JP6320700B2 - Metal-carbon fiber composite and production method thereof, and carbon fiber and production method thereof - Google Patents
Metal-carbon fiber composite and production method thereof, and carbon fiber and production method thereof Download PDFInfo
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- JP6320700B2 JP6320700B2 JP2013160479A JP2013160479A JP6320700B2 JP 6320700 B2 JP6320700 B2 JP 6320700B2 JP 2013160479 A JP2013160479 A JP 2013160479A JP 2013160479 A JP2013160479 A JP 2013160479A JP 6320700 B2 JP6320700 B2 JP 6320700B2
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 87
- 239000004917 carbon fiber Substances 0.000 title claims description 87
- 239000002131 composite material Substances 0.000 title claims description 55
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 58
- 239000002184 metal Substances 0.000 claims description 58
- 239000011148 porous material Substances 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- 239000002105 nanoparticle Substances 0.000 claims description 29
- 239000002905 metal composite material Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- -1 iron and cobalt Chemical class 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000635 electron micrograph Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
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- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
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- 239000011261 inert gas Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 238000004050 hot filament vapor deposition Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000009692 water atomization Methods 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- OQKFGIANPCRSSK-UHFFFAOYSA-N azanium;methanol;acetate Chemical compound [NH4+].OC.CC([O-])=O OQKFGIANPCRSSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000004663 powder metallurgy Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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Description
本発明は、金属−炭素繊維複合体及び該金属−炭素繊維複合体の製造方法、並びに炭素繊維及び該炭素繊維の製造方法に関する。 The present invention relates to a metal-carbon fiber composite, a method for producing the metal-carbon fiber composite, a carbon fiber, and a method for producing the carbon fiber.
従来、各種ガスの吸蔵材料、二次電池の電極材料、電気二重層キャパシタ材料、触媒の坦持材料等の分野に応用する目的で、炭素材料に関する様々な研究がなされている。 Conventionally, various researches on carbon materials have been made for the purpose of application to fields such as various gas storage materials, secondary battery electrode materials, electric double layer capacitor materials, and catalyst support materials.
例えば、下記特許文献１では、触媒と反応温度の適正化を図ることにより得られた、高比表面積をもつ炭素ナノ繊維が開示されている。そして、この炭素ナノ繊維は、高性能触媒調製用担体や電気二重層キャパシタへの使用が期待される旨が記載されている。 For example, Patent Document 1 below discloses carbon nanofibers having a high specific surface area obtained by optimizing the catalyst and reaction temperature. And it is described that this carbon nanofiber is expected to be used for a carrier for preparing a high-performance catalyst and an electric double layer capacitor.
また、下記特許文献２では、ＣＶＤ法により、基材となる触媒表面からカーボンナノチューブを成長させる方法が記載されている。 Patent Document 2 below describes a method of growing carbon nanotubes from a catalyst surface serving as a base material by a CVD method.
しかしながら、特許文献１の炭素ナノ繊維や特許文献２のカーボンナノチューブは、メソ孔又はマクロ孔を炭素繊維自体が持たず、また、炭素ナノ繊維と引出電極への接続が必要あるため、電気二重層キャパシタ等の二次電池の電極材料等への応用が困難であった。 However, the carbon nanofibers of Patent Document 1 and the carbon nanotubes of Patent Document 2 do not have mesopores or macropores in the carbon fibers themselves and need to be connected to the carbon nanofibers and the extraction electrode. Application to electrode materials of secondary batteries such as capacitors has been difficult.
本発明の目的は、炭素繊維自体に複数の細孔が存在しており、二次電池の電極材料、導電性ペースト又は電気二重層キャパシタ材料等への応用が可能である、金属−炭素繊維複合体を提供することにある。 An object of the present invention is a metal-carbon fiber composite in which a plurality of pores are present in the carbon fiber itself and can be applied to an electrode material, a conductive paste or an electric double layer capacitor material of a secondary battery. To provide a body.
本発明に係る金属−炭素繊維複合体は、マトリックスとなる触媒活性のない第１の金属と、上記第１の金属の表面と内部のうち少なくとも一方に分散されている、触媒活性のある２種以上の第２の金属からなるナノ微粒子とを含む金属複合体と、上記ナノ微粒子から延びている複数の細孔を有する炭素繊維とを備える。 The metal-carbon fiber composite according to the present invention includes two types of catalytically active materials dispersed in at least one of the first metal having no catalytic activity as a matrix and the surface and the inside of the first metal. A metal composite including the above-described second metal nanoparticle and a carbon fiber having a plurality of pores extending from the nanoparticle.
本発明に係る金属−炭素繊維複合体のある特定の局面では、上記第１の金属が、周期表第８族〜第１０族の遷移金属以外の金属である。 In a specific aspect of the metal-carbon fiber composite according to the present invention, the first metal is a metal other than a transition metal of Group 8 to Group 10 of the periodic table.
本発明に係る金属−炭素繊維複合体の他の特定の局面では、上記第２の金属は、周期表第８族〜第１０族に属する少なくとも１種の遷移金属である。 In another specific aspect of the metal-carbon fiber composite according to the present invention, the second metal is at least one transition metal belonging to Groups 8 to 10 of the periodic table.
