Next, 1 part of toluene was added to 1 part of the MCMB after the primary washing obtained above, and the mixture was subjected to a washing treatment at 20 ° C. for 1 hour with stirring, followed by centrifugal separation and secondary washing to obtain purified MCMB. . FIG. 10 shows the properties of the primary washed MCMB and the purified MCMB. FIG. 4 (a) shows the result of observation of the raw MCMB using a polarizing microscope. In FIG. 4A, it can be seen that the pitch component around the sphere has been completely removed. The purified MCMB raw material was calcined at 1000 ° C. for 1 hour in a nitrogen atmosphere while keeping the powder, and carbonized. FIG. 4 (b) shows the results of observation of the carbonized MCMB with a polarizing microscope. This MCMB carbonized product was calcined in a nitrogen atmosphere at 2800 ° C. for 1 hour in the form of a powder to be graphitized. FIG. 4 (c) shows the results of observation of the graphitized MCMB with a polarizing microscope.
実施例５
１００℃以下の沸点留分を除去したコールタール（一次ＱＩ含有率２．０％）を高温遠心分離し、清澄液（一次ＱＩ含有率トレース）を得た。遠心分離機としては、保有容積４０リットルの横型遠心分離機を使用し、回転数３０００ｒｐｍ、遠心力２２８０Ｇ、温度２００℃、処理量１ｔｏｎ／ｈｒの条件下に操作した。次いで、清澄液を温度４１０℃、圧力０．４ＭＰａに１６時間熱処理することにより、反応生成物（二次ＱＩ分２０重量％）を得た後、上記と同様の第二の遠心分離機を使用して、回転数６０００ｒｐｍ、遠心力３０００Ｇ、温度２７０℃、処理量１ｔｏｎ／ｈｒの条件下に再度遠心分離に供し、粗ＭＣＭＢを収得した。次いで、上記のようにして得た粗ＭＣＭＢ１部に対し、１部のタール中油（沸点範囲２３０〜３３０℃）を加え、攪拌下に１５０℃で１時間洗浄処理した後、遠心分離して一次洗浄したＭＣＭＢを得た。次いで、上記で得た一次洗浄後のＭＣＭＢ１部に対し、トルエン１部を加え、攪拌下に２０℃で１時間洗浄処理をした後、遠心分離して二次洗浄を行い、精製ＭＣＭＢを得た。図１１に一次洗浄ＭＣＭＢと精製ＭＣＭＢの性状を示す。この精製ＭＣＭＢの偏光顕微鏡での観察結果を図５に示す。図５においてＭＣＭＢ球体の粒径は１００μｍ、ＭＣＭＢの球体の周囲を覆っているピッチ成分の膜厚は１μｍである。しかも球体同士が癒着または凝集していないことがわかる。
Example 5
Coal tar (primary QI content: 2.0%) from which a boiling point fraction of 100 ° C. or less was removed was centrifuged at high temperature to obtain a clear liquid (primary QI content trace). As the centrifugal separator, a horizontal centrifuge having a holding volume of 40 liters was used, and operated under the conditions of a rotation speed of 3000 rpm, a centrifugal force of 2280 G, a temperature of 200 ° C., and a processing amount of 1 ton / hr. Next, the clarified liquid is heat-treated at a temperature of 410 ° C. and a pressure of 0.4 MPa for 16 hours to obtain a reaction product (secondary QI content: 20% by weight), and then a second centrifuge similar to the above is used. Then, the mixture was again subjected to centrifugal separation under the conditions of a rotation number of 6000 rpm, a centrifugal force of 3000 G, a temperature of 270 ° C., and a processing amount of 1 ton / hr, to obtain crude MCMB. Next, 1 part of the crude MCMB obtained above was added with 1 part of a medium in tar (boiling point range of 230 to 330 ° C.), washed at 150 ° C. for 1 hour with stirring, and then centrifuged to perform primary washing. MCMB was obtained. Next, 1 part of toluene was added to 1 part of the MCMB after the primary washing obtained above, and the mixture was subjected to a washing treatment at 20 ° C. for 1 hour with stirring, followed by centrifugal separation and secondary washing to obtain purified MCMB. . FIG. 11 shows the properties of the primary washed MCMB and the purified MCMB. FIG. 5 shows the results of observation of the purified MCMB with a polarizing microscope. In FIG. 5, the particle size of the MCMB sphere is 100 μm, and the film thickness of the pitch component covering the periphery of the MCMB sphere is 1 μm. Moreover, it can be seen that the spheres do not adhere or aggregate.
