JP2016083618A - Carbon material produced by supporting metal on carbon nanotube and method for producing the same - Google Patents
Carbon material produced by supporting metal on carbon nanotube and method for producing the same Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 85
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 85
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000000446 fuel Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000002612 dispersion medium Substances 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract 2
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002134 carbon nanofiber Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
Abstract
Description
本発明は、金属がカーボンナノチューブに担持されてなるカーボン材料およびその製造方法に関する。 The present invention relates to a carbon material in which a metal is supported on carbon nanotubes and a method for producing the same.
特許文献１（特開２０１１−１７８８７８号公報）には、カーボンナノチューブ自体の特性を損なうことなく、外観上、および／または性能上、欠陥や異物の少ない導電層を簡便な方法で得ることができる長期安定性に優れたカーボンナノチューブ組成物を得るために、カーボンナノチューブと、導電性ポリマーと、溶剤とを含有するカーボンナノチューブ含有組成物であって、動的光散乱法で測定した粒径分布において、１ｎｍ以上１μｍ未満の累計散乱強度（Ｉ）と１μｍ以上１００μｍ未満の累計散乱強度（ＩＩ）の比（（Ｉ）／（ＩＩ））が３．０以上であるカーボンナノチューブ含有組成物が開示されている。
カーボンナノチューブは、特許文献１で開示されたカーボンナノチューブ含有組成物を始めとして、樹脂等の改質を目指した複合化に関する研究開発が盛んに実施されている。しかし、研究開発は発展途上の段階にあり、カーボンナノチューブをさらに多様な分野において活用する方法が求められていた。
In Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-178878), a conductive layer with few defects and foreign matters can be obtained by a simple method in terms of appearance and / or performance without impairing the characteristics of the carbon nanotube itself. In order to obtain a carbon nanotube composition having excellent long-term stability, a carbon nanotube-containing composition containing a carbon nanotube, a conductive polymer, and a solvent, and having a particle size distribution measured by a dynamic light scattering method Disclosed is a carbon nanotube-containing composition having a ratio ((I) / (II)) of 3.0 or more of a cumulative scattering intensity (I) of 1 nm or more and less than 1 μm and a cumulative scattering intensity (II) of 1 μm or more and less than 100 μm. ing.
Carbon nanotubes are actively researched and developed for composites aimed at modifying resins and the like, including the carbon nanotube-containing composition disclosed in Patent Document 1. However, research and development is in a developing stage, and a method for utilizing carbon nanotubes in various fields has been demanded.
本発明は、上記背景技術を鑑みてなされたものであり、樹脂等の改質だけでなく、燃料電池触媒等にも活用可能なカーボン材料、より具体的には金属がカーボンナノチューブに担持されてなるカーボン材料およびその製造方法を提供することを目的とする。 The present invention has been made in view of the above-described background art. A carbon material that can be used not only for reforming of a resin or the like but also for a fuel cell catalyst or the like, more specifically, a metal is supported on a carbon nanotube. An object of the present invention is to provide a carbon material and a manufacturing method thereof.
すなわち、本発明は下記の発明を含む。
［１］ 金属と、
数平均繊維径３０ｎｍ以下であるカーボンナノチューブＡと、
数平均繊維径１００ｎｍ以上であるカーボンナノチューブＢと、
を含み、
前記金属の一部または全てが前記カーボンナノチューブＡおよびカーボンナノチューブＢに担持されてなることを特徴とするカーボン材料。
［２］ 前記カーボンナノチューブＡ：１００質量部に対し、前記カーボンナノチューブＢが１００〜１５００質量部含有される［１］に記載のカーボン材料。
［３］ 前記カーボンナノチューブＡおよびＢを合計２０〜９５質量％含有する［１］または［２］に記載のカーボン材料。
［４］ 前記金属が、Ｐｔ、Ｉｒ、Ａｇ、ＰｄおよびＲｕから選ばれる少なくとも１種からなる［１］〜［３］のいずれかに記載のカーボン材料。
［５］ 前記金属を５〜８０質量％含む［１］〜［４］のいずれかに記載のカーボン材料。
［６］ 前記金属の平均粒子径が１〜２０ｎｍである［１］〜［５］に記載のいずれかに記載のカーボン材料。
［７］ ［１］〜［６］のいずれかに記載のカーボン材料からなる燃料電池用触媒。
［８］ ［１］〜［６］のいずれかに記載のカーボン材料の製造方法であって、
分散媒に、前記カーボンナノチューブＡおよびＢを湿式ジェットミルを用いて混合して前記カーボンナノチューブＡおよびＢの分散液を得る工程と、
得られた分散液と、前記金属を含む前駆体の溶液とを混合して、金属が吸着したカーボンナノチューブ組成物を得る工程と、
前記カーボンナノチューブ組成物を水素ガス含有不活性ガス中で熱処理する工程と、
を含むことを特徴とするカーボン材料の製造方法。
That is, the present invention includes the following inventions.
[1] metal,
Carbon nanotubes A having a number average fiber diameter of 30 nm or less;
Carbon nanotubes B having a number average fiber diameter of 100 nm or more;
Including
A carbon material, wherein a part or all of the metal is supported on the carbon nanotubes A and B.
