JP5182776B2 - Graphite intercalation compound and catalyst using modified graphite, and production method thereof - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 155
- 229910002804 graphite Inorganic materials 0.000 title claims description 100
- 239000010439 graphite Substances 0.000 title claims description 100
- 150000001875 compounds Chemical class 0.000 title claims description 53
- 238000009830 intercalation Methods 0.000 title claims description 53
- 230000002687 intercalation Effects 0.000 title claims description 50
- 239000003054 catalyst Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 24
- 238000010298 pulverizing process Methods 0.000 claims description 21
- 238000006722 reduction reaction Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 238000001237 Raman spectrum Methods 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- 229910001510 metal chloride Inorganic materials 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000001069 Raman spectroscopy Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 35
- 229910052697 platinum Inorganic materials 0.000 description 24
- 239000000463 material Substances 0.000 description 21
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- 239000003990 capacitor Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910021382 natural graphite Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000007770 graphite material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- -1 surface and the like Chemical compound 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
Description
本発明は黒鉛の結晶性を維持し、比表面積が大きい表面改質黒鉛およびその改質黒鉛を用いる黒鉛層間化合物に関する。より詳細には、燃料電池用触媒やキャパシタやリチウムイオン電池等の電池材料などに広く応用される表面構造を制御した改質黒鉛を用いる層間化合物および触媒に関する。 The present invention relates to surface-modified graphite that maintains the crystallinity of graphite and has a large specific surface area, and a graphite intercalation compound that uses the modified graphite. More specifically, the present invention relates to an intercalation compound and catalyst using a modified graphite having a controlled surface structure widely applied to fuel cell catalysts, battery materials such as capacitors and lithium ion batteries.
環境問題、省エネルギー対策などの推進により、燃料電池車や電気自動車、ハイブリッド自動車に搭載されるクリーンな電池技術の開発が加速されており、燃料電池においてはコスト低減策の中で、白金坦持量の少ない白金系触媒の開発が急務となっている。また、リチウムイオン電池においては高容量、高出力な材料が望まれ、キャパシターについてはさらなるエネルギー密度の向上が望まれている。 The development of clean battery technology installed in fuel cell vehicles, electric vehicles, and hybrid vehicles has been accelerated through the promotion of environmental issues and energy conservation measures. There is an urgent need to develop a platinum-based catalyst with a low content. In addition, high capacity and high output materials are desired for lithium ion batteries, and further improvement in energy density is desired for capacitors.
燃料電池用触媒としては、一般にＶｕｌｃａｎ（登録商標）ＸＣ−７２などのカーボンブラックに白金やルテニウム等を担持した材料が使用されているが、白金量の削減、また発電時の触媒劣化などが問題になっている。発電時における白金粒子の凝集による反応効率の低下は、重要な課題であり、最近の研究においては黒鉛層間化合物（ＧＩＣ）に白金を担持させるなどの試みが進められている。しかし、黒鉛層間化合物を形成する黒鉛は、粒径が大きく且つ比表面積が小さいために反応効率が劣る点で問題である。 As fuel cell catalysts, materials such as Vulcan (registered trademark) XC-72, which are supported by platinum or ruthenium on carbon black, are generally used. However, there are problems such as reduction of platinum amount and catalyst deterioration during power generation. It has become. Reduction of reaction efficiency due to aggregation of platinum particles during power generation is an important issue. In recent research, attempts such as supporting platinum on a graphite intercalation compound (GIC) have been advanced. However, graphite forming a graphite intercalation compound has a problem in that the reaction efficiency is inferior because the particle size is large and the specific surface area is small.
リチウムイオン電池については、高容量化、高出力化の改良が進められており、結晶性のよい黒鉛材料の使用においては、高容量化への対応は可能であるが、高出力の点で劣り課題が多い。また、黒鉛化度が低い難黒鉛化カーボンであるハードカーボンを使用した場合は、高出力が得られるが、高容量の電池には適応が難しい点で問題である。 Lithium-ion batteries are being improved for higher capacity and higher output, and the use of graphite materials with good crystallinity can cope with higher capacity, but they are inferior in terms of high output. There are many challenges. In addition, when hard carbon, which is non-graphitizable carbon having a low graphitization degree, is used, high output can be obtained, but it is problematic in that it is difficult to adapt to high capacity batteries.
また、キャパシタ材料としては炭素材表面に多くの電気二重層を形成できる比表面積の大きい活性炭が用いられているが、更なる高容量化のためには、炭素表面に多くの電気二重層を形成でき、さらにリチウムイオンがインターカレーションする炭素材料の開発が進められている。また、電池材料に用いられる導電助剤としてカーボンブラックが用いられているが、電池の内部抵抗を下げるために、更なる低抵抗化材料が望まれている。 In addition, as the capacitor material, activated carbon with a large specific surface area that can form many electric double layers on the carbon material surface is used, but in order to further increase the capacity, many electric double layers are formed on the carbon surface. Carbon materials that can intercalate lithium ions are being developed. In addition, carbon black is used as a conductive additive used for battery materials, but in order to lower the internal resistance of the battery, a further low resistance material is desired.
また、粉砕雰囲気と粉砕機を変えた天然黒鉛の粉砕に関する報告があり、例えば、アルゴン雰囲気中、窒素雰囲気中又は空気雰囲気中における、遊星ボールミルまたは振動ミルを使用した天然黒鉛の粉砕では、天然黒鉛の比表面積と結晶子の大きさＬｃとの間には一定の相関があるために、結晶子の大きさを維持しつつ、且つ比表面積を増大させることは困難であると報告されている（非特許文献１参照）。 In addition, there are reports on the pulverization of natural graphite with different pulverization atmosphere and pulverizer. For example, in the pulverization of natural graphite using a planetary ball mill or vibration mill in an argon atmosphere, a nitrogen atmosphere or an air atmosphere, It is reported that there is a certain correlation between the specific surface area and the crystallite size Lc, and it is difficult to increase the specific surface area while maintaining the crystallite size ( Non-patent document 1).
