JPH04280809A - Production of highly conductive hollow carbon - Google Patents
Production of highly conductive hollow carbonInfo
- Publication number
- JPH04280809A JPH04280809A JP3041774A JP4177491A JPH04280809A JP H04280809 A JPH04280809 A JP H04280809A JP 3041774 A JP3041774 A JP 3041774A JP 4177491 A JP4177491 A JP 4177491A JP H04280809 A JPH04280809 A JP H04280809A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- hollow
- substrate
- base material
- diameter
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 239000012808 vapor phase Substances 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000011796 hollow space material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- -1 alkenes and alkynes Natural products 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 229910017049 AsF5 Inorganic materials 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910005185 FSO3H Inorganic materials 0.000 description 1
- 229910005258 GaBr3 Inorganic materials 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910015218 MoCl4 Inorganic materials 0.000 description 1
- 229910015221 MoCl5 Inorganic materials 0.000 description 1
- 229910015686 MoOCl4 Inorganic materials 0.000 description 1
- 229910019804 NbCl5 Inorganic materials 0.000 description 1
- 229910019787 NbF5 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021174 PF5 Inorganic materials 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004537 TaCl5 Inorganic materials 0.000 description 1
- 229910004546 TaF5 Inorganic materials 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- OYMJNIHGVDEDFX-UHFFFAOYSA-J molybdenum tetrachloride Chemical compound Cl[Mo](Cl)(Cl)Cl OYMJNIHGVDEDFX-UHFFFAOYSA-J 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- SFPKXFFNQYDGAH-UHFFFAOYSA-N oxomolybdenum;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.[Mo]=O SFPKXFFNQYDGAH-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- ARUUTJKURHLAMI-UHFFFAOYSA-N xenon hexafluoride Chemical compound F[Xe](F)(F)(F)(F)F ARUUTJKURHLAMI-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、高い導電性を有する中
空炭素材料を製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing hollow carbon materials having high electrical conductivity.
【０００２】0002
【従来の技術】導電性の中空炭素材料の製造方法として
は、次の様な２種類のものが知られている。2. Description of the Related Art Two types of methods for producing conductive hollow carbon materials are known as follows.
【０００３】第１の方法は、有機前駆体（例えば、フェ
ノール樹脂、ポリアクリロニトリル、レーヨンなど）を
適当な雰囲気下で熱処理することにより有機前駆体を炭
化、黒鉛化することにより導電性の炭素材料を得る方法
である。有機前駆体は、炭素以外の原子（例えば、窒素
）を含むので、炭化、黒鉛化時に炭素以外の原子はガス
化し脱離するために、得られた炭素材料には微小空孔が
できる。この微小空孔径を任意に制御することは従来困
難であったが、空孔径を任意に制御できる炭素繊維の製
造方法が開示されている（特公平１−５３３６２号公報
参照）。それによれば炭素収率の高い有機物と炭素収率
の低い有機物または除去可能な無機物の２層構造を有す
る前駆体を用い、熱処理または薬品処理によって内側層
の炭素収率の低い有機物または無機物を除去する。内側
層の有機物あるいは無機物の直径を変えることで任意の
中空径を有する炭素繊維を得ることができるとしている
。The first method is to heat-treat an organic precursor (for example, phenol resin, polyacrylonitrile, rayon, etc.) in an appropriate atmosphere to carbonize and graphitize it, thereby producing a conductive carbon material. This is the way to obtain. Since the organic precursor contains atoms other than carbon (for example, nitrogen), the atoms other than carbon are gasified and eliminated during carbonization and graphitization, so that micropores are formed in the obtained carbon material. Conventionally, it has been difficult to arbitrarily control the diameter of the micropores, but a method for producing carbon fibers that allows the diameter of the pores to be arbitrarily controlled has been disclosed (see Japanese Patent Publication No. 1-53362). According to this, a precursor with a two-layer structure of an organic substance with a high carbon yield and an organic substance with a low carbon yield or a removable inorganic substance is used, and the organic substance or inorganic substance with a low carbon yield in the inner layer is removed by heat treatment or chemical treatment. do. It is said that carbon fibers with any hollow diameter can be obtained by changing the diameter of the organic or inorganic material in the inner layer.
