JP2804217B2 - Graphitized vapor grown carbon fiber, method for producing graphitized vapor grown carbon fiber, molded article and composite - Google Patents
Graphitized vapor grown carbon fiber, method for producing graphitized vapor grown carbon fiber, molded article and compositeInfo
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- JP2804217B2 JP2804217B2 JP5160954A JP16095493A JP2804217B2 JP 2804217 B2 JP2804217 B2 JP 2804217B2 JP 5160954 A JP5160954 A JP 5160954A JP 16095493 A JP16095493 A JP 16095493A JP 2804217 B2 JP2804217 B2 JP 2804217B2
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- Prior art keywords
- carbon fiber
- grown carbon
- vapor
- graphitized vapor
- graphitized
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】この発明は黒鉛化気相成長炭素繊
維、その製造方法、成形体および複合体に関し、更に詳
しくは、複合材料や複合成形体などの複合体あるいはそ
れのみで形成される成形体に好適な黒鉛化気相成長炭素
繊維、その製造方法、実質的に黒鉛化気相成長炭素繊維
のみからなる成形体および黒鉛化気相成長炭素繊維とマ
トリックスとからなる複合体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graphitized vapor-grown carbon fiber, a method for producing the same, a molded article and a composite, and more particularly, a composite such as a composite material or a composite molded article, or a composite formed solely. The present invention relates to a graphitized vapor-grown carbon fiber suitable for a molded article, a method for producing the same, a molded article consisting essentially of graphitized vapor-grown carbon fiber, and a composite comprising a graphitized vapor-grown carbon fiber and a matrix.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】気相成長
炭素繊維は、超微粒子状の鉄やニッケルなどの金属を触
媒として炭素化合物を８００〜１，３００℃に加熱する
ことによりこれを熱分解して製造することができる。こ
の気相成長炭素繊維は熱処理することにより容易に黒鉛
構造に転化する特徴を有している。例えば２，８００℃
以上で加熱処理した黒鉛化気相成長炭素繊維は、結晶欠
陥の少ない黒鉛網面が繊維軸に平行して発達している。
それ故にこの黒鉛化気相成長炭素繊維は、高強度かつ高
弾性であり、しかも高い熱伝導性や電気導電性を有して
いる。2. Description of the Related Art Vapor-grown carbon fibers are heated by heating a carbon compound to 800 to 1,300 ° C. using a metal such as iron or nickel in the form of ultrafine particles as a catalyst. It can be manufactured by disassembly. This vapor-grown carbon fiber has a feature that it can be easily converted to a graphite structure by heat treatment. For example, 2,800 ° C
In the graphitized vapor-grown carbon fiber subjected to the heat treatment as described above, the graphite net surface having few crystal defects is developed in parallel with the fiber axis.
Therefore, the graphitized vapor-grown carbon fiber has high strength and high elasticity, and has high thermal conductivity and high electrical conductivity.
【０００３】したがって、この黒鉛化気相成長炭素繊維
を利用して、優れた複合材料が得られるものと期待され
る。その期待の下にこの発明者らは、充填密度が高い、
また、実質的に黒鉛化気相成長炭素繊維単独から成る成
形体を検討してきた。[0003] Therefore, it is expected that an excellent composite material can be obtained by using the graphitized vapor-grown carbon fiber. Under these expectations, the present inventors have high packing density,
Also, a molded article substantially consisting of graphitized vapor-grown carbon fiber alone has been studied.
【０００４】しかしながら、この発明者らの検討の結
果、充填密度が高い、また、実質的に黒鉛化気相成長炭
素繊維単独から成る成形体を形成することは困難であっ
た。その理由は、以下のようであるとこの発明者らは推
定している。However, as a result of the study by the present inventors, it was difficult to form a compact having a high packing density and consisting essentially of graphitized vapor grown carbon fiber alone. The inventors presume that the reason is as follows.
【０００５】すなわち、黒鉛化気相成長炭素繊維を他の
材料と混合して複合材料とする場合、分散が不均一にな
ることを防止するため、適当な長さ例えばアスペクト比
が１００以下になるように気相成長炭素繊維をボールミ
ルなどの手段により長さを調整した後に、そのような気
相成長炭素繊維を黒鉛化処理し、得られた黒鉛化気相成
長炭素繊維を使用していた。しかしながら、この黒鉛化
気相成長炭素繊維は、結晶欠陥が少ないので他の材料と
の濡れ性が悪く、また、弾性率が高い。したがって充填
密度を高く、また、実質的に黒鉛化気相成長炭素繊維単
独で成形体を形成しようとしたとき、その形状を維持す
ることができなかった。また、維持することができたと
しても非常に脆いものであった。That is, when the graphitized vapor-grown carbon fiber is mixed with another material to form a composite material, an appropriate length, for example, an aspect ratio becomes 100 or less in order to prevent non-uniform dispersion. After adjusting the length of the vapor-grown carbon fiber by means such as a ball mill, such a vapor-grown carbon fiber is graphitized, and the obtained graphitized vapor-grown carbon fiber is used. However, the graphitized vapor-grown carbon fiber has low crystal defects and thus poor wettability with other materials, and has a high elastic modulus. Therefore, when it was attempted to form a compact with a high packing density and substantially with only the graphitized vapor-grown carbon fiber, the shape could not be maintained. Even if it could be maintained, it was very brittle.
【０００６】一方、近年、炭素を電極活物質として用い
たリチウムイオン二次電池が検討されている。On the other hand, in recent years, lithium ion secondary batteries using carbon as an electrode active material have been studied.
【０００７】リチウム二次電池はその高エネルギー密度
故に注目されているが、電極に反応性の高い金属リチウ
ムを使用するので、シール不良があると非常に危険であ
るとか、リチウム電極の表面にリチウムの針状結晶いわ
ゆるデンドライトが生成して両電極間の短絡を起こすと
かの問題点がある。そこで、リチウム二次電池の有する
高エネルギー密度の特徴を若干犠牲にするとしても、前
記問題点のない、リチウムイオンと層間化合物を形成す
る炭素を電極に使用したリチウムイオン二次電池に関心
が移行している。[0007] Lithium secondary batteries have attracted attention due to their high energy density. However, since highly reactive metallic lithium is used for the electrodes, it is very dangerous if there is a bad seal, or lithium on the surface of the lithium electrodes. In other words, there is a problem that a dendrite is generated, which causes a short circuit between both electrodes. Therefore, even if the characteristics of the high energy density of the lithium secondary battery are slightly sacrificed, interest has shifted to a lithium ion secondary battery using carbon, which forms an intercalation compound with lithium ions, as an electrode without the above-mentioned problems. doing.
【０００８】炭素−リチウムイオン間層間化合物の内
で、リチウムイオンを最も多量に包含するものは、第１
ステージ化合物であり、その炭素原子とリチウム原子と
の数の比は６対１であり、充電および放電においてすべ
ての炭素が第１ステージの層間化合物を形成し、かつそ
のすべてのリチウムが出入りするとすると放電可能な電
気量は計算上最大３７２ｍＡ・Ｈｒ．／ｇ（ｇで示され
る重量は炭素の重量である。）であるが、この理論放電
量を達成するべく、多くの努力が払われているものの、
いまだ十分に高放電量の第１ステージ化合物が得られて
いない。Among the intercalation compounds between carbon and lithium ions, those containing lithium ions in the largest amount are the first compounds.