また、黒鉛層間化合物は、黒鉛の層間にゲスト剤（インターカラント）として原子や分子が挿入された化合物であり、その物理的性質や化学的性質はゲスト剤の種類や挿入量によって異なり、さまざまな機能性材料として注目されている。従来から白金やパラジウムなどは触媒材料として非常に有用であることが知られており、これらの物質をゲスト剤として合成された黒鉛層間化合物は更なる高機能化が期待できる（非特許文献２、３参照）。一般に黒鉛層間化合物の合成条件の１つにホストとなる黒鉛の結晶性が高いことが挙げられる。最近では天然黒鉛の結晶性が高いほど、つまり結晶子の大きさが大きいほど、生成された黒鉛層間化合物は構造の明確なものが得られることがＫ−ＧＩＣの合成などの例で報告されている（非特許文献４参照）。一方、従来の黒鉛やカーボンを用いた担持触媒では担体の比表面積の大きい方が触媒機能が発現され易い傾向がある。ところが、従来の一般的な粉砕法で比表面積の大きな黒鉛粒子を生成しようとすると，比表面積の増加に伴い黒鉛結晶そのものが破壊されてアモルファス化するために、本発明の目的とするような比表面積の大きな結晶性の黒鉛は得られていない。 A graphite intercalation compound is a compound in which atoms and molecules are inserted as a guest agent (intercalant) between graphite layers, and its physical and chemical properties vary depending on the type and insertion amount of the guest agent, It is attracting attention as a functional material. Conventionally, platinum and palladium are known to be very useful as catalyst materials, and graphite intercalation compounds synthesized using these substances as guest agents can be expected to have higher functionality (Non-Patent Document 2, 3). In general, one of the synthesis conditions for a graphite intercalation compound is that the crystallinity of graphite as a host is high. Recently, it has been reported in examples such as the synthesis of K-GIC that the higher the crystallinity of natural graphite, that is, the larger the crystallite size, the clearer the structure of the generated graphite intercalation compound. (See Non-Patent Document 4). On the other hand, in the conventional supported catalyst using graphite or carbon, the larger the specific surface area of the carrier, the more easily the catalytic function tends to be expressed. However, when graphite particles having a large specific surface area are generated by a conventional general pulverization method, the graphite crystal itself is destroyed and becomes amorphous as the specific surface area increases. Crystalline graphite with a large surface area has not been obtained.
また、特許文献１には、電極活物質材料に加圧力とせん断力を加えて粒子を複合化してＢＥＴ比表面積を低下せしめるリチウムイオン電池の電極材料の製造方法が開示されている。しかし、この発明に係る電極材料の場合は、容積密度・体積エネルギー密度が高まり、電極の吸水性を低下させてサイクル劣化を抑制する点では優れているが、ＢＥＴ比表面積が減少する結果、リチウムイオンの移動を容易にして出力特性を改善することは困難である。 Patent Document 1 discloses a method for producing an electrode material for a lithium ion battery, in which a pressure and shear force are applied to an electrode active material to form a composite of particles to reduce the BET specific surface area. However, in the case of the electrode material according to the present invention, the volume density / volume energy density is increased, and it is excellent in terms of suppressing cycle deterioration by lowering the water absorption of the electrode. It is difficult to improve the output characteristics by facilitating ion movement.
黒鉛を燃料電池用触媒の担持体に使用する場合は、カーボンブラックを使用するより酸化、還元に対する安定性で優れているが、比表面積が小さく白金などの分散性が悪く、また、ガスの拡散も悪いため反応効率が低い点で問題があった。また、黒鉛材料をリチウムイオン電池用負極材料に用いる場合には、黒鉛の結晶性を重視する限り、層間距離は黒鉛固有の３．３５Åから変化できず、すなわち、リチウムイオンの移動を容易にするように結晶構造を制御することが困難なために、出力特性を大幅に改善することは困難であった。 When graphite is used as a carrier for a fuel cell catalyst, it has better stability against oxidation and reduction than carbon black, but it has a small specific surface area and poor dispersibility such as platinum, and gas diffusion. However, there was a problem in that the reaction efficiency was low. In addition, when the graphite material is used for the negative electrode material for a lithium ion battery, as long as the crystallinity of graphite is emphasized, the interlayer distance cannot be changed from 3.35 mm inherent to graphite, that is, it facilitates the movement of lithium ions. Thus, since it is difficult to control the crystal structure, it has been difficult to significantly improve the output characteristics.
また、キャパシタを高容量化するために、材料表面に多くの電気二重層を形成して、さらにリチウムイオンがインターカレーションする炭素材料の開発が進められているが、前述のとおり、黒鉛材料を用いた場合、結晶構造を維持して比表面積を大きくすることができないと言う課題があった。電池用の導電助剤としては、電解液の保持性がよいことが重要であり、大きな比表面積が必要である。さらに、抵抗値の低い炭素材料の開発が望まれている。そこで、本発明は、前記の問題を解決するため、従来の黒鉛の結晶性のよい構造を維持した状態で、黒鉛表面のアモルファス化を進めた材料、即ち比表面積を増加させた材料を提供し、更に、前記材料を用いた層間化合物、触媒及びそれらの製造方法を提供することを目的とする。 In addition, in order to increase the capacity of capacitors, carbon materials in which many electric double layers are formed on the material surface and lithium ions are intercalated are being developed. When used, there is a problem that the specific surface area cannot be increased while maintaining the crystal structure. As a conductive additive for batteries, it is important that the electrolyte retainability is good, and a large specific surface area is required. Furthermore, development of a carbon material having a low resistance value is desired. In order to solve the above problems, the present invention provides a material in which the graphite surface has been amorphized, that is, a material having an increased specific surface area, while maintaining the crystallinity structure of conventional graphite. Furthermore, it aims at providing the intercalation compound using the said material, a catalyst, and those manufacturing methods.
本発明は、上記した課題を解決するために、本発明者等は、第一に、白金粒子が比表面積の高い黒鉛表面に均一に固着する黒鉛構造は如何にあるべきか、また黒鉛系白金触媒を反応に用いた後に白金粒子の凝集の少ない黒鉛構造は如何にあるべきか、第二に、高出力、エネルギー密度の高い黒鉛材料とは如何にあるべきかの点で鋭意研究を重ねた結果、結晶性のよい黒鉛粒子の表面を比表面積の高い黒鉛構造に改質することによって前述の問題が解決できるとの結論に達し、本発明に至った。 In order to solve the above-mentioned problems, the present inventors firstly clarified how a graphite structure in which platinum particles are uniformly fixed to a graphite surface having a high specific surface area should be present. We have earnestly studied how the graphite structure should have little aggregation of platinum particles after the catalyst is used in the reaction, and secondly, what should be the graphite material with high power and high energy density. As a result, it was concluded that the above-mentioned problems can be solved by modifying the surface of graphite particles having good crystallinity to a graphite structure having a high specific surface area, and the present invention has been achieved.