【０００４】第２の方法は、炭化水素（例えば、メタン
、ベンゼン）を気相熱分解する方法である。この方法で
は炭化水素を気相熱分解することにより直接炭素材料を
得ることができるため、有機前駆体の熱処理によって得
られる炭素材料に見られる異種原子のガス化と脱離によ
る微小空孔は形成されず、緻密な炭素材料が得られる。
また多くの場合、気相熱分解法によって得られた炭素材
料は易黒鉛化性であり、３０００℃以上の高温処理によ
って単結晶グラファイトに匹敵する導電性を示す。
またこの黒鉛化した炭素材料を母材として黒鉛層間化合
物を形成することによって、１０５Ｓ／ｃｍを越える金
属と同等の導電性を得ることも可能である。この気相熱
分解法によって得られる炭素材料に中空部分が賦与され
ている例としては気相成長炭素繊維が挙げられる。気相
成長炭素繊維は、鉄などの金属微粒子（粒径、例えば、
５〜２０ｎｍ）を触媒とし、炭化水素を約１１００℃で
気相熱分解することによって得られると同時に、繊維中
央に触媒金属の粒径とほぼ同一の直径を有する中空が形
成される。[0004] The second method involves gas-phase thermal decomposition of hydrocarbons (eg, methane, benzene). In this method, carbon materials can be obtained directly by gas-phase pyrolysis of hydrocarbons, so micropores are formed due to gasification and desorption of foreign atoms found in carbon materials obtained by heat treatment of organic precursors. A dense carbon material can be obtained. Further, in many cases, carbon materials obtained by vapor phase pyrolysis are easily graphitized, and exhibit electrical conductivity comparable to single crystal graphite when treated at high temperatures of 3000° C. or higher. Furthermore, by forming a graphite intercalation compound using this graphitized carbon material as a base material, it is also possible to obtain conductivity exceeding 105 S/cm equivalent to that of metal. An example of a carbon material obtained by this vapor phase pyrolysis method in which a hollow portion is provided is vapor grown carbon fiber. Vapor-grown carbon fiber is made of fine metal particles such as iron (particle size, e.g.
It is obtained by gas-phase pyrolysis of hydrocarbons at about 1100° C. using a catalyst (5 to 20 nm), and at the same time, a hollow having a diameter almost the same as the particle size of the catalyst metal is formed in the center of the fiber.
【０００５】[0005]
【発明が解決しようとする課題】以上に述べた従来の導
電性の中空炭素材料の製造方法においては次の様な問題
点がある。有機前駆体を熱処理する第１の方法において
は、炭素材料を得るための有機前駆体として、通常フェ
ノール樹脂、ポリアクリロニトリル、レーヨンなどが用
いられるが、これらを熱処理して得られる炭素材料の電
導度は高々１０３Ｓ／ｃｍである。この値は有機前駆体
の熱処理物によって得られた値であり、炭素材料に中空
が形成されている場合、炭素材料の実質的な電導度は更
に低い値である。また得られた炭素材料は難黒鉛化性で
あるため、たとえ３０００℃を越える高温での処理を行
っても、電導度の増加はほとんどみられず、また、黒鉛
構造が形成されていないため、黒鉛層間化合物の形成に
よる高導電性を得ることができない。即ち、この方法に
よると、中空の制御はある程度可能なものの、高導電性
は実現し得ない。[Problems to be Solved by the Invention] The conventional method for producing conductive hollow carbon materials described above has the following problems. In the first method of heat-treating an organic precursor, phenol resin, polyacrylonitrile, rayon, etc. are usually used as the organic precursor to obtain a carbon material, and the conductivity of the carbon material obtained by heat-treating these materials is is at most 103 S/cm. This value is a value obtained by heat-treating the organic precursor, and when a hollow is formed in the carbon material, the substantial electrical conductivity of the carbon material is an even lower value. In addition, the obtained carbon material is difficult to graphitize, so even if it is treated at a high temperature exceeding 3000°C, there is almost no increase in electrical conductivity, and since no graphite structure is formed, High conductivity cannot be obtained due to the formation of graphite intercalation compounds. That is, according to this method, although it is possible to control the hollow space to some extent, high conductivity cannot be achieved.
