JP5741897B2 - カーボンナノチューブ製造方法 - Google Patents
カーボンナノチューブ製造方法 Download PDFInfo
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- JP5741897B2 JP5741897B2 JP2010211617A JP2010211617A JP5741897B2 JP 5741897 B2 JP5741897 B2 JP 5741897B2 JP 2010211617 A JP2010211617 A JP 2010211617A JP 2010211617 A JP2010211617 A JP 2010211617A JP 5741897 B2 JP5741897 B2 JP 5741897B2
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- Prior art keywords
- substrate
- catalyst
- carbon nanotubes
- catalyst solution
- concentration
- Prior art date
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- Expired - Fee Related
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 128
- 239000002041 carbon nanotube Substances 0.000 title claims description 118
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 118
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000003054 catalyst Substances 0.000 claims description 170
- 239000000758 substrate Substances 0.000 claims description 98
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 59
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 59
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical group [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
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- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
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- 238000004220 aggregation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
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- 229910021389 graphene Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
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- 239000001294 propane Substances 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
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- 230000000903 blocking effect Effects 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
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- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
- H01M14/005—Photoelectrochemical storage cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8817—Treatment of supports before application of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/842—Manufacture, treatment, or detection of nanostructure for carbon nanotubes or fullerenes
- Y10S977/843—Gas phase catalytic growth, i.e. chemical vapor deposition
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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Description
以下、試験例1〜12について説明する。試験例1〜12について、触媒液の濃度を0.05M〜1.1Mの範囲内において複数段階として変化させた。他の条件は共通化させた。
触媒粒子の下地層となるアルミニウム(純アルミニウム)をスパッタリング処理より基板(基体)の表面に成膜させた。アルミニウムの膜の厚みは4〜6ナノメートル(5ナノメートル)とした。その後、基板の表面をアセトンで洗浄した。基板は10.16センチメートル四方のシリコン基板(厚み:0.5ミリメートル)とした。全部の試験例について共通条件とした。