[2] The carbon material according to [1], wherein 100 to 1500 parts by mass of the carbon nanotube B is contained with respect to 100 parts by mass of the carbon nanotube A.
[3] The carbon material according to [1] or [2], containing a total of 20 to 95% by mass of the carbon nanotubes A and B.
[4] The carbon material according to any one of [1] to [3], wherein the metal is at least one selected from Pt, Ir, Ag, Pd, and Ru.
[5] The carbon material according to any one of [1] to [4], containing 5 to 80% by mass of the metal.
[6] The carbon material according to any one of [1] to [5], wherein the metal has an average particle diameter of 1 to 20 nm.
[7] A fuel cell catalyst comprising the carbon material according to any one of [1] to [6].
[8] A method for producing a carbon material according to any one of [1] to [6],
Mixing the carbon nanotubes A and B with a dispersion medium using a wet jet mill to obtain a dispersion of the carbon nanotubes A and B;
Mixing the obtained dispersion and the precursor solution containing the metal to obtain a carbon nanotube composition having the metal adsorbed thereon;
Heat treating the carbon nanotube composition in an inert gas containing hydrogen gas;
A method for producing a carbon material, comprising:
本発明によれば、樹脂等の改質だけでなく、燃料電池触媒等にも活用可能なカーボン材料、より具体的には金属がカーボンナノチューブに担持されてなるカーボン材料を製造することができる。
さらに、本発明のカーボン材料は、例えば燃料電池触媒として使用すると、高い触媒能を発揮する。
According to the present invention, it is possible to produce a carbon material that can be used not only for reforming a resin or the like but also for a fuel cell catalyst or the like, more specifically, a carbon material in which a metal is supported on a carbon nanotube.
Furthermore, when the carbon material of the present invention is used as, for example, a fuel cell catalyst, it exhibits high catalytic ability.
本発明のカーボン材料は、金属と、数平均繊維径３０ｎｍ以下であるカーボンナノチューブＡと、数平均繊維径１００ｎｍ以上であるカーボンナノチューブＢと、を含み、前記金属の一部または全てが前記カーボンナノチューブＡおよびカーボンナノチューブＢに担持されてなる。
また、本発明のカーボン材料は、分散媒に、前記カーボンナノチューブＡおよびＢを湿式ジェットミルを用いて混合して前記カーボンナノチューブＡおよびＢの分散液を得る工程と、得られた分散液と、前記金属を含む前駆体の溶液とを混合して、金属が吸着したカーボンナノチューブ組成物を得る工程と、前記カーボンナノチューブ組成物を水素ガス含有不活性ガス中で熱処理する工程と、を含む方法により製造することができる。
The carbon material of the present invention includes a metal, a carbon nanotube A having a number average fiber diameter of 30 nm or less, and a carbon nanotube B having a number average fiber diameter of 100 nm or more, and a part or all of the metal is the carbon nanotube. A and carbon nanotubes B are supported.
Further, the carbon material of the present invention comprises a step of mixing the carbon nanotubes A and B with a dispersion medium using a wet jet mill to obtain a dispersion of the carbon nanotubes A and B, and the resulting dispersion. By mixing the precursor solution containing the metal to obtain a carbon nanotube composition on which the metal has been adsorbed, and heat treating the carbon nanotube composition in an inert gas containing hydrogen gas. Can be manufactured.
本発明においては、以下に定義するカーボンナノチューブＡ及びＢを含む。カーボンナノチューブを２種類使用することによりカーボンナノチューブが分散する効果があり、これはジェットミルでカーボンナノチューブＢの周りにカーボンナノチューブＡが絡まるような形態をつくることが要因であると考えられる。
また、本発明においてはカーボンナノチューブを担体として利用する。カーボンナノチューブは導電性材料として用いられる場合もあるが、本発明のように担体として使用する場合、酸化劣化耐性、腐食耐性効果がある。これはカーボンナノチューブは、六員環ネットワークを形成した結晶性のカーボンであるため、化学的に安定で酸化劣化を受けにくく、耐食性に優れていることが要因であると考えられる。
In the present invention, carbon nanotubes A and B defined below are included. The use of two types of carbon nanotubes has the effect of dispersing the carbon nanotubes, and this is considered to be caused by the fact that the carbon nanotubes A are entangled around the carbon nanotubes B by a jet mill.
In the present invention, carbon nanotubes are used as a carrier. Carbon nanotubes may be used as a conductive material, but when used as a carrier as in the present invention, they have oxidation deterioration resistance and corrosion resistance effects. This is considered to be due to the fact that the carbon nanotube is a crystalline carbon having a six-membered ring network, and thus is chemically stable and hardly subject to oxidative degradation and is excellent in corrosion resistance.