Stage compound, the ratio of the number of carbon atoms to the number of lithium atoms is 6 to 1. If all the carbons form a first stage intercalation compound during charging and discharging, and all of the lithium enters and exits, The maximum amount of electricity that can be discharged is 372 mA · Hr. / G (the weight in g is the weight of carbon), although much effort has been made to achieve this theoretical discharge,
A sufficiently high discharge amount of the first stage compound has not yet been obtained.
【０００９】この発明は前述したようなこの発明者らの
推定および研究の結果完成したものである。The present invention has been completed as a result of the above-mentioned estimation and research by the present inventors.
【００１０】すなわち、この発明の目的は、実質的に黒
鉛化気相成長炭素繊維単独からなる複合材料もしくは複
合成形体などの複合体を形成することができる黒鉛化気
相成長炭素繊維およびその製造方法、並びにそのような
黒鉛化気相成長炭素繊維を用いたところの充填密度の高
い成形体および複合体を提供することにある。[0010] That is, an object of the present invention is to provide a graphitized vapor-grown carbon fiber capable of forming a composite such as a composite material or a composite formed article consisting essentially of graphitized vapor-grown carbon fiber alone, and its production. It is an object of the present invention to provide a molded article and a composite having a high packing density using such a graphitized vapor-grown carbon fiber.
【００１１】前記課題を解決するための請求項１に記載
の発明は、高衝撃処理をしてなり、フッ化黒鉛を含ま
ず、平均直径が５μｍ以下であり、平均長さが９０μｍ
以下であり、平均アスペクト比が１〜１８であり、電子
スピン共鳴吸収法により測定したスピン密度が８×１０
18spins/g 以下であることを特徴とする黒鉛化気相成長
炭素繊維であり、請求項２に記載の発明は、実質的に破
断されていず、かつフッ化黒鉛を含んでいない気相成長
炭素繊維を２，０００℃以上に加熱して黒鉛化処理をし
た後に、得られた黒鉛化処理気相成長炭素繊維を、電子
スピン共鳴吸収法により測定したスピン密度が８×１０
18spins/g 以下になるまで、高衝撃力で破断することを
特徴とする前記請求項１に記載の黒鉛化気相成長炭素繊
維の製造方法であり、請求項３に記載の発明は、実質的
に前記請求項１に記載の黒鉛化気相成長炭素繊維のみか
らなることを特徴とする成形体であり、請求項４に記載
の発明は、前記請求項１に記載の黒鉛化気相成長炭素繊
維とマトリックスとを含有することを特徴とする複合体
であり、請求項５に記載の発明は、黒鉛化気相成長炭素
繊維は、その平均直径が１．５〜３．０μｍである前記
請求項３に記載の成形体である。[0011] The invention according to claim 1 for solving the above-mentioned problem is obtained by performing high impact treatment and containing fluorinated graphite.
And the average diameter is 5 μm or less and the average length is 90 μm
Below, the average aspect ratio is 1 to 18, and the spin density measured by the electron spin resonance absorption method is 8 × 10
18 spins / g is graphitized vapor grown carbon fiber, characterized in that less, the invention of claim 2 is not been substantially broken, and the gas phase contains no graphite fluoride After the growth carbon fiber was heated to 2,000 ° C. or more to be graphitized, the obtained graphitized vapor-grown carbon fiber was measured to have a spin density of 8 × 10 3 measured by an electron spin resonance absorption method.
The method for producing a graphitized vapor-grown carbon fiber according to claim 1, wherein the carbon fiber is broken by a high impact force until the spinning rate reaches 18 spins / g or less. It is a compact formed solely of the graphitized vapor grown carbon fiber according to the first aspect, and the invention according to the fourth aspect is the graphitized vapor phase growth according to the first aspect. A composite material comprising a carbon fiber and a matrix. The invention according to claim 5, wherein the graphitized vapor-grown carbon fiber has an average diameter of 1.5 to 3.0 µm. A molded article according to claim 3.
【００１２】以下にこの発明について詳述する。Hereinafter, the present invention will be described in detail.
【００１３】−黒鉛化気相成長炭素繊維− この発明の黒鉛化気相成長炭素繊維は、高衝撃処理をし
てなり、その平均直径が５μｍ以下であり、好ましくは
０．１〜３μｍであり、更に好ましくは０．３〜２μｍ
であり、また、特定の用途に利用するときにはその平均
直径は１．５〜３．０μｍであり、その平均長さが９０
μｍ以下であり、平均アスペクト比が１〜１８であり、
好ましくは２〜１６、さらに好ましくは５〜１５であ
る。しかも、この黒鉛化気相成長炭素繊維は後述するそ
の製造方法から明らかなようにフッ化黒鉛を含有してい
ない。-Graphitized vapor-grown carbon fiber-The graphitized vapor-grown carbon fiber of the present invention has been subjected to a high impact treatment and has an average diameter of 5 µm or less, preferably 0.1 to 3 µm. , More preferably 0.3 to 2 μm
When used for a specific application, the average diameter is 1.5 to 3.0 μm, and the average length is 90 μm.
μm or less, the average aspect ratio is 1 to 18,
Preferably it is 2-16, More preferably, it is 5-15. Moreover, the graphitized vapor-grown carbon fiber does not contain fluorinated graphite, as is apparent from the production method described later.
【００１４】この黒鉛化気相成長炭素繊維の平均アスペ
クト比が１８を越えると良好な複合成形体を得ることが
できなくなる。When the average aspect ratio of the graphitized vapor-grown carbon fiber exceeds 18, it is impossible to obtain a good composite molded product.
【００１５】特に、黒鉛化気相成長炭素繊維の平均直径
が１．５〜３．０μｍであると、この黒鉛化気相成長炭
素繊維を用いてリチウム二次電池を形成した場合、繰り
返しの充放電による性能の低下が著しく小さくなる。 In particular, the average diameter of the graphitized vapor grown carbon fiber
Is 1.5 to 3.0 μm, the graphitized vapor-grown carbon
When a lithium secondary battery is formed using raw fibers,
Performance degradation due to repeated charging and discharging is significantly reduced.
【００１６】複合材料や複合成形体などの複合体を考慮
すると、マトリックスと繊維との結合は、繊維の長さが
長い場合、繊維の長さ方向の側面とマトリックスとの結
合が支配的となる。しかしながら、黒鉛化気相成長炭素
繊維の長さ方向の側面には結晶欠陥がほとんどないため
マトリックスとの結合が非常に弱いものとなる。Considering a composite such as a composite material or a composite molded article, when the length of the fiber is long, the bond between the matrix and the fiber is dominant when the length of the fiber is long. . However, since there are almost no crystal defects on the side surfaces in the longitudinal direction of the graphitized vapor-grown carbon fiber, the bond with the matrix becomes very weak.
【００１７】一方繊維の長さが短い場合、その端面の結
合効果は大きなものとなる。On the other hand, when the length of the fiber is short, the bonding effect of the end face becomes large.
【００１８】この発明の黒鉛化気相成長炭素繊維は、電
子スピン共鳴吸収法により測定したスピン密度が８×１
０18spins/g 以下、好ましくは７×１０18spins/g 以下
である。The graphitized vapor-grown carbon fiber of the present invention is
The spin density measured by the child spin resonance absorption method is 8 × 1
0 18 spins / g or less, preferably 7 × 10 18 spins / g or less.
