JPS6310405A - Conducting graphite material and manufacture thereof - Google Patents
Conducting graphite material and manufacture thereofInfo
- Publication number
- JPS6310405A JPS6310405A JP15267886A JP15267886A JPS6310405A JP S6310405 A JPS6310405 A JP S6310405A JP 15267886 A JP15267886 A JP 15267886A JP 15267886 A JP15267886 A JP 15267886A JP S6310405 A JPS6310405 A JP S6310405A
- Authority
- JP
- Japan
- Prior art keywords
- graphite material
- carbon
- conductive graphite
- layer
- fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000007770 graphite material Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 239000000835 fiber Substances 0.000 claims description 43
- 229910002804 graphite Inorganic materials 0.000 claims description 27
- 239000010439 graphite Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 22
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 150000001639 boron compounds Chemical class 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 239000004917 carbon fiber Substances 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011247 coating layer Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 5
- 229910021469 graphitizable carbon Inorganic materials 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 4
- 239000000758 substrate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000005979 thermal decomposition reaction Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- -1 alkyl boron compound Chemical class 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000010575 Pueraria lobata Nutrition 0.000 description 1
- 241000219781 Pueraria montana var. lobata Species 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WIDQNNDDTXUPAN-UHFFFAOYSA-I tungsten(v) chloride Chemical compound Cl[W](Cl)(Cl)(Cl)Cl WIDQNNDDTXUPAN-UHFFFAOYSA-I 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はホウ素を含有する導電性グラファイト材料及び
その製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a conductive graphite material containing boron and a method for producing the same.
従来、ベンゼンをモノマに用いて炭素繊維上に易グラフ
ァイト化炭素の被覆層を堆積したｆ！２５○Ｏ℃以上の
温度で熱処理することで層面間隔ｄ（００２＞が３．３
６３Ａ以下のグラファイト層を外皮層とするグラファイ
ト繊維が得られている（特開昭５９−１８７６２２号公
報）ａしかしこの方法で得られたグラファイト繊維は３
０００’Ｃの熱処理後でも外皮層のグラファイトの層面
間隔ｄ （００２＞が３．３６２Ａになるにすぎない。Conventionally, a coating layer of easily graphitized carbon was deposited on carbon fiber using benzene as a monomer. The layer spacing d(002>) is reduced to 3.3 by heat treatment at a temperature of 250°C or higher.
Graphite fibers having a graphite layer of 63A or less as an outer skin layer have been obtained (Japanese Patent Application Laid-Open No. 187622/1983)a However, the graphite fibers obtained by this method are
Even after heat treatment at 000'C, the interlayer spacing d(002>) of graphite in the outer skin layer is only 3.362A.
ホウ素を易グラファイト化のための触媒に用いる方法と
しては、アルキルホウ素化合物の雰囲気中で炭素繊維を
熱処理しグラファイト繊維を得る方法が知られている（
米国特許３６５６９０４号明細書）。ホウ素は易グラフ
ァイト化触媒として広く知られており、種々の炭素材に
対する応用例がある。これらを大別すると以下の３項目
に分類できる。すなわち、
（１）炭素化を行う前にホウ素を添加する。As a method of using boron as a catalyst for easily graphitizing, there is a known method of heat-treating carbon fibers in an atmosphere of an alkyl boron compound to obtain graphite fibers (
(U.S. Pat. No. 3,656,904). Boron is widely known as a catalyst that facilitates graphitization, and there are examples of its application to various carbon materials. These can be roughly classified into the following three categories. That is, (1) boron is added before carbonization.
（２）炭素化を行った後グラフ１イト化を行う前にホウ
素を添加する。(2) Boron is added after carbonization and before graphitization.
（３）グラファイト化を行った後ホウ素を添加し再度グ
ラファイト化を行う。(3) After graphitizing, boron is added and graphitizing is performed again.
米国特許３６５６９０４号明細書に記載の方法は上記分
類の（２）に対応する。The method described in US Pat. No. 3,656,904 corresponds to category (2) above.