本発明に用いるカーボンナノチューブＡは、数平均繊維径３０ｎｍ以下であり、好ましくは１〜３０ｎｍ、より好ましくは５〜２０ｎｍである。長さとしては、好ましくは０．１〜１０μｍ、より好ましくは０．２〜８μｍ、さらに好ましくは０．２〜５μｍである。このようなカーボンナノチューブＡの市販品としては、昭和電工株式会社製のＶＧＣＦ（登録商標）−Ｘ（数平均繊維径１５ｎｍ、数平均繊維長：２μｍ、非直線的形状）、ナノシル社製のＮＣ２１００、ＮＣ２１０１、ＮＣ１１００、株式会社名城ナノカーボン製のＭＷＮＴ ＭＴＣ（繊維径１０−４０ｎｍ）等が挙げられる。 The carbon nanotube A used in the present invention has a number average fiber diameter of 30 nm or less, preferably 1 to 30 nm, more preferably 5 to 20 nm. The length is preferably 0.1 to 10 μm, more preferably 0.2 to 8 μm, and still more preferably 0.2 to 5 μm. Examples of such commercially available carbon nanotubes A include VGCF (registered trademark) -X (number average fiber diameter 15 nm, number average fiber length: 2 μm, non-linear shape) manufactured by Showa Denko KK, NC2100 manufactured by Nanosil Corporation. , NC2101, NC1100, MWNT MTC (fiber diameter 10-40 nm) manufactured by Meijo Nanocarbon Co., Ltd., and the like.
本発明に用いるカーボンナノチューブＢは、数平均繊維径１００ｎｍ以上であり、好ましくは１００〜１０００ｎｍ、より好ましくは１００〜３００ｎｍである。長さとしては、好ましくは０．２〜２０μｍ 、より好ましくは０．５〜１５μｍ、さらに好ましくは０．５〜１３μｍである。このようなカーボンナノチューブの市販品としては、昭和電工株式会社製のＶＧＣＦ（登録商標）−Ｈ（数平均繊維径１５０ｎｍ、数平均繊維長：１０〜２０μｍ、直線的形状）、保土ヶ谷化学工業株式会社製のＣＴ−１２（平均繊維径：１１０ｎｍ）、ＣＴ−２５（平均繊維径：１５０ｎｍ）等が挙げられる。 The carbon nanotubes B used in the present invention have a number average fiber diameter of 100 nm or more, preferably 100 to 1000 nm, more preferably 100 to 300 nm. The length is preferably 0.2 to 20 μm, more preferably 0.5 to 15 μm, and still more preferably 0.5 to 13 μm. Examples of such commercially available carbon nanotubes include VGCF (registered trademark) -H (number average fiber diameter 150 nm, number average fiber length: 10 to 20 μm, linear shape) manufactured by Showa Denko KK, Hodogaya Chemical Co., Ltd. Examples thereof include CT-12 (average fiber diameter: 110 nm), CT-25 (average fiber diameter: 150 nm), and the like.
なお、数平均繊維径は、カーボンナノチューブＡおよびＢいずれにおいても、透過型電子顕微鏡（ＴＥＭ）で観察される繊維１００個の数平均値である。これは、１００本の繊維を撮影して画像処理によって二値化して求めた値を平均して計算することができる。 The number average fiber diameter is the number average value of 100 fibers observed with a transmission electron microscope (TEM) in both the carbon nanotubes A and B. This can be calculated by averaging the values obtained by photographing 100 fibers and binarizing them by image processing.
本発明のカーボン材料中、カーボンナノチューブＡ：１００質量部に対し、カーボンナノチューブＢは１００〜１５００質量部含有されることが好ましい。カーボンナノチューブＢの含有量は、２００〜１２００質量部であることがより好ましく、３００〜１０００質量部であることがさらに好ましい。
なお、カーボン材料中のカーボンナノチューブＡ：１００質量部に対するカーボンナノチューブＢの質量部は、カーボンナノチューブＡおよびＢの仕込み量をもとに算出可能である。また前記ＴＥＭにおけるカーボンナノチューブＡとカーボンナノチューブＢの数量比と各密度からも算出可能である。
In the carbon material of the present invention, the carbon nanotube B is preferably contained in an amount of 100 to 1500 parts by mass with respect to 100 parts by mass of the carbon nanotube A. The content of the carbon nanotube B is more preferably 200 to 1200 parts by mass, and further preferably 300 to 1000 parts by mass.
In addition, the mass part of the carbon nanotube B with respect to 100 mass parts of the carbon nanotube A in the carbon material can be calculated based on the charged amount of the carbon nanotubes A and B. It can also be calculated from the quantity ratio of the carbon nanotubes A and B and the respective densities in the TEM.
本発明のカーボン材料中のカーボンナノチューブＡおよびＢの合計の含有量は２０〜９５質量％であることが好ましい。カーボンナノチューブＡおよびＢの合計の含有量は、３０〜９５質量％であることがより好ましく、４０〜９５質量％であることがさらに好ましい。
なお、カーボン材料中のカーボンナノチューブＡおよびＢの合計の含有量は、後述する担持金属の質量比を差し引くことにより算出可能である。
The total content of carbon nanotubes A and B in the carbon material of the present invention is preferably 20 to 95% by mass. The total content of the carbon nanotubes A and B is more preferably 30 to 95% by mass, and further preferably 40 to 95% by mass.
The total content of carbon nanotubes A and B in the carbon material can be calculated by subtracting the mass ratio of the supported metal described later.