【０００６】また、第２の方法においては、気相熱分解
によって得られる気相成長炭素繊維は通常５〜２０ｎｍ
の粒径を有する金属微粒子の触媒作用により製造され、
同時に５〜２０ｎｍ径の中空が形成される。この繊維の
電導度は１０３Ｓ／ｃｍ程度と従来の有機前駆体を用い
た方法とほぼ同一であるが、炭素繊維は易黒鉛化炭素で
あり３０００℃以上の高温処理によって黒鉛構造が発達
し、黒鉛層間化合物の形成により１０５Ｓ／ｃｍと金属
並の導電性が実現される。しかし、気相成長炭素繊維の
中空径は、触媒金属粒子の粒径に依存するが、粒径を２
０ｎｍ以上にした場合、触媒作用が極度に低下するため
、炭素繊維の中空径は２０ｎｍまでに制限されている。
従って、μｍオーダー径の中空を形成することは不可能
であり、中空部の工業的利用も実現していない。In the second method, the vapor-grown carbon fiber obtained by vapor-phase pyrolysis usually has a thickness of 5 to 20 nm.
Produced by the catalytic action of fine metal particles having a particle size of
At the same time, hollows with a diameter of 5 to 20 nm are formed. The electrical conductivity of this fiber is about 103 S/cm, which is almost the same as that of the conventional method using organic precursors, but carbon fiber is easily graphitized carbon, and a graphite structure develops by high temperature treatment at 3000°C or higher. By forming the interlayer compound, conductivity of 105 S/cm, which is comparable to metal, is achieved. However, the hollow diameter of vapor-grown carbon fibers depends on the particle size of the catalyst metal particles, but the particle size is
If the diameter is 0 nm or more, the catalytic action is extremely reduced, so the hollow diameter of the carbon fiber is limited to 20 nm. Therefore, it is impossible to form a hollow space with a diameter on the order of μm, and industrial use of the hollow space has not been realized.
【０００７】従来の導電性の中空炭素材料の製造方法に
おいては、導電性あるいは、中空部分の制御の少なくと
も一方を犠牲にせねばならないといった問題点がある。
本発明の目的は、中空部分の制御が容易である高い導電
性を有する中空炭素材料の製造方法を提供することにあ
る。[0007] Conventional methods for manufacturing conductive hollow carbon materials have the problem that at least one of the conductivity and the control of the hollow portion must be sacrificed. An object of the present invention is to provide a method for manufacturing a hollow carbon material having high conductivity and allowing easy control of the hollow portion.
【０００８】[0008]
【課題を解決するための手段】本発明の要旨は、熱処理
または薬品処理により除去可能な遷移金属または遷移金
属を含む合金からなる基材上に、基材の融点よりも低い
温度で、炭化水素からなる原料を気相熱分解することに
より炭素層を形成し、基材および炭素層からなる炭素複
合体を得た後、基材を熱処理または薬品処理により除去
し、中空部分を有する炭素材料を形成することからなる
高導電性中空炭素材料の製造方法に存する。[Means for Solving the Problems] The gist of the present invention is to apply hydrocarbons onto a substrate made of a transition metal or an alloy containing a transition metal that can be removed by heat treatment or chemical treatment at a temperature lower than the melting point of the substrate. A carbon layer is formed by vapor-phase pyrolysis of a raw material consisting of a carbon material, a carbon composite consisting of a base material and a carbon layer is obtained, and then the base material is removed by heat treatment or chemical treatment to form a carbon material having a hollow portion. The present invention resides in a method of manufacturing a highly conductive hollow carbon material, which comprises forming a highly conductive hollow carbon material.
【０００９】基材は、熱処理あるいは薬品処理によって
除去可能な金属からなる。基材は、遷移金属あるいは遷
移金属を含む合金である。基材は、例えば、鉄、コバル
ト、ニッケル、銅等の遷移金属、あるいはステンレス等
の遷移金属を含む合金などである。基材の形状は、線材
、線材から形成された織物、テープ、粉末、発泡体、ま
たはその他の成形品の形状であってよい。基材の形状お
よび寸法は、所望の中空炭素材料に応じて、選択する。[0009] The base material is made of metal that can be removed by heat treatment or chemical treatment. The base material is a transition metal or an alloy containing a transition metal. The base material is, for example, a transition metal such as iron, cobalt, nickel, or copper, or an alloy containing a transition metal such as stainless steel. The shape of the substrate may be in the form of a wire, a fabric formed from a wire, a tape, a powder, a foam, or other molded article. The shape and dimensions of the substrate are selected depending on the desired hollow carbon material.