本発明に係る金属−炭素繊維複合体では、好ましくは、上記第１の金属が、銅である。 In the metal-carbon fiber composite according to the present invention, preferably, the first metal is copper.
本発明に係る金属−炭素繊維複合体では、好ましくは、上記第２の金属が、鉄、コバルト、ニッケル又はパラジウムから成る群から選択された２種以上の金属からなる。
上記第２の金属は、鉄、コバルト、ニッケル又はパラジウムからなる群から選択された２種以上の金属からなることがより好ましく、鉄とコバルトであることが、さらに好ましい。
In the metal-carbon fiber composite according to the present invention, preferably, the second metal is composed of two or more metals selected from the group consisting of iron, cobalt, nickel, or palladium.
The second metal is more preferably made of two or more metals selected from the group consisting of iron, cobalt, nickel or palladium, and more preferably iron and cobalt.
本発明に係る金属−炭素繊維複合体では、好ましくは、上記第２の金属が、上記金属中に、０．３〜１８重量％の割合で含有されている。 In the metal-carbon fiber composite according to the present invention, preferably, the second metal is contained in the metal in a proportion of 0.3 to 18% by weight.
本発明に係る金属−炭素繊維複合体では、好ましくは、上記細孔が、メソ孔又はマクロ孔を含んでいる。上記メソ孔又はマクロ孔の孔径は、１０ｎｍ〜２００ｎｍであることがより好ましい。 In the metal-carbon fiber composite according to the present invention, preferably, the pores include mesopores or macropores. The diameter of the mesopores or macropores is more preferably 10 nm to 200 nm.
本発明に係る金属−炭素繊維複合体では、好ましくは、上記細孔が、上記炭素繊維の側面と横断面の双方に存在している。 In the metal-carbon fiber composite according to the present invention, preferably, the pores are present on both the side surface and the cross section of the carbon fiber.
本発明に係る金属−炭素繊維複合体の製造方法では、上記第１の金属と、上記第１の金属の表面と内部のうち少なくとも一方に分散している上記第２の金属のナノ微粒子とを含む、金属複合体を準備する工程と、上記ナノ微粒子に加熱下で炭素源を接触させる工程とを備える。 In the method for producing a metal-carbon fiber composite according to the present invention, the first metal and the second metal nanoparticles dispersed on at least one of the surface and the inside of the first metal are included. Including a step of preparing a metal complex and a step of bringing the nanoparticle into contact with a carbon source under heating.
本発明に係る金属−炭素繊維複合体の製造方法では、上記金属複合体を準備する工程が、上記第１の金属と上記第２の金属に熱処理を施すことにより行われる。 In the method for producing a metal-carbon fiber composite according to the present invention, the step of preparing the metal composite is performed by subjecting the first metal and the second metal to a heat treatment.
本発明に係る複数の細孔を有する炭素繊維の製造方法では、金属−炭素繊維複合体から、酸やアルカリにより金属複合体を除去する方法や炭素繊維を粉砕処理などで切断した後に分級する方法により、金属複合体を単離する工程を備える。 In the method for producing a carbon fiber having a plurality of pores according to the present invention, a method of removing the metal composite from the metal-carbon fiber composite with acid or alkali, or a method of classifying the carbon fiber after cutting it by pulverization or the like A step of isolating the metal complex.
本発明に係る複数の細孔を有する炭素繊維は、金属−炭素繊維複合体から、酸やアルカリにより金属複合体を除去する方法や炭素繊維を粉砕処理などで切断した後に分級する方法により、金属複合体を単離することにより得られた炭素繊維である。 The carbon fiber having a plurality of pores according to the present invention is obtained by a method of removing a metal complex from a metal-carbon fiber complex with an acid or an alkali, or a method of classifying a carbon fiber after being cut by pulverization or the like. It is a carbon fiber obtained by isolating the composite.
本発明によれば、炭素繊維自体に複数の細孔が存在している、金属−炭素繊維複合体が得られる。 According to the present invention, a metal-carbon fiber composite is obtained in which a plurality of pores are present in the carbon fiber itself.
本発明に係る金属−炭素繊維複合体の製造方法によれば、炭素繊維に複数の細孔が存在している、金属−炭素繊維複合体を提供することが可能となる。 According to the method for producing a metal-carbon fiber composite according to the present invention, it is possible to provide a metal-carbon fiber composite in which a plurality of pores are present in the carbon fiber.
以下、本発明の具体的な実施形態を説明することにより、本発明を明らかにする。 Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention.