本発明のカーボン材料中の金属は特に制限はなく、公知の触媒金属を用いることができ、例えばＰｔ、Ｉｒ、Ａｇ、Ｐｄ、Ｒｕ、Ｏｓ、Ｒｈ、Ａｕ等の貴金属や、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｗ等の卑金属が挙げられる。これらのうち、Ｐｔ、Ｉｒ、Ａｇ、ＰｄおよびＲｕから選ばれる少なくとも一種からなることが好ましい。Ｐｔ、Ｒｕ、Ｐｄから選ばれる少なくとも一種がより好ましく、Ｐｔ、Ｐｄ、から選ばれる少なくとも一種がさらに好ましく、Ｐｔからなることがもっとも好ましい。なお、金属としてこれらの合金を用いてもよい。 The metal in the carbon material of the present invention is not particularly limited, and a known catalyst metal can be used. For example, noble metals such as Pt, Ir, Ag, Pd, Ru, Os, Rh, Au, Ti, V, Cr , Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, W, and other base metals. Among these, it is preferable to consist of at least one selected from Pt, Ir, Ag, Pd and Ru. At least one selected from Pt, Ru, and Pd is more preferable, at least one selected from Pt and Pd is more preferable, and Pt is most preferable. In addition, you may use these alloys as a metal.
本発明のカーボン材料中の金属の含有量は、５〜８０質量％であることが好ましい。金属の含有量は、５〜７０質量％であることがより好ましく、５〜６０質量％であることがさらに好ましい。
なお、カーボン材料中の金属の含有量は、カーボン材料と金属の仕込み量をもとに算出可能である。
The metal content in the carbon material of the present invention is preferably 5 to 80% by mass. As for metal content, it is more preferable that it is 5-70 mass%, and it is further more preferable that it is 5-60 mass%.
Note that the metal content in the carbon material can be calculated based on the amounts of the carbon material and metal charged.
本発明のカーボン材料中の金属の平均粒子径は、１〜２０ｎｍであることが好ましく、２〜２０ｎｍであることがより好ましく、３〜１８ｎｍであることがさらに好ましく、３〜１５ｎｍであることがもっとも好ましい。
なお、平均粒子径は、透過型電子顕微鏡（ＴＥＭ）で観察される粒子１００個の数平均値を示す。
The average particle diameter of the metal in the carbon material of the present invention is preferably 1 to 20 nm, more preferably 2 to 20 nm, further preferably 3 to 18 nm, and 3 to 15 nm. Most preferred.
In addition, an average particle diameter shows the number average value of 100 particle | grains observed with a transmission electron microscope (TEM).
本発明のカーボン材料は、分散媒に、前記カーボンナノチューブＡおよびＢを湿式ジェットミルを用いて混合して前記カーボンナノチューブＡおよびＢの分散液を得る工程と、得られた分散液と、前記金属を含む前駆体の溶液とを混合して、金属が吸着したカーボンナノチューブ組成物を得る工程と、前記カーボンナノチューブ組成物を水素ガス含有不活性ガス中で熱処理する工程と、を含む方法により製造することができる。 The carbon material of the present invention includes a step of mixing the carbon nanotubes A and B with a dispersion medium using a wet jet mill to obtain a dispersion of the carbon nanotubes A and B, the obtained dispersion, and the metal And a solution of a precursor containing carbon to obtain a carbon nanotube composition on which a metal is adsorbed, and a heat treatment of the carbon nanotube composition in an inert gas containing hydrogen gas. be able to.
分散媒としては、水、アルコール（イソプロピルアルコールなど）、ＴＨＦ、アセトン、水−アルコール混液が使用できる。水、アルコール、水−アルコール混液が好ましく、水、水−アルコール混液がより好ましく、水がさらに好ましい。 As the dispersion medium, water, alcohol (such as isopropyl alcohol), THF, acetone, or a water-alcohol mixture can be used. Water, alcohol, and a water-alcohol mixture are preferable, water and a water-alcohol mixture are more preferable, and water is more preferable.
湿式ジェットミルとしては、株式会社常光製ナノジェットパル（登録商標）、アドバンストナノテクノロジー社製ナノメーカー、ナノマイザー株式会社製ナノマイザー（登録商標）、スギノマシン社製スターバースト（登録商標）、吉田工業株式会社製超高圧湿式微粒子化装置等が使用できる。
湿式ジェットミルでの混合の際の圧力は、好ましくは５０ＭＰｓ以上、より好ましくは７５ＭＰｓ以上、さらに好ましくは１００ＭＰｓ以上である。
As a wet jet mill, Nanojet Pal (registered trademark) manufactured by Joko, Nanomaker manufactured by Advanced Nanotechnology, Nanomizer (registered trademark) manufactured by Nanomizer, Starburst (registered trademark) manufactured by Sugino Machine, Yoshida Kogyo Co., Ltd. A company-made ultra-high pressure wet micronizer can be used.
The pressure during mixing in the wet jet mill is preferably 50 MPs or more, more preferably 75 MPs or more, and even more preferably 100 MPs or more.
金属を含む前駆体とは、前駆体に含まれる金属が所定の処理によりカーボンナノチューブに担持される化合物のことを示す。具体的には、塩化白金酸、塩化イリジウム、硝酸銀、塩化パラジウムなどが挙げられる。前記前駆体は、水素ガス、ヒドラジン、アルデヒド等を用いて還元され、金属となる。 The precursor containing a metal indicates a compound in which the metal contained in the precursor is supported on the carbon nanotubes by a predetermined treatment. Specific examples include chloroplatinic acid, iridium chloride, silver nitrate, and palladium chloride. The precursor is reduced to a metal by using hydrogen gas, hydrazine, aldehyde, or the like.