【００１９】黒鉛化気相成長炭素繊維のスピン密度が前
記範囲にあると、それから得られる被膜や成形品の形状
保持性が良く、リチウムイオンとの層間化合物形成能を
利用した電池の電極として放電容量の高い材料になる。When the spin density of the graphitized vapor-grown carbon fiber is in the above-mentioned range, the film and the molded product obtained therefrom have good shape retention and discharge as an electrode of a battery utilizing the ability to form an interlayer compound with lithium ions. It becomes a high capacity material.
【００２０】この発明の黒鉛化気相成長炭素繊維は、高
度に発達した黒鉛構造を有し、縮合環状の黒鉛網面の発
達度合いの点から、黒鉛網面間距離（ｄoo2 ）は通常
３．４５Å以下、好ましくは３．３５〜３．４２Å、更
に好ましくは３．３５〜３．３７Åであり、また縮合環
状の黒鉛網面が重なった厚さすなわち黒鉛結晶子の厚さ
（Ｌc ）は通常３０Å以上、好ましくは３００Å以上、
更に好ましくは１，０００Å以上である。The graphitized vapor-grown carbon fiber of the present invention has a highly developed graphite structure, and the distance between the graphite screens (d oo2 ) is usually 3 in view of the degree of development of the condensed cyclic graphite screen. .45 ° or less, preferably 3.35 to 3.42 °, more preferably 3.35 to 3.37 °, and the thickness of the condensed cyclic graphite network planes, that is, the thickness of the graphite crystallite (L c ). Is usually 30 ° or more, preferably 300 ° or more,
More preferably, it is 1,000 ° or more.
【００２１】この発明の黒鉛化気相成長炭素繊維は、プ
ラスチック、ゴム、金属、セラミックス、塗料、接着剤
などに高い充填密度で複合した複合材料やわずかな結着
材を使用した、実質的に黒鉛化気相成長炭素繊維単独よ
り成る複合成形体などの複合体の製造に好適である。こ
れらの複合材料もしくは複合成形体は、高導電材料、熱
伝導度の優れた材料、触媒の担体などとして使用するこ
とができる。The graphitized vapor-grown carbon fiber of the present invention is substantially made of a composite material or a small amount of binder which is composited with plastic, rubber, metal, ceramics, paint, adhesive or the like at a high packing density. It is suitable for the production of a composite such as a composite molded article made of graphitized vapor grown carbon fiber alone. These composite materials or composite molded articles can be used as a highly conductive material, a material having excellent thermal conductivity, a carrier for a catalyst, and the like.
【００２２】−黒鉛化気相成長炭素繊維の製造方法− この発明の黒鉛化気相成長炭素繊維すなわち複合材料に
好適な複合材料用黒鉛化気相成長炭素繊維は、この発明
の方法により製造することができる。-Method for producing graphitized vapor-grown carbon fiber-The graphitized vapor-grown carbon fiber of the present invention, that is, the graphitized vapor-grown carbon fiber suitable for a composite material for a composite material, is produced by the method of the present invention. be able to.
【００２３】すなわち、黒鉛化気相成長炭素繊維は、気
相成長炭素繊維をたとえば２，０００℃以上で加熱する
黒鉛化処理をした後に、この黒鉛化処理気相成長炭素繊
維を高衝撃力で破断することによって製造することがで
きる。That is, the graphitized vapor-grown carbon fiber is subjected to a graphitization treatment in which the vapor-grown carbon fiber is heated at, for example, 2,000 ° C. or higher, and then the graphitized vapor-grown carbon fiber is subjected to a high impact force. It can be manufactured by breaking.
【００２４】気相成長炭素繊維は、気相成長法により製
造することができる。The vapor grown carbon fiber can be produced by a vapor growth method.
【００２５】気相成長法により気相成長炭素繊維を製造
する方法としては、いわゆる基板成長法と流動気相法と
がある。基板成長法は、基板に触媒金属例えば遷移金属
もしくは遷移金属化合物を担持させ、高温度に加熱しな
がら、その基板上に炭素源ガスである炭化水素ガスを流
通させることにより、基板表面に炭素繊維を生成させる
方法であり、流動気相法は、基板を使用せず、触媒金属
になり得る金属化合物と炭素源である炭素化合物とを気
化して高温の反応管中に流通させることにより、空間中
に炭素繊維を生成させる方法である。As a method for producing a vapor grown carbon fiber by a vapor growth method, there are a so-called substrate growth method and a fluidized gas phase method. In the substrate growth method, a catalyst metal such as a transition metal or a transition metal compound is supported on a substrate, and while heating to a high temperature, a hydrocarbon gas, which is a carbon source gas, is allowed to flow on the substrate so that carbon fibers are formed on the substrate surface. In the fluidized gas phase method, a substrate is not used, and a metal compound that can be a catalyst metal and a carbon compound that is a carbon source are vaporized and passed through a high-temperature reaction tube, so that space can be obtained. This is a method for producing carbon fibers therein.
【００２６】具体的には、特開昭５２−１０７３２０
号、特開昭５７−１１７６２２号、特開昭５８−１５６
５１２号、特開昭５８−１８０６１５号、特開昭６０−
１８５８１８号、特開昭６０−２２４８１５号、特開昭
６０−２３１８２１号、特開昭６１−１３２６３０号、
特開昭６１−１３２６００号、特開昭６１−１３２６６
３号、特開昭６１−２２５３１９号、特開昭６１−２２
５３２２号、特開昭６１−２２５３２５号、特開昭６１
−２２５３２７号、特開昭６１−２２５３２８号、特開
昭６１−２２７５４２５号、特開昭６１−２８２４２７
号の各公報に記載の方法により製造される気相成長炭素
繊維をこの発明の方法における原料として使用すること
ができる。Specifically, Japanese Patent Application Laid-Open No. 52-107320
JP-A-57-117622, JP-A-58-156
No. 512, JP-A-58-180615 and JP-A-60-180
185818, JP-A-60-224815, JP-A-60-231821, JP-A-61-132630,
JP-A-61-13600, JP-A-61-13266
No. 3, JP-A-61-225319, JP-A-61-22
No. 5322, JP-A-61-225325, JP-A-61-225325
JP-A-225327, JP-A-61-225328, JP-A-61-2275425, JP-A-61-282427
The vapor-grown carbon fibers produced by the methods described in each of the above publications can be used as raw materials in the method of the present invention.
【００２７】この発明の方法に用いられる気相成長炭素
繊維は、２，０００℃以上で加熱処理することにより黒
鉛化され、黒鉛化処理気相成長炭素繊維が得られる。The vapor-grown carbon fiber used in the method of the present invention is graphitized by heat treatment at 2,000 ° C. or higher to obtain graphitized vapor-grown carbon fiber.