【００１０】原料として用いる炭化水素は、ガスとなり
得る炭化水素、例えば、メタン、エタン、プロパン等の
脂肪族化合物ＣｎＨ２ｎ＋２；アルケン、アルキン等の
不飽和炭化水素、即ち、１つまたはそれ以上の２重結合
または３重結合を有する炭化水素；ベンゼン、ナフタレ
ン、アントラセン、ピレン等の芳香族炭化水素である。The hydrocarbons used as raw materials are hydrocarbons that can become gases, such as aliphatic compounds CnH2n+2 such as methane, ethane, and propane; unsaturated hydrocarbons such as alkenes and alkynes, that is, one or more double Hydrocarbons having bonds or triple bonds; aromatic hydrocarbons such as benzene, naphthalene, anthracene, and pyrene.
【００１１】炭化水素を気相熱分解し、炭素を基材上に
堆積させる。気相熱分解は、減圧下あるいは適当なキャ
リアガス存在下で、基材融点よりも低い温度に、基材お
よび炭化水素を加熱することによって行う。基材および
炭化水素の加熱は、基材に直接通電することによる方法
、基材近傍に配置されたヒーターによる方法等によって
行う。加熱温度は、通常６００〜１５００℃、好ましく
は９００〜１２００℃である。炭化水素の供給量は、通
常、４〜１０ｃｃ／ｈであり、成長室内の炭化水素分圧
は１Ｔｏｒｒ程度であることが望ましい。[0011] Hydrocarbons are vapor-phase pyrolyzed and carbon is deposited on a substrate. Gas phase pyrolysis is carried out by heating the substrate and hydrocarbon to a temperature below the substrate melting point under reduced pressure or in the presence of a suitable carrier gas. Heating of the base material and the hydrocarbon is carried out by applying electricity directly to the base material, by using a heater placed near the base material, or the like. The heating temperature is usually 600 to 1500°C, preferably 900 to 1200°C. The amount of hydrocarbon supplied is usually 4 to 10 cc/h, and the hydrocarbon partial pressure in the growth chamber is preferably about 1 Torr.
【００１２】炭化水素の気相熱分解時に原料分解エネル
ギーを供給する補助手段として、プラズマ放電、光照射
、イオン照射などを併用することもできる。気相熱分解
による炭素層形成時に、原料分解エネルギー供給補助手
段を併用すると、エネルギー供給補助手段によるエネル
ギーは熱エネルギーの代替となり、より低温で高い導電
性を有する炭素層を形成することが可能である。例えば
、基材としてステンレス鋼（ＳＵＳ３０４）を用い、原
料としてベンゼンを用い、気相熱分解時に、１３．５６
ＭＨｚの高周波電界を印加し、プラズマ放電させた場合
、９５０℃程度に基材を加熱することによって１×１０
３〜５×１０３Ｓ／ｃｍの電導度が得られ、この電導度
は同温度による従来の気相熱分解や有機物の熱処理によ
って得られる炭素材料のものよりも高い。[0012] Plasma discharge, light irradiation, ion irradiation, etc. can also be used in combination as an auxiliary means for supplying raw material decomposition energy during gas phase thermal decomposition of hydrocarbons. When a raw material decomposition energy supply auxiliary means is used in conjunction with the formation of a carbon layer by vapor phase pyrolysis, the energy supplied by the energy supply auxiliary means can substitute for thermal energy, making it possible to form a carbon layer with high conductivity at a lower temperature. be. For example, if stainless steel (SUS304) is used as the base material and benzene is used as the raw material, 13.56
When a high frequency electric field of MHz is applied and a plasma discharge is caused, 1×10
An electrical conductivity of 3 to 5 x 103 S/cm is obtained, which is higher than that of carbon materials obtained by conventional gas phase pyrolysis or heat treatment of organic matter at the same temperature.
【００１３】得られた基材および炭素層からなる炭素複
合体から、基材を除去して、中空炭素材料を得る。基材
の除去は、基材の融点以上の温度に加熱する熱処理また
は酸などの薬品による薬品処理によって行える。[0013] The base material is removed from the obtained carbon composite consisting of the base material and the carbon layer to obtain a hollow carbon material. Removal of the base material can be performed by heat treatment to a temperature higher than the melting point of the base material or chemical treatment using chemicals such as acids.