金属が担持されたカーボンナノチューブ組成物を水素ガス含有不活性ガス中で熱処理する際、熱処理温度は２００〜１０００℃の範囲が好ましく、２００〜９００℃の範囲がより好ましい。前記熱処理温度が前記範囲内であると、結晶性および均一性が良好な点で好ましい。
加熱時間は、０．１〜２０時間であることが好ましく、１〜１０時間であることがより好ましい。
不活性ガスとしては、コストの観点から、窒素ガスおよびアルゴンガスが好ましく、窒素ガスがより好ましい。
水素ガスの濃度範囲は、加熱時間および加熱温度に依存するが、０．０１〜４容量％であることが好ましく、０．１〜４容量％であることがより好ましい。
When the carbon nanotube composition carrying a metal is heat-treated in an inert gas containing hydrogen gas, the heat treatment temperature is preferably in the range of 200 to 1000 ° C, more preferably in the range of 200 to 900 ° C. When the heat treatment temperature is within the above range, it is preferable in terms of good crystallinity and uniformity.
The heating time is preferably 0.1 to 20 hours, and more preferably 1 to 10 hours.
As the inert gas, nitrogen gas and argon gas are preferable from the viewpoint of cost, and nitrogen gas is more preferable.
The concentration range of the hydrogen gas depends on the heating time and the heating temperature, but is preferably 0.01 to 4% by volume, and more preferably 0.1 to 4% by volume.
このようにして得られた本発明のカーボン材料は、医薬・医療・バイオ、大型輸送機分野、環境分野、電気・電子分野、スポーツ・レジャー、産業資材、触媒、摺動・潤滑材、磁性材料として好適に用いることができる。具体的には、Ｌｉ電池・Ｌｉ−空気電池・金属−空気電池・Ｒｅｄｏｘ Ｆｌｏｗ電池等の電極や、燃料電池触媒・光触媒等の触媒、電気二重層コンデンサ・固体コンデンサの電極材料、平面蛍光管・冷陰極管等の光学機器の陰極材料、タッチパネルや太陽電池等の透明電極の材料、水素吸蔵剤等に使用できる。
さらに、本発明のカーボン材料を電極基板上に含有させた電界放出ディスプレイ（Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ Ｄｉｓｐｌａｙ）、本発明の炭素材を複合材として用いたハイパービルディング・大型橋梁用ケーブル・自動車・航空機・宇宙船等も活用例として考えられる。
特に、本発明のカーボン材料は、燃料電池触媒として使用すると、高い触媒能を発揮する。
The carbon material of the present invention thus obtained includes pharmaceuticals / medicine / biotechnology, large transport aircraft field, environmental field, electrical / electronic field, sports / leisure, industrial material, catalyst, sliding / lubricant, magnetic material. Can be suitably used. Specifically, electrodes such as Li batteries, Li-air batteries, metal-air batteries, Redox Flow batteries, catalysts such as fuel cell catalysts and photocatalysts, electrode materials for electric double layer capacitors and solid capacitors, flat fluorescent tubes, It can be used for cathode materials for optical devices such as cold cathode tubes, transparent electrode materials such as touch panels and solar cells, and hydrogen storage agents.
Further, a field emission display including the carbon material of the present invention on an electrode substrate, a hyper building using the carbon material of the present invention as a composite material, a cable for a large bridge, an automobile, an aircraft, a spacecraft, etc. Is also considered as an example.
In particular, the carbon material of the present invention exhibits high catalytic ability when used as a fuel cell catalyst.
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited only to a following example.
＜実施例１＞
１．触媒の調製
カーボンナノチューブＡとしてＶＧＣＦ（登録商標）−Ｘ（数平均繊維径１５ｎｍ、０．２０ｇ）、カーボンナノチューブＢとしてＶＧＣＦ（登録商標）−Ｈ（数平均繊維径１５０ｎｍ、１．８０ｇ）を蒸留水１００ｍｌに加え、湿式ジェットミルを用いて分散させた。この時の圧力は１５０ＭＰｓで、１回２分の操作を６回繰り返した。
得られた分散液に蒸留水４００ｍｌを加え、超音波洗浄機により６０分間振とうさせた。この時、溶液は温水浴により８０℃に保温した。
次に、炭酸ナトリウム（０．１９１ｇ、１．８０ｍｍｏｌ）を加えた。
続いて、蒸留水１０ｍｌに塩化白金酸（Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ）２６６ｍｇ（０．５１３ｍｍｏｌ、白金量１００ｍｇ）を溶解させた溶液を予め調製し、３０分間かけてゆっくり滴下した。この時、溶液は温水浴により８０℃に保温した。滴下後、溶液を８０℃に保温したまま２時間撹拌した。
次にホルムアルデヒド水溶液（市販品：３７％、１０ｍｌ）をゆっくり加えた。加えた後、溶液を８０℃に保温したまま１時間撹拌した。撹拌後、室温まで冷却して濾過し、前駆体が吸着したカーボンナノチューブ組成物を３００℃、４％水素ガス含有窒素ガス気流下で２時間加熱することにより、１０質量％白金担持ＶＧＣＦ（触媒（１））を１．１ｇ得た。
<Example 1>
1. Preparation of catalyst Distilling VGCF (registered trademark) -X (number average fiber diameter 15 nm, 0.20 g) as carbon nanotube A and VGCF (registered trademark) -H (number average fiber diameter 150 nm, 1.80 g) as carbon nanotube B In addition to 100 ml of water, it was dispersed using a wet jet mill. The pressure at this time was 150 MPs, and the operation for 2 minutes was repeated 6 times.