【００２８】加熱処理の雰囲気としては不活性ガス雰囲
気が通常採用される。加熱処理時間は通常５分以上であ
る。この加熱処理によって得られる黒鉛化処理気相成長
炭素繊維は、高度に発達した黒鉛構造を有し、縮合環状
の黒鉛網面の発達度合いの点から、黒鉛網面間距離（ｄ
oo2 ）は通常３．４５〜３．３５Å以下、好ましくは
３．４２〜３．３５Å、更に好ましくは３．３７〜３．
３５Åであり、また縮合環状の黒鉛網面が重なった厚さ
すなわち黒鉛結晶子の厚さ（Ｌc ）は通常３０Å以上で
あり、好ましくは３００Å以上、更に好ましくは１，０
００Å以上である。As an atmosphere for the heat treatment, an inert gas atmosphere is usually employed. The heat treatment time is usually 5 minutes or more. The graphitized vapor-grown carbon fiber obtained by this heat treatment has a highly developed graphite structure, and the distance between the graphite screens (d
oo2 ) is usually 3.45 to 3.35 ° or less, preferably 3.42 to 3.35 °, more preferably 3.37 to 3.35 °.
The thickness is 35 ° or more, and the thickness (L c ) of the graphite crystallites at which the condensed cyclic graphite network planes overlap is usually 30 ° or more, preferably 300 ° or more, more preferably 1,0 or more.
It is more than 00 °.
【００２９】この発明の方法では、この黒鉛化処理気相
成長炭素繊維に高衝撃力を付加してこれを破断する。In the method of the present invention, a high impact force is applied to the graphitized vapor-grown carbon fiber to break it.
【００３０】ところで、一般に黒鉛化気相成長炭素繊維
から成形体や複合体を製造する場合には、得られる気相
成長炭素繊維そのままの長さでは他の成分との混合が困
難であるから、その気相成長炭素繊維を破断する必要が
ある。通常は黒鉛化処理を効率的に行うために、黒鉛化
処理の前に破断を行って嵩高性を下げてから黒鉛化処理
が行われている。In general, when a molded article or a composite is produced from graphitized vapor-grown carbon fiber, it is difficult to mix it with other components if the obtained vapor-grown carbon fiber has the same length. It is necessary to break the vapor grown carbon fiber. Usually, in order to efficiently perform the graphitization process, the graphitization process is performed after the fracture is performed to reduce the bulkiness before the graphitization process.
【００３１】この発明者らは破断処理を、黒鉛化前に行
うのと黒鉛化後に行うのとで得られる成形体や複合体に
大きな相違があることを見いだした。The inventors of the present invention have found that there is a great difference between the molded article and the composite obtained when the fracture treatment is performed before the graphitization and after the graphitization.
【００３２】何故にそのような大きな相違があるのかは
不明であるが、破断を高衝撃力で行う場合、黒鉛化処理
前に気相成長炭素繊維を破断したときには、得られる黒
鉛化気相成長炭素繊維のＥＳＲのｇ＝２．０１５でのス
ピン密度が高く、黒鉛化処理前に実質的な破断を行わず
に、黒鉛化後に高衝撃力で破断を行うときには、高衝撃
力による破断処理時間と共にスピン密度が低下し、得ら
れる成形体や複合体の物性が改善されることを見いだし
た。なお、ｇ＝２．０１５は酸素ラジカルに相当する。It is not clear why there is such a large difference. However, when the fracture is performed with a high impact force, when the vapor-grown carbon fiber is fractured before the graphitization treatment, the obtained graphitized vapor-grown When the spin density at g = 2.015 of the ESR of the carbon fiber is high and the fracture is performed with a high impact force after graphitization without substantial fracture before the graphitization treatment, the breaking time due to the high impact force is required. In addition, it was found that the spin density was lowered and the physical properties of the obtained molded article and composite were improved. Note that g = 2.015 corresponds to an oxygen radical.
【００３３】上記の知見から、この発明の方法では、こ
の黒鉛化処理気相成長炭素繊維に高衝撃力を付加してこ
れを破断するのである。From the above findings, in the method of the present invention, a high impact force is applied to the graphitized vapor-grown carbon fiber to break it.
【００３４】一般に、微細なものを更に小さくするには
ボールミルやローラーミルのように押し砕く方法が採用
されるが、ボールミルやローラーミルでは繊維形状をと
どめない部分が生じ、繊維の長さを所望の値に制御する
のが困難であり、また、要処理時間も長くなる。この発
明の方法では、黒鉛化処理気相成長炭素繊維を、単独で
高衝撃力処理をすることが好ましく、この方法によっ
て、黒鉛化処理気相成長炭素繊維をこの発明で規定する
平均長さに、任意に、数分の短い処理時間で調節するこ
とができる。In general, a method of crushing fine particles such as a ball mill or a roller mill is used to further reduce the size of the fine particles. Is difficult to control, and the required processing time is long. In the method of the present invention, it is preferable that the graphitized vapor-grown carbon fiber is subjected to a high impact force treatment alone, and the graphitized vapor-grown carbon fiber is made to have an average length specified in the present invention by this method. , Optionally with a short processing time of a few minutes.
【００３５】高衝撃処理の一例として、具体的には例え
ば図１に示すように、気流の通路である自己循環回路
１、衝撃羽根２を有する容器３を備える、高衝撃力処理
装置に、前記黒鉛化処理気相成長炭素繊維を入れて回転
させ、高衝撃力を与えることを内容とする処理を挙げる
ことができる。As one example of the high impact processing, specifically, as shown in FIG. 1, for example, a high impact force processing apparatus including a container 3 having a self-circulation circuit 1 as an airflow passage and an impact blade 2 Graphitization treatment A treatment that involves putting a vapor-grown carbon fiber and rotating it to give a high impact force can be mentioned.
【００３６】このような高衝撃処理において、最終的に
得ようとする黒鉛化気相成長炭素繊維の長さの調節は、
主に衝撃力を変化させることにより可能である。衝撃力
を与える方法としては回転ではなく、一方向あるいは往
復で羽根、壁に打ちつけることも可能であるが、回転が
最も容易である。衝撃による繊維の切断は繊維が羽根に
当たったときと繊維が壁に打ちつけられたときとの双方
で起こる。In such a high impact treatment, the length of the graphitized vapor-grown carbon fiber finally obtained is adjusted by:
This is possible mainly by changing the impact force. As a method of applying the impact force, it is possible to hit the blade or the wall in one direction or reciprocation instead of rotating, but the rotation is easiest. Fiber cutting by impact occurs both when the fibers hit the blades and when the fibers are struck against a wall.
【００３７】衝撃を与える条件としては、その高衝撃力
処理装置の種類などによって種々様々であるが、要する
に、高衝撃処理の結果、得られる黒鉛化気相成長炭素繊
維の電子スピン共鳴吸収法により測定したスピン密度が
８×１０18spins/g 以下になるように決定されるのが良
い。The conditions for applying the impact are various depending on the type of the high impact force treatment apparatus and the like. In short, the effect of the high impact treatment is that the graphitized vapor grown carbon fiber obtained by the electron spin resonance absorption method is obtained. It is preferable that the measured spin density is determined to be 8 × 10 18 spins / g or less.