特開昭５９−１８７６２２号公報に記載の方法は、２５
００℃以上の温度を必要とするため工業的量産を行う見
地からするとエネルギー消費最が−多く、また熱処理炉
に多大な断熱材が必要である。The method described in JP-A-59-187622 is based on 25
Since it requires a temperature of 00° C. or higher, it consumes the most energy from the standpoint of industrial mass production, and requires a large amount of heat insulating material in the heat treatment furnace.
・１
゛従って高導電性グラフ１イト繊維を得るための熱ｉ理
温度はできるだけ低い方が望ましい。一方、−一電体と
して用いる場合、電気抵抗による電気エネルギーの損失
を最小限に抑えるために導電性はできるだけ高い方が望
ましいが、高い導電性を得るためには必然的に高い熱処
理温度を必要とする。・1 ゛Therefore, it is desirable that the thermal temperature for obtaining highly conductive graphite fibers be as low as possible. On the other hand, when used as a - monoelectric material, it is desirable to have as high conductivity as possible in order to minimize the loss of electrical energy due to electrical resistance, but in order to obtain high conductivity, high heat treatment temperatures are inevitably required. shall be.
この両者を同時に満足することは不可能であるため、現
実的には費用と効果の関係で最適な熱処理温度が決定さ
れる。Since it is impossible to satisfy both of these requirements at the same time, the optimum heat treatment temperature is actually determined based on the relationship between cost and effectiveness.
また米国特許３６５６９０４号明細書に記載の方法は、
炭素化を行った後ホウ素を添加する方法であるので、繊
維中にホウ素が均一に分散しにくいため、高導電性グラ
ファイト繊維を得るためには高い熱処理温度を必要とす
る。Furthermore, the method described in US Pat. No. 3,656,904 is
Since this is a method in which boron is added after carbonization, it is difficult for boron to be uniformly dispersed in the fibers, so a high heat treatment temperature is required to obtain highly conductive graphite fibers.
本発明の目的は高導電性グラフ１イト材料（とくには繊
維）を提供すること、さらに高導電性グラファイト材料
（とくには繊維）をできるだけ低い熱処理温度で得る方
法、又は同じ熱処理温度であればできるだけ高い導電性
を有するグラフ１イト材料（とくには繊維）を得る方法
を提供することにある。The object of the present invention is to provide a highly conductive graphite material (especially fiber), and a method for obtaining a highly conductive graphite material (especially fiber) at a heat treatment temperature as low as possible, or as low as possible at the same heat treatment temperature. The object of the present invention is to provide a method for obtaining graphite materials (especially fibers) having high electrical conductivity.
上記目的を達成するため本発明は下記の構成からなる。 In order to achieve the above object, the present invention consists of the following configuration.
［（１）基材の表層にグラファイト層を有する材料にお
いて、層面間隔ｄ （００２）が３．３６０Ａ以下でか
つホウ素をモル比０．０５％以上含有するグラファイト
層を外皮層とすることを特徴とする導電性グラファイト
材料。[(1) In a material having a graphite layer on the surface layer of the base material, a graphite layer having a interlayer spacing d (002) of 3.360 A or less and containing boron at a molar ratio of 0.05% or more is used as the outer skin layer. conductive graphite material.
（２） 基材の表層にグラファイト層を製造する方法
において、基材上にホウ素を含んだ易グラファイト化炭
素の被覆層を堆積し、しかる後加熱処理することを特徴
とする導電性グラファイト材料の製造方法。」
以下、本発明の詳細な説明する。(2) A method for producing a graphite layer on the surface layer of a base material, in which a coating layer of easily graphitizable carbon containing boron is deposited on the base material, and then heat-treated. Production method. ” Hereinafter, the present invention will be explained in detail.
本発明において基材とは、繊維、成形体、板状、フィル
ム、シートなどいかなる形状であってもよい。とくに好
ましい基材としては、炭素繊維である。基材として炭素
繊維を用いたときはグラファイト繊維を製造することが
できるからである。In the present invention, the base material may be in any shape such as fiber, molded body, plate shape, film, or sheet. A particularly preferred base material is carbon fiber. This is because graphite fibers can be produced when carbon fibers are used as the base material.