（金属−炭素繊維複合体）
本発明に係る金属−炭素繊維複合体は、金属と、該金属の表面から延びている、複数の炭素繊維とを備える。上記金属の形状としては、特に限定されず、例えば、粉体状、箔状又は線状のものを用いることができる。粉体状である場合、その数平均粒子径は、好ましくは、０．５〜４５μｍである。上記金属は、マトリックスとなる触媒活性のない第１の金属と、触媒活性のある２種以上の第２の金属とを含む、金属複合体である。上記第２の金属は、上記第１の金属の表面と内部のうち少なくとも一方に分散されているナノ微粒子である。上記ナノ微粒子は、上記第１の金属の表面と内部の双方、又は表面のみに分散されていることが望ましい。この上記ナノ微粒子は触媒として作用し、上記炭素繊維は、上記ナノ微粒子から延びている構造をとることができる。
(Metal-carbon fiber composite)
The metal-carbon fiber composite according to the present invention includes a metal and a plurality of carbon fibers extending from the surface of the metal. The shape of the metal is not particularly limited, and for example, a powder shape, a foil shape, or a linear shape can be used. In the case of powder, the number average particle diameter is preferably 0.5 to 45 μm. The metal is a metal complex including a first metal having no catalytic activity as a matrix and two or more second metals having catalytic activity. The second metal is a nanoparticle dispersed on at least one of the surface and the inside of the first metal. The nanoparticles are preferably dispersed on both the surface and the inside of the first metal or only on the surface. The nanoparticle acts as a catalyst, and the carbon fiber can take a structure extending from the nanoparticle.
上記第１の金属としては、例えば、銅、ニオブ、タンタル、アルミニウム、銀、クロム、モリブデン、マンガン、マグネシウム、タングステン、金又はチタンを用いることができる。そして、銅又は銀を用いることが好ましく、銅を用いることがより好ましい。 As the first metal, for example, copper, niobium, tantalum, aluminum, silver, chromium, molybdenum, manganese, magnesium, tungsten, gold, or titanium can be used. And it is preferable to use copper or silver, and it is more preferable to use copper.
上記第２の金属としては、特に限定されないが、触媒種となる周期表第８族〜第１０族の遷移金属を好適に用いることができる。上記周期表第８族〜第１０族の遷移金属としては、例えば、鉄、ニッケル、コバルト又はパラジウムが挙げられ、鉄又はコバルトであることが好ましい。鉄とコバルトを組み合わせて用いることが好ましい。 Although it does not specifically limit as said 2nd metal, The transition metal of the periodic table group 8-10 used as a catalyst seed | species can be used suitably. Examples of the transition metal of Group 8 to Group 10 of the periodic table include iron, nickel, cobalt, and palladium, and iron or cobalt is preferable. It is preferable to use a combination of iron and cobalt.
上記金属複合体全体に対する、上記第２金属の総含有量は、０．０３〜１８重量％であることが好ましく、０．１〜１２重量％であることがより好ましい。さらに好ましくは０．３〜８重量％である。含有率が上記範囲にある場合、簡易な熱処理によりナノ微粒子が析出し易いため好適である。 The total content of the second metal with respect to the entire metal composite is preferably 0.03 to 18% by weight, and more preferably 0.1 to 12% by weight. More preferably, it is 0.3-8 weight%. When the content is in the above range, it is preferable because the nanoparticles are likely to precipitate by a simple heat treatment.
本発明において、より多くの上記ナノ微粒子を表面に分散させるために、上記金属複合体の表面をエッチングしてもよい。金属複合体表面における、ナノ微粒子の占める面積は、３〜５０％であることが好ましい。この面積が小さすぎると触媒反応が弱く、大きすぎるとナノ微粒子同士が接触し粗大化してしまうことがある。 In the present invention, the surface of the metal composite may be etched in order to disperse more nanoparticles on the surface. The area occupied by the nano-particles on the surface of the metal composite is preferably 3 to 50%. If this area is too small, the catalytic reaction is weak, and if it is too large, the nanoparticles may come into contact with each other and become coarse.
上記金属複合体を形成する上記第１の金属と上記第２の金属の組み合わせとしては、特に限定されないが、上記第１の金属に銅を用い、上記第２の金属に鉄又はコバルトを用いることが好ましい。銅マトリックス中に鉄とコバルトを組み合わせて使用した場合、熱処理などにより、鉄とコバルトは混ざった状態で、ナノ微粒子としてマトリックス中に自己組織化的に析出するためである。 The combination of the first metal and the second metal forming the metal composite is not particularly limited, but copper is used for the first metal and iron or cobalt is used for the second metal. Is preferred. This is because when iron and cobalt are used in combination in a copper matrix, the iron and cobalt are mixed in a self-organized form as nanoparticles in a matrix by heat treatment or the like.
上記金属複合体の構成成分として、第３の金属を含有してもよい。このような成分としては、例えば、ケイ素、リン、マグネシウム、アルミニウム、マンガン、ニオブ、バナジウム、亜鉛又はすずを挙げることができる。上記第３の金属は、上記第２の金属と混合してナノ微粒子を形成することができ、ナノ微粒子の触媒能をより一層高めたり、細孔の発生をより高めることができる。上記第３の金属は、第２の金属と同程度の割合で含まれていることが好ましい。 You may contain a 3rd metal as a structural component of the said metal complex. Examples of such components include silicon, phosphorus, magnesium, aluminum, manganese, niobium, vanadium, zinc, and tin. The third metal can be mixed with the second metal to form nanoparticles, and the catalytic ability of the nanoparticles can be further increased and the generation of pores can be further increased. It is preferable that the third metal is contained in the same proportion as the second metal.