前記の課題を解決するために、本発明は、比表面積が２００〜１０００ｍ２／g 、ラマンスペクトルのＤバンド（１３５０ｃｍ−１）とＧバンド（１５８０ｃｍ−１）のピーク強度比であるＲ値（Ｄ／Ｇ）が０．３〜０．７、およびＸ線回折法の（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上である改質黒鉛（比表面積が２２０ｃｍ ２ ／ｇ、Ｒ値（Ｄ／Ｇ）が０．５０及びＬｃ（００２）が６０ｎｍである黒鉛を除く）に金属塩化物がインターカレートされてなることを特徴とする黒鉛層間化合物とする（請求項１）。 In order to solve the above-mentioned problems, the present invention has a specific surface area of 200 to 1000 m 2 / g, an R value which is a peak intensity ratio of a D band (1350 cm −1 ) and a G band (1580 cm −1 ) of a Raman spectrum ( D / G) of 0.3 to 0.7, and modified graphite having a crystallite size Lc (002) in the c-axis direction of the (002) plane of X-ray diffraction method of 30 nm or more (specific surface area is 220 cm) 2 / g, R value (D / G) is 0.50, and Lc (002) is excluding graphite having a thickness of 60 nm). Claim 1).
また、前記の課題を解決するために、本発明は、Ｘ線回折法による回折角度（２θ）が２１〜２３．５°にピークを発現することを特徴とする前記の黒鉛層間化合物とすることが好ましい（請求項２）。 In order to solve the above-mentioned problems, the present invention provides the above-mentioned graphite intercalation compound characterized in that the diffraction angle (2θ) by X-ray diffraction method exhibits a peak at 21 to 23.5 °. (Claim 2).
また、前記の課題を解決するために、本発明は、Ｘ線回折法による回折角度（２θ）が５〜７°にピークを発現することを特徴とする前記の黒鉛層間化合物とすることが好ましい（請求項３）。 In order to solve the above-mentioned problems, the present invention is preferably the graphite intercalation compound described above, wherein the diffraction angle (2θ) by X-ray diffraction method exhibits a peak at 5 to 7 °. (Claim 3).
また、前記の課題を解決するために、本発明は、ラマン分光スペクトルのピークが１６００〜１６１０ｃｍ−１に発現することを特徴とする前記の黒鉛層間化合物とすることが好ましい（請求項４）。 In order to solve the above-mentioned problems, the present invention is preferably the graphite intercalation compound characterized in that the peak of the Raman spectrum is expressed at 1600 to 1610 cm −1 (Claim 4).
また、前記の課題を解決するために、本発明は、比表面積が２００〜１０００ｍ２／g 、ラマンスペクトルのＤバンド（１３５０ｃｍ−１）とＧバンド（１５８０ｃｍ−１）のピーク強度比であるＲ値（Ｄ／Ｇ）が０．３〜０．７、およびＸ線回折法の（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上である改質黒鉛（比表面積が２２０ｃｍ２／ｇ、Ｒ値（Ｄ／Ｇ）が０．５０及びＬｃ（００２）が６０ｎｍである黒鉛を除く）の表面に触媒機能を備える金属が坦持されなることを特徴とする燃料電池用触媒とする（請求項５）。 In order to solve the above problems, the present invention has a specific surface area of 200 to 1000 m 2 / g, and a peak intensity ratio of a D band (1350 cm −1 ) and a G band (1580 cm −1 ) of a Raman spectrum. Modified graphite (specific surface area) having a value (D / G) of 0.3 to 0.7 and a crystallite size Lc (002) in the c-axis direction of the (002) plane of the X-ray diffraction method of 30 nm or more There 220 cm 2 / g, the fuel cell, wherein a metal having a catalytic function on the surface of the R value (D / G) excluding graphite 0.50 and Lc (002) is 60 nm) is being carrying and use the catalyst (claim 5).
また、前記の課題を解決するために、本発明は、少なくとも真空雰囲気中、低酸素雰囲気中、減圧雰囲気中、窒素雰囲気中又は希ガス元素雰囲気中において、５ｍｍφ以下の小質量粉砕媒体を用いて、乾式粉砕法により高結晶性粒子を含む黒鉛を粉砕してなる改質黒鉛を用いることを特徴とする前記の黒鉛層間化合物の製造方法とすることが好ましい（請求項６）。 In order to solve the above-described problems, the present invention uses a small-size grinding medium of 5 mmφ or less in at least a vacuum atmosphere, a low oxygen atmosphere, a reduced pressure atmosphere, a nitrogen atmosphere, or a rare gas element atmosphere. Preferably, the method for producing a graphite intercalation compound is characterized by using modified graphite obtained by pulverizing graphite containing highly crystalline particles by a dry pulverization method (Claim 6).
また、前記の課題を解決するために、本発明は、前記改質黒鉛と金属塩化物を混合し、気相法または溶媒法により調整することを特徴とする前記何れかに記載の黒鉛層間化合物の製造方法とすることが好ましい（請求項７）。 In order to solve the above-mentioned problem, the present invention provides the graphite intercalation compound according to any one of the above, wherein the modified graphite and metal chloride are mixed and adjusted by a gas phase method or a solvent method. Preferably, the production method is as follows.
また、前記の課題を解決するために、本発明は、前記何れかに記載の黒鉛層間化合物であって、触媒機能を備える金属からなる金属塩化物がインターカレートされた黒鉛層間化合物を用い、焼成による還元または化学的な還元により前記金属を黒鉛層間に析出させるとともに該金属を黒鉛エッジ部分または黒鉛表面に固着した状態で坦持させることを特徴とする燃料電池用触媒の製造方法とすることが好ましい（請求項８）。 In order to solve the above-mentioned problem, the present invention uses any of the graphite intercalation compounds according to any one of the above, wherein the metal chloride comprising a metal having a catalytic function is intercalated. A method for producing a catalyst for a fuel cell , characterized in that the metal is deposited between graphite layers by reduction by calcination or chemical reduction, and the metal is supported while being fixed to a graphite edge portion or a graphite surface. (Claim 8).