400 ml of distilled water was added to the obtained dispersion and shaken for 60 minutes with an ultrasonic cleaner. At this time, the solution was kept at 80 ° C. by a warm water bath.
Next, sodium carbonate (0.191 g, 1.80 mmol) was added.
Subsequently, distilled water 10ml chloroplatinic acid (H 2 PtCl 6 · 6H 2 O) 266mg (0.513mmol, amount of platinum 100mg) was previously prepared a solution of a slowly added dropwise over 30 minutes. At this time, the solution was kept at 80 ° C. by a warm water bath. After the dropping, the solution was stirred for 2 hours while being kept at 80 ° C.
Next, an aqueous formaldehyde solution (commercial product: 37%, 10 ml) was slowly added. After the addition, the solution was stirred for 1 hour while being kept at 80 ° C. After stirring, the mixture was cooled to room temperature and filtered, and the carbon nanotube composition on which the precursor was adsorbed was heated at 300 ° C. under a nitrogen gas stream containing 4% hydrogen gas for 2 hours, whereby 10 mass% platinum-supported VGCF (catalyst ( 1.1 g of 1)) was obtained.
２．燃料電池用電極の製造
触媒（１）０．０３０ｇに、蒸留水９．５ｍｌ、５％ナフィオン（登録商標）０．５ｍｌを混合し、超音波洗浄機で撹拌、縣濁した。この混合物２０μｌをグラッシーカーボン電極（ＰＩＮＥ社製、径：５．０ｍｍ）に塗布し、自然乾燥し、燃料電池用電極（１）を得た。（Ｐｔ量：１５μg／ｃｍ２）
2. Production of Fuel Cell Electrode 0.030 g of catalyst (1) was mixed with 9.5 ml of distilled water and 0.5 ml of 5% Nafion (registered trademark), and stirred and suspended in an ultrasonic cleaner. 20 μl of this mixture was applied to a glassy carbon electrode (PINE, diameter: 5.0 mm) and air-dried to obtain a fuel cell electrode (1). (Pt amount: 15 μg / cm 2 )
３．酸素還元能の評価
以上のようにして作製した燃料電池用電極（１）の触媒能（酸素還元能）を以下の方法で評価した。
まず、作製した燃料電池用電極（１）を、酸素雰囲気で、０．５ｍｏｌ／ｄｍ３の硫酸溶液中、３０℃、５ｍＶ／秒の電位走査速度で分極し、回転数６００ｒｐｍ、走査電位範囲０．３−１．０５Ｖの範囲で測定を行った。その際、同濃度の硫酸溶液中での可逆水素電極を参照電極とした。
上記測定結果から、酸素雰囲気での０．９０Ｖでの電流密度で燃料電池用電極（１）の触媒能（酸素還元能）を評価した。
すなわち、酸素還元の電流密度が高いほど、燃料電池用電極（１）の触媒能（酸素還元能）が高いことを示す。
実施例１で作製した燃料電池用電極（１）は、酸素還元開始電位が０．９０Ｖでの電流密度は、０．３５４ｍＡ／ｃｍ２であることがわかった。また、白金量に対する電流量は、２３．６０Ａ／ｇであった。
3. Evaluation of oxygen reducing ability The catalytic ability (oxygen reducing ability) of the fuel cell electrode (1) produced as described above was evaluated by the following method.
First, the produced fuel cell electrode (1) was polarized in an oxygen atmosphere in a 0.5 mol / dm 3 sulfuric acid solution at 30 ° C. and a potential scanning speed of 5 mV / sec. Measurements were made in the range of .3-1.05V. At that time, a reversible hydrogen electrode in a sulfuric acid solution having the same concentration was used as a reference electrode.
From the above measurement results, the catalytic ability (oxygen reducing ability) of the fuel cell electrode (1) was evaluated at a current density of 0.90 V in an oxygen atmosphere.
That is, the higher the current density of oxygen reduction, the higher the catalytic ability (oxygen reducing ability) of the fuel cell electrode (1).
The fuel cell electrode (1) produced in Example 1 was found to have a current density of 0.354 mA / cm 2 when the oxygen reduction starting potential was 0.90 V. The amount of current relative to the amount of platinum was 23.60 A / g.