上記炭素繊維は、上記金属複合体の表面から延びている。上記炭素繊維としては、例えば、カーボンナノチューブ、カーボンフィラメント、カーボンナノフィラメント、カーボンナノコイル、を用いる事ができる。上記炭素繊維の横断面の形状は、特に限定されず、円形、角形のような形状のものが挙げられ、角形であることが好ましい。上記、炭素繊維は、単一の繊維であってもよく、複数の繊維からなる繊維束であってもよい。上記単一の繊維の繊維径は、５〜１００ｎｍであることが好ましい。また、上記繊維束の繊維径は、２０〜２０００ｎｍであることが好ましい。 The carbon fiber extends from the surface of the metal composite. As said carbon fiber, a carbon nanotube, a carbon filament, a carbon nanofilament, a carbon nanocoil can be used, for example. The shape of the cross section of the carbon fiber is not particularly limited, and examples thereof include a circular shape and a rectangular shape, and a rectangular shape is preferable. The carbon fiber may be a single fiber or a fiber bundle composed of a plurality of fibers. The fiber diameter of the single fiber is preferably 5 to 100 nm. Moreover, it is preferable that the fiber diameter of the said fiber bundle is 20-2000 nm.
本発明の金属−炭素繊維複合体では、上記炭素繊維に複数の細孔が存在している。上記細孔が存在していることにより、比表面積が大きくでき有用である。 In the metal-carbon fiber composite of the present invention, the carbon fiber has a plurality of pores. The presence of the pores is useful because the specific surface area can be increased.
上記細孔としては、特に限定されないが、直径２ｎｍ以下のマイクロ孔（ミクロ孔）、直径２ｎｍ〜５０ｎｍのメソ孔、直径５０ｎｍ以上のマクロ孔を用いることができる。なかでも、メソ孔又はマクロ孔であることが好ましい。上記メソ孔又はマクロ孔は、細孔全体の５０％以上の割合で含まれていることが好ましい。また、上記細孔の孔径は、１０〜２００ｎｍであることが好ましい。上記範囲にある場合、二次電池の電解質が付着しやすく好適に用いることができる。また、上記細孔は、繊維の横断面だけでなく、側面にも存在していることが好ましい。側面にも細孔が存在していることにより、より一層比表面積を大きくすることができる。 The pores are not particularly limited, and micropores having a diameter of 2 nm or less (micropores), mesopores having a diameter of 2 nm to 50 nm, and macropores having a diameter of 50 nm or more can be used. Of these, mesopores or macropores are preferable. The mesopores or macropores are preferably contained at a ratio of 50% or more of the entire pores. The pore diameter is preferably 10 to 200 nm. When it exists in the said range, the electrolyte of a secondary battery can adhere easily and can be used suitably. Moreover, it is preferable that the said pore exists not only in the cross section of a fiber but in a side surface. The presence of pores on the side surface can further increase the specific surface area.
本発明に係る金属−炭素繊維複合体には、上述したように、炭素繊維に複数の細孔が存在している。従って、比表面積が大きく、特定のサイズの分子が接着、吸着し易いという特徴を有する。よって、各種ガスの吸蔵材料、二次電池の電極材料、導電性ペースト、電気二重層キャパシタ材料、電線、熱伝導シート、熱伝導チューブ、熱伝導性コンポジット等の素材又は触媒の坦持材料など、広範な分野で好適に使用することができる。例えば、上記金属−炭素繊維複合体の金属複合体の上記第１の金属として線状、箔状の銅を用いれば、メソ孔炭素繊維よりなる電極と、該電極から配線された上記銅を引き出し電極とする電極材料を作製することができる。上記電極材料は、内部抵抗を小さくできるため、有用である。また、本発明の金属−炭素繊維複合体は、耐摩耗性に優れ、かつ高い導電性を有するので、カーボンブラシ等の接点材料や粉末冶金用材料として用いることができる。 As described above, the metal-carbon fiber composite according to the present invention has a plurality of pores in the carbon fiber. Therefore, the specific surface area is large, and a specific size molecule is easily adhered and adsorbed. Therefore, various gas storage materials, secondary battery electrode materials, conductive pastes, electric double layer capacitor materials, electric wires, thermal conductive sheets, thermal conductive tubes, thermal conductive composite materials, etc. or catalyst support materials, It can be suitably used in a wide range of fields. For example, if linear or foil-like copper is used as the first metal of the metal composite of the metal-carbon fiber composite, an electrode made of mesoporous carbon fiber and the copper wired from the electrode are drawn out. An electrode material used as an electrode can be manufactured. The electrode material is useful because the internal resistance can be reduced. Moreover, since the metal-carbon fiber composite of the present invention has excellent wear resistance and high conductivity, it can be used as a contact material such as a carbon brush or a material for powder metallurgy.