【００３８】衝撃を与える羽根の速度（あるいは繊維が
壁に打ちつけられる速度）としては、繊維径や所望する
アスペクト比に応じて適宜に選択されるのであるが、好
ましくは４０ｍ／ｓｅｃ以上、更に好ましくは６０ｍ／
ｓｅｃが良い。高速である程切断効果は大きいが、速度
が１００ｍ／ｓｅｃ以上になると、安全対策上周辺に防
護装置等を設けるなど、装置が大型化し、使用しにくく
なったり、経済的な問題を生じることがある。また、処
理時間も５分以内が良く、あまり長時間の処理は経済的
観点から好ましくない。尚、回転により衝撃を与える場
合の速度は、回転羽根の場合、最も外側の部分の速度に
より示した。回転羽根の場合、最も外側における速度が
最大であり効果的であるからである。The speed of the impinging blade (or the speed at which the fibers are struck against the wall) is appropriately selected according to the fiber diameter and the desired aspect ratio, but is preferably 40 m / sec or more, more preferably. Is 60m /
sec is good. The higher the speed is, the greater the cutting effect is. However, if the speed is 100 m / sec or more, the size of the device becomes large, such as installing a protective device etc. in the vicinity for safety measures, and it may be difficult to use or an economic problem may occur. is there. Also, the processing time is preferably within 5 minutes, and the processing for too long time is not preferable from an economic viewpoint. The speed at which an impact is given by rotation is indicated by the speed of the outermost portion in the case of a rotating blade. This is because in the case of a rotating blade, the speed on the outermost side is maximum and effective.
【００３９】以上のように黒鉛化処理気相成長炭素繊維
を高衝撃破断処理をすると、得られる黒鉛化気相成長炭
素繊維は、電子スピン共鳴吸収法により測定したスピン
密度が８×１０18spins/g 以下になる。When the graphitized vapor grown carbon fiber is subjected to a high impact fracture treatment as described above, the resulting graphitized vapor grown carbon fiber is obtained.
The raw fiber has a spin density of 8 × 10 18 spins / g or less measured by an electron spin resonance absorption method.
【００４０】[0040]
【００４１】また、黒鉛化処理後に前記高衝撃破断処理
をすると前記スピン密度の減少によって示されるところ
の酸素ラジカルが減少する理由は明らかではない。しか
し、ラジカル量が多いと、ラジカルは繊維破断面に局在
すると思われるので、この黒鉛化気相成長炭素繊維をリ
チウム二次電池に使用すると、繊維破断面で溶媒等と反
応を起こし、その生成物がリチウムイオンの繊維内炭素
格子内と電解液との間を往復することを妨害する可能性
は十分に考えられる。It is not clear why the high impact fracture treatment after the graphitization treatment reduces oxygen radicals as indicated by the decrease in spin density. However, if the amount of radicals is large, the radicals are considered to be localized in the fiber fracture surface, so when this graphitized vapor-grown carbon fiber is used in a lithium secondary battery, it reacts with a solvent or the like in the fiber fracture surface, It is quite possible that the product will interfere with the reciprocation of lithium ions between the carbon fiber grid within the fiber and the electrolyte.
【００４２】この発明の効果が得られる原因は不明であ
るが、次のような推定もある。The reason why the effects of the present invention can be obtained is unknown, but the following is also presumed.
【００４３】切断した後に黒鉛化処理を行なうと、切断
により生じた端面の炭素原子は、黒鉛化処理により再結
合してしまうか、切断時に生じた親和性のある官能基が
黒鉛化により消失するため複合材料とした時や、結着材
との結合に有効に働かなくなってしまう。When the graphitization treatment is performed after the cutting, the carbon atoms on the end faces generated by the cutting are recombined by the graphitization treatment, or the affinity functional groups generated at the time of the cutting disappear by the graphitization. Therefore, when it is used as a composite material, it does not work effectively for bonding with a binder.
【００４４】一方、黒鉛化処理後に切断した場合、その
端面に生じた酸素ラジカルがマトリックスや結着材また
は自分たち同士の結合に有効に働く酸素含有官能基にな
るので、マトリックスや結着材との濡れ性を高めること
が可能となる。On the other hand, when cut after the graphitization treatment, oxygen radicals generated on the end face become a matrix, a binder, or an oxygen-containing functional group which effectively works for bonding between themselves, so that the matrix and the binder are not combined. Can be improved.
【００４５】−成形体および複合体− この発明の成形体は、実質的に前述黒鉛化気相成長炭素
繊維のみからなる。もっともこの発明の目的を阻害しな
い範囲で黒鉛化気相成長炭素繊維同士を結合する結着剤
を使用しても良い。その場合、成形体中の結着剤の量と
しては、通常、２０重量％以下である。実質的にこの黒
鉛化気相成長炭素のみからなる成形体は、例えば静水圧
等方加圧成形法などにより成形加工をすることができ
る。-Molded Article and Composite- The molded article of the present invention consists essentially of only the above-mentioned graphitized vapor-grown carbon fibers. However, a binder that binds the graphitized vapor-grown carbon fibers may be used as long as the object of the present invention is not impaired. In that case, the amount of the binder in the molded body is usually 20% by weight or less. The molded body substantially composed of only the graphitized vapor-grown carbon can be formed by, for example, isostatic pressing.
【００４６】この成形体は、実質的に黒鉛化気相成長炭
素繊維のみからなるので、全ての黒鉛化気相成長炭素繊
維が他の繊維と接触し、その結果電気導電性、熱伝導性
に優れ、また、実質的に繊維のみからなることによって
触媒担体として優れ、また、リチウムと層間化合物を形
成することを利用した電池の電極材料としても優れてい
るという利点を有する。Since this molded article is substantially composed of only the graphitized vapor grown carbon fiber, all of the graphitized vapor grown carbon fiber comes into contact with other fibers, and as a result, the electric conductivity and the heat conductivity are reduced. It also has the advantage that it is excellent as a catalyst carrier by being substantially composed of only fibers, and also as an electrode material of a battery utilizing the formation of an interlayer compound with lithium.
【００４７】この発明の複合体としては、例えば熱硬化
性樹脂をマトリックスとしこのマトリックス中にこの黒
鉛化気相成長炭素繊維を分散してなる複合材料を挙げる
ことができる。また、この発明の複合体としては、黒鉛
化気相成長炭素繊維とマトリックスとからなる成形体を
挙げることができる。この複合体におけるマトリックス
としては、樹脂、金属、ゴム、接着剤組成物、塗料組成
物などを挙げることができる。この発明の複合体中の黒
鉛化気相成長炭素繊維の量としては、通常５０重量％以
上である。この複合体は、成形状態が良好で高充填が可
能であるので、この複合体を塗料や接着剤などとした場
合には、被膜強度の大きな、しかも電気導電性、熱伝導
性に優れた被膜を形成することができる。またこの複合
体が成形体であるときには、上記特性の他に加工面の仕
上げが美麗になるという優れた加工特性が発揮される。
したがって、この成形体および複合体は、高導電材料、
熱伝導度の優れた材料、触媒の担体などとして使用する
ことができる。Examples of the composite of the present invention include a composite material comprising a thermosetting resin as a matrix and the graphitized vapor-grown carbon fibers dispersed in the matrix. Further, as the composite of the present invention, a molded article comprising a graphitized vapor-grown carbon fiber and a matrix can be exemplified. Examples of the matrix in the composite include resin, metal, rubber, an adhesive composition, a coating composition, and the like. The amount of the graphitized vapor-grown carbon fibers in the composite of the present invention is usually 50% by weight or more. Since this composite has a good molded state and can be highly filled, when this composite is used as a paint or an adhesive, a coating having high coating strength and excellent electrical and thermal conductivity is provided. Can be formed. In addition, when the composite is a molded product, excellent processing characteristics such as beautiful finish of a processed surface are exhibited in addition to the above characteristics.