炭素繊維の一例としては連続繊維である。連続繊維とし
ては、モノフィラメントでおってもマルチフィラメント
であってもよい。炭素繊維は、ポリアクリロニトリル系
、ピッチ系、セルローズ系、ビニロン系、リグニン／ポ
パール系など、どのようなものでおってもよい。通常５
〜１０μｍ程度の単糸径を有するものを使用する。An example of carbon fiber is continuous fiber. The continuous fibers may be monofilaments or multifilaments. The carbon fiber may be of any type, such as polyacrylonitrile type, pitch type, cellulose type, vinylon type, lignin/popal type, etc. Usually 5
A single yarn having a diameter of about 10 μm is used.
−より結合した６員環炭素から構成される面がファ゛シ
デルワールス結合により結合して成る構造が発達した炭
素を主成分とする化合物であり、特にＣｕ−にα線を使
用したＸ線回折によって００２面から求めた層面間隔が
３．３６０Ａ以下であるということによって特徴付けら
れる化合物である。- It is a compound whose main component is carbon, which has a developed structure in which planes composed of 6-membered ring carbons are bonded by Fasider-Waals bonds. This is a compound characterized by the interlayer spacing determined from the 002 plane being 3.360A or less.
導電性とは、４端子法により’ｇ温かつ空気中において
測定した電気伝導度（以下、電導度という）が１ｘ１０
３Ｓ／Ｃｍ以上であるものとして定義される。Conductivity means that the electrical conductivity (hereinafter referred to as electrical conductivity) measured in air at a temperature of
Defined as 3S/Cm or higher.
上記特性値による層面間隔ｄ （００２＞が３゜３６０
Ａ以下でかつホウ素をモル比０．０５％以゛上含有する
グラファイト層を有すれば、本発明の目的とする導電性
の高いグラファイト材料を１ｑることかできる。Layer spacing d (002> according to the above characteristic values is 3°360
If it has a graphite layer containing A or less and a boron content of 0.05% or more by molar ratio, it is possible to produce 1 q of highly conductive graphite material, which is the object of the present invention.
また本発明において、基材の表層にグラファイト層を外
皮層として有することは、外皮層は導電性に大きく寄与
するからである。Further, in the present invention, the reason why the surface layer of the base material has a graphite layer as an outer skin layer is that the outer skin layer greatly contributes to electrical conductivity.
次に製造方法を説明する。Next, the manufacturing method will be explained.
本発明において、基材上にホウ素を含んだ易グラファイ
ト化炭素を堆積する方法としては、化学気相蒸着法（Ｃ
ｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ
）を用いる。すなわち、上記炭素材料基材を連続的に走
行させながら加熱し、基材上で有機ホウ素化合物を熱分
解することにより易グラファイト化炭素の被覆層を堆積
せしめる。熱分解温度は使用する有機ホウ素化合物によ
るが、１２００〜２０００℃である。好ましくは１３０
０〜１７００℃である。In the present invention, the chemical vapor deposition method (C
chemical vapor deposition
) is used. That is, the carbon material base material is heated while being continuously moved to thermally decompose the organic boron compound on the base material, thereby depositing a coating layer of easily graphitizable carbon. The thermal decomposition temperature depends on the organic boron compound used, but is 1200 to 2000°C. Preferably 130
The temperature is 0 to 1700°C.
１２００℃未満では易グラフ１イト化炭素の被覆層の堆
積速度が著しく遅くなる。ｉた２０００℃を越えると、
難グラファイト化炭素の生成量が多くなりがちであり、
何れも好ましくない。If the temperature is lower than 1200°C, the deposition rate of the easily graphitized carbon coating layer becomes extremely slow. If the temperature exceeds 2000℃,
The amount of carbon that is difficult to graphitize tends to be large,
I don't like either of them.
熱分解させる有機ホウ素化合物は、炭素、水素、ホウ素
から成るものであれば何でも良いが、好ましくは、アル
キルホウ素化合物、芳香族炭化水素基を含む有機ホウ素
化合物、ビニル基を含む有機ホウ素化合物が良い。さら
に好ましくは、トリエチルボロン、フェニルジボラン、
ビニルジボランが良い。The organic boron compound to be thermally decomposed may be any compound consisting of carbon, hydrogen, and boron, but preferably an alkyl boron compound, an organic boron compound containing an aromatic hydrocarbon group, or an organic boron compound containing a vinyl group. . More preferably, triethylboron, phenyldiborane,
Vinyl diborane is good.