（金属−炭素繊維複合体の製造方法）
本発明に係る金属−炭素繊維複合体の製造方法では、まず、マトリックスとなる第１の金属と、上記第１の金属の表面と内部のうち少なくとも一方に分散している、触媒活性のある２種以上の第２の金属のナノ微粒子とを含む、金属複合体を準備する工程１と、上記ナノ微粒子に加熱下で炭素源を接触させる化学気相成長法（ＣＶＤ法）により、上記金属−炭素繊維複合体を生成する工程２とを備える。
(Method for producing metal-carbon fiber composite)
In the method for producing a metal-carbon fiber composite according to the present invention, first, a catalytically active 2 dispersed in at least one of the first metal serving as a matrix and the surface and the inside of the first metal. Step 1 of preparing a metal composite containing at least two kinds of second metal nanoparticles, and chemical vapor deposition (CVD method) in which a carbon source is brought into contact with the nanoparticles under heating, the metal- And a step 2 of producing a carbon fiber composite.
上記金属複合体を準備する工程１の一例としては、まず、溶融や溶体化処理により、上記第２の金属を上記第１の金属中に固溶させる。次に、触媒種である上記第２の金属を自己組織化させ、ナノ微粒子を得る。上記自己組織化は、熱処理によって行うことができる。そして、上記熱処理の温度としては、特に限定されないが３００℃〜１０５０℃であることが好ましい。 As an example of step 1 for preparing the metal composite, first, the second metal is solid-dissolved in the first metal by melting or solution treatment. Next, the second metal, which is a catalyst species, is self-assembled to obtain nanoparticles. The self-assembly can be performed by heat treatment. And although it does not specifically limit as temperature of the said heat processing, It is preferable that it is 300 to 1050 degreeC.
上記ナノ微粒子を得るための上記熱処理は、工程２の炭素源に上記ナノ微粒子を接触する直前に行ってもよく、別の工程で行っても良い。また、上記金属が粉体状の場合は、工程２の前半に行ってもよい。また、この方法においては、冷却速度を制御することにより、ナノ微粒子の大きさを調整することができる。 The heat treatment for obtaining the nano fine particles may be performed immediately before contacting the nano fine particles with the carbon source in Step 2 or may be performed in a separate step. Moreover, when the said metal is a powder form, you may carry out to the first half of the process 2. FIG. Further, in this method, the size of the nano fine particles can be adjusted by controlling the cooling rate.
工程１の他の例としては、第１の金属及び第２の金属を溶体化処理した後、熱処理によりナノ粒子を析出させる方法が挙げられる。また、金属体が粉体である場合は、例えば、第１の金属及び第２の金属を溶解し、得られた液体を噴霧する、アトマイズ法により作製してもよい。アトマイズ法としては、水アトマイズ法、ガスアトマイズ法又は遠心力アトマイズ法などが挙げられる。上記溶体化処理又は上記アトマイズ処理を施された金属体は、その後、酸化防止雰囲気中で３００℃〜７００℃、数分〜数百時間の熱処理をする事により、ナノ微粒子を析出し、第１の金属中に分散することができる。なお、ナノ粒子の大きさ及び密度は、第２の金属の含有量や熱処理条件（温度、時間）等で制御できる。 Another example of step 1 is a method in which the first metal and the second metal are subjected to a solution treatment, and then nanoparticles are deposited by heat treatment. Moreover, when a metal body is powder, you may produce by the atomizing method which melt | dissolves a 1st metal and a 2nd metal and sprays the obtained liquid, for example. Examples of the atomizing method include a water atomizing method, a gas atomizing method, and a centrifugal atomizing method. The metal body that has been subjected to the solution treatment or the atomization treatment is then subjected to heat treatment at 300 ° C. to 700 ° C. for several minutes to several hundred hours in an oxidation-preventing atmosphere, thereby precipitating nano-particles. Can be dispersed in the metal. The size and density of the nanoparticles can be controlled by the content of the second metal, the heat treatment conditions (temperature, time), and the like.
得られた金属複合体の表面により多くのナノ粒子が表出するように、得られた金属複合体の表面をエッチングしてもよい。エッチングは、例えば、ナイタール液、又は酢酸アンモニウム−メタノール溶液等で金属複合体の表面を処理することによって実施できる。 The surface of the obtained metal composite may be etched so that more nanoparticles are exposed on the surface of the obtained metal composite. Etching can be carried out, for example, by treating the surface of the metal composite with a nital solution or an ammonium acetate-methanol solution.
工程２では、上記ナノ微粒子に加熱下で炭素源を接触させるＣＶＤ法により、上記金属−炭素繊維複合体を生成する。工程２は、反応容器内で行うことができる。上記反応容器としては、上記細孔を有する炭素繊維が得られる限り、特に限定されない。回転型、縦型、流動層型又は自由落下型の反応容器を適宜用いることができる。 In step 2, the metal-carbon fiber composite is produced by a CVD method in which the nanoparticle is brought into contact with a carbon source under heating. Step 2 can be performed in a reaction vessel. The reaction vessel is not particularly limited as long as the carbon fiber having the pores is obtained. A rotary type, vertical type, fluidized bed type or free-fall type reaction vessel can be used as appropriate.