本発明の改質黒鉛は、前記のように黒鉛の結晶性を維持しつつ、なお比表面積が大きいことを特徴とし、かかる改質黒鉛に金属塩化物がインターカレートして特有の物性を備えた黒鉛層間化合物が形成される。この黒鉛層間化合物を還元して得られる白金系黒鉛触媒を例えば燃料電池用触媒として用いる場合は、従来の白金系黒鉛触媒と違って、白金粒子が改質黒鉛表面へ均一に固着しているので、白金粒子の凝集による触媒劣化が極力抑制される結果、発電時の反応効率の低下を防ぎ、電池の寿命を延ばすばかりでなく、白金の使用量を削減する効果に優れる。また、リチウムイオン電池用負極材料に用いる場合は、高出力で且つ高容量の電池が得られる効果がある。キャパシタ材料として用いる場合は、比表面積が大きいのでより多くの電気二重層が形成され、より高容量のキャパシタが得られる効果がある。更に、本発明の改質黒鉛は、高比表面積で大きな結晶子を備えることから、電気抵抗値が低く電池の内部抵抗を下げる効果を奏し、低抵抗電気材料としての利用価値が高い。 The modified graphite of the present invention is characterized in that the specific surface area is still large while maintaining the crystallinity of the graphite as described above, and the modified graphite has specific physical properties by intercalating metal chloride. A graphite intercalation compound is formed. When using a platinum-based graphite catalyst obtained by reducing this graphite intercalation compound as a catalyst for a fuel cell, for example, unlike conventional platinum-based graphite catalysts, platinum particles are uniformly fixed on the surface of the modified graphite. As a result, catalyst deterioration due to the aggregation of platinum particles is suppressed as much as possible. As a result, the reaction efficiency during power generation is prevented from being lowered, and not only the battery life is extended, but also the effect of reducing the amount of platinum used is excellent. Moreover, when it uses for the negative electrode material for lithium ion batteries, there exists an effect of obtaining a high output and a high capacity | capacitance battery. When used as a capacitor material, since the specific surface area is large, more electric double layers are formed, and there is an effect that a capacitor having a higher capacity can be obtained. Furthermore, since the modified graphite of the present invention has a large specific surface area and large crystallites, it has an effect of reducing the internal resistance of the battery with a low electrical resistance value, and is highly useful as a low-resistance electrical material.
本発明を実施するための最良の形態について、以下に詳細に説明する。
本発明に係る改質黒鉛は、黒鉛粒子表面が高比表面積からなる黒鉛構造に改質された結果、比表面積が２００〜１０００ｍ２／g 、ラマンスペクトルのＤバンド（１３５０ｃｍ−１）とＧバンド（１５８０ｃｍ−１）のピーク強度比であるＲ値が０．３〜０．７、およびＸ線回折法の（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上であることを特徴とする。
The best mode for carrying out the present invention will be described in detail below.
The modified graphite according to the present invention has a specific surface area of 200 to 1000 m 2 / g, a Raman spectrum D band (1350 cm −1 ), and a G band, as a result of modification of the graphite particle surface to a graphite structure having a high specific surface area. The R value which is the peak intensity ratio of (1580 cm −1 ) is 0.3 to 0.7, and the crystallite size Lc (002) in the c-axis direction of the (002) plane of the X-ray diffraction method is 30 nm or more. It is characterized by being.
本発明に係る改質黒鉛について更に具体的に説明する。Ｘ線回折法の（００２）面の結晶子の大きさが３０ｎｍ以上の黒鉛は、黒鉛層間化合物を形成し易く、電池材料や触媒材料が調整しやすい特徴がある。また、黒鉛の構造表面因子としてラマン分光で測定した１３５０ｃｍ−１のＤバンドと１５８０ｃｍ−１のＧバンドのピーク強度比であるＲ値（黒鉛化度と黒鉛表面のエッジ比率を反映している）の高い材料は、黒鉛化度の低下と黒鉛ベーサル面に対するエッジ面の比率が増加することが報告されている（炭素材料学会編：「最新の炭素材料実験技術（分析・解析編）」、サイベック、（2001）89-99参照）。 The modified graphite according to the present invention will be described more specifically. Graphite whose crystallite size on the (002) plane of the X-ray diffraction method is 30 nm or more is easy to form a graphite intercalation compound, and has characteristics that battery materials and catalyst materials are easy to adjust. In addition, R value is the peak intensity ratio of G-band of the D band and 1580 cm -1 in 1350 cm -1 measured by Raman spectroscopy as a structural surface element of the graphite (reflecting the edge ratio of graphitization degree and graphite surface) Higher material has been reported to have a lower graphitization degree and an increased ratio of edge surface to graphite basal surface (Carbon Society of Japan: “Latest Carbon Materials Experiment Technology (Analysis and Analysis)”), CYBEC , (2001) 89-99).
本発明の黒鉛構造は、Ｒ値が０．３以上で、黒鉛表面の黒鉛エッジ面の比率が増加し、表面の結晶性が低下している。即ち、黒鉛のバルクの結晶構造と表面の結晶構造に違いがあることを示す。一方、ラマンスペクトルのＲ値が０．７以上では結晶子が小さくなり、黒鉛の結晶性がほぼ消失しアモルファス化することから、Ｒ値は０．３〜０．７が好ましい。従来の粉砕方法で得られる黒鉛の中で、Ｘ線回折法の（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上ある黒鉛材料においては、比表面積が５０ｍ２／ｇ以下となり、高比表面積な材料は得られなかった。 In the graphite structure of the present invention, the R value is 0.3 or more, the ratio of the graphite edge surface of the graphite surface is increased, and the crystallinity of the surface is decreased. That is, there is a difference between the bulk crystal structure of graphite and the crystal structure of the surface. On the other hand, when the R value of the Raman spectrum is 0.7 or more, the crystallite becomes small and the crystallinity of graphite is almost lost and becomes amorphous. Therefore, the R value is preferably 0.3 to 0.7. Among graphites obtained by a conventional pulverization method, a graphite material having a crystallite size Lc (002) in the c-axis direction of the (002) plane of the X-ray diffraction method of 30 nm or more has a specific surface area of 50 m 2 / g or less, and a material having a high specific surface area could not be obtained.