＜実施例２＞
１．触媒の調製
カーボンナノチューブＡを株式会社名城ナノカーボン製ＭＷＮＴ ＭＴＣ（繊維径１０−４０ｎｍ、０．２０ｇ）に変更した以外は実施例１と同様にして、１０質量％白金担持 ＶＧＣＦ（触媒（２））を１．１ｇ得た。
２．燃料電池用電極の製造
触媒（１）を触媒（２）０．０３１ｇとしたこと以外は実施例１と同様にして、燃料電池用電極（２）を得た。（Ｐｔ量：１５μg／ｃｍ２）
３．酸素還元能の評価
実施例１と同様に、燃料電池用電極（２）の触媒能（酸素還元能）を評価した。
燃料電池用電極（２）において、酸素還元開始電位が０．９０Ｖでの電流密度は、０．３４２ｍＡ／ｃｍ２であることがわかった。また、白金量に対する電流は、２２．８０Ａ／ｇであった。
<Example 2>
1. Catalyst preparation
Except for changing the carbon nanotube A to MWNT MTC (fiber diameter 10-40 nm, 0.20 g) manufactured by Meijo Nanocarbon Co., Ltd. 0.1 g was obtained.
2. Production of Fuel Cell Electrode A fuel cell electrode (2) was obtained in the same manner as in Example 1 except that the catalyst (1) was changed to 0.031 g of the catalyst (2). (Pt amount: 15 μg / cm 2 )
3. Evaluation of oxygen reduction ability In the same manner as in Example 1, the catalytic ability (oxygen reduction ability) of the fuel cell electrode (2) was evaluated.
In the fuel cell electrode (2), the current density at an oxygen reduction starting potential of 0.90 V was found to be 0.342 mA / cm 2 . Moreover, the electric current with respect to the amount of platinum was 22.80 A / g.
＜実施例３＞
１．触媒の調製
カーボンナノチューブＢを保土ヶ谷化学工業株式会社製のＣＴ−２５（平均繊維径：１５０ｎｍ、１．８０ｇ）に変更した以外は実施例１と同様にして、１０質量％白金担持 ＶＧＣＦ（触媒（３））を１．１ｇ得た。
２．燃料電池用電極の製造
触媒（１）を触媒（３）０．０３１ｇとしたこと以外は実施例１と同様にして、燃料電池用電極（３）を得た。（Ｐｔ量：１５μg／ｃｍ２）
３．酸素還元能の評価
実施例１と同様に、燃料電池用電極（３）の触媒能（酸素還元能）を評価した。
燃料電池用電極（３）において、酸素還元開始電位が０．９０Ｖでの電流密度は、０．３４４ｍＡ／ｃｍ２であることがわかった。また、白金量に対する電流は、２２．９５Ａ／ｇであった。
<Example 3>
1. Catalyst preparation
10 mass% platinum supported VGCF (catalyst (3)) in the same manner as in Example 1 except that the carbon nanotube B was changed to CT-25 (average fiber diameter: 150 nm, 1.80 g) manufactured by Hodogaya Chemical Co., Ltd. 1.1 g was obtained.
2. Production of Fuel Cell Electrode A fuel cell electrode (3) was obtained in the same manner as in Example 1 except that the catalyst (1) was changed to 0.031 g of the catalyst (3). (Pt amount: 15 μg / cm 2 )
3. Evaluation of oxygen reduction ability In the same manner as in Example 1, the catalytic ability (oxygen reduction ability) of the fuel cell electrode (3) was evaluated.
In the fuel cell electrode (3), it was found that the current density when the oxygen reduction starting potential was 0.90 V was 0.344 mA / cm 2 . Moreover, the electric current with respect to the amount of platinum was 22.95 A / g.
＜比較例１＞
１．触媒の調製
白金カーボン（田中貴金属製 ＴＥＣ１０Ｅ５０Ｅ、白金担持量：４６．７質量％）を触媒（４）とした。
２．燃料電池用電極の製造
触媒（１）を触媒（４）０．０３２ｇとしたこと以外は実施例１と同様にして、燃料電池用電極（４）を得た。（Ｐｔ量：３３μg／ｃｍ２）
３．酸素還元能の評価
実施例１と同様に、燃料電池用電極（４）の触媒能（酸素還元能）を評価した。
燃料電池用電極（４）において、酸素還元開始電位が０．９０Ｖでの電流密度は、０．６８０ｍＡ／ｃｍ２であることがわかった。また、白金量に対する電流は、２０．６２Ａ／ｇであった。
<Comparative Example 1>
1. Preparation of catalyst Platinum carbon (TEC10E50E made by Tanaka Kikinzoku, platinum loading: 46.7 mass%) was used as catalyst (4).
2. Production of Fuel Cell Electrode A fuel cell electrode (4) was obtained in the same manner as in Example 1 except that the catalyst (1) was changed to 0.032 g of the catalyst (4). (Pt amount: 33 μg / cm 2 )
3. Evaluation of oxygen reduction ability In the same manner as in Example 1, the catalytic ability (oxygen reduction ability) of the fuel cell electrode (4) was evaluated.
In the fuel cell electrode (4), it was found that the current density at an oxygen reduction starting potential of 0.90 V was 0.680 mA / cm 2 . Moreover, the electric current with respect to the amount of platinum was 20.62 A / g.