工程２の操作は、例えば、触媒化学気相成長法（Ｃａｔ−ＣＶＤ法）によって、実施することができる。詳細には、上記金属複合体の所定量を反応管に充填した後、所定温度まで加熱し、炭素繊維の原料である炭素源を、上記ナノ微粒子の表面上に供給することにより行う。上記加熱の温度としては、３００℃〜９００℃であることが好ましく、４００℃〜８００℃であることがより好ましい。４５０℃〜７５０℃であることがさらに好ましい。上記炭素源は、単独で触媒上に供給してもよく、キャリアガスとともに触媒上に供給してもよい。このようなキャリアガスとしては、例えば、不活性ガス、還元性ガスを用いることができるし、上記還元性ガスと不活性ガスとの混合ガスを用いることもでき、特に限定されないが、酸素以外を用いることが好ましい。より好ましくは、窒素、アルゴン、水素、ヘリウムを用いることができる。これらのガスは、炭素含有化合物の線速及び濃度のコントロールができる。なお、酸素ガスについては、爆発範囲外であれば使用してもよい。また、単独で触媒上に供給する場合は、真空ポンプなどによる減圧下で行うことができる。 The operation of step 2 can be performed by, for example, catalytic chemical vapor deposition (Cat-CVD method). Specifically, after a predetermined amount of the metal composite is filled in the reaction tube, the reaction tube is heated to a predetermined temperature, and a carbon source that is a raw material of carbon fiber is supplied onto the surface of the nanoparticle. The heating temperature is preferably 300 ° C to 900 ° C, more preferably 400 ° C to 800 ° C. More preferably, it is 450 degreeC-750 degreeC. The carbon source may be supplied alone on the catalyst, or may be supplied on the catalyst together with the carrier gas. As such a carrier gas, for example, an inert gas or a reducing gas can be used, or a mixed gas of the reducing gas and the inert gas can be used. It is preferable to use it. More preferably, nitrogen, argon, hydrogen, or helium can be used. These gases can control the linear velocity and concentration of the carbon-containing compound. Note that oxygen gas may be used as long as it is outside the explosion range. Moreover, when supplying on a catalyst independently, it can carry out under pressure reduction with a vacuum pump etc.
上記炭素源である炭素含有化合物としては、特に限定されないが、炭素数１〜３０の化合物を用いることができ、炭素数１〜７であることが好ましい。より好ましくは、炭素数１〜４であり、更に好ましくは炭素数１又は２の化合物が用いられる。また、炭化水素は芳香族であっても、非芳香族であってもよい。加えて、アルコール類、ケトン類、アルデヒド類、エーテル類等の酸素含有炭素化合物を用いることもできる。これらの炭素含有化合物としては、例えば、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、エチレン、プロピレン、アセチレン、ベンゼン、トルエン、キシレン、クメン、エチルベンゼン、ジエチルベンゼン、トリメチルベンゼン、ナフタレン、フェナントレン、アントラセン、メタノール、エタノール、プロパノール、ブタノール、アセトン、ホルムアルデヒド、アセトアルデヒド、トリオキサン、ジオキサン、ジメチルエーテル、ジエチルエーテル、酢酸エチル、一酸化炭素またはこれらの混合物が挙げられる。これらの中でも、メタン、エタン、エチレン、アセチレン、プロパンおよびプロピレンから選ばれた炭素化合物が、純度の高いカーボンナノチューブを得られる点で好ましい。そして、これらは常温、常圧中で気体であるため、ガスとして供給量を規定して反応に供することができる。一方、他の炭素含有化合物は、常圧で反応を行う場合、気化などの工程を追加する必要がある。 Although it does not specifically limit as a carbon containing compound which is the said carbon source, A C1-C30 compound can be used and it is preferable that it is C1-C7. More preferably, it is C1-C4, More preferably, a C1-C2 compound is used. Further, the hydrocarbon may be aromatic or non-aromatic. In addition, oxygen-containing carbon compounds such as alcohols, ketones, aldehydes, and ethers can be used. Examples of these carbon-containing compounds include methane, ethane, propane, butane, pentane, hexane, heptane, ethylene, propylene, acetylene, benzene, toluene, xylene, cumene, ethylbenzene, diethylbenzene, trimethylbenzene, naphthalene, phenanthrene, anthracene. , Methanol, ethanol, propanol, butanol, acetone, formaldehyde, acetaldehyde, trioxane, dioxane, dimethyl ether, diethyl ether, ethyl acetate, carbon monoxide or a mixture thereof. Among these, a carbon compound selected from methane, ethane, ethylene, acetylene, propane and propylene is preferable in that a carbon nanotube with high purity can be obtained. And since these are gases in normal temperature and a normal pressure, supply amount can be prescribed | regulated as gas and it can use for reaction. On the other hand, when other carbon-containing compounds are reacted at normal pressure, it is necessary to add a process such as vaporization.
上記工程１及び上記工程２の一例としてのヒートプロファイルを図１に示す。ここで、図中１−Ａ及び１−Ｂの工程は、上記工程１であり、図中１−Ｃの工程は上記工程２を示す。図中、斜線部分では、エチレンガス雰囲気下において、その他の部分については、窒素ガス雰囲気下で処理を行っている。 A heat profile as an example of the step 1 and the step 2 is shown in FIG. Here, the steps 1-A and 1-B in the drawing are the step 1 and the step 1-C in the drawing shows the step 2. In the drawing, the shaded portion is treated in an ethylene gas atmosphere, and the other portions are treated in a nitrogen gas atmosphere.