【００１４】得られた中空炭素材料を１５００〜３００
０℃、例えば３０００℃で加熱し、黒鉛化した後、この
中空炭素材料に適当な化学種を層間に挿入し、層間化合
物を形成することにより、更に導電性を増すことができ
る。適当な化学種は、電子受容性試薬または電子供与性
試薬である。電子受容性試薬の例は、ハロゲン（例えば
、Ｃｌ２、Ｂｒ２、Ｉ２、ＩＣｌ、ＩＣｌ３、ＩＢｒ）
、ルイス酸、プロトン酸（例えば、ＰＦ５、ＡｓＦ５、
ＳｂＦ５、ＡｇＣｌＯ４、ＡｇＢＦ４、ＢＦ３、ＢＣｌ
３、ＢＢｒ３、ＦＳＯ２ＯＯＳＯ２Ｆ、（ＮＯ２）（Ｓ
ｂＦ６）、（ＮＯ）ＳｂＣｌ６、（ＮＯ２）（ＢＦ４）
、ＳＯ３、ＴｉＦ４、ＮｂＦ５、ＴａＦ５、ＮｂＣｌ５
、ＴａＣｌ５、ＭｎＣｌ２、ＭｏＣｌ４、ＭｏＣｌ５、
ＭｏＯＣｌ４、ＮｉＣｌ２、ＺｎＣｌ２、ＣｒＯ２Ｃｌ
２、ＦｅＣｌ３、ＣｄＣｌ２、ＡｕＣｌ３、ＣｒＣｌ３
、ＡｌＣｌ３、ＡｌＢｒ３、ＧａＢｒ３、ＰｔＣｌ４、
ＳｂＣｌ５、ＵＣｌ５、ＳＯＣｌ２、ＸｅＦ６、Ｈ２Ｓ
Ｏ４、ＨＣｌＯ４、ＨＮＯ３、ＦＳＯ３Ｈ、ＣＦ３ＳＯ
３Ｈ）である。電子供与性試薬の例は、Ｌｉ、Ｎａ、Ｋ
、Ｒｂ、Ｃｓ、Ｂａ、Ｓｒ、Ｃａ、Ｅｕ、Ｙｂ、Ｓｍ、
Ｔｍである。[0014] The obtained hollow carbon material
After graphitizing by heating at 0° C., for example, 3000° C., the conductivity can be further increased by inserting an appropriate chemical species between the layers of this hollow carbon material to form an interlayer compound. Suitable species are electron-accepting or electron-donating reagents. Examples of electron-accepting reagents are halogens (e.g. Cl2, Br2, I2, ICl, ICl3, IBr)
, Lewis acids, protic acids (e.g. PF5, AsF5,
SbF5, AgClO4, AgBF4, BF3, BCl
3, BBr3, FSO2OOSO2F, (NO2) (S
bF6), (NO)SbCl6, (NO2) (BF4)
, SO3, TiF4, NbF5, TaF5, NbCl5
, TaCl5, MnCl2, MoCl4, MoCl5,
MoOCl4, NiCl2, ZnCl2, CrO2Cl
2, FeCl3, CdCl2, AuCl3, CrCl3
, AlCl3, AlBr3, GaBr3, PtCl4,
SbCl5, UCl5, SOCl2, XeF6, H2S
O4, HClO4, HNO3, FSO3H, CF3SO
3H). Examples of electron donating reagents are Li, Na, K
, Rb, Cs, Ba, Sr, Ca, Eu, Yb, Sm,
It is Tm.
【００１５】本発明の製造方法の概略を図１に示す。遷
移金属あるいは遷移金属を含む合金からなる基材１を気
相合成装置の成長室内に設置し、成長室内を１０−３ｍ
ｍＨｇ程度に減圧するかあるいは適当なガス雰囲気（好
ましくはアルゴン、窒素等の不活性ガス雰囲気あるいは
水素等の還元性ガス雰囲気）のもとで、直接あるいは間
接的な方法により基材を融点よりも低い温度に加熱する
。図示するような円形断面の線材の場合、円形断面の直
径は、通常、８〜１００μｍである。次いで、成長室内
に原料炭化水素を導入し、気相熱分解によって基材上に
炭素層２を形成し、炭素複合体３を得る。炭素層の厚さ
は、通常１〜１００μｍである。また、炭素層の厚さは
中空形成のための基材径によって決まり、炭素層形成後
の直径は基材の直径の１．４倍以上であることが望まし
い。炭素複合体３を真空中で基材１の融点より高い温度
で熱処理するかあるいは適当な薬品（例えば硫酸、塩酸
）で処理することにより、炭素複合体３から基材１を除
去して中空炭素材料４を得る。FIG. 1 shows an outline of the manufacturing method of the present invention. A base material 1 made of a transition metal or an alloy containing a transition metal is placed in a growth chamber of a vapor phase synthesis apparatus, and the inside of the growth chamber is 10-3 m.