Therefore, the molded body and the composite are made of a highly conductive material,
It can be used as a material having excellent thermal conductivity, a carrier for a catalyst, and the like.
【００４８】[0048]
【実施例】以下にこの発明の実施例を示す。なお、この
発明は以下の実施例に限定されるものではなく、この発
明の要旨の範囲内において適宜に変更することができる
このはいうまでもない。Embodiments of the present invention will be described below. The present invention is not limited to the following embodiments, and it goes without saying that the present invention can be appropriately modified within the scope of the present invention.
【００４９】（実施例１）平均直径が０．８μｍ、平均
長さが１３２μｍ、平均アスペクト比が１６５の気相成
長炭素繊維をアルゴンガス零囲気中で２８００℃で３０
分間黒鉛化処理した。その後に、高速気流中で衝撃処理
をするハイブリダイザー（ＮＨＳ−１、（株）奈良機械
製作所製）を用い、８，０００γｐｍ（周速１００ｍ／
ｓ）にて２分間高衝撃処理をした。処理後、走査型電子
顕微鏡観察により、ランダムに選ばれた１００本の繊維
について測定したところ、得られた黒鉛化気相成長炭素
繊維はその平均直径が０．８μｍであり、平均長さが
８．４μｍ、平均アスペクト比が１０．５であった。こ
れを、日本電子製電子スピン共鳴吸収装置ＪＥＳ−ＦＥ
３ＸＧに磁場掃引範囲３２５．４±２５ｍＴで試験した
ところ、ｇ値が２．０１５のところにスピン密度６．２
×１０18spins/g の吸収が見られた。衝撃処理を４０分
継続すると、吸収は１．６×１０18spins/g にまで低下
した。衝撃処理２分の黒鉛化気相成長炭素繊維を、フェ
ノール樹脂とメタノールとの混合溶液に、メタノール気
化後の黒鉛化気相成長炭素繊維の割合がそれぞれ６０、
７０、８０ｗｔ％になるように混合した。その後、脱泡
した後、ガラス板にコーティングし、８０℃で１０分
間、１５０℃で１０分間の条件で乾燥（メタノール気
化）、硬化させた後、表面観察、表面抵抗を測定した。
その結果を表１に示す。Example 1 A vapor-grown carbon fiber having an average diameter of 0.8 μm, an average length of 132 μm, and an average aspect ratio of 165 was obtained at 30 ° C. in an argon gas atmosphere at 2800 ° C.
Graphitized for minutes. Then, using a hybridizer (NHS-1, manufactured by Nara Machinery Co., Ltd.) that performs an impact treatment in a high-speed airflow, 8,000 γpm (peripheral speed 100 m /
In s), a high impact treatment was performed for 2 minutes. After the treatment, measurement was performed on 100 randomly selected fibers by observation with a scanning electron microscope. The obtained graphitized vapor-grown carbon fibers had an average diameter of 0.8 μm and an average length of 8 μm. 0.4 μm, and the average aspect ratio was 10.5. This is supplied to JEOL's electron spin resonance absorber JES-FE.
When a test was performed at 3XG in a magnetic field sweep range of 325.4 ± 25 mT, the spin density was 6.2 at a g value of 2.015.
An absorption of × 10 18 spins / g was observed. When the shock treatment was continued for 40 minutes, the absorption dropped to 1.6 × 10 18 spins / g. The graphitized vapor-grown carbon fiber after 2 minutes of impact treatment was added to a mixed solution of phenol resin and methanol, and the ratio of the graphitized vapor-grown carbon fiber after vaporization of methanol was 60,
70 and 80 wt%. Then, after defoaming, coating on a glass plate, drying (methanol vaporization) and curing at 80 ° C. for 10 minutes and 150 ° C. for 10 minutes, surface observation and surface resistance were measured.
Table 1 shows the results.
【００５０】[0050]
【表１】 [Table 1]
【００５１】（比較例１）平均直径が０．８μｍ、平均
長さが１３２μｍ、平均アスペクト比が１６５の気相成
長炭素繊維をハイブリダイザー（ＮＨＳ−１、（株）奈
良機械製作所製）を用い、８，０００γｐｍにて２分間
高衝撃処理した後、アルゴンガス雰囲気中で２，８００
℃で３０分間黒鉛化処理した。得られた黒鉛化気相成長
炭素繊維のアスペクト比は１２であった。これを実施例
１と同様にして電子スピン共鳴吸収を調べたところ、ｇ
値が２．０１５のところにスピン密度９．３×１０18sp
ins/g の吸収が見られた。衝撃処理を４０分まで継続し
たがスピン密度に大きな変化が認められなかった。その
後、実施例１と同様にして得られた結果を表２に示す。Comparative Example 1 A vapor-grown carbon fiber having an average diameter of 0.8 μm, an average length of 132 μm, and an average aspect ratio of 165 was used using a hybridizer (NHS-1, manufactured by Nara Machinery Co., Ltd.). 8,000 gpm for 2 minutes and then 2,800 g in an argon gas atmosphere.
It was graphitized at 30 ° C for 30 minutes. The aspect ratio of the obtained graphitized vapor-grown carbon fiber was 12. When the electron spin resonance absorption was examined in the same manner as in Example 1, g
When the value is 2.015, the spin density is 9.3 × 10 18 sp
Ins / g absorption was observed. The impact treatment was continued for up to 40 minutes, but no significant change in spin density was observed. Thereafter, the results obtained in the same manner as in Example 1 are shown in Table 2.
【００５２】[0052]
【表２】 [Table 2]
【００５３】（実施例２）平均直径が１．３μｍ、平均
長さが１１０μｍ、平均アスペクト比が８４．６の気相
成長炭素繊維をアルゴンガス中で２，５００℃で２０分
間黒鉛化処理した。その後に、高速気流中衝撃処理装置
を用い、７，２００γｐｍ（周速９０ｍ／ｓ）にて２分
間高衝撃処理をした。Example 2 A vapor-grown carbon fiber having an average diameter of 1.3 μm, an average length of 110 μm, and an average aspect ratio of 84.6 was graphitized in an argon gas at 2,500 ° C. for 20 minutes. . Thereafter, high impact treatment was performed at 7,200 γpm (peripheral speed 90 m / s) for 2 minutes using a high-speed airflow impact treatment device.
【００５４】高衝撃処理後に、走査型電子顕微鏡観察に
より、ランダムに選ばれた１００本の繊維について測定
したところ、得られた黒鉛化気相成長炭素繊維はその平
均直径が１．３μｍであり、平均長さが２０μｍ、平均
アスペクト比が１５．４、スピン密度５．９×１０18sp
ins/g であった。その後、結着材の割合が０、５、１０
ｗｔ％となるように混合し、得られた混合物を内径２５
ｍｍ、長さ６０ｍｍのゴム型に詰めＢＩＰ（日機装
（株）製）を用いて圧力７，０００ｋｇ／ｃｍ2 にて加
圧形成した。形成品を取り出し形成品の見かけ密度、形
成状況を観察した結果を表３に示す。After the high impact treatment, 100 randomly selected fibers were measured by scanning electron microscope observation. The obtained graphitized vapor-grown carbon fibers had an average diameter of 1.3 μm. Average length 20 μm, average aspect ratio 15.4, spin density 5.9 × 10 18 sp
ins / g. Then, the ratio of the binder is 0, 5, 10
wt% and the resulting mixture
It was packed in a rubber mold having a length of 60 mm and a length of 60 mm, and press-formed at a pressure of 7,000 kg / cm 2 using BIP (manufactured by Nikkiso Co., Ltd.). Table 3 shows the results obtained by taking out the formed product and observing the apparent density and the state of formation of the formed product.