有機ホウ素化合物の熱分解は、有機ホウ素化合物の分圧
が１〜１００ｍｍＨｇの範囲内で行う。特に、５〜６０
ｍｍＨ！ｌ］の範囲内が好ましく用いられる。熱分解は
窒素やアルゴンの共存下で、必要に応じてざらに水素の
共存下で行うこともできる。Thermal decomposition of the organic boron compound is carried out at a partial pressure of the organic boron compound within a range of 1 to 100 mmHg. In particular, 5 to 60
mmH! l] is preferably used. Thermal decomposition can be carried out in the presence of nitrogen or argon, or if necessary, in the presence of hydrogen.
熱分解時間は、使用する有機ホウ素化合物の種類、有機
ホウ素化合物の濃度、熱分解温度により異なるが、通常
、数分から数十分程度である。より均質な易グラフ１イ
ト化炭素の被覆層を形成するためには、熱分解温度を低
くし、熱分解時間を長くするのが好ましい。The thermal decomposition time varies depending on the type of organic boron compound used, the concentration of the organic boron compound, and the thermal decomposition temperature, but is usually about several minutes to several tens of minutes. In order to form a more homogeneous coating layer of easily graphitized carbon, it is preferable to lower the thermal decomposition temperature and to increase the thermal decomposition time.
易グラファイト化炭素の被覆層の厚みは、有機ホウ素化
合物の濃度、熱分解温度、熱分解時間な、どによって調
節できるが、最終的に得られる高専；１電性材料の可撓
性が著しく損われないように、ま：た高導電性材料とす
るために、１５〜２００μｍ程度であるのが好ましい。The thickness of the coating layer of easily graphitized carbon can be adjusted by adjusting the concentration of the organic boron compound, the thermal decomposition temperature, the thermal decomposition time, etc., but the flexibility of the final electrically conductive material will be significantly impaired. It is preferable that the thickness is about 15 to 200 μm to prevent corrosion and to make the material highly conductive.
なお、炭素繊維をマルチフィラメントの形態で供する場
合には、堆積した易グラファイト化炭素によって単糸同
士が結着されることで、可撓性が失われがちになるので
、被覆層の形成速度を極力遅くすることが好ましい。In addition, when carbon fibers are provided in the form of multifilaments, the single fibers tend to be bound together by the deposited easily graphitized carbon, which tends to cause a loss of flexibility. It is preferable to slow down as much as possible.
上記の方法により得られた易グラファイト化炭素被覆炭
素材料について、次に、熱処理をすることにより高導電
性グラファイト材料を得る。この際の熱処理温度は２０
００″Ｃ以上２９００′Ｃ以下である。好ましくは２３
００〜２７００’Ｃが良い。The easily graphitized carbon-coated carbon material obtained by the above method is then subjected to heat treatment to obtain a highly conductive graphite material. The heat treatment temperature at this time was 20
00''C or more and 2900'C or less. Preferably 23
00-2700'C is good.
熱処理時間は５〜６０分が好ましい。The heat treatment time is preferably 5 to 60 minutes.
また、より導電性の高い材料を得るために、グラファイ
ト化の後、電子供与性または電子受容性の物質をグラフ
ァイトの層間に挿入（Ｉｎｔｅｒｃａｌａｔｉｏｎ ）
することも可能でおる。そのような、インターカレーシ
ョン法は、たとえば炭素材料学会列、雑誌炭素、第１１
１巻、第１７１ページ（１９８２年）に記載されている
。電子供与性または電子受容性の物質としては、たとえ
ばリチウム、ナトリウム等のアルリ金属、塩素、臭素等
のハロゲンガス、ＩＦｓなとのハロゲン化合物、ＭｇＣ
１５、ＷＣｌ５等の金属ハロゲン化物、硝酸、硫酸、Ａ
ＳＦｓ等の酸、Ｋ−ナフタレン等の有機金属化合物など
、いろいろ知られているが、安価かつ無毒であり、しか
も生成物が安定している硝酸が最も好ましい。In addition, in order to obtain a material with higher conductivity, after graphitization, an electron-donating or electron-accepting substance is inserted between the graphite layers (intercalation).