本発明に係る粉砕方法で得られる改質黒鉛においてはＸ線回折法の（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上で、結晶性のよい黒鉛状態を保ちながら、表面構造因子であるラマンスペクトルのＲ値が０．３以上に変化し、また高比表面積を有しており、表面を改質した黒鉛材料として従来の黒鉛にはない特有の材料である。さらに、高比表面積にもかかわらず、大きな結晶子を維持しているため、電気抵抗値が低いことも特徴の１つである。 In the modified graphite obtained by the pulverization method according to the present invention, the crystallite size Lc (002) in the c-axis direction of the (002) plane of the X-ray diffraction method is 30 nm or more, and the graphite state with good crystallinity is maintained. However, the R value of the Raman spectrum, which is a surface structure factor, is changed to 0.3 or more, and has a high specific surface area, which is a unique material that is not present in conventional graphite as a graphite material with a modified surface. . Furthermore, since the large crystallite is maintained despite the high specific surface area, one of the characteristics is that the electric resistance value is low.
次に、本発明に係る改質黒鉛を得る製造方法の一例について説明する。４ｍｍφ以下、好ましくは２ｍｍφ以下、特に好ましくは１ｍｍφ以下のビーズ系粉砕媒体を用い、真空雰囲気中で乾式粉砕により黒鉛を粉砕することによって、良好な改質黒鉛が得られることを見出した。つまり、真空雰囲気中では、粉砕媒体と黒鉛粒子間の摩擦係数が大きくなり、１ｍｍφ以下の小さな粉砕媒体での粉砕においては、黒鉛表面から粉砕が進行し、結晶性の発達した黒鉛表面だけが選択的に改質される。 Next, an example of a production method for obtaining the modified graphite according to the present invention will be described. It has been found that good modified graphite can be obtained by pulverizing graphite by dry pulverization in a vacuum atmosphere using a bead-based pulverization medium of 4 mmφ or less, preferably 2 mmφ or less, particularly preferably 1 mmφ or less. In other words, in a vacuum atmosphere, the friction coefficient between the grinding medium and the graphite particles increases, and in grinding with a small grinding medium of 1 mmφ or less, grinding proceeds from the graphite surface, and only the graphite surface with improved crystallinity is selected. Modified.
すなわち、ビーズ径が小さな質量の小さい粉砕媒体を用い、粉砕媒体と黒鉛粒子間の摩擦係数の大きな真空雰囲気中などで粉砕を行うと、黒鉛の微細化が進行し難いために、黒鉛の結晶性の低下が少なく、黒鉛表面においては剥離や衝撃による変形が優先的に進行する結果、黒鉛粒子の比表面積が高く且つ結晶性の高い黒鉛構造に改質されるものと推測される。真空雰囲気中以外に、減圧下又は低酸素雰囲気中において、或いは窒素ガス雰囲気中又はアルゴン、ヘリウム、ネオン、クリプトン、キセノン、ラドン等の希ガス元素雰囲気中でもよい。また、前記真空雰囲気中、窒素ガス雰囲気中又は希ガス元素雰囲気中等以外の条件において得られる本発明に係る改質黒鉛、その改質黒鉛を用いる触媒並びにその製造方法は本願発明に含まれる。 In other words, using a pulverizing medium with a small bead diameter and a small mass, and pulverizing in a vacuum atmosphere where the friction coefficient between the pulverizing medium and the graphite particles is large, it is difficult to refine the graphite. It is presumed that the graphite surface is reformed into a graphite structure having a high specific surface area and high crystallinity as a result of preferential progress of deformation due to peeling or impact on the graphite surface. In addition to the vacuum atmosphere, it may be in a reduced pressure or low oxygen atmosphere, or in a nitrogen gas atmosphere or in a rare gas element atmosphere such as argon, helium, neon, krypton, xenon, or radon. Further, the modified graphite according to the present invention obtained under conditions other than the vacuum atmosphere, the nitrogen gas atmosphere or the rare gas element atmosphere, the catalyst using the modified graphite, and the production method thereof are included in the present invention.
反応容器中で改質黒鉛粉末とＰｔＣｌ４（塩化白金 Platinum chloride ）を混合し、塩素ガス雰囲気下（圧力０．３ＭＰａ）、約４５０℃で熱処理して、ＰｔＣｌ４−ＧＩＣが合成される（気相法）。また、アルゴン雰囲気中で塩化白金酸Ｈ２ＰｔＣｌ６・６Ｈ２Ｏと改質黒鉛を混合し、塩化チオニルＳＯＣｌ２を溶媒として８０℃で７時間還流することによっても調整される（溶媒法）。このようにして、改質黒鉛を用いた黒鉛層間化合物は、気相法、溶媒法の何れによっても調整できる。 In the reaction vessel, the modified graphite powder and PtCl 4 (platinum chloride) are mixed and heat-treated at about 450 ° C. in a chlorine gas atmosphere (pressure 0.3 MPa) to synthesize PtCl 4 -GIC (gas). Phase law). Further, by mixing chloroplatinic acid H 2 PtCl 6 · 6H 2 O and the reforming graphite in an argon atmosphere, is also adjusted by thionyl chloride SOCl 2 and refluxed for 7 hours at 80 ° C. as a solvent (solvent method). Thus, the graphite intercalation compound using the modified graphite can be adjusted by either the gas phase method or the solvent method.
また、水素雰囲気中での還元焼成や、ヒドラジンへの浸漬による化学的な還元により黒鉛層間から白金が容易に析出し触媒が調整できる。層間より析出した白金粒子は、黒鉛エッジ部分と強く固着して存在する部分と、黒鉛表面のナノ構造からなる構造内に析出して分散している部分に大きく分けられるが、白金粒子はともに黒鉛表面と強く固着しているので、従来の黒鉛に坦持した白金系触媒の欠点であった反応後における白金粒子が凝集する現象が抑制される。 Moreover, platinum can be easily deposited from the graphite layer by reduction firing in a hydrogen atmosphere or chemical reduction by immersion in hydrazine, and the catalyst can be adjusted. The platinum particles deposited from the interlayer are broadly divided into a portion that is firmly fixed to the graphite edge portion and a portion that is precipitated and dispersed in the nanostructure on the graphite surface. Since it is firmly fixed to the surface, the phenomenon of aggregation of platinum particles after the reaction, which was a drawback of the conventional platinum catalyst supported on graphite, is suppressed.