実施例６
実施例５と同様にして得られた粗ＭＣＭＢ１部に対し、１部のタール中油（沸点範囲２３０〜３３０℃）を加え、攪拌下に２０℃で１時間洗浄処理した後、遠心分離して一次洗浄したＭＣＭＢを得た。次いで、上記で得た一次洗浄後のＭＣＭＢ１部に対し、トルエン１部を加え、攪拌下に２０℃で１時間洗浄処理した後、遠心分離して二次洗浄を行い、精製ＭＣＭＢを得た。図１２に一次洗浄ＭＣＭＢと精製ＭＣＭＢの性状を示す。この精製ＭＣＭＢ生品の偏光顕微鏡での観察結果を図６に示す。図６においてＭＣＭＢ球体の粒径は１００μｍ、ＭＣＭＢの球体の周囲を覆っているピッチ成分の膜厚は５μｍである。しかも球体同士が癒着または凝集していないことがわかる。
Example 6
To 1 part of the crude MCMB obtained in the same manner as in Example 5, 1 part of a medium in tar (boiling point range of 230 to 330 ° C.) was added, washed with stirring at 20 ° C. for 1 hour, and then centrifuged to separate the primary A washed MCMB was obtained. Next, 1 part of toluene was added to 1 part of the MCMB obtained above after the primary washing, and the mixture was subjected to a washing treatment at 20 ° C. for 1 hour with stirring, followed by centrifugal separation for secondary washing to obtain purified MCMB. FIG. 12 shows the properties of the primary washed MCMB and the purified MCMB. FIG. 6 shows the results of observation of the purified MCMB raw product by a polarizing microscope. In FIG. 6, the particle size of the MCMB sphere is 100 μm, and the film thickness of the pitch component covering the periphery of the MCMB sphere is 5 μm. Moreover, it can be seen that the spheres do not adhere or aggregate.
尚、特許請求の範囲の項に図面との対照を便利にするために符号を記すが、該記入により本発明は添付図面の構成に限定されるものではない。 Incidentally, reference numerals are written in the claims for convenience of comparison with the drawings, but the present invention is not limited to the configuration of the attached drawings by the entry.
１ ＭＣＭＢ
２ ピッチ成分
３ ピッチ成分同士の癒着部分
1 MCMB
2
Claims (6)
6. Raw mesocarbon microbeads, graphitized mesocarbon microbeads or mesocarbon for use as a negative electrode material for a lithium secondary battery according to claim 1, which is covered with a pitch component having a thickness of 1 to 10 [mu] m. Carbonized product of micro beads.
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| JP2003388690A JP3674623B2 (en) | 2003-11-19 | 2003-11-19 | Mesocarbon micro beads |
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| JP2003388690A JP3674623B2 (en) | 2003-11-19 | 2003-11-19 | Mesocarbon micro beads |
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| JP07625194A Division JP3539755B2 (en) | 1994-04-15 | 1994-04-15 | Method for producing mesocarbon microbeads |
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| JP2004227643A Division JP2005050819A (en) | 2004-08-04 | 2004-08-04 | Meso carbon micro beads |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008127334A1 (en) * | 2007-04-13 | 2008-10-23 | Kirby Beard | Centrifugally cast electrochemical cell components |
| CN103570008A (en) * | 2012-08-09 | 2014-02-12 | 中国钢铁股份有限公司 | Isotropic graphite material and method for producing same |
| CN107934934A (en) * | 2018-01-11 | 2018-04-20 | 中国科学院过程工程研究所 | A kind of method for efficiently preparing asphalt base mesocarbon microspheres |
| CN115744868A (en) * | 2022-10-09 | 2023-03-07 | 江西浩然智能科技有限公司 | High-capacity lithium battery negative electrode material and preparation method thereof |
| CN117816025A (en) * | 2024-03-04 | 2024-04-05 | 常州钠金智能科技有限公司 | Carbon cladding equipment of positive electrode material of sodium ion battery |
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2003
- 2003-11-19 JP JP2003388690A patent/JP3674623B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008127334A1 (en) * | 2007-04-13 | 2008-10-23 | Kirby Beard | Centrifugally cast electrochemical cell components |
| CN103570008A (en) * | 2012-08-09 | 2014-02-12 | 中国钢铁股份有限公司 | Isotropic graphite material and method for producing same |
| CN107934934A (en) * | 2018-01-11 | 2018-04-20 | 中国科学院过程工程研究所 | A kind of method for efficiently preparing asphalt base mesocarbon microspheres |
| CN115744868A (en) * | 2022-10-09 | 2023-03-07 | 江西浩然智能科技有限公司 | High-capacity lithium battery negative electrode material and preparation method thereof |
| CN117816025A (en) * | 2024-03-04 | 2024-04-05 | 常州钠金智能科技有限公司 | Carbon cladding equipment of positive electrode material of sodium ion battery |
| CN117816025B (en) * | 2024-03-04 | 2024-05-10 | 常州钠金智能科技有限公司 | Carbon cladding equipment of positive electrode material of sodium ion battery |
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