It is also possible to do so. Such an intercalation method is described in, for example, Carbon Materials Society Series, Magazine Carbon, No. 11.
1, page 171 (1982). Examples of electron-donating or electron-accepting substances include aryl metals such as lithium and sodium, halogen gases such as chlorine and bromine, halogen compounds such as IFs, and MgC.
15. Metal halides such as WCl5, nitric acid, sulfuric acid, A
Various acids such as SFs and organometallic compounds such as K-naphthalene are known, but nitric acid is the most preferred because it is inexpensive, non-toxic, and produces a stable product.
以上述べてきた本発明による製造法によって、炭素材料
を基材とし、層面間隔ｄ （００２＞が３゜３６０Ａ以
下でかつホウ素をモル比０．０５％以上含有するグラフ
ァイト層を外皮層とすることを特徴とする導電性グラフ
ァイト材料が得られる。By the manufacturing method according to the present invention described above, a graphite layer using a carbon material as a base material, having a layer spacing d (002> of 3°360A or less and containing boron in a molar ratio of 0.05% or more) is made into an outer skin layer. A conductive graphite material having the following characteristics is obtained.
・〔実施例〕
比較実施例１
米国ｕｃｃ社製の炭素繊維、Ｔｈ０ｒｎｅｌ−Ｐ７５を
アルゴン雰囲気で直径１５皿、全長４５ｃｍの石英製反
応管中を連続的に走行させ、金属製のローうにより１５
００℃に通電加熱を行いながら、ベンゼンを分圧１０ｍ
ｍＨＱで導入し、炭素を炭素繊維上に堆積させた。この
ようにして得た繊維をアルゴン気流中で２５００℃、３
０分間、熱処理を行った。・[Example] Comparative Example 1 Th0rnel-P75, a carbon fiber manufactured by UCC Corporation in the United States, was continuously run in an argon atmosphere through a quartz reaction tube with a diameter of 15 plates and a total length of 45 cm.
Benzene was heated at a partial pressure of 10 m while heating to 00°C.
mHQ was introduced and the carbon was deposited onto the carbon fibers. The fibers thus obtained were heated at 2500°C for 3 hours in an argon stream.
Heat treatment was performed for 0 minutes.
得られた繊維の繊維径は９０μｍであった。直流四端子
法により室温での電導度を測定したところ、１．６Ｘ１
０３Ｓ／ｃｍであった。The fiber diameter of the obtained fiber was 90 μm. When the electrical conductivity was measured at room temperature using the DC four-terminal method, it was found to be 1.6X1.
It was 0.03 S/cm.
比較実施例２
比較実施例１と同様にしてアルゴン気流中で２７００℃
、３０分間、熱処理を行って得られた繊維の室温での電
導度を測定したところ、２．１×１０３３／ｃｍであっ
た。Comparative Example 2 At 2700°C in an argon stream in the same manner as in Comparative Example 1.
The conductivity at room temperature of the fiber obtained by heat treatment for 30 minutes was measured and found to be 2.1 x 1033/cm.
比較実施例３
比較実施例１と同様にしてアルゴン気流中で３０００℃
、３０分間、熱処理を行って得られた繊維の室温での電
導度を測定したところ、１．４×１０４Ｓ／Ｃｍであっ
た。Comparative Example 3 In the same manner as Comparative Example 1, at 3000°C in an argon stream.
When the conductivity at room temperature of the fiber obtained by heat treatment for 30 minutes was measured, it was 1.4 x 104 S/Cm.