【００５５】[0055]
【表３】 [Table 3]
【００５６】（比較例２）高速気流中衝撃処理した後、
黒鉛化処理したことを除き、実施例２と同様にして行な
った結果を表４に示す。このとき得られた黒鉛化気相成
長炭素繊維のアスペクト比は１７、スピン密度９．１×
１０18spins/g であった。(Comparative Example 2) After impact treatment in a high-speed air stream,
The results obtained in the same manner as in Example 2 except for the graphitization treatment are shown in Table 4. The aspect ratio of the graphitized vapor-grown carbon fiber obtained at this time was 17, and the spin density was 9.1 ×.
It was 10 18 spins / g.
【００５７】[0057]
【表４】 [Table 4]
【００５８】（比較例３）高速気流中衝撃処理装置を用
い、２０００γｐｍ（周速２５ｍ／ｓ）にて２分間処理
し、得られた黒鉛化気相成長炭素繊維の平均アスペクト
比が５３、スピン密度９．３×１０18spins/g であるこ
とを除き実施例２と同様に行なった。結果を表５に示
す。(Comparative Example 3) Using a high-speed airflow impact treatment apparatus, the carbon fiber was treated at 2000 γpm (peripheral speed: 25 m / s) for 2 minutes, and the obtained graphitized vapor-grown carbon fiber had an average aspect ratio of 53 and a spin rate of 53%. The procedure was performed in the same manner as in Example 2 except that the density was 9.3 × 10 18 spins / g. Table 5 shows the results.
【００５９】[0059]
【表５】 [Table 5]
【００６０】（実施例３）流動法により得られた気相成
長炭素繊維（直径２．３μｍ、長さ２００μｍ以上）を
アルゴンガス中で２，８００℃で加熱して黒鉛化した。
この黒鉛化気相成長炭素繊維をハイブリダイザーに装填
し、このハイブリダイザーを８，０００ｒｐｍの回転数
で３分間高速回転させた。その結果、直径２．２μｍ、
長さ１４．６μｍ、ｇ値が２．０１５でのスピン密度が
３．７×１０18spins/g である黒鉛化気相成長炭素繊維
を得た。Example 3 A vapor grown carbon fiber (diameter 2.3 μm, length 200 μm or more) obtained by a flow method was heated at 2,800 ° C. in an argon gas to be graphitized.
The graphitized vapor-grown carbon fiber was loaded into a hybridizer, and the hybridizer was rotated at a high speed of 8,000 rpm for 3 minutes. As a result, the diameter was 2.2 μm,
Graphitized vapor grown carbon fibers having a length of 14.6 μm, a g value of 2.015, and a spin density of 3.7 × 10 18 spins / g were obtained.
【００６１】一方、ポリビニリデンフルオライド０．０
５ｇを正確に計り取り瑪瑙の乳鉢に入れ、それに１−メ
チル−２−ピロリドン０．５ｃｃを加えて完全に溶解し
た。On the other hand, polyvinylidene fluoride 0.0
5 g was accurately weighed, placed in an agate mortar, and completely dissolved by adding 0.5 cc of 1-methyl-2-pyrrolidone.
【００６２】この溶液に前記黒鉛化気相成長炭素繊維
０．９５ｇを加え十分に混合してペーストを得た。To this solution was added 0.95 g of the graphitized vapor-grown carbon fiber, and the mixture was mixed well to obtain a paste.
【００６３】十分にアセトンで洗浄した１０×４０ｍｍ
のニッケルメッシュにおける先端領域である１０×１０
ｍｍの部分に、前記ペーストを１０×１０ｍｍの広さに
塗布し、１００℃で２３時間かけて真空乾燥した。 10 × 40 mm sufficiently washed with acetone
10 × 10 which is the tip region in the nickel mesh
The paste was applied to an area of 10 mm in a size of 10 × 10 mm, and vacuum-dried at 100 ° C. for 23 hours.
【００６４】このようにして得られた電極を、酸素と水
分とを十分に除去したアルゴンガス雰囲気のグローブボ
ックス内でルギン管を使用して３電極セルを組み立て
た。対極と参照電極として１０×４０×２ｍｍの金属リ
チウムを、電解液として、濃度１モル／リットルとなる
ようにＬｉＣｌＯ4 をエチレンカーボネートとジエチル
カーボネートとの１対１混合溶媒に、溶解して得られる
溶液を、それぞれ使用した。A three-electrode cell was assembled from the thus obtained electrode in a glove box in an argon gas atmosphere from which oxygen and moisture had been sufficiently removed using a luggin tube. It is obtained by dissolving LiClO 4 in a one-to-one mixed solvent of ethylene carbonate and diethyl carbonate so as to have a concentration of 1 mol / liter as an electrolyte, using 10 × 40 × 2 mm metallic lithium as a counter electrode and a reference electrode. The solutions were each used.
【００６５】各極を充放電装置に接続し、電圧が一定に
なるまで放置し、その後に作用電極と参照電極との電位
差が０〜２．５Ｖとなる範囲で充放電を繰り返した。繰
り返し３回までの結果を表６に示した。Each electrode was connected to a charging / discharging device and allowed to stand until the voltage became constant. Thereafter, charging / discharging was repeated within a range where the potential difference between the working electrode and the reference electrode was 0 to 2.5 V. The results of up to three repetitions are shown in Table 6.
【００６６】（比較例４）流動法により得られた気相成
長炭素繊維（直径２．３μｍ、長さ２００μｍ以上）を
ハイブリダイザーに装填し、このハイブリダイザーを
８，０００ｒｐｍの回転数で３分間高速回転し、得られ
た破断気相法成長炭素繊維をアルゴンガス中で２，８０
０℃で加熱して黒鉛化することにより、直径２．２μ
ｍ、長さ１８．３μｍ、ｇ値が２．０１５でのスピン密
度が９．３×１０18spins/g である黒鉛化気相成長炭素
繊維を得た。Comparative Example 4 A vapor-grown carbon fiber (diameter 2.3 μm, length 200 μm or more) obtained by a flow method was loaded into a hybridizer, and the hybridizer was rotated at 8,000 rpm for 3 minutes. After rotating at high speed, the obtained fractured vapor grown carbon fiber was
By heating at 0 ° C. and graphitizing, a 2.2 μm diameter is obtained.
Graphitized vapor-grown carbon fibers having a m, a length of 18.3 μm, a g value of 2.015, and a spin density of 9.3 × 10 18 spins / g were obtained.
【００６７】得られた黒鉛化気相成長炭素繊維を用いて
前記実施例３と同様にして３電極セルを組み立て、前記
実施例３と同様にして充放電を繰り返した。その結果を
表６に示した。Using the obtained graphitized vapor-grown carbon fiber, a three-electrode cell was assembled in the same manner as in Example 3, and charging and discharging were repeated in the same manner as in Example 3. Table 6 shows the results.