また、本発明を実施するための最良の形態には、白金又はその化合物をゲストとしてインターカレーションする例について説明したが、本発明は、これらに限定されるものではなく、例えばハロゲン化物、アルカリ金属、遷移金属、希土類金属やその化合物等を改質黒鉛にゲストとしてインターカレーションする黒鉛層間化合物とその触媒、更に、黒鉛層間化合物に代えて、改質黒鉛のそれぞれ異なった層間に複数の前記挿入物質（インターカラント）を周期的にインターカレーションする黒鉛複層層間化合物（ＧＢＣ）とその触媒及びその製造方法も本発明に含まれる。 In the best mode for carrying out the present invention, an example in which platinum or a compound thereof is intercalated as a guest has been described. However, the present invention is not limited to these examples. A graphite intercalation compound that intercalates a metal, transition metal, rare earth metal or a compound thereof as a guest with a modified graphite and its catalyst, and, in place of the graphite intercalation compound, a plurality of the above-mentioned A graphite multilayer intercalation compound (GBC) that periodically intercalates an intercalating substance (intercalant), its catalyst, and its production method are also included in the present invention.
以下に実施例を挙げて本発明を詳細に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。
〈改質黒鉛の調整方法１〉
粉砕原料粉として鱗片状天然黒鉛（粒径１６μｍ）３３ｇを容積４５０ｃｍ３のスチール製ポットに仕込み、振動ボールミル（ＳＵＳ製ボール４．５ｍｍφまたは１ｍｍφ、振動振幅５ｍｍ、振動数１２００Ｈｚ）で粉砕した。粉砕の条件は、１０−３Ｔｏｒｒの真空雰囲気中で、粉砕時間０．５〜９６時間の範囲とした。さらに、粉砕生成物の一部は、窒素雰囲気中で１５００℃の温度で１時間、焼成処理を行った。
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
<Method 1 for preparing modified graphite>
As a pulverized raw material powder, 33 g of scaly natural graphite (particle size 16 μm) was charged into a steel pot having a volume of 450 cm 3 and pulverized with a vibration ball mill (SUS ball 4.5 mmφ or 1 mmφ, vibration amplitude 5 mm, vibration frequency 1200 Hz). The pulverization conditions were in the range of 0.5 to 96 hours in a vacuum atmosphere of 10 −3 Torr. Furthermore, a part of the pulverized product was baked at a temperature of 1500 ° C. for 1 hour in a nitrogen atmosphere.
〈改質黒鉛の調整方法２〉
粉砕原料粉として鱗片状天然黒鉛（粒径１６μｍ）３０ｇを容積４５０ｃｍ３のスチール製ポットに仕込み、遊星ボールミル（ジルコニア製ボール４ｍｍφから０．２ｍｍφ、自転４００ｒｐｍ、公転４００ｒｐｍ）で粉砕した。粉砕の条件は、１０−３Ｔｏｒｒの真空雰囲気中で、粉砕時間０．５〜２４時間の範囲とした。
<Method 2 for adjusting modified graphite>
As a pulverized raw material powder, 30 g of scaly natural graphite (particle size 16 μm) was charged into a steel pot having a volume of 450 cm 3 and pulverized with a planetary ball mill (zirconia balls 4 mmφ to 0.2 mmφ, rotation 400 rpm, revolution 400 rpm). The pulverization conditions were in the range of 0.5 to 24 hours in a vacuum atmosphere of 10 −3 Torr.
〈層間化合物の合成方法〉
１）溶媒法による合成方法
原料粉である黒鉛を約５ｇ、真空容器内に入れた後、真空ラインを用いて２×１０-2Ｔｏｒｒ、８０℃で２４時間焼き出しを行った。次に、アルゴン雰囲気中グローブボックス内で黒鉛２．０５ｇ、インターカラントとしてＨ２ＰｔＣｌ６・６Ｈ２Ｏを２．８９ｇ（Ｃ：Ｐｔのモル比＝３０：１とした）、溶媒としてＳＯＣl２ ２５ｍｌをナス形フラスコに入れた後、アルゴンガスを１５ｍｌ／ｍｉｎで流しながら１１９時間撹拌を行った後オイルバスを設置し、アルゴンガス流量を３０ｍｌ／ｍｉｎにし、８０℃で７時間還流を行った。還流後トルエンで洗浄し、真空ラインで乾燥し試料とした。
<Synthesis method of intercalation compound>
1) Synthesis Method by Solvent Method After placing about 5 g of raw material graphite in a vacuum vessel, it was baked out at 2 × 10 −2 Torr and 80 ° C. for 24 hours using a vacuum line. Next, the graphite in a glove box in an argon atmosphere 2.05 g, 2.89 g of H 2 PtCl 6 · 6H 2 O as intercalant (C: Pt mole ratio of = 30: 1 as the), SOCl 2 25 ml as solvent Was placed in an eggplant-shaped flask and stirred for 119 hours while flowing argon gas at 15 ml / min. Then, an oil bath was installed, the argon gas flow rate was adjusted to 30 ml / min, and reflux was performed at 80 ° C. for 7 hours. After refluxing, the sample was washed with toluene and dried on a vacuum line to prepare a sample.
〈粒子物性のキャラクタリゼーション〉
黒鉛粒子の粒径は、レーザー回折式粒度分布計（日機装製MICROTRAC-3000EX）を用いて測定した。黒鉛微粒子の比表面積はQantachrom製Autosorb-1を用いて、ＢＥＴ多点法により算出した。また、黒鉛微粒子および合成した層間化合物の結晶構造はＸ線回折装置（Rigaku製Multiflex）を用いて測定した。さらに調整したサンプルの表面部分が黒鉛層間化合物を形成しているか確認するため、Renishow社製NRS-2100を用いラマン散乱分光分析を行った。
<Characteristics of particle properties>
The particle size of the graphite particles was measured using a laser diffraction particle size distribution analyzer (MICROTRAC-3000EX manufactured by Nikkiso). The specific surface area of the graphite fine particles was calculated by the BET multipoint method using Autosorb-1 manufactured by Qantachrom. The crystal structures of the graphite fine particles and the synthesized intercalation compound were measured using an X-ray diffractometer (Rigaku Multiflex). Further, in order to confirm whether the surface portion of the prepared sample formed a graphite intercalation compound, Raman scattering spectroscopic analysis was performed using NRS-2100 manufactured by Renishow.
〈比抵抗の測定〉
（粉体抵抗）
三菱化学製粉体抵抗計ＰＤ―５１を用い、650ｋｇ／ｃｍ２加圧時の粉体抵抗を測定した。
<Measurement of resistivity>
(Powder resistance)
Using a powder resistance meter PD-51 made by Mitsubishi Chemical, the powder resistance at the time of 650 kg / cm 2 pressurization was measured.