実施例１
米国ｕｃｃ社製の炭素繊維、Ｔｈｏｒｎｅｌ−Ｐ７５を
アルゴン雰囲気で直径１５ｍｍ、全長４５ｃｍの石英製
反応管中を連続的に走行させ、金属製の口′−ラにより
１３５０℃に通電加熱を行いながら、トリエチルボロン
を分圧３ｍｍＨＯで導入し、ホウ素を含んだ炭素を炭素
繊維上に堆積させた。このようにして得た繊維をアルゴ
ン気流中で２５００℃、３０分間、熱処理を行った。得
られた繊維の繊維径は９０μｍであった。直流四端子法
により室温での電導度を測定したところ、３．１ Ｘ
１０３ Ｓ／ｃｍであった。比較実施例１により得られ
た熱処理温度が２５００’Ｃの繊維、ざらに比較実施例
２により得られた熱処理温度が２７００℃の繊維と比べ
ても高い電導度が得られている。Example 1 Carbon fiber, Thornel-P75 manufactured by UCC Corporation in the United States, was continuously run in an argon atmosphere through a quartz reaction tube with a diameter of 15 mm and a total length of 45 cm, and heated to 1350° C. using a metal lug. During this process, triethylboron was introduced at a partial pressure of 3 mm HO to deposit boron-containing carbon onto the carbon fibers. The fibers thus obtained were heat treated at 2500° C. for 30 minutes in an argon stream. The fiber diameter of the obtained fiber was 90 μm. When the electrical conductivity was measured at room temperature using the DC four-terminal method, it was 3.1
It was 103 S/cm. A higher electrical conductivity was obtained compared to the fiber obtained in Comparative Example 1, which was heat-treated at a temperature of 2500°C, and the fiber obtained in Comparative Example 2, which was heat-treated at a temperature of 2700°C.
実施例２
実施例１と同様にしてアルゴン気流中で３００Ｏ℃、３
０分間、熱処理を行って得られた繊維の室温での電導度
を測定したところ、４．９×１０３３／ｃｍであった。Example 2 In the same manner as in Example 1, the temperature was 300°C in an argon stream.
When the conductivity at room temperature of the fiber obtained by heat treatment for 0 minutes was measured, it was 4.9 x 1033/cm.
比較実施例３により得られた熱処理温度が３０００℃の
繊維と比べると、むしろ電導度が低い。Compared to the fiber obtained in Comparative Example 3, which was heat-treated at a temperature of 3000° C., the conductivity is rather low.
実施例３
比較実施例１および比較実施例２および実施例１により
得られたグラファイト繊維に対し、理学電機製広角Ｘ線
ディフラクトメータを用いて、ＣＬＪ−にα線を使用し
たＸ線回折を透過法で測定した。その結果を第１図に示
す。第１図において、（ａ）は比較実施例１で得られた
ものを、（ｂ）は比較実施例２で得られたものを、（Ｃ
）は実施例１で得られたグラファイト繊維を示す。Example 3 The graphite fibers obtained in Comparative Example 1, Comparative Example 2, and Example 1 were subjected to X-ray diffraction using α-rays for CLJ- using a wide-angle X-ray diffractometer manufactured by Rigaku Corporation. Measured by transmission method. The results are shown in FIG. In FIG. 1, (a) shows what was obtained in Comparative Example 1, (b) shows what was obtained in Comparative Example 2, and (C
) indicates the graphite fiber obtained in Example 1.
また、（００２＞回折線から１謬られる層面間隔を、表
１に示す。Further, Table 1 shows the interlayer spacing determined from the (002> diffraction line).
表 １
このように、本発明による高導電性グラファイト繊維は
層面間隔が小ざく、グラファイト化度が高いことが分る
。Table 1 Thus, it can be seen that the highly conductive graphite fiber according to the present invention has a small interlayer spacing and a high degree of graphitization.
実施例４
米国１００社製の炭素繊維、Ｔｈｏｒｎｅｌ−Ｐ７５を
アルゴン雰囲気で直径１５ｍｍ、全長４５ｃｍの石英製
反応管中を連続的に走行させ、金属製のローラにより１
５５０’Ｃに通電加熱を行いながら、フェニルジボラン
を分圧１０ｍｍＨ（］で導入し、ホウ素を含／ｖだ炭素
を炭素域維上に堆積させた。このようにして得た繊維を
アルゴン気流中で２５００℃１３０分間、熱処理を行っ
た。１ｑられた繊維の繊維径は１５０μｍであった。直
流四端子法により室温での電導度を測定したところ、３
．３Ｘ１０３Ｓ／Ｃｍであった。（００２＞回折線から
得られる層面間隔は、３．３５７Ａでめった。Example 4 Carbon fiber, Thornel-P75 manufactured by 100 companies in the United States, was continuously run in an argon atmosphere through a quartz reaction tube with a diameter of 15 mm and a total length of 45 cm.