＜比較例２＞
１．触媒の調製
カーボンナノチューブＢを入れないで、カーボンナノチューブＡとしてＶＧＣＦ（登録商標）−Ｘ（数平均繊維径１５ｎｍ、２．００ｇ）のみにした以外は、実施例１と同様にして、１０質量％白金担持 ＶＧＣＦ（触媒（５））を１．０ｇ得た。
２．燃料電池用電極の製造
触媒（１）を触媒（５）０．０３１ｇとしたこと以外は実施例１と同様にして、燃料電池用電極（５）を得た。（Ｐｔ量：１５μg／ｃｍ２）
３．酸素還元能の評価
実施例１と同様に、燃料電池用電極（５）の触媒能（酸素還元能）を評価した。
燃料電池用電極（５）において、酸素還元開始電位が０．９０Ｖでの電流密度は、０．２５０ｍＡ／ｃｍ２であることがわかった。また、白金量に対する電流は、１６．６７Ａ／ｇであった。
<Comparative Example 2>
1. Catalyst preparation
10 mass% platinum-supported VGCF in the same manner as in Example 1 except that the carbon nanotube B was not used and the carbon nanotube A was only VGCF (registered trademark) -X (number average fiber diameter 15 nm, 2.00 g). 1.0 g of (catalyst (5)) was obtained.
2. Production of Fuel Cell Electrode A fuel cell electrode (5) was obtained in the same manner as in Example 1 except that the catalyst (1) was changed to 0.031 g of the catalyst (5). (Pt amount: 15 μg / cm 2 )
3. Evaluation of oxygen reduction ability In the same manner as in Example 1, the catalytic ability (oxygen reduction ability) of the fuel cell electrode (5) was evaluated.
In the fuel cell electrode (5), it was found that the current density at an oxygen reduction starting potential of 0.90 V was 0.250 mA / cm 2 . Moreover, the electric current with respect to the amount of platinum was 16.67 A / g.
表１に、実施例１〜３、比較例１〜２の各種条件および酸素還元能の評価結果をまとめて示す。表１より、実施例１〜３は比較例１〜２よりも酸素還元開始電位、白金量に対する電流量が高く、酸素還元能が高いことが確認された。 In Table 1, the various conditions of Examples 1-3 and Comparative Examples 1-2 and the evaluation result of oxygen reduction ability are shown collectively. From Table 1, it was confirmed that Examples 1 to 3 had higher oxygen reduction starting potential and higher current amount with respect to the platinum amount and higher oxygen reducing ability than Comparative Examples 1 and 2.
本発明のカーボン材料は、例えば燃料電池触媒として使用すると、高い触媒能を発揮する。 When used as a fuel cell catalyst, for example, the carbon material of the present invention exhibits high catalytic ability.
Claims (8)
数平均繊維径３０ｎｍ以下であるカーボンナノチューブＡと、
数平均繊維径１００ｎｍ以上であるカーボンナノチューブＢと、
を含み、
前記金属の一部または全てが前記カーボンナノチューブＡおよびカーボンナノチューブＢに担持されてなることを特徴とするカーボン材料。 Metal,
Carbon nanotubes A having a number average fiber diameter of 30 nm or less;
Carbon nanotubes B having a number average fiber diameter of 100 nm or more;
Including
A carbon material, wherein a part or all of the metal is supported on the carbon nanotubes A and B.
分散媒に、前記カーボンナノチューブＡおよびＢを湿式ジェットミルを用いて混合して前記カーボンナノチューブＡおよびＢの分散液を得る工程と、
得られた分散液と、前記金属を含む前駆体の溶液とを混合して、金属が吸着したカーボンナノチューブ組成物を得る工程と、
前記カーボンナノチューブ組成物を水素ガス含有不活性ガス中で熱処理する工程と、
を含むことを特徴とするカーボン材料の製造方法。 It is a manufacturing method of the carbon material in any one of Claims 1-6,
Mixing the carbon nanotubes A and B with a dispersion medium using a wet jet mill to obtain a dispersion of the carbon nanotubes A and B;
Mixing the obtained dispersion and the precursor solution containing the metal to obtain a carbon nanotube composition having the metal adsorbed thereon;
Heat treating the carbon nanotube composition in an inert gas containing hydrogen gas;
A method for producing a carbon material, comprising:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019212054A1 (en) * | 2018-05-02 | 2019-11-07 | 昭和電工株式会社 | Electrode sheet and manufacturing method thereof, and redox flow battery |
| WO2019212055A1 (en) * | 2018-05-02 | 2019-11-07 | 昭和電工株式会社 | Electrode sheet manufacturing method |
| CN114751399A (en) * | 2022-04-29 | 2022-07-15 | 北京航空航天大学 | Carbon nanotube confinement metal nanowire material and preparation method and application thereof |
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2014
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019212054A1 (en) * | 2018-05-02 | 2019-11-07 | 昭和電工株式会社 | Electrode sheet and manufacturing method thereof, and redox flow battery |
| WO2019212055A1 (en) * | 2018-05-02 | 2019-11-07 | 昭和電工株式会社 | Electrode sheet manufacturing method |
| CN114751399A (en) * | 2022-04-29 | 2022-07-15 | 北京航空航天大学 | Carbon nanotube confinement metal nanowire material and preparation method and application thereof |
| CN114751399B (en) * | 2022-04-29 | 2024-04-09 | 北京航空航天大学 | Carbon nanotube domain-limited metal nanowire material, and preparation method and application thereof |
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