The base material is heated below its melting point by direct or indirect methods under reduced pressure to about mHg or in an appropriate gas atmosphere (preferably an inert gas atmosphere such as argon or nitrogen, or a reducing gas atmosphere such as hydrogen). Heat to low temperature. In the case of a wire having a circular cross section as shown in the figure, the diameter of the circular cross section is usually 8 to 100 μm. Next, a raw material hydrocarbon is introduced into the growth chamber, and a carbon layer 2 is formed on the base material by vapor phase pyrolysis to obtain a carbon composite 3. The thickness of the carbon layer is usually 1 to 100 μm. Further, the thickness of the carbon layer is determined by the diameter of the base material for forming the hollow, and it is desirable that the diameter after forming the carbon layer is 1.4 times or more the diameter of the base material. The base material 1 is removed from the carbon composite 3 by heat treating the carbon composite 3 at a temperature higher than the melting point of the base material 1 in a vacuum or by treating it with an appropriate chemical (e.g. sulfuric acid, hydrochloric acid) to form a hollow carbon. Obtain material 4.
【００１６】本発明において基材の形状をかえることに
より中空の形状および寸法は任意に制御することができ
る。また、基材を構成する材料を選択することによりそ
の基材に含まれる遷移金属の効果により、従来のものに
比べ高い導電性を有する炭素層を形成することが可能で
あり、更に、黒鉛化温度の低減にも有効となり得る。In the present invention, the shape and dimensions of the hollow space can be controlled as desired by changing the shape of the base material. In addition, by selecting the material that constitutes the base material, it is possible to form a carbon layer with higher conductivity than conventional ones due to the effect of the transition metal contained in the base material. It can also be effective in reducing temperature.
【００１７】[0017]
【実施例】以下に実施例を示し、本発明を具体的に説明
する。
実施例１
直径２０μｍのステンレス鋼ＳＵＳ３０４の線材を基材
とし、炭素層の成長室内に静置し、成長室内を１０−２
ｍｍＨｇまで減圧し、基材を９００℃に加熱した。次い
で、系内圧力を１ｍｍＨｇに保つように、ベンゼン蒸気
を成長室内に導入した。高周波電界（１３．５６ＭＨｚ
、１００Ｗ）を印加し、プラズマ放電を起こし、基材上
に炭素層を形成し、直径約６０μｍの炭素複合体を得た
。この炭素複合体を１５００および２０００℃で真空中
で熱処理することによって基材を除去し、約２０μｍの
中空径を有する炭素材料を得た。この中空炭素材料の電
導度は１５００℃で処理したものでは３．４×１０３Ｓ
／ｃｍ、２０００℃で処理したものは６．５×１０３Ｓ
／ｃｍと高い電導度を示した。[Examples] The present invention will be explained in detail with reference to Examples below. Example 1 A wire rod of stainless steel SUS304 with a diameter of 20 μm was used as a base material, and it was placed in a growth chamber of a carbon layer, and the growth chamber was heated to 10-2.
The pressure was reduced to mmHg and the substrate was heated to 900°C. Next, benzene vapor was introduced into the growth chamber so as to maintain the internal pressure at 1 mmHg. High frequency electric field (13.56MHz
, 100 W) was applied to generate plasma discharge to form a carbon layer on the base material to obtain a carbon composite with a diameter of about 60 μm. The base material was removed by heat-treating this carbon composite in vacuum at 1500 and 2000° C. to obtain a carbon material having a hollow diameter of about 20 μm. The conductivity of this hollow carbon material is 3.4×103S when treated at 1500℃.
/cm, 6.5 x 103S for those treated at 2000℃
It showed a high conductivity of /cm.
【００１８】実施例２
直径８μｍ、３０μｍおよび１００μｍの３種の銅線上
に実施例１と同様の手順で炭素層を形成した。その後、
１５００℃および３０００℃で熱処理を行い、銅線の除
去を行った。その結果、銅線の直径と同一の中空径を有
する繊維状中空炭素材料を得た。この繊維状中空炭素材
料の電導度を測定した。結果を表１に示すが、高い電導
度が得られた。Example 2 Carbon layers were formed on three types of copper wires having diameters of 8 μm, 30 μm and 100 μm in the same manner as in Example 1. after that,
Heat treatment was performed at 1500°C and 3000°C to remove the copper wire. As a result, a fibrous hollow carbon material having the same hollow diameter as the diameter of the copper wire was obtained. The electrical conductivity of this fibrous hollow carbon material was measured. The results are shown in Table 1, and high electrical conductivity was obtained.