Phenyldiborane was introduced at a partial pressure of 10 mmH (] while heating with electricity to 550'C, and boron-containing carbon was deposited on the carbon fibers. The fibers thus obtained were placed in an argon stream. Heat treatment was performed at 2500°C for 130 minutes.The fiber diameter of the 1q fiber was 150μm.When the electrical conductivity at room temperature was measured by the DC four-probe method, it was found that 3.
．． It was 3X103S/Cm. (The interlayer spacing obtained from the 002> diffraction line was determined to be 3.357A.
実施例５
有機ホウ素化合物としてビニルジボランを使用、レナほ
かは、実施例４と同様にして高導電性グラファイト繊維
を得た。（００２）回折線から得られる層面間隔は、３
．３５７Ａであった。Example 5 Highly conductive graphite fibers were obtained in the same manner as in Example 4 except that Lena et al. used vinyl diborane as the organic boron compound. The interlayer spacing obtained from the (002) diffraction line is 3
．． It was 357A.
実施例６
実施例１で得られた高導電性グラファイト繊維を発煙硝
酸に約５０分間晒し、硝酸をインター力レイションとし
たところ、電導度が１．５Ｘ１０ＳＳ／ｃｍと向上した
。Example 6 The highly conductive graphite fiber obtained in Example 1 was exposed to fuming nitric acid for about 50 minutes, and when the nitric acid was used as an interforcement, the conductivity improved to 1.5×10 SS/cm.
本発明は構造自体が新規で、かつ高い導電性を有するグ
ラファイト材料（とくには繊維）を効率よく製造するこ
とができる。ざらに高導電性グラファイト材料（とくに
は繊維）をできるだけ低い熱処理温度で得る製造方法、
又は同じ熱処理温度であればできるだけ高い導電性を有
するグラファイト材料（とくには繊維）を得る製造方法
を提供することができた。INDUSTRIAL APPLICABILITY The present invention has a novel structure and can efficiently produce a graphite material (especially fiber) having high conductivity. A manufacturing method for obtaining highly conductive graphite materials (especially fibers) at the lowest possible heat treatment temperature,
Alternatively, it was possible to provide a manufacturing method for obtaining a graphite material (particularly fiber) having as high electrical conductivity as possible at the same heat treatment temperature.
第１図は各種グラファイト繊維を理学電数製広角Ｘ線デ
ィフラクトメータを用いて、Ｃｕ−にα線を使用したＸ
線回折を透過法で測定した結果を示す。
（ａ）は比較実施例１でｊｑられたグラファイト繊維（
ベンゼンを七ツマとし、２５００℃で熱処理したもの）
を示す。
（ｂ）は比較実施例２で１ｑられたグラファイト繊維（
ベンゼンをモノマとし、２７００℃で熱処理したもの）
を示す。
（Ｃ）は実施例１で得られたグラファイト繊維（トリエ
チルボロンをモノマとし、２５００’Ｃで熱処理したも
の）を示す。
特許出願人 工 業 技 術 院 長Ｘ線回折角（４
） ｃｔ４−Ｋｅ＜葛１０ Ｘ機回苅バク−／Figure 1 shows how various graphite fibers were measured using a wide-angle X-ray diffractometer manufactured by Rigaku Denshi.
The results of line diffraction measurements using a transmission method are shown. (a) shows the graphite fiber (
Heat treated at 2500℃ using benzene as a salt)
shows. (b) is the graphite fiber (1q) obtained in Comparative Example 2 (
Heat treated at 2700℃ using benzene as a monomer)
shows. (C) shows the graphite fiber obtained in Example 1 (using triethyl boron as a monomer and heat-treated at 2500'C). Patent applicant Director of Industrial Technology X-ray diffraction angle (4
) ct4-Ke<Kudzu 10
Claims (12)
て、層面間隔ｄ（００２）が３．３６０Ａ以下でかつホ
ウ素をモル比０．０５％以上含有するグラファイト層を
外皮層とすることを特徴とする導電性グラファイト材料
。(1) A material having a graphite layer on the surface layer of the base material, characterized in that the graphite layer having a layer spacing d(002) of 3.360 A or less and containing boron at a molar ratio of 0.05% or more is used as the outer skin layer. conductive graphite material.