【００６８】[0068]
【表６】 [Table 6]
【００６９】[0069]
【発明の効果】この発明の黒鉛化気相成長炭素繊維は、
プラスチック、ゴム、金属、セラミックス、塗料、接着
剤などに高い充填密度で複合した複合材料やわずかな結
着剤を使用した実質的に黒鉛化気相成長炭素繊維単独よ
りなる複合成形体などの複合体の製造に好適である。The graphitized vapor grown carbon fiber of the present invention is
Composites such as composites composed of plastics, rubbers, metals, ceramics, paints, adhesives, etc. with a high packing density, or composite molded bodies consisting essentially of graphitized vapor-grown carbon fiber alone with a small amount of binder Suitable for body production.
【００７０】この発明の方法によると、気相成長炭素繊
維の黒鉛化処理をした後に高衝撃処理をしているので、
酸素ラジカルの少ない破断面を有する黒鉛化気相成長炭
素繊維を製造することができる。According to the method of the present invention, since the high impact treatment is performed after the graphitization treatment of the vapor grown carbon fiber,
Graphitized vapor-grown carbon fibers having a fracture surface with few oxygen radicals can be produced.
【００７１】この発明の成形体は、実質的に黒鉛化気相
成長炭素繊維のみからなるので、すべての黒鉛化気相成
長炭素繊維が他の繊維と接触し、その結果、電気導電
性、熱伝導性に優れ、また、触媒担体としても優れてい
る。この発明の成形体は、リチウムと層間化合物を形成
することを利用した電池の電極材料としても優れてい
る。Since the molded article of the present invention consists essentially of only the graphitized vapor grown carbon fiber, all of the graphitized vapor grown carbon fiber comes into contact with other fibers, and as a result, the electrical conductivity and the thermal conductivity are reduced. It has excellent conductivity and is also excellent as a catalyst carrier. The molded article of the present invention is also excellent as a battery electrode material utilizing the formation of an interlayer compound with lithium.
【００７２】この発明の複合体は、成形状態が良好で高
充填が可能であるので、この複合体を塗料や接着剤など
とした場合には、被膜強度の大きな、しかも電気導電
性、熱伝導性に優れた被膜を形成することができる。ま
たこの複合体が成形体であるときには、上記特性の他に
加工面の仕上げが美麗になるという優れた加工特性が発
揮される。The composite of the present invention has a good molded state and can be filled with a high degree of charge. Therefore, when this composite is used as a paint or an adhesive, it has a high coating strength, electrical conductivity and heat conductivity. A film having excellent properties can be formed. In addition, when the composite is a molded product, excellent processing characteristics such as beautiful finish of a processed surface are exhibited in addition to the above characteristics.
【００７３】したがって、この発明の成形体および複合
体は、高導電材料、熱伝導度の優れた材料、触媒の担体
などとして使用することができる。Therefore, the molded article and composite of the present invention can be used as a highly conductive material, a material having excellent thermal conductivity, a carrier for a catalyst, and the like.
【図１】この発明の方法において好適に使用することの
できる高衝撃処理装置の構成の一例を示す説明図であ
る。FIG. 1 is an explanatory diagram showing an example of the configuration of a high impact processing device that can be suitably used in the method of the present invention.
１ 気流の通路である自己循環回路 ２ 衝撃羽根 ３ 容器 DESCRIPTION OF SYMBOLS 1 Self-circulation circuit which is an air flow path 2 Impact blade 3 Container
Claims (5)
まず、平均直径が５μｍ以下であり、平均長さが９０μ
ｍ以下であり、平均アスペクト比が１〜１８であり、電
子スピン共鳴吸収法により測定したスピン密度が８×１
０18spins/g 以下であることを特徴とする黒鉛化気相成
長炭素繊維。Claims: 1. A high-impact treatment, comprising fluorinated graphite.
First, the average diameter is 5 μm or less and the average length is 90 μm.
m, the average aspect ratio is 1 to 18, and the spin density measured by the electron spin resonance absorption method is 8 × 1.
A graphitized vapor-grown carbon fiber having a density of not more than 0 18 spins / g.
鉛を含まない気相成長炭素繊維を２，０００℃以上に加
熱して黒鉛化処理をした後に、得られた黒鉛化処理気相
成長炭素繊維を、電子スピン共鳴吸収法により測定した
スピン密度が８×１０18spins/g 以下になるまで、高衝
撃力で破断することを特徴とする前記請求項１に記載の
黒鉛化気相成長炭素繊維の製造方法。Wherein not been substantially broken, and fluoride black
After the lead- free vapor-grown carbon fiber is heated to 2,000 ° C. or more to be graphitized, the obtained graphitized vapor-grown carbon fiber has a spin density measured by an electron spin resonance absorption method. 2. The method for producing graphitized vapor-grown carbon fiber according to claim 1, wherein the fiber is broken by a high impact force until the spinning rate becomes 8 × 10 18 spins / g or less.
相成長炭素繊維のみからなることを特徴とする成形体。3. A molded article comprising substantially only the graphitized vapor-grown carbon fiber according to claim 1.
素繊維とマトリックスとを含有することを特徴とする複
合体。4. A composite comprising the graphitized vapor-grown carbon fiber according to claim 1 and a matrix.
径が１．５〜３．０μｍである前記請求項３に記載の成
形体。5. The molded article according to claim 3, wherein the graphitized vapor-grown carbon fiber has an average diameter of 1.5 to 3.0 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5160954A JP2804217B2 (en) | 1992-07-06 | 1993-06-30 | Graphitized vapor grown carbon fiber, method for producing graphitized vapor grown carbon fiber, molded article and composite |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-178687 | 1992-07-06 | ||
| JP17868792 | 1992-07-06 | ||
| JP5160954A JP2804217B2 (en) | 1992-07-06 | 1993-06-30 | Graphitized vapor grown carbon fiber, method for producing graphitized vapor grown carbon fiber, molded article and composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0673615A JPH0673615A (en) | 1994-03-15 |
| JP2804217B2 true JP2804217B2 (en) | 1998-09-24 |
Family
ID=26487268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5160954A Expired - Lifetime JP2804217B2 (en) | 1992-07-06 | 1993-06-30 | Graphitized vapor grown carbon fiber, method for producing graphitized vapor grown carbon fiber, molded article and composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2804217B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10247495A (en) * | 1997-02-28 | 1998-09-14 | Nikkiso Co Ltd | Carbon material for secondary battery negative electrode, its manufacture, and nonaqueous electrolyte secondary battery using carbon material |
| JP2002059257A (en) * | 2000-08-11 | 2002-02-26 | Yazaki Corp | Composite material |
| US7150840B2 (en) | 2002-08-29 | 2006-12-19 | Showa Denko K.K. | Graphite fine carbon fiber, and production method and use thereof |
| JP4796769B2 (en) * | 2004-12-20 | 2011-10-19 | 株式会社キャタラー | Carbon material for electric double layer capacitor and electric double layer capacitor |
| JP2011216231A (en) * | 2010-03-31 | 2011-10-27 | Jx Nippon Oil & Energy Corp | Carbon material for lithium ion secondary battery, and electrode using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62235204A (en) * | 1986-04-04 | 1987-10-15 | Asahi Chem Ind Co Ltd | Fluorinated graphite material |
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1993
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