【００１９】[0019]
【表１】
基材径 繊維径 熱処
理温度 電 導 度 ８μ
ｍ ３０μｍ １５００℃
１．０×１０３Ｓ／ｃｍ ８μｍ
８５μｍ ３０００℃ ０．９×１０
４Ｓ／ｃｍ ３０μｍ ９８μｍ
１５００℃ ０．４×１０３Ｓ／ｃｍ
３０μｍ ６５μｍ ３００
０℃ １．０×１０４Ｓ／ｃｍ １００μｍ
１５４μｍ １５００℃ １．０
×１０３Ｓ／ｃｍ １００μｍ １８０μｍ
３０００℃ ７．２×１０３Ｓ／ｃｍ[Table 1] Base material diameter Fiber diameter Heat treatment temperature Electrical conductivity 8μ
m 30μm 1500℃
1.0×103S/cm 8μm
85μm 3000℃ 0.9×10
4S/cm 30μm 98μm
1500℃ 0.4×103S/cm
30μm 65μm 300
0℃ 1.0×104S/cm 100μm
154μm 1500℃ 1.0
×103S/cm 100μm 180μm
3000℃ 7.2×103S/cm
【００２０】実施例３
直径３０μｍの銅線上に実施例１と同様の手順で炭素層
を形成した後、３０００℃で熱処理を行い、銅線の除去
および黒鉛化処理を行い、直径７２μｍ、中空径３０μ
ｍの中空黒鉛繊維を得た。この中空黒鉛繊維をガラス製
容器に入れ、１０−３ｍｍＨｇに減圧した後、ＩＣｌ蒸
気を容器内に導入し、黒鉛層間化合物を形成した。その
後大気中に取出し、この中空黒鉛層間化合物繊維の電導
度を測定したところ、８．１×１０４Ｓ／ｃｍの高電導
度を示した。Example 3 After forming a carbon layer on a copper wire with a diameter of 30 μm in the same manner as in Example 1, heat treatment was performed at 3000° C. to remove the copper wire and graphitize the wire. 30μ
m hollow graphite fibers were obtained. This hollow graphite fiber was placed in a glass container, and after the pressure was reduced to 10 −3 mmHg, ICl vapor was introduced into the container to form a graphite intercalation compound. Thereafter, it was taken out into the atmosphere and the electrical conductivity of this hollow graphite intercalation compound fiber was measured, and it showed a high electrical conductivity of 8.1 x 104 S/cm.
【００２１】実施例４
直径３０μｍの銅線上に実施例１と同様の手順で炭素層
を形成し、得た直径６７μｍの炭素複合体を１８ｍｏｌ
／ｌの硫酸に浸漬した。これにより基材である銅が溶解
し、炭素複合体より除去され、中空炭素材料を得ること
ができた。中空炭素材料の電導度は０．６×１０３Ｓ／
ｃｍであった。Example 4 A carbon layer was formed on a copper wire with a diameter of 30 μm in the same manner as in Example 1, and 18 mol of the carbon composite with a diameter of 67 μm was obtained.
/l of sulfuric acid. As a result, the base material copper was dissolved and removed from the carbon composite, making it possible to obtain a hollow carbon material. The conductivity of the hollow carbon material is 0.6×103S/
It was cm.
【００２２】実施例５
ニッケルで作られた発泡金属シート（空孔径４００μｍ
、気孔率９７％）を基材として用い、実施例１と同様の
手順によって発泡金属シート上に炭素層を形成した。
その後２０００℃の真空中で熱処理し、ニッケルを除去
し、シート状の中空炭素材料（寸法５０ｍｍ×２５ｍｍ
×１．５ｍｍ、中空径５０μｍ、空孔径４００μｍ）を
得た。
中空炭素材料の電導度は２×１０２Ｓ／ｃｍであった。Example 5 Foamed metal sheet made of nickel (pore diameter 400 μm)
, porosity 97%) was used as the base material, and a carbon layer was formed on the foamed metal sheet by the same procedure as in Example 1. After that, heat treatment was performed in a vacuum at 2000°C to remove nickel, and a sheet-shaped hollow carbon material (dimensions 50 mm x 25 mm) was prepared.
x 1.5 mm, hollow diameter 50 μm, and pore diameter 400 μm). The conductivity of the hollow carbon material was 2×10 2 S/cm.