の範囲第（１）項記載の導電性グラファイト材料。(2) The conductive graphite material according to claim (1), wherein the base material is carbon fiber.
特許請求の範囲第（１）項記載の導電性グラファイト材
料。(3) The conductive graphite material according to claim (1), wherein the graphite material is a fiber.
いて、基材上にホウ素を含んだ易グラファイト化炭素の
被覆層を堆積し、しかる後加熱処理することを特徴とす
る導電性グラファイト材料の製造方法。(4) A method for producing a graphite layer on the surface layer of a base material, which comprises depositing a coating layer of easily graphitizable carbon containing boron on the base material, and then heat-treating the conductive graphite material. Production method.
徴とする特許請求の範囲第（４）項記載の導電性グラフ
ァイト材料の製造方法。(5) The method for producing a conductive graphite material according to claim (4), wherein the heat treatment is performed at a temperature of 2000° C. or higher.
範囲であることを特徴とする特許請求の範囲第（５）項
記載の導電性グラファイト材料の製造方法。(6) The method for producing a conductive graphite material according to claim (5), wherein the heat treatment is performed at a temperature range of 2300°C or higher and 2800°C or lower.
たはそれを主たるモノマとして温度１３００〜２０００
℃、圧力１〜１００ｍｍＨｇで熱分解し、炭素繊維基材
上に易グラファイト化炭素の被覆層を堆積した後２００
０℃以上の温度で熱処理することを特徴とする特許請求
の範囲第（４）項記載の導電性グラファイト材料の製造
方法。(7) Organic boron compound consisting of carbon, hydrogen, and boron, or using it as the main monomer at a temperature of 1300 to 2000
℃ and a pressure of 1 to 100 mmHg to deposit a coating layer of easily graphitizable carbon on the carbon fiber substrate.
A method for producing a conductive graphite material according to claim (4), characterized in that the conductive graphite material is heat-treated at a temperature of 0° C. or higher.
芳香族炭化水素基を含む有機ホウ素化合物であることを
特徴とする特許請求の範囲第（４）項記載の導電性グラ
ファイト材料の製造方法。(8) The method for producing a conductive graphite material according to claim (4), wherein the organic boron compound consisting of carbon, hydrogen, and boron is an organic boron compound containing an aromatic hydrocarbon group.
ビニル基を含む有機ホウ素化合物であることを特徴とす
る特許請求の範囲第（４）項記載の導電性グラファイト
材料の製造方法。(9) The method for producing a conductive graphite material according to claim (4), wherein the organic boron compound consisting of carbon, hydrogen, and boron is an organic boron compound containing a vinyl group.
がトリエチルボロン、フエニルジボラン、ビニルジボラ
ンから選ばれる少なくとも一つであることを特徴とする
特許請求の範囲第（４）項記載の導電性グラファイト材
料の製造方法。(10) The conductive graphite material according to claim (4), wherein the organic boron compound consisting of carbon, hydrogen, and boron is at least one selected from triethylboron, phenyldiborane, and vinyldiborane. Production method.
求の範囲第（４）項記載の導電性グラファイト材料の製
造方法。(11) The method for producing a conductive graphite material according to claim (4), wherein the base material is carbon fiber.
る特許請求の範囲第（４）項記載の導電性グラファイト
材料の製造方法。(12) The method for producing a conductive graphite material according to claim (4), wherein the graphite material is a fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15267886A JPS6310405A (en) | 1986-07-01 | 1986-07-01 | Conducting graphite material and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15267886A JPS6310405A (en) | 1986-07-01 | 1986-07-01 | Conducting graphite material and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6310405A true JPS6310405A (en) | 1988-01-18 |
Family
ID=15545719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15267886A Expired - Lifetime JPS6310405A (en) | 1986-07-01 | 1986-07-01 | Conducting graphite material and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6310405A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63293164A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
-
1986
- 1986-07-01 JP JP15267886A patent/JPS6310405A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63293164A (en) * | 1987-05-27 | 1988-11-30 | Agency Of Ind Science & Technol | Manufacture of carbon material |
| JPH0258352B2 (en) * | 1987-05-27 | 1990-12-07 | Kogyo Gijutsuin |
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