〈チオフェンの水素化脱硫反応〉
触媒の機能性の評価の一つとしてチオフェンの水素化脱硫反応を行った。装置は常圧固定床流通式反応装置を用いた。触媒を反応管に０．１ｇ充填し、前処理として５００℃で１時間ヘリウム（Ｈｅ）処理をした。その後、水素還元を４５０℃で１時間行い反応に用いた。反応はモル比で、チオフェン：水素＝１：３０の混合ガスを装置内に導入することによって行い、反応温度は３５０℃とした。分析にはガスクロマトグラフ（ＦＩＤ）を用いた。
以上の結果を表１及び表２に示す。表１は、〈改質黒鉛の調整方法１〉により調整された試料の結果を示し、表２の試料９から１１は、〈改質黒鉛の調整方法２〉により調整された試料の結果を示す。
<Hydrodesulfurization reaction of thiophene>
As one of the evaluation of the functionality of the catalyst, the hydrodesulfurization reaction of thiophene was performed. The apparatus used was a normal pressure fixed bed flow type reaction apparatus. The reaction tube was filled with 0.1 g of catalyst, and pretreated with helium (He) at 500 ° C. for 1 hour. Thereafter, hydrogen reduction was performed at 450 ° C. for 1 hour and used for the reaction. The reaction was carried out by introducing a mixed gas of thiophene: hydrogen = 1: 30 into the apparatus at a molar ratio, and the reaction temperature was 350 ° C. A gas chromatograph (FID) was used for the analysis.
The above results are shown in Tables 1 and 2. Table 1 shows the results of the samples adjusted by <Modified Graphite Adjustment Method 1>, and Samples 9 to 11 in Table 2 show the results of the samples adjusted by <Modified Graphite Adjustment Method 2>. .
表１より、ＰｔＣｌ４と層間化合物を形成し易い黒鉛の結晶子の大きさは、試料５、６より（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上の黒鉛であることを示す。また、このような材料はリチウムイオンのインターカレートによる充電容量も確保できることが知られている。また、ＰｔＣｌ４−ＧＩＣを調整後、還元により黒鉛表面に白金を析出させる場合、比表面積が大きく、白金が分散し易いほど反応収率がよいと考えられる。 From Table 1, the size of graphite crystallites that easily form an intercalation compound with PtCl 4 is larger than that of samples 5 and 6, in which the crystallite size Lc (002) in the c-axis direction of the (002) plane is 30 nm or more. Indicates that Moreover, it is known that such a material can also ensure the charge capacity by lithium ion intercalation. Moreover, when platinum is deposited on the graphite surface by reduction after adjusting PtCl 4 -GIC, it is considered that the reaction yield is better as the specific surface area is larger and platinum is more easily dispersed.
表１には、チオフェンの水素化脱硫反応結果が示される。試料１から３は、原料黒鉛を０．５〜２時間粉砕した改質黒鉛の作成法と物性値、層間化合物の特性および反応試験結果を示す。何れも改質黒鉛の比表面積は２００ｍ２／g以下の試料であり、ＰｔＣｌ４との層間化合物を形成するが、還元後のチオフェンの水素化脱硫反応率は低く、また、３００分後の反応率低下も大きい傾向がある。それに対し、試料４から６は粉砕時間を４〜２４時間に増加させた試料であって、特に、試料５は、（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上であり層間化合物を形成でき、ラマン分光スペクトルのＲ値が０．３７であり、比表面積が５２０ｍ２／ｇと高い値を示す。 Table 1 shows the hydrodesulfurization reaction results of thiophene. Samples 1 to 3 show the preparation method and physical properties of modified graphite obtained by pulverizing raw graphite for 0.5 to 2 hours, the properties of intercalation compounds, and reaction test results. In any case, the modified graphite has a specific surface area of 200 m 2 / g or less, and forms an intercalation compound with PtCl 4. However, the hydrodesulfurization reaction rate of thiophene after reduction is low, and the reaction after 300 minutes. The rate decline tends to be large. On the other hand, Samples 4 to 6 are samples in which the pulverization time was increased to 4 to 24 hours. In particular, Sample 5 has a crystallite size Lc (002) in the c-axis direction of (002) plane of 30 nm. As described above, an intercalation compound can be formed, the R value of the Raman spectrum is 0.37, and the specific surface area is as high as 520 m 2 / g.
その結果、チオフェンの水素化脱硫反応は反応率７０％、反応低下率０．９であり、ともに良好であった。一方、粉砕時間が２４時間の試料６は、（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が１５ｎｍまで低下し、ＰｔＣｌ４との層間化合物を形成できなかった。この水素還元品は、初期の反応率は比表面積が高いため良好であるが、３００分後の反応率の低下割合が０．８５と大きくなった。また、比表面積が大きい試料６，７を比較した場合、層間化合物を還元した試料５は、層間化合物を形成しない試料６より、１０分後の反応収率が高く、３００分反応後の収率の低下が少なく、すなわち反応時の白金の凝集も抑制され、反応収率が維持されることが確認できた。 As a result, the hydrodesulfurization reaction of thiophene was good with a reaction rate of 70% and a reaction decrease rate of 0.9. On the other hand, in Sample 6 with a pulverization time of 24 hours, the crystallite size Lc (002) in the c-axis direction on the (002) plane was reduced to 15 nm, and an intercalation compound with PtCl 4 could not be formed. This hydrogen-reduced product is good because the initial reaction rate is high due to its high specific surface area, but the rate of decrease in the reaction rate after 300 minutes was as large as 0.85. When samples 6 and 7 having a large specific surface area are compared, sample 5 obtained by reducing the intercalation compound has a higher reaction yield after 10 minutes than sample 6 that does not form the intercalation compound, and yield after 300 minutes reaction. That is, it was confirmed that the reaction yield was maintained by suppressing the aggregation of platinum during the reaction.
更に、表面改質効果を確認するため、粉砕時間は２４時間であるが、粉砕媒体の質量を変えて（粉砕媒体をＳＵＳ製ボール４．５ｍｍφから同１ｍｍφに変更）、黒鉛表面の改質効果を確認した結果を示す（試料７）。粉砕媒体と黒鉛表面の摩擦力が大きい真空雰囲気中での粉砕であるため、比表面積は６３０ｍ２／g、ラマン分光スペクトルのＲ値は０．４１に増加している。しかし、粉砕媒体の質量を下げたことで、（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）は４０ｎｍで減少が少ない。その結果、ＰｔＣｌ４と層間化合物を形成でき、水素還元後のチオフェンの水素化脱硫反応では高い反応率と触媒劣化の低減が確認できた。 Furthermore, in order to confirm the surface modification effect, the grinding time is 24 hours, but the mass of the grinding media is changed (the grinding media is changed from SUS balls 4.5 mmφ to 1 mmφ) to improve the graphite surface The result of having confirmed (sample 7) is shown. Since the grinding is performed in a vacuum atmosphere where the frictional force between the grinding medium and the graphite surface is large, the specific surface area is 630 m 2 / g, and the R value of the Raman spectrum is increased to 0.41. However, by reducing the mass of the grinding medium, the crystallite size Lc (002) in the c-axis direction of the (002) plane is 40 nm and decreases little. As a result, it was possible to form an intercalation compound with PtCl 4, and in the hydrodesulfurization reaction of thiophene after hydrogen reduction, a high reaction rate and a reduction in catalyst deterioration were confirmed.
以上より、黒鉛層間化合物を形成でき、反応効率が高く、反応劣化の少ないＰｔ系触媒を得るための改質黒鉛の物性は、（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）が３０ｎｍ以上、比表面積が２００ｍ２／ｇ以上、ラマン分光スペクトルのＲ値が０．３以上の範囲が良好であることが確認できた。また、ＰｔＣｌ４と層間化合物を形成させ、還元することで、黒鉛エッジ面などへの白金粒子の固着が容易になり、白金粒子の凝集などによる反応劣化抑制に有効である。ＰｔＣｌ４−ＧＩＣのＸＲＤの２θピーク値は、２１〜２３．５°の位置、または／および５〜７°の位置にピークを有することが確認できる。さらに、層間化合物が形成された場合ラマン分光スペクトルのピークが、１６００〜１６１０ｃｍ−１に確認できる。 From the above, the physical properties of the modified graphite for obtaining a Pt-based catalyst capable of forming a graphite intercalation compound, having high reaction efficiency and little reaction deterioration are the crystallite size Lc (002) in the c-axis direction of the (002) plane. ) Is 30 nm or more, the specific surface area is 200 m 2 / g or more, and the R spectrum R value is 0.3 or more. Further, by forming and reducing an intercalation compound with PtCl 4 , the platinum particles can be easily fixed to the graphite edge surface and the like, which is effective in suppressing reaction deterioration due to aggregation of the platinum particles. It can be confirmed that the XRD 2θ peak value of PtCl 4 -GIC has a peak at a position of 21 to 23.5 ° and / or a position of 5 to 7 °. Further, when an intercalation compound is formed, the peak of the Raman spectrum can be confirmed at 1600 to 1610 cm −1 .
次に、表２において、試料９から１１は、〈改質黒鉛の調整方法２〉によって、真空雰囲気中で４時間粉砕した結果を示す。粉砕媒体として１ｍｍφのジルコニア製ボールを用いた場合（試料９）は、改質黒鉛の比表面積は４５２ｍ２／ｇと大きく、（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）も９０ｎｍと大きく、黒鉛表面の改質が優先的に行われたことがわかる。この表面改質効果は粉砕媒体の直径が大きくなるほど低下し、３ｍｍφのジルコニア製ボールを用いた場合（試料１１）は比表面積が２８１ｍ２／ｇに対し、（００２）面のｃ軸方向の結晶子の大きさＬｃ（００２）は、４０ｎｍになっている。これらの実施例（試料９〜１１）と試料１３の専用触媒（比較例）と比較すると、水素還元後のチオフェンの水素化脱硫反応は、実施例の方が初期の反応率、触媒劣化ともに良好であるが確認された。 Next, in Table 2, Samples 9 to 11 show the results of pulverization for 4 hours in a vacuum atmosphere by <Modified graphite adjustment method 2>. When a 1 mmφ zirconia ball is used as the grinding medium (sample 9), the specific surface area of the modified graphite is as large as 452 m 2 / g, and the crystallite size Lc (002) in the c-axis direction of the (002) plane. Is as large as 90 nm, indicating that the graphite surface was preferentially modified. This surface modification effect decreases as the diameter of the grinding medium increases, and when a 3 mmφ zirconia ball is used (sample 11), the specific surface area is 281 m 2 / g, while the (002) plane c-axis direction crystal is The child size Lc (002) is 40 nm. Compared to these examples (samples 9 to 11) and the dedicated catalyst (comparative example) of sample 13, the examples show better initial reaction rate and catalyst degradation in the hydrodesulfurization reaction of thiophene after hydrogen reduction. It was confirmed.
また、表１及び表２には示されていないが、比表面積が５００ｍ２／ｇ前後で黒鉛層間化合物作製前の表面改質黒鉛について、試料５と試料９の比抵抗を比較すると、試料５の改質黒鉛の比抵抗は０．０１０６Ωｃｍ（１．６５ｇ／ｃｍ３）であったのに対し、試料９の改質黒鉛は、比表面積が大きい（４５２ｍ２／ｇ）割りに大きな結晶子（９０ｎｍ）を保っており、比抵抗は０．００６８５Ωｃｍ（１．８９ｇ／ｃｍ３）と低い。すなわち、抵抗値が低く且つ比表面積が大きな改質黒鉛を得るには、質量の小さな粉砕媒体（１ｍｍφのジルコニア製ボールなど）を使用して粉砕することが効果的である。 Although not shown in Tables 1 and 2, when the specific surface area of the surface-modified graphite before the preparation of the graphite intercalation compound with a specific surface area of around 500 m 2 / g is compared, the resistivity of Sample 5 and Sample 9 is compared. The specific resistance of the modified graphite was 0.0106 Ωcm (1.65 g / cm 3 ), whereas the modified graphite of Sample 9 had a large specific crystallite (452 m 2 / g). 90 nm) and the specific resistance is as low as 0.00685 Ωcm (1.89 g / cm 3 ). That is, in order to obtain modified graphite having a low resistance value and a large specific surface area, it is effective to grind using a grinding medium having a small mass (such as a 1 mmφ zirconia ball).
本発明に係る改質黒鉛、その改質黒鉛を用いる黒鉛層間化合物及び触媒は、燃料電池用触媒、リチウムイオン電池用負極材、キャパシタ材料、低抵抗電気材料などのさまざまな用途に適用でき、極めて有用である。 The modified graphite, graphite intercalation compound and catalyst using the modified graphite according to the present invention can be applied to various uses such as a catalyst for fuel cells, a negative electrode material for lithium ion batteries, a capacitor material, and a low resistance electric material. Useful.
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