【００２３】[0023]
【発明の効果】本発明の方法によれば、中空の形状およ
び寸法が任意に制御でき、高導電性を有する中空炭素材
料が得られる。本発明によって得られる中空炭素材料は
、軽量導電材料として利用することが可能である。また
、中空の制御によって、表面積の制御や断熱性などの諸
特性の制御も可能となる。本発明によって得られる中空
炭素材料は、電気材料、電子材料、熱機械材料、電気化
学材料として利用するとその効果は極めて大きく、具体
的には、電磁シールド、電池電極などとして使用できる
。According to the method of the present invention, the shape and dimensions of the hollow can be arbitrarily controlled, and a hollow carbon material having high conductivity can be obtained. The hollow carbon material obtained by the present invention can be used as a lightweight conductive material. Furthermore, by controlling the hollow space, it is also possible to control various properties such as surface area and heat insulation. The hollow carbon material obtained by the present invention is extremely effective when used as an electrical material, electronic material, thermomechanical material, or electrochemical material, and specifically, it can be used as an electromagnetic shield, a battery electrode, etc.
【図１】 本発明の中空炭素材料の製造方法を示す概
略図である。FIG. 1 is a schematic diagram showing a method for manufacturing a hollow carbon material of the present invention.
１ 基材 ２ 炭素層 ３ 炭素複合体 ４ 中空炭素材料 1 Base material 2 Carbon layer 3 Carbon composite 4 Hollow carbon material
Claims (1)
な遷移金属または遷移金属を含む合金からなる基材上に
、基材の融点よりも低い温度で、炭化水素からなる原料
を気相熱分解することにより炭素層を形成し、基材およ
び炭素層からなる炭素複合体を得た後、基材を熱処理ま
たは薬品処理により除去し、中空部分を有する炭素材料
を形成することからなる高導電性中空炭素材料の製造方
法。Claim 1: Vapor-phase pyrolysis of a raw material consisting of a hydrocarbon at a temperature lower than the melting point of the substrate on a substrate consisting of a transition metal or an alloy containing a transition metal that can be removed by heat treatment or chemical treatment. to form a carbon layer to obtain a carbon composite consisting of a base material and carbon layer, and then remove the base material by heat treatment or chemical treatment to form a carbon material having a hollow part.Highly conductive hollow carbon Method of manufacturing the material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3041774A JPH04280809A (en) | 1991-03-07 | 1991-03-07 | Production of highly conductive hollow carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3041774A JPH04280809A (en) | 1991-03-07 | 1991-03-07 | Production of highly conductive hollow carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04280809A true JPH04280809A (en) | 1992-10-06 |
Family
ID=12617726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3041774A Pending JPH04280809A (en) | 1991-03-07 | 1991-03-07 | Production of highly conductive hollow carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04280809A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342014A (en) * | 2000-03-31 | 2001-12-11 | Osaka Gas Co Ltd | Method of preparing nano-scale acicular materials |
| JP2006512746A (en) * | 2002-12-23 | 2006-04-13 | マイクロセル コーポレーション | Manufacturing method supported on substrate of microfibrous fuel cell |
| JP2006247758A (en) * | 2005-03-08 | 2006-09-21 | Nagoya Institute Of Technology | Method of manufacturing carbon nano-structural material, field emission display and scanning probe microscope |
| US8048584B2 (en) | 2003-03-07 | 2011-11-01 | Microcell Corporation | Fuel cell structures and assemblies |
-
1991
- 1991-03-07 JP JP3041774A patent/JPH04280809A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001342014A (en) * | 2000-03-31 | 2001-12-11 | Osaka Gas Co Ltd | Method of preparing nano-scale acicular materials |
| JP2006512746A (en) * | 2002-12-23 | 2006-04-13 | マイクロセル コーポレーション | Manufacturing method supported on substrate of microfibrous fuel cell |
| US8048584B2 (en) | 2003-03-07 | 2011-11-01 | Microcell Corporation | Fuel cell structures and assemblies |
| JP2006247758A (en) * | 2005-03-08 | 2006-09-21 | Nagoya Institute Of Technology | Method of manufacturing carbon nano-structural material, field emission display and scanning probe microscope |
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