図１における、１−Ａの工程において、３００℃〜４００℃で銅粉をエチレンガスに接触させる（凝集防止工程）。次に、図中、１−Ｂの工程で、不活性ガス中で４００℃〜６５０℃に保持し銅粉中及び銅粉表面にナノ触媒を析出させる（触媒析出工程）。そして、図中、１−Ｃの工程で、ナノ微粒子から炭素同素体が生成する（炭素生成工程）。 In step 1-A in FIG. 1, the copper powder is brought into contact with ethylene gas at 300 to 400 ° C. (aggregation preventing step). Next, in the figure, in step 1-B, the nanocatalyst is deposited in the copper powder and on the surface of the copper powder while being kept at 400 ° C. to 650 ° C. in an inert gas (catalyst deposition step). In the figure, a carbon allotrope is generated from the nanoparticles in the step 1-C (carbon generation step).
本製造方法により得られた、金属−炭素繊維複合体は、そのまま使用することが好ましいが、使用形態によっては、金属−炭素繊維複合体から、金属複合体を単離して用いても構わない。例えば、金属−炭素繊維複合体から、酸やアルカリにより金属複合体を除去することができる。また、箔状、線状の金属複合体から延びている炭素繊維は、掻き取る事により分離することができる。粉体状の金属複合体から延びている炭素繊維は、粉砕処理後に風力分級、沈降法による分級、磁界による分離が可能である。 The metal-carbon fiber composite obtained by this production method is preferably used as it is, but the metal composite may be isolated from the metal-carbon fiber composite and used depending on the form of use. For example, the metal composite can be removed from the metal-carbon fiber composite with acid or alkali. Moreover, the carbon fibers extending from the foil-like or linear metal composite can be separated by scraping. The carbon fibers extending from the powdered metal composite can be separated by wind classification, sedimentation, and magnetic field after pulverization.
次に、具体的な実施例につき説明する。なお、本発明は以下の実施例に限定されるものではない。 Next, specific examples will be described. In addition, this invention is not limited to a following example.
（実施例１〜５及び比較例１〜３）
（金属複合体の作製）
表１の組成の金属複合体の溶解物から、水アトマイズ法、又はガスアトマイズ法により、Ｃｕ−Ｆｅ−Ｃｏ及びＣｕ−Ｃｏ等の各金属微粒子（粉体）を製造した。
(Examples 1-5 and Comparative Examples 1-3)
(Production of metal composite)
Each metal fine particle (powder) such as Cu—Fe—Co and Cu—Co was produced from the melted metal composite having the composition shown in Table 1 by a water atomizing method or a gas atomizing method.
（ＣＶＤ法による金属−炭素繊維複合体の作製）
４gの上記金属複合体粉を、内径２６ｍｍ長さ７０ｍｍの石英セル中に投入し、内径３２ｍｍ、長さ７００ｍｍのロータリー円筒形石英管を用いた、銅炭素複合ＣＶＤ反応器（ロータリーキルン）により、表１の条件で金属複合体上に炭素繊維を生成し、表１に示す実施例１〜５及び比較例１〜３の金属−炭素繊維複合体を作製した。
(Production of metal-carbon fiber composite by CVD method)
4 g of the above metal composite powder was put into a quartz cell having an inner diameter of 26 mm and a length of 70 mm, and a copper carbon composite CVD reactor (rotary kiln) using a rotary cylindrical quartz tube having an inner diameter of 32 mm and a length of 700 mm was used. Carbon fiber was produced | generated on the metal composite on 1 conditions, and the metal-carbon fiber composite of Examples 1-5 shown in Table 1 and Comparative Examples 1-3 was produced.
なお、図２は、銅マトリックス中に鉄とコバルトよりなるナノ微粒子が析出したナノ微粒子の透過顕微鏡写真を示す図である。このナノ微粒子はＥＤＳ元素像により鉄及びコバルトで構成されている事が確認出来ている。 In addition, FIG. 2 is a figure which shows the transmission micrograph of the nanoparticle which the nanoparticle consisting of iron and cobalt precipitated in the copper matrix. It was confirmed from the EDS element image that the nano fine particles were composed of iron and cobalt.
（金属−炭素繊維複合体の評価）
１）ＳＥＭによる観察
実施例１〜５及び比較例１〜３の金属−炭素繊維複合体をＦＥ−ＳＥＭによって観察した。結果を、図３〜図１１及び表２に示す。実施例１〜５においては、細孔を側面に持つ炭素繊維が生成していることを観察できた。
(Evaluation of metal-carbon fiber composite)
1) Observation by SEM The metal-carbon fiber composites of Examples 1 to 5 and Comparative Examples 1 to 3 were observed by FE-SEM. The results are shown in FIGS. In Examples 1 to 5, it was observed that carbon fibers having pores on the side surfaces were generated.