所定濃度となるように、アルコールであるエタノールに硝酸鉄(III)・9水和物を常温にて投入した。その後、常温にてスターラ(攪拌機)により攪拌し、触媒液を形成した。触媒液には、テルピネオールは配合されていない。従って触媒液はテルピネオールを含まない。更に、触媒液には、増粘作用をもつポリアクリル酸ナトリウム、ポリビニルアルコール、ポリエチレンオキシド、ポリビニルピロリドン、精油も配合されていない。このため触媒液には、テルピネオール、ポリアクリル酸ナトリウム、ポリビニルアルコール、ポリエチレンオキシド、ポリビニルピロリドン、精油は含まれていない。この場合、試験例1では触媒液の濃度は0.05Mとした。試験例2では触媒液の濃度は0.1Mとした。試験例3では触媒液の濃度は0.2Mとした。試験例4では触媒液の濃度は0.3Mとした。試験例5では触媒液の濃度は0.4Mとした。試験例6では触媒液の濃度は0.5Mとした。試験例7では触媒液の濃度は0.6Mとした。試験例8では触媒液の濃度は0.7Mとした。試験例9では触媒液の濃度は0.8Mとした。試験例10では触媒液の濃度は0.9Mとした。試験例11では触媒液の濃度は1Mとした。試験例12では触媒液の濃度は1.1Mとした。
常温にて基板をディップコータにより上記触媒液に10秒間浸漬させた。その後、60ミリメートル/minの速度で基板を触媒液から引き上げた。その後、100℃×5分間で大気中において基板を乾燥させた。これにより触媒粒子を有する触媒層を基板の表面に形成した。これにより複数の島状をなす複数個の触媒粒子が分散した群を基板の表面に形成した。
熱CVD装置を用い、予め10Paに真空引きされた反応容器中にキャリヤガスとして窒素ガスを導入し、容器内の圧力を0.1MPaに調整した。その後、反応容器内の基板の温度を750℃に昇温させた状態で、流量10sccmのアセチレンガスと45sccmの窒素とが混合した原料ガスを反応容器内に供給した。sccmは、standard cc/minの略であり、1atm、0℃で規格化されたccmを示す。そして原料ガスの雰囲気下で、基板温度750℃ 、266Paの雰囲気において10分間反応させることにより、カーボンナノチューブを基板の表面に生成させた。この結果、基板の表面においてカーボンナノチューブからなる群が得られた。なお基板温度は750℃であり、金属塩触媒上における反応ガスの分解の促進を考慮したものである。
上記した試験例1〜12は、テルピネオール等の増粘剤を配合していない触媒液を用いて実施されている。この場合、触媒液の溶媒はエタノール100%とされている。試験例1〜12によって製造されたカーボンナノチューブのSEM写真を、触媒液の濃度毎に図1に示す。図1から理解できるように、テルピネオールを配合していない触媒液が用いられている場合には、試験例1(触媒液の濃度:0.05M)ではカーボンナノチューブは良好に成長せず、カーボンナノチューブの垂直配向性は良好ではなかった。更に、試験例2(触媒液の濃度:0.1M)ではカーボンナノチューブの垂直配向性は良好ではなかった。
試験例1(触媒液の濃度:0.05M)… 3マイクロメートル程度
試験例2(触媒液の濃度:0.1M)… 7〜30マイクロメートル程度
試験例3(触媒液の濃度:0.2M)… 50マイクロメートル程度
試験例4(触媒液の濃度:0.3M)… 35マイクロメートル程度
試験例5(触媒液の濃度:0.4M)… 60マイクロメートル程度
試験例6(触媒液の濃度:0.5M)… 60マイクロメートル程度
試験例7(触媒液の濃度:0.6M)… 40マイクロメートル程度
試験例8(触媒液の濃度:0.7M)… 25マイクロメートル程度
試験例9(触媒液の濃度:0.8M)… 45マイクロメートル程度
試験例10(触媒液の濃度:0.9M)… 2マイクロメートル程度
試験例11(触媒液の濃度:1M)… 2マイクロメートル程度
試験例12(触媒液の濃度:1.1M)… 17マイクロメートル程度
図1から理解できるように、鉄塩をエタノール溶媒に溶解させた所定濃度(0.2M〜0.8M)をもち且つテルピネオールを配合していない触媒液を用いれば、アルミニウムまたはアルミニウム合金が配置された基板の表面に対して垂直方向に沿った高い垂直配向性をもつカーボンナノチューブの群が基板の表面に得られることがわかった。カーボンナノチューブはブラシ状に成長している。
図3はシート型の高分子形の燃料電池の要部の断面を模式的に示す。燃料電池は、燃料極用の配流板101と、燃料極用のガス拡散層102と、燃料極用の触媒を有する触媒層103と、炭化フッ素系または炭化水素系の高分子材料で形成されたイオン伝導性(プロトン伝導性)を有する電解質膜104と、酸化剤極用の触媒を有する触媒層105と、酸化剤極用のガス拡散層106と、酸化剤極用の配流板107とを厚み方向に順に積層して形成されている。ガス拡散層102,106は、反応ガスを透過できるようにガス透過性を有する。電解質膜104はイオン伝導性(プロトン伝導性)を有するガラス系で形成しても良い。
図4は集電用のキャパシタを模式的に示す。キャパシタは、炭素系材料で形成された多孔質の正極201と、炭素系材料で形成された多孔質の負極202と、正極201および負極202を仕切るセパレータ203とを有する。正極201の表面に対して垂直方向に沿った垂直配向性をもつカーボンナノチューブが正極201の表面に設けられている。負極202の表面に対して垂直方向に沿った垂直配向性をもつカーボンナノチューブが負極202の表面に設けられている。本発明に係るカーボンナノチューブは、大きな比表面積をもち、多孔質であるため、正極201および/または負極202に使用されるとき、集電容量の増加を期待でき、キャパシタの能力を向上できる。基板に形成されたカーボンナノチューブを負極202、正極201の表面に転写させることができる。
Claims (3)
- 鉄塩をエタノール溶媒に溶解させた所定濃度(0.2M〜0.8M)をもち且つテルピネオールを配合していない触媒液と、表面をもち該表面にアルミニウムまたはアルミニウム合金が配置された基体とを用意する準備工程と、
前記触媒液と前記基体の前記表面を接触させ、触媒粒子を前記基体の前記表面に担持させる触媒担持工程と、
炭素成分を含むカーボンナノチューブ形成ガスをカーボンナノチューブ形成温度領域において前記基体の前記表面に接触させ、前記基体の前記表面に対して垂直な方向に配向する垂直配向性をもつカーボンナノチューブの群を前記基体の前記表面に成長させるカーボンナノチューブ成長工程とを順に実施するカーボンナノチューブ製造方法。 - 前記鉄塩は硝酸鉄である請求項1に記載のカーボンナノチューブ製造方法。
- 前記アルミニウムまたはアルミニウム合金の厚さは3〜30ナノメートルである請求項1または請求項2に記載のカーボンナノチューブ製造方法。
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