一方、第２の金属に鉄又はコバルトを使用していない比較例１、３においては、炭素繊維の側面に細孔は観察されなかった。比較例２においては太い繊維（５００ｎｍ）の先に細い繊維（１０〜５０ｎｍ）が観察された。 On the other hand, in Comparative Examples 1 and 3 in which iron or cobalt was not used as the second metal, no pores were observed on the side surfaces of the carbon fibers. In Comparative Example 2, thin fibers (10 to 50 nm) were observed at the tip of thick fibers (500 nm).
２）比表面積測定
本発明のメソ孔性炭素繊維の比表面積や、メソ孔及びマクロ孔の測定方法は、多孔質材料の同定法として使用される、Ｎ２（メソ〜マクロ孔の場合）を用いたガス吸着法による細孔分布測定法を用いる。本発明の比表面積測定と細孔分布測定は、島津製作所株式会社製の定容量式ガス吸着法測定装置ＢＥＬＳＯＲＰ−ｍｉｎｉを用いた。対象試料の前処理としては、８０℃、２時間脱ガス処理を行った。吸着ガスとしてＮ２を使用した。比表面積は、ＢＥＴ法で算出される。メソ孔〜マクロ孔測定の場合、液体Ｎ２温度-１９６℃で相対圧約０．０１〜０．９９までの等温吸着測定を実施した。メソ孔〜マクロ孔の場合、同装置のＤＨ解析法にて約２０〜２０００Åの範囲のメソ孔〜マクロ孔の細孔分布を算出した。ピーク微分細孔容積とは上記解析ソフトにて導出されるメソ孔〜マクロ孔の細孔分布のピークまたはショルダー中心値の細孔容量値のことを指す。メソ孔〜マクロ孔の細孔分布におけるピーク径とは、横軸を対数表示したその細孔分布に現れるピークやショルダー状のピーク系及びショルダーの中心値を意味する。
2) Specific surface area measurement The specific surface area of the mesoporous carbon fiber of the present invention, and the method for measuring mesopores and macropores are N 2 (in the case of meso-macropores) used as a method for identifying porous materials. The pore distribution measurement method by the gas adsorption method used is used. The specific surface area measurement and pore distribution measurement of the present invention were performed using a constant volume gas adsorption method measuring apparatus BELSORP-mini manufactured by Shimadzu Corporation. As pretreatment of the target sample, degassing treatment was performed at 80 ° C. for 2 hours. N 2 was used as the adsorption gas. The specific surface area is calculated by the BET method. In the case of mesopore-macropore measurement, isothermal adsorption measurement was performed at a liquid N 2 temperature of −196 ° C. and a relative pressure of about 0.01 to 0.99. In the case of mesopores to macropores, the pore distribution of mesopores to macropores in the range of about 20 to 2000 mm was calculated by the DH analysis method of the same apparatus. The peak differential pore volume refers to the peak of the pore distribution of mesopores to macropores derived from the analysis software or the pore volume value of the shoulder center value. The peak diameter in the pore distribution of mesopores to macropores means a peak appearing in the pore distribution logarithmically expressed on the horizontal axis, a shoulder-like peak system, and the center value of the shoulder.
表中にはピークの細孔サイズを記した。また２山分布になっている物は２点記入した。 The peak pore size is shown in the table. In addition, two points are entered for the two mountain distribution.
結果を、表２に示す。 The results are shown in Table 2.
実施例１〜５において、比表面積が比較例１〜３よりも大きくなっていることを確認した。特に、実施例１においては、１−Ｂの工程が長時間で有るため比表面積が大きくなった事が考えられる。また、比較例１〜３も平均細孔径及び細孔サイズは測定されるが、これは複数の繊維の間の空間が細孔として測定された物が主であり、本発明の細孔とは異なる。 In Examples 1-5, it confirmed that the specific surface area was larger than Comparative Examples 1-3. In particular, in Example 1, it can be considered that the specific surface area increased because the step 1-B was performed for a long time. Moreover, although the average pore diameter and pore size are also measured in Comparative Examples 1 to 3, this is mainly a product in which the space between a plurality of fibers is measured as pores. Different.
Claims (8)
前記ナノ微粒子から延びている複数の細孔を有する炭素繊維とを備える、金属−炭素繊維複合体。 A metal composite comprising copper as a matrix, and nanoparticles formed of two or more metals including iron and cobalt, dispersed in the copper;
A metal-carbon fiber composite comprising a carbon fiber having a plurality of pores extending from the nanoparticle.
前記銅と、前記銅の内部に分散している前記鉄及びコバルトを含む２種以上の金属のナノ微粒子とを含む、金属複合体を準備する工程と、
前記ナノ微粒子に加熱下で炭素源を接触させる工程とを備える、金属−炭素繊維複合体の製造方法。 A method for producing a metal-carbon fiber composite according to any one of claims 1 to 5,
Preparing a metal composite comprising the copper and nanoparticles of two or more metals including the iron and cobalt dispersed in the copper;
And a step of bringing a carbon source into contact with the nanoparticle under heating.
The metal composite is simply separated from the metal-carbon fiber composite according to any one of claims 1 to 5 by a method of removing the metal composite with an acid or alkali, or a method of classifying after cutting the carbon fiber. A method for producing a carbon fiber having a plurality of pores, comprising a step of separating.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |