JP2002154814A - Functional expanded graphite and method for producing the same - Google Patents
Functional expanded graphite and method for producing the sameInfo
- Publication number
- JP2002154814A JP2002154814A JP2000349819A JP2000349819A JP2002154814A JP 2002154814 A JP2002154814 A JP 2002154814A JP 2000349819 A JP2000349819 A JP 2000349819A JP 2000349819 A JP2000349819 A JP 2000349819A JP 2002154814 A JP2002154814 A JP 2002154814A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- intercalation compound
- alkali metal
- expanded graphite
- expanded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 209
- 239000010439 graphite Substances 0.000 title claims abstract description 209
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 84
- 230000002687 intercalation Effects 0.000 claims description 81
- 238000009830 intercalation Methods 0.000 claims description 81
- 229910052783 alkali metal Inorganic materials 0.000 claims description 52
- 150000001340 alkali metals Chemical class 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000007770 graphite material Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 229910052792 caesium Inorganic materials 0.000 description 12
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 11
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000005297 pyrex Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000012937 correction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 229910021382 natural graphite Inorganic materials 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 polyphenylene oxadiazole Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SBGIDVNCUDTMNZ-UHFFFAOYSA-N [Cs].C=C Chemical group [Cs].C=C SBGIDVNCUDTMNZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229940126543 compound 14 Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- SWTCCCJQNPGXLQ-UHFFFAOYSA-N acetaldehyde di-n-butyl acetal Natural products CCCCOC(C)OCCCC SWTCCCJQNPGXLQ-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y02E60/12—
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、例えば吸着剤、
触媒用担持体、電極材料などとして好適な機能性膨張黒
鉛に係り、特に加工適性に優れ、取扱いが容易で、かつ
低コストでの製造が可能な機能性膨張黒鉛に関する。The present invention relates to, for example, an adsorbent,
The present invention relates to a functional expanded graphite suitable as a support for a catalyst, an electrode material, and the like, and particularly to a functional expanded graphite which has excellent workability, is easy to handle, and can be manufactured at low cost.
【０００２】[0002]
【従来の技術】黒鉛は導電性が高く、耐食性、機械強度
などにも優れるため、様々な形状の機能性黒鉛に加工さ
れ、広く利用されている。このような機能性黒鉛として
知られるものには、黒鉛の層間にインターカレートを挿
入することにより作られる黒鉛層間化合物、この黒鉛層
間化合物を高温で急速加熱することにより作られる膨張
黒鉛などがある。2. Description of the Related Art Graphite has high conductivity, is excellent in corrosion resistance, mechanical strength, etc., and is therefore processed into various forms of functional graphite and widely used. Known as such functional graphites are graphite intercalation compounds made by inserting intercalates between graphite layers, and expanded graphite made by rapidly heating this graphite intercalation compound at high temperatures. .
【０００３】特開昭６２−８７４０７号公報には、ポリ
フェニレンオキサジアゾールから作られた黒鉛フィルム
の黒鉛層間に、インターカレートが挿入されたフィルム
状黒鉛層間化合物が開示されている。Japanese Patent Application Laid-Open No. 62-87407 discloses a film-like graphite interlayer compound in which an intercalate is inserted between graphite layers of a graphite film made of polyphenylene oxadiazole.
【０００４】また特開平５−９６１５７号公報には、膨
張黒鉛を加圧成形した後バインダーで処理する油吸着剤
の製造方法が開示されている。[0004] Japanese Patent Application Laid-Open No. 5-96157 discloses a method for producing an oil adsorbent in which expanded graphite is subjected to pressure molding and then treated with a binder.
【０００５】鱗片状天然黒鉛から層間化合物を作り、こ
の層間化合物を急激に加熱すると２００〜３００倍に膨
れ、膨張黒鉛が生成される。この膨張黒鉛は、微視的に
はじゃばら状（もしくはアコーディオン状）の構造をし
ている。また、学術研究レベルにおいては、炭化水素ガ
スの化学蒸着法（ＣＶＤ）で作成した板状の高配向性熱
分解黒鉛を出発物質として膨張黒鉛を作る方法も知られ
ている。[0005] An intercalation compound is formed from flaky natural graphite, and when this intercalation compound is rapidly heated, it expands 200 to 300 times to produce expanded graphite. This expanded graphite is microscopically in a bellows-like (or accordion-like) structure. At the level of scientific research, there is also known a method of producing expanded graphite by using plate-shaped highly oriented pyrolytic graphite prepared by a chemical vapor deposition method (CVD) of hydrocarbon gas as a starting material.
【０００６】膨張黒鉛は特徴的な細孔構造を有している
ために、吸着剤など様々な用途に利用されている。Since expanded graphite has a characteristic pore structure, it is used for various uses such as an adsorbent.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、斯かる
従来の膨張黒鉛のうち、鱗片状天然黒鉛から得られるじ
ゃばら状の膨張黒鉛は、非常に軽くて飛散しやすいため
に扱いにくいという欠点があった。しかも、これらの欠
点を解決するために型に詰めるという方法（成形方法）
を採ると、機械的強度を要求されるものや小型で精密な
ものには使用できず、膨張黒鉛特有の異方構造の利用性
も失われてしまうという新たな問題が生じる。However, among such conventional expanded graphites, bristle-shaped expanded graphite obtained from flaky natural graphite has a drawback that it is difficult to handle because it is very light and easily scattered. . Moreover, in order to solve these drawbacks, a method of packing in a mold (molding method)
However, it cannot be used for those requiring mechanical strength or for small and precise ones, and there is a new problem that the utility of the anisotropic structure peculiar to expanded graphite is lost.
【０００８】また、板状の高配向性熱分解黒鉛を利用し
た膨張黒鉛の製造方法についても、大量生産には向かな
い上、コストも高いという欠点があった。Also, the method for producing expanded graphite using plate-like highly oriented pyrolytic graphite has drawbacks in that it is not suitable for mass production and is expensive.
【０００９】本発明は、上述の問題点に着目してなされ
たものであり、その目的とするところは、優れた加工適
性と適度な強度を持ち、取扱いが容易で、しかも側面部
だけに黒鉛の端面が広く露出した特徴的に異方性のある
構造の機能性膨張黒鉛を提供することにある。The present invention has been made in view of the above-mentioned problems, and it is an object of the present invention to have excellent workability and moderate strength, easy to handle, and graphite only on the side surface. The present invention provides a functional expanded graphite having a characteristically anisotropic structure whose end face is widely exposed.
【００１０】また、本発明の他の目的は、優れた加工適
性と適度な強度を持ち、取扱いが容易で、しかも側面部
だけに黒鉛の端面が広く露出した特徴的に異方性のある
構造の機能性膨張黒鉛を安価かつ容易な操作で製造する
方法を提供することにある。Another object of the present invention is to provide a characteristically anisotropic structure which has excellent workability and moderate strength, is easy to handle, and has a wide exposed end face of graphite only on the side surfaces. It is an object of the present invention to provide a method for producing the functional expanded graphite of the present invention by an inexpensive and easy operation.
【００１１】また、本発明の他の目的は、腐食物質の残
留を改善した機能性膨張黒鉛を提供することにある。It is another object of the present invention to provide a functional expanded graphite having an improved residual corrosion substance.
【００１２】また、本発明の他の目的は、従来の加熱方
法では膨張黒鉛生成が困難であるような黒鉛層間化合物
から膨張黒鉛を容易な操作で製造する方法を提供するこ
とにある。Another object of the present invention is to provide a method for producing expanded graphite from a graphite intercalation compound which is difficult to produce expanded graphite by a conventional heating method by an easy operation.
【００１３】また、本発明の他の目的は、膨張率の制御
が容易である機能性膨張黒鉛を提供することにある。It is another object of the present invention to provide a functional expanded graphite in which the expansion coefficient can be easily controlled.
【００１４】また、本発明の他の目的は、大量生産が可
能でしかも低コストである機能性膨張黒鉛の製造方法を
提供することにある。Another object of the present invention is to provide a method for producing functional expanded graphite that can be mass-produced and that is inexpensive.
【００１５】この発明のさらに他の目的乃至作用効果に
ついては、以下の明細書の記載に基づいて当業者であれ
ば容易に理解されるであろう。Still other objects and operational effects of the present invention will be easily understood by those skilled in the art based on the description in the following specification.
【００１６】[0016]
【課題を解決するための手段】上記の目的を達成するた
めに、本発明の機能性膨張黒鉛は、膨張黒鉛粉末を加圧
成形してなる黒鉛シートを再膨張させることを特徴とす
る。Means for Solving the Problems In order to achieve the above object, the functional expanded graphite of the present invention is characterized in that a graphite sheet formed by press-molding expanded graphite powder is re-expanded.
【００１７】このような構成によれば、優れた加工適性
と適度な強度を持ち、取扱いが容易で、しかも側面部だ
けに黒鉛の端面が広く露出した特徴的に異方性のある構
造の機能性膨張黒鉛を得ることができる。According to such a structure, it has excellent workability and moderate strength, is easy to handle, and has a characteristic anisotropic structure in which the graphite end face is widely exposed only on the side surface. Expanded graphite can be obtained.
【００１８】これは、膨張黒鉛の凝集体である黒鉛シー
トを再度膨張させることによって、膨張黒鉛粒の集合体
として機能性膨張黒鉛を得ることができるからであり、
このため本発明の機能性膨張黒鉛は複雑な細孔構造を持
ち、扱いにくいという膨張黒鉛の欠点も解消される。This is because a functional expanded graphite can be obtained as an aggregate of expanded graphite particles by expanding the graphite sheet which is an aggregate of expanded graphite again.
For this reason, the functional expanded graphite of the present invention has a complicated pore structure and eliminates the drawback of the expanded graphite, which is difficult to handle.
【００１９】また、黒鉛シートは柔軟性に富み望みの形
に加工することが容易であるため、原料である黒鉛シー
トを加工することにより、生成品である機能性膨張黒鉛
を任意の形とすることが可能である。Further, since the graphite sheet is flexible and can be easily processed into a desired shape, by processing the graphite sheet as a raw material, the functional expanded graphite as a product can be formed into an arbitrary shape. It is possible.
【００２０】本発明の機能性膨張黒鉛製造方法は、原料
となる黒鉛材料の層間にインターカレートを保持させた
後、該インターカレートを熱分解させることにより、黒
鉛材料全体を膨張させて機能性膨張黒鉛を得る機能性膨
張黒鉛の製造方法において、前記原料となる黒鉛材料と
して、膨張黒鉛粉末を加圧成形してなる黒鉛シートを用
いることを特徴とする。In the method for producing a functional expanded graphite according to the present invention, the intercalate is held between layers of a graphite material as a raw material, and the intercalate is thermally decomposed to expand the entire graphite material. In the method for producing functional expanded graphite for obtaining expandable graphite, a graphite sheet obtained by press-molding expanded graphite powder is used as the raw material graphite material.
【００２１】このような構成によれば、優れた加工適性
と適度な強度を持ち、取扱いが容易で、しかも側面部だ
けに黒鉛の端面が広く露出した特徴的に異方性のある構
造の機能性膨張黒鉛を製造することができる。According to such a structure, it has excellent workability and moderate strength, is easy to handle, and has a characteristic anisotropic structure in which the graphite end face is widely exposed only on the side surface. Expansive graphite can be produced.
【００２２】本発明の好ましい実施の形態においては、
インターカレートとしてアルカリ金属を用いてもよい。In a preferred embodiment of the present invention,
An alkali metal may be used as the intercalate.
【００２３】このような構成によれば、腐食物質の残留
を改善した機能性膨張黒鉛を製造することができる。According to such a configuration, it is possible to manufacture functional expanded graphite in which the residual of corrosive substances is improved.
【００２４】本発明の好ましい実施の形態においては、
インターカレートとして更に不飽和結合を持つ炭化水素
を用いてもよい。In a preferred embodiment of the present invention,
A hydrocarbon having an unsaturated bond may be used as the intercalate.
【００２５】このような構成によれば、層間化合物の安
定性がよいため加熱前に分解が起こりにくい。According to such a configuration, the decomposition of the interlayer compound is less likely to occur before heating because of good stability.
【００２６】本発明の好ましい実施の形態においては、
黒鉛層間化合物を膨張させるための加熱を酸素過剰雰囲
気中で行ってもよい。In a preferred embodiment of the present invention,
Heating for expanding the graphite intercalation compound may be performed in an oxygen excess atmosphere.
【００２７】このような構成によれば、従来の加熱方法
では膨張黒鉛生成が困難であるような黒鉛層間化合物か
ら膨張黒鉛を生成することができる。従来の加熱方法で
はほとんど膨らまない層間化合物としては、例えば、ア
ルカリ金属とエチレンからなる三成分系層間化合物があ
る。According to such a configuration, it is possible to generate expanded graphite from a graphite intercalation compound for which it is difficult to generate expanded graphite by a conventional heating method. As an intercalation compound that hardly expands by a conventional heating method, for example, there is a ternary intercalation compound composed of an alkali metal and ethylene.
【００２８】ここで『酸素過剰雰囲気中』とは、通常大
気中よりも酸素が多く含まれた状態を示し、酸素バーナ
での燃焼、酸素を供給しながらの燃焼、その他様々な方
法で高酸素状態で燃焼させることを示す。Here, "in an oxygen-excess atmosphere" refers to a state in which oxygen is contained more than in the normal atmosphere, and includes combustion with an oxygen burner, combustion while supplying oxygen, and various other methods. Indicates burning in a state.
【００２９】本発明に用いられる三成分系黒鉛層間化合
物の製造方法は、前記三成分系黒鉛層間化合物は黒鉛原
料とアルカリ金属と不飽和結合を持つ炭化水素とから成
り、前記三成分系黒鉛層間化合物の製造方法は、黒鉛原
料の層間にアルカリ金属を挿入させてアルカリ金属層間
化合物を生成する第１の過程と、前記アルカリ金属層間
化合物に不飽和結合を持つ炭化水素を挿入させて三成分
系黒鉛層間化合物を生成する第２の過程からなり、前記
第１の過程は、黒鉛原料とアルカリ金属との配合比を調
整し、アルカリ金属黒鉛層間化合物中に第１ステージ構
造と第２ステージ構造が任意の割合で混在するようにし
たものであってもよい。The method for producing a ternary graphite intercalation compound used in the present invention is characterized in that the ternary graphite intercalation compound comprises a graphite raw material and a hydrocarbon having an unsaturated bond with an alkali metal; The method for producing a compound comprises a first step of producing an alkali metal intercalation compound by inserting an alkali metal between layers of a graphite raw material, and a three-component system comprising inserting a hydrocarbon having an unsaturated bond into the alkali metal intercalation compound. It comprises a second step of producing a graphite intercalation compound. In the first step, the mixing ratio of the graphite raw material and the alkali metal is adjusted, and the first stage structure and the second stage structure are contained in the alkali metal graphite intercalation compound. The components may be mixed at an arbitrary ratio.
【００３０】このような構成によれば、膨張率の制御が
容易である機能性膨張黒鉛が得られる。According to such a configuration, it is possible to obtain functional expanded graphite whose expansion coefficient can be easily controlled.
【００３１】[0031]
【発明の実施の形態】以下、この発明の好適な実施の一
形態を、添付図面を参照しつつ詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.
【００３２】先に示したように、本発明の機能性膨張黒
鉛は黒鉛シートを原料としているため、膨張黒鉛粒の凝
集体とみなすことができ、複雑な微細構造をもつ。この
ような機能性膨張黒鉛の模式図が、図１に示されてお
り、図１（ａ）は黒鉛シートの図、図１（ｂ）は黒鉛層
間化合物の図、図１（ｃ）は機能性膨張黒鉛の図であ
る。同図において、１は黒鉛シート、２は黒鉛層間化合
物、３は機能性膨張黒鉛、４は黒鉛結晶層、５はインタ
ーカレート、６は膨張黒鉛粒、７はマクロ孔である。As described above, since the functional expanded graphite of the present invention uses a graphite sheet as a raw material, it can be regarded as an aggregate of expanded graphite particles and has a complicated fine structure. A schematic diagram of such a functional expanded graphite is shown in FIG. 1, in which FIG. 1 (a) is a diagram of a graphite sheet, FIG. 1 (b) is a diagram of a graphite intercalation compound, and FIG. FIG. 3 is a diagram of an expanded graphite. In the figure, 1 is a graphite sheet, 2 is a graphite interlayer compound, 3 is a functional expanded graphite, 4 is a graphite crystal layer, 5 is an intercalate, 6 is expanded graphite grains, and 7 is macropores.
【００３３】図１（ａ）に示されるように、黒鉛シート
１は微視的には黒鉛結晶層４が黒鉛結晶の面方向に積層
した構造であり、この黒鉛シート１にインターカレート
５を挿入することにより、黒鉛結晶層４の間にインター
カレート５を保持した黒鉛層間化合物２が得られる。こ
こで図１（ｂ）に示される黒鉛層間化合物２は第１ステ
ージ構造の黒鉛層間化合物であるが、本発明の黒鉛層間
化合物は第１ステージ構造のものに限らない。得られた
黒鉛層間化合物２を高温で加熱することにより、黒鉛結
晶の面方向のみに膨張し、機能性膨張黒鉛３が得られ
る。図１（ｃ）に示されるように、機能性膨張黒鉛３は
微視的には膨張黒鉛粒６が凝集した構造をなし、マクロ
孔７の他に膨張黒鉛粒６の内部にも微細な孔を有し、複
雑な細孔構造をしている。As shown in FIG. 1A, the graphite sheet 1 has a structure in which a graphite crystal layer 4 is microscopically laminated in the plane direction of the graphite crystal. By inserting, the graphite intercalation compound 2 holding the intercalate 5 between the graphite crystal layers 4 is obtained. Here, the graphite intercalation compound 2 shown in FIG. 1B is a graphite intercalation compound having a first stage structure, but the graphite intercalation compound of the present invention is not limited to the first stage structure. By heating the obtained graphite intercalation compound 2 at a high temperature, it expands only in the plane direction of the graphite crystal, and functional expanded graphite 3 is obtained. As shown in FIG. 1 (c), the functional expanded graphite 3 microscopically has a structure in which the expanded graphite particles 6 are aggregated, and fine holes are formed inside the expanded graphite particles 6 in addition to the macro holes 7. And has a complicated pore structure.
【００３４】ところで、図１（ｂ）に示されるような黒
鉛層間化合物は様々なステージ構造を採りうる。具体的
には、全ての黒鉛層間にインターカレートが挿入された
第１ステージ構造、一層おきにインターカレートが挿入
された第２ステージ構造、以下、二層おきにインターカ
レートが挿入された第３ステージ構造、三層おきにイン
ターカレートが挿入された第４ステージ構造、・・・な
どの構造を採りうる。このような黒鉛層間化合物のステ
ージ構造の説明図が、図２に示されており、図２（ａ）
は黒鉛シートの拡大図、図２（ｂ）は第１ステージ構造
の拡大図、図２（ｃ）は第２ステージ構造の拡大図、図
２（ｄ）は第１ステージ構造と第２ステージ構造が混在
した構造の拡大図である。本発明においては、図２
（ａ）に示される黒鉛シートにインターカレート５を挿
入して黒鉛層間化合物を生成するとき両者のモル比を調
整することにより、図２（ｂ）に示される第１ステージ
構造、図２（ｃ）に示される第２ステージ構造、図２
（ｄ）に示される第１ステージと第２ステージが混在し
た構造、或いはその他のステージ構造を任意に採らせる
ことができる。Incidentally, the graphite intercalation compound as shown in FIG. 1B can have various stage structures. Specifically, a first stage structure in which intercalates are inserted between all graphite layers, a second stage structure in which intercalates are inserted every other layer, and thereafter, intercalates are inserted every two layers Structures such as a third stage structure, a fourth stage structure in which intercalates are inserted every third layer,... An explanatory view of the stage structure of such a graphite intercalation compound is shown in FIG. 2 and FIG.
Is an enlarged view of a graphite sheet, FIG. 2B is an enlarged view of a first stage structure, FIG. 2C is an enlarged view of a second stage structure, and FIG. 2D is a first stage structure and a second stage structure. It is an enlarged view of the structure where. In the present invention, FIG.
The intercalation 5 is inserted into the graphite sheet shown in FIG. 2A to produce a graphite intercalation compound, and the molar ratio between the two is adjusted, whereby the first stage structure shown in FIG. Second stage structure shown in c), FIG.
A structure in which the first stage and the second stage are mixed as shown in (d) or another stage structure can be arbitrarily adopted.
【００３５】さて、先に示したように、本発明の黒鉛層
間化合物に好適なインターカレートの一例としてアルカ
リ金属がある。アルカリ金属黒鉛層間化合物の合成に用
いる装置の一例が、図３に示されており、図３（ａ）は
管状電気炉の外観図、図３（ｂ）は管状電気炉（ａ）を
線Ａで切断した際の内部構造である。同図において、８
は中実の金属製円筒体である管状電気炉、９はムライト
製炉心管、１０は黒鉛シート、１１はアルカリ金属、１
２はパイレックス管（『パイレックス』はコーニングイ
ンコーポレーテッド社の商標である）、１３は金属製円
筒体内部に埋め込まれたヒーターである。As described above, an alkali metal is an example of an intercalate suitable for the graphite intercalation compound of the present invention. An example of an apparatus used for synthesizing an alkali metal graphite intercalation compound is shown in FIG. 3, in which FIG. 3A is an external view of a tubular electric furnace, and FIG. Internal structure when cut at In FIG.
Is a tubular electric furnace which is a solid metal cylindrical body, 9 is a mullite core tube, 10 is a graphite sheet, 11 is an alkali metal, 1
2 is a Pyrex tube ("Pyrex" is a trademark of Corning Incorporated), and 13 is a heater embedded inside a metal cylinder.
【００３６】同図に示される装置で、黒鉛シート１０と
アルカリ金属１１とをパイレックス管１２に入れ真空状
態として封入し、管状電気炉８で３００℃〜４００℃で
加熱することによりアルカリ金属を黒鉛層間に保持した
アルカリ金属黒鉛層間化合物が得られる。In the apparatus shown in the figure, a graphite sheet 10 and an alkali metal 11 are put in a Pyrex tube 12, sealed in a vacuum state, and heated at 300 ° C. to 400 ° C. in a tubular electric furnace 8 to convert the alkali metal into graphite. An alkali metal graphite intercalation compound held between the layers is obtained.
【００３７】上記過程で得られたアルカリ金属黒鉛層間
化合物に有機分子を導入する工程の一例が、図４に示さ
れている。同図において、１４はアルカリ金属層間化合
物、１５は恒温槽、１６は冷媒、１７は圧力計、１８は
ガスリザーバー、１９はコックである。FIG. 4 shows an example of the step of introducing an organic molecule into the alkali metal graphite intercalation compound obtained in the above process. In the figure, 14 is an alkali metal intercalation compound, 15 is a thermostat, 16 is a refrigerant, 17 is a pressure gauge, 18 is a gas reservoir, and 19 is a cock.
【００３８】同図に示される装置で、アルカリ金属黒鉛
層間化合物１４に−１７３℃〜室温の所定の温度で気体
状の有機分子を数時間接触させることによって、層間に
有機分子が吸収され、三成分系黒鉛層間化合物が得られ
る。In the apparatus shown in the figure, by bringing gaseous organic molecules into contact with the alkali metal graphite intercalation compound 14 at a predetermined temperature of -173 ° C. to room temperature for several hours, the organic molecules are absorbed between the layers. A component-based graphite intercalation compound is obtained.
【００３９】以上で述べた方法以外にも、例えばインタ
ーカレートを溶媒に溶かし、この溶媒に原料である黒鉛
シートを浸すことにより、黒鉛層間化合物を生成する方
法なども本発明に用いることができる。このような溶媒
を用いた黒鉛層間化合物合成方法の一例が、図５に示さ
れている。同図において、２０はインターカレートを溶
かした溶媒、２１はネジ口瓶である。In addition to the above-mentioned method, a method of dissolving intercalate in a solvent and immersing a graphite sheet as a raw material in the solvent to form a graphite intercalation compound can be used in the present invention. . An example of a method for synthesizing a graphite intercalation compound using such a solvent is shown in FIG. In the figure, 20 is a solvent in which the intercalate is dissolved, and 21 is a screw cap bottle.
【００４０】インターカレートを溶かした溶媒２０（溶
媒に一種又は二種以上のインターカレートが溶かしてあ
る）に室温で黒鉛シート１０を浸すことにより、ステー
ジ１構造の黒鉛層間化合物が得られる。また、同図にお
いては反応を行う容器をネジ口瓶としているが、高い気
密性が得られ実験に影響を与えない材質の容器であれ
ば、材質、形状は特に問わない。By immersing the graphite sheet 10 in a solvent 20 in which an intercalate is dissolved (one or more intercalates are dissolved in the solvent) at room temperature, a graphite intercalation compound having a stage 1 structure is obtained. In addition, although the container in which the reaction is performed is a screw-necked bottle in the same figure, the material and shape are not particularly limited as long as the container is made of a material that can achieve high airtightness and does not affect the experiment.
【００４１】以下、本発明に用いる黒鉛シート、黒鉛層
間化合物、各種インターカレートについて図を参照しつ
つ詳説する。Hereinafter, the graphite sheet, graphite intercalation compound, and various intercalates used in the present invention will be described in detail with reference to the drawings.
【００４２】黒鉛シートは一般的に、天然黒鉛の粉末か
ら作られた層間化合物を高温（約９００〜１０００℃）
で急激に熱分解し、黒鉛層間からの急激なガス放出させ
ることにより膨張黒鉛を作り、これを高温下で加圧ロー
ル成形する、という方法で作られる。The graphite sheet is generally prepared by heating an intercalation compound made of natural graphite powder at a high temperature (about 900 to 1000 ° C.).
The expanded graphite is produced by rapid thermal decomposition and rapid gas release from the graphite layer, and is formed into a pressurized roll at a high temperature.
【００４３】黒鉛シートは、高温下で一方向から力を加
え加圧成形することで、容易に配向を平行方向に揃える
ことができ、本発明で用いる黒鉛シートは図１（ａ）に
示されるように配向が平行方向に揃ったものであれば、
作り方は上記の方法に限らない。The orientation of the graphite sheet can be easily aligned in a parallel direction by applying pressure from one direction at a high temperature, and the graphite sheet used in the present invention is shown in FIG. 1 (a). If the orientation is aligned in the parallel direction like this
The method of making is not limited to the above method.
【００４４】よって、黒鉛シートの配向が揃っていれ
ば、黒鉛シートの原材料である黒鉛は特に限定せず、天
然黒鉛と人造黒鉛のどちらでもよく、その形状も鱗片状
の他、繊維状、粉末状、など他の形状でもよい。Accordingly, as long as the orientation of the graphite sheet is uniform, the graphite as a raw material of the graphite sheet is not particularly limited, and it may be either natural graphite or artificial graphite. And other shapes.
【００４５】黒鉛層間はファンデルワールス力によって
のみ結合しているため、この層間には他の原子や分子を
容易に挿入させることができ、インターカレートの種
類、合成条件、ホスト黒鉛の種類などの条件を変えるこ
とによって、様々な特性を持った黒鉛層間化合物を生成
することができる。Since the graphite layers are bonded only by Van der Waals forces, other atoms and molecules can be easily inserted between the layers, and the types of intercalates, synthesis conditions, types of host graphite, etc. By changing the above conditions, graphite intercalation compounds having various characteristics can be produced.
【００４６】本発明において、原料黒鉛シートの層間に
インターカレートを導入する方法は問わないが、例え
ば、黒鉛シートとインターカレートを真空中で加熱する
方法、インターカレートを溶かし込んだ溶媒に黒鉛シー
トを浸す方法、などが考えられる。In the present invention, the method of introducing the intercalate between layers of the raw graphite sheet is not limited. For example, a method of heating the graphite sheet and the intercalate in a vacuum, a method of dissolving the intercalate in a solvent in which the intercalate is dissolved, or the like. A method of immersing the graphite sheet can be considered.
【００４７】ここで、本発明に用いるインターカレート
の種類は特に限定しないが、反応性の面からアルカリ金
属と有機分子の組合せが好ましく、特に、第１ステージ
構造と第２ステージ構造を化合物中に任意の割合で存在
させて膨張率の制御を行う場合、アルカリ金属が最適で
ある。Here, the type of the intercalate used in the present invention is not particularly limited, but a combination of an alkali metal and an organic molecule is preferable from the viewpoint of reactivity. In particular, the first stage structure and the second stage structure are used in a compound. When the expansion ratio is controlled by allowing the metal to be present at an arbitrary ratio, an alkali metal is optimal.
【００４８】本発明に用いるアルカリ金属は特に限定し
ないが、アルカリ金属導入後に有機分子を導入する場合
は、カリウム、ルビジウム、セシウムが好適であり、ま
た、溶媒に浸すことにより、アルカリ金属と他のインタ
ーカレートを同時に導入する場合は、リチウム、ナトリ
ウムが好適である。The alkali metal used in the present invention is not particularly limited. When an organic molecule is introduced after the introduction of the alkali metal, potassium, rubidium and cesium are preferred. When intercalate is introduced simultaneously, lithium and sodium are preferred.
【００４９】アルカリ金属と共に導入され三成分系黒鉛
層間化合物をなすものとしては、有機分子が好適であ
る。本発明で使用する有機分子は特に限定しないが、ア
ルカリ金属としてカリウム、ルビジウム、セシウムのい
ずれかを用いる場合は不飽和結合をもつ炭化水素が最適
であり、リチウム、ナトリウムのいずれかを用いる場合
はエーテル種有機化合物が最適である。Organic molecules are preferably used as the ternary graphite intercalation compound introduced together with the alkali metal. The organic molecule used in the present invention is not particularly limited, but when using any of potassium, rubidium and cesium as the alkali metal, a hydrocarbon having an unsaturated bond is most suitable, and when using any of lithium and sodium, Most preferred are ether-type organic compounds.
【００５０】ここで、カリウム、ルビジウム、セシウム
のいずれかを用いた場合に不飽和結合をもつ炭化水素が
最も好ましいとされるのは、黒鉛層間で重合がおき空気
中でも比較的安定な物質が作れるため、膨張黒鉛の材料
として使いやすいからである。このような不飽和結合を
もつ炭化水素の例としては、エチレン、プロピレン、ア
セチレンなどがある。Here, when any one of potassium, rubidium and cesium is used, the most preferable is a hydrocarbon having an unsaturated bond because polymerization occurs between the graphite layers and a relatively stable substance can be produced even in air. Therefore, it is easy to use as a material of expanded graphite. Examples of the hydrocarbon having such an unsaturated bond include ethylene, propylene, and acetylene.
【００５１】一方、リチウム、ナトリウムのいずれかを
用いた場合にエーテル種有機化合物が最も好ましいとさ
れるのは、エーテル種有機化合物がリチウム、ナトリウ
ムを溶かしやすいからである。このようなエーテル種有
機化合物の例としては、テトラヒドロフラン、エチレン
グリコールジメチルエーテルなどがある。On the other hand, when either lithium or sodium is used, the ether-type organic compound is most preferred because the ether-type organic compound easily dissolves lithium and sodium. Examples of such ether-type organic compounds include tetrahydrofuran and ethylene glycol dimethyl ether.
【００５２】以下に、黒鉛シートの層間に、アルカリ金
属、有機分子を保持した三成分系黒鉛層間化合物を生成
し、この三成分系黒鉛層間化合物を膨張させることによ
って機能性膨張黒鉛を作る例を図３及び図４を参照しな
がら示すが、本発明はこれに限定されるものではない。An example of producing a functional expanded graphite by generating a ternary graphite intercalation compound holding an alkali metal and an organic molecule between layers of a graphite sheet and expanding the ternary graphite intercalation compound will be described below. Although shown with reference to FIGS. 3 and 4, the present invention is not limited to this.
【００５３】任意の形に切り取った黒鉛シート１０とア
ルカリ金属１１とをパイレックス管１２に真空（１０-4
Pa以下）になるように封入し、管状電気炉８中で３００
℃〜４００℃で加熱する。このようにしてアルカリ金属
の蒸気を黒鉛に接触させることにより、アルカリ金属を
黒鉛層間に保持したアルカリ金属黒鉛層間化合物が得ら
れる。A graphite sheet 10 and an alkali metal 11 cut into an arbitrary shape are vacuumed (10 -4)
Pa or less) and placed in a tubular electric furnace 8 at 300
Heat at <RTIgt; By bringing the vapor of the alkali metal into contact with the graphite in this way, an alkali metal graphite intercalation compound holding the alkali metal between the graphite layers is obtained.
【００５４】この際、使用する黒鉛シートとアルカリ金
属のモル比を、８：１〜２４：１の範囲で調整すること
により、図２（ｄ）に示される様に第１ステージ構造と
第２ステージ構造とが任意の割合で混在したアルカリ金
属層間化合物を得ることができる。At this time, by adjusting the molar ratio of the graphite sheet and the alkali metal to be used in the range of 8: 1 to 24: 1, the first stage structure and the second stage structure as shown in FIG. An alkali metal intercalation compound in which the stage structure and the stage structure are mixed at an arbitrary ratio can be obtained.
【００５５】より具体的には、黒鉛シートとアルカリ金
属を８：１の割合で３００℃、１昼夜加熱することによ
り、組成がＸＣ8である第１ステージ構造のみのアルカ
リ金属層間化合物が得られる。ここで組成式中のＸは、
アルカリ金属を示し、Ｋ、Ｒｂ、Ｃｓのいずれかであ
る。More specifically, by heating the graphite sheet and the alkali metal at a ratio of 8: 1 at 300 ° C. for one day and night, an alkali metal intercalation compound having a composition of XC 8 and having only the first stage structure can be obtained. . Here, X in the composition formula is
Indicates an alkali metal and is any of K, Rb, and Cs.
【００５６】同様に、黒鉛シートとアルカリ金属を２
４：１の割合で３００℃、１昼夜加熱することにより、
組成がＸＣ24である第２ステージ構造のみのアルカリ金
属層間化合物が得られる。Similarly, a graphite sheet and an alkali metal
By heating at 300 ° C for one day and night at a ratio of 4: 1,
An alkali metal intercalation compound having only the second stage structure and having a composition of XC 24 is obtained.
【００５７】また、黒鉛シートとアルカリ金属を８：１
〜２４：１の任意の割合で使用し、これを同様の条件で
加熱することにより、第１ステージ構造と第２ステージ
構造が任意の割合で混在したアルカリ金属層間化合物が
得られる。Further, the graphite sheet and the alkali metal were mixed at a ratio of 8: 1.
By using the mixture at an arbitrary ratio of ２４24: 1 and heating it under the same conditions, an alkali metal intercalation compound in which the first stage structure and the second stage structure are mixed at an arbitrary ratio can be obtained.
【００５８】前記過程で得られたアルカリ金属黒鉛層間
化合物１４に、−１７３℃〜室温の所定の温度で気体状
の有機分子を図４の装置で、数時間接触させることによ
って層間に有機分子が吸収され、黒鉛シートの層間にア
ルカリ金属と有機分子を保持した三成分系黒鉛層間化合
物を得ることができる。By contacting gaseous organic molecules at a predetermined temperature of -173 ° C. to room temperature with the alkali metal graphite intercalation compound 14 obtained in the above process for several hours using the apparatus shown in FIG. A ternary graphite intercalation compound that is absorbed and retains alkali metals and organic molecules between layers of the graphite sheet can be obtained.
【００５９】ここで有機分子はステージ２構造の部分に
吸収されやすく、ステージ１構造の部分には吸収されな
いため、ステージ１構造とステージ２構造との混在の割
合で、有機分子を吸収する層間の数を調節することがで
きる。Here, since the organic molecules are easily absorbed by the stage 2 structure portion and are not absorbed by the stage 1 structure portion, the organic molecules between the layers absorbing the organic molecules are mixed at a mixed ratio of the stage 1 structure and the stage 2 structure. The number can be adjusted.
【００６０】また、有機分子の総吸収量は吸収時の温度
に依存し、液体窒素中などの低温では可逆的かつ比較的
多量の吸収が起こり、室温などの比較的高い温度では不
可逆的かつ少量の吸収が起こる。The total amount of organic molecules absorbed depends on the temperature at the time of absorption, and reversible and relatively large amounts of absorption occur at low temperatures such as in liquid nitrogen, and irreversible and small amounts at relatively high temperatures such as room temperature. Absorption occurs.
【００６１】よって、第１ステージ構造と第２ステージ
構造の割合の調節と、有機分子を吸収させる温度の調節
とを併用することで、より確実に有機分子の吸収量を制
御することができ、熱分解時に黒鉛層を押し広げて膨張
の駆動力を生む熱分解ガスの量をうまく制御できるとい
う利点がある。Therefore, by controlling the ratio between the first stage structure and the second stage structure and controlling the temperature at which organic molecules are absorbed, the amount of organic molecules absorbed can be more reliably controlled. There is an advantage that the amount of pyrolysis gas that generates a driving force for expansion by expanding the graphite layer during pyrolysis can be controlled well.
【００６２】前記過程で得られた三成分系黒鉛層間化合
物を、大気中で約１０００℃程度で電気炉中で急激に燃
焼させることにより黒鉛シートの積層方向のみに膨張
し、図１の１ｃに示される機能性膨張黒鉛が得られる。The ternary graphite intercalation compound obtained in the above process is rapidly burned in an electric furnace at about 1000 ° C. in the air to expand only in the lamination direction of the graphite sheet. The functional expanded graphite shown is obtained.
【００６３】この機能性膨張黒鉛の膨張率は、最大で原
料黒鉛シートの約１０倍で、含有有機分子量と有機分子
を含む層間の数とに依存し、有機分子を含む層間の数と
含まれる有機分子の量が多いほど膨張率は高い。The coefficient of expansion of this functional expanded graphite is about 10 times the maximum of the raw graphite sheet and depends on the organic molecular weight contained and the number of layers containing organic molecules, and is included in the number of layers containing organic molecules. The larger the amount of organic molecules, the higher the expansion rate.
【００６４】また、有機分子としてエチレンを使用した
三成分系層間化合物は、この方法ではほとんど膨張しな
いが、酸素ガスバーナなどの酸素過剰雰囲気中で急激に
燃焼させることにより、膨張させることができる。The ternary intercalation compound using ethylene as an organic molecule hardly expands by this method, but can be expanded by rapidly burning in an oxygen-rich atmosphere such as an oxygen gas burner.
【００６５】エチレンを用いた層間化合物を膨張させる
ために酸素が大量に必要であるのは、この層間化合物が
非常に安定であるため、熱分解を起こさせるために他の
層間化合物よりも厳しい燃焼条件が必要であるためと考
えられる。A large amount of oxygen is required to expand the intercalation compound using ethylene because the intercalation compound is very stable and, therefore, requires more severe combustion than other intercalation compounds to cause thermal decomposition. It is considered that conditions are required.
【００６６】上述の方法以外にも、例えばインターカレ
ートを溶媒に溶かし、この溶媒に原料である黒鉛シート
を浸すことにより、黒鉛層間化合物を生成する方法など
も本発明に用いることができる。このような方法の一例
が図５に示されている。この方法を用いることによっ
て、前記方法では得られない構造の化合物を得ることが
できる。In addition to the above method, a method of dissolving intercalate in a solvent and immersing a graphite sheet as a raw material in the solvent to form a graphite intercalation compound can be used in the present invention. One example of such a method is shown in FIG. By using this method, a compound having a structure that cannot be obtained by the above method can be obtained.
【００６７】例えば、アルカリ金属をナフタレンと共に
溶媒に溶かし、この溶媒に黒鉛シートを浸すことによ
り、アルカリ金属と溶媒分子が共に層間に保持された三
成分系の黒鉛層間化合物が生成される。この反応は気密
性の高い容器中で室温で行われ、アルカリ金属としては
リチウム、ナトリウム、カリウム、溶媒としては、テト
ラヒドロフラン、エチレングリコールジメチルエーテ
ル、テトラヒドロピラン、ジブトキシエタンなどが用い
られる。For example, by dissolving an alkali metal in a solvent together with naphthalene, and immersing the graphite sheet in this solvent, a ternary graphite intercalation compound in which the alkali metal and the solvent molecules are held between the layers is generated. This reaction is performed in a highly airtight container at room temperature, and lithium, sodium, and potassium are used as alkali metals, and tetrahydrofuran, ethylene glycol dimethyl ether, tetrahydropyran, dibutoxyethane, and the like are used as solvents.
【００６８】溶媒中で得られた三成分系層間化合物は、
すべての層間に有機分子が導入されており、前記方法で
は生成不可能な構造である。また、この層間化合物は大
気中で電気炉を用いて１０００℃程度で急熱するという
従来の加熱方法で膨張し、その膨張率は最大で約４０倍
に達し、前記方法では得られない高い膨張率の機能性膨
張黒鉛を得ることができる。The ternary intercalation compound obtained in the solvent is
Organic molecules are introduced between all layers, and the structure cannot be generated by the above method. In addition, this intercalation compound expands by a conventional heating method of rapidly heating at about 1000 ° C. using an electric furnace in the air, and its expansion coefficient reaches a maximum of about 40 times, which is a high expansion that cannot be obtained by the above method. Functional expanded graphite can be obtained.
【００６９】[0069]
【実施例】以下、実施例によって本発明を詳しく説明す
るが、本発明はこれによって限定されるものではない。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited thereto.
【００７０】［試薬］ 黒鉛シート（製品名『グラフォイル』、ユニオンカーバ
イド社製） 金属セシウム（試薬特級） エチレンガス（純度９９．８％） 金属ナトリウム（試薬特級） ナフタレン（試薬特級） エチレングリコールジメチルエーテル（試薬特級）[Reagent] Graphite sheet (product name “GRAFOYL” manufactured by Union Carbide) Metal cesium (special grade reagent) Ethylene gas (purity 99.8%) Metal sodium (special grade reagent) Naphthalene (special grade reagent) Ethylene glycol dimethyl ether ( Reagent grade)
【００７１】［第１実施例］金属セシウム０．１〜０．
２ｇと、直径６ｍｍ、厚さ０．３５ｍｍの円状に切り取
った黒鉛シートとを、モル比がＣ：Ｃｓ＝８：１〜３
６：１になるように秤量してパイレックス管に入れ、
１．３×１０-2Pa以下まで減圧して封入した。この状態
で、管状電気炉を用いて３００℃で１〜３日加熱を行う
ことにより、組成がそれぞれＣｓＣ8、ＣｓＣ16、Ｃｓ
Ｃ24、ＣｓＣ36であるセシウム黒鉛層間化合物が得られ
た。[First Embodiment] Metal cesium 0.1-0.
2 g and a graphite sheet cut into a circle having a diameter of 6 mm and a thickness of 0.35 mm were obtained by molar ratio C: Cs = 8: 1 to 3
Weigh it to 6: 1 and place it in a Pyrex tube,
It was sealed under reduced pressure to 1.3 × 10 -2 Pa or less. In this state, heating is performed at 300 ° C. for 1 to 3 days using a tubular electric furnace, whereby the compositions are CsC 8 , CsC 16 , and Cs, respectively.
Cesium graphite intercalation compounds of C 24 and CsC 36 were obtained.
【００７２】次に、得られたセシウム黒鉛層間化合物を
パイレックス管に入れたままで、エチレンガスを導入す
るための真空ラインにつなぎ、恒温槽を用いてパイレッ
クス管内部が０℃になるように調節し、エチレンガスを
パイレックス管に徐々に導入する。このまま大気圧下で
平衡に達するまでエチレンを吸収させ、平衡状態に達し
た後、真空ポンプで可逆的吸収の分のエチレンを排気す
る。Next, while keeping the obtained cesium-graphite intercalation compound in the Pyrex tube, it was connected to a vacuum line for introducing ethylene gas, and the inside of the Pyrex tube was adjusted to 0 ° C. using a thermostat. Then, ethylene gas is gradually introduced into the Pyrex tube. Ethylene is absorbed under the atmospheric pressure until equilibrium is reached, and after the equilibrium state is reached, ethylene is exhausted by a vacuum pump for reversible absorption.
【００７３】以上により、エチレンが層間に含まれた安
定なセシウム−エチレン黒鉛層間化合物が得られた。得
られた化合物の組成はそれぞれ、Ｃｓ（Ｅｔ）
0.02Ｃ8、Ｃｓ（Ｅｔ）0.31Ｃ16、Ｃｓ（Ｅｔ）0.65Ｃ
24、Ｃｓ（Ｅｔ）0.36Ｃ36であった。As described above, a stable cesium-ethylene graphite intercalation compound containing ethylene between layers was obtained. The compositions of the obtained compounds were respectively Cs (Et)
0.02 C 8 , Cs (Et) 0.31 C 16 , Cs (Et) 0.65 C
24 , Cs (Et) 0.36 C 36 .
【００７４】上記過程で生成したセシウム−エチレン層
間化合物をアルミナ製の坩堝（るつぼ）に入れ、汎用の
都市ガス−酸素バーナで加熱すると、層間化合物は面に
対して垂直方向のみに瞬時に膨張し、円柱状の機能性膨
張黒鉛が生成された。このようにして得られた機能性膨
張黒鉛の膨張率をノギスを用いて測定した結果を元にし
て得られた膨張率とセシウムに対する黒鉛の使用量（モ
ル比）との相関図が、図６に示されている。When the cesium-ethylene intercalation compound formed in the above process is put into a crucible (crucible) made of alumina and heated with a general-purpose city gas-oxygen burner, the intercalation compound expands instantaneously only in the direction perpendicular to the surface. As a result, a columnar functional expanded graphite was produced. FIG. 6 shows a correlation diagram between the expansion coefficient obtained based on the results obtained by measuring the expansion coefficient of the functional expanded graphite thus obtained using calipers and the amount of graphite used relative to cesium (molar ratio). Is shown in
【００７５】図６から明らかなように、セシウム−エチ
レン層間化合物の膨張率はセシウムの含有率が少なくな
るほど大きくなり、組成がＣｓＣ24のときに最大とな
り、原料黒鉛シートの約１０倍であった。エチレンを最
もよく吸収するステージ２構造の部分が多い化合物ほど
膨張の駆動力となるエチレンが多量に保持され、その結
果高膨張率の機能性膨張黒鉛が得られたのは明らかであ
る。[0075] As apparent from FIG. 6, cesium - expansion of ethylene intercalation compound increases as the content of cesium is reduced, composition becomes maximum when the CsC 24, was about 10 times that of the raw material graphite sheet . It is clear that a compound having a greater portion of the stage 2 structure that absorbs ethylene best retains a larger amount of ethylene as a driving force for expansion, and as a result, a functional expanded graphite having a high expansion coefficient was obtained.
【００７６】以上より、セシウムの含有量を調整するこ
とでエチレン吸収量を容易に制御し、ひいては膨張率を
も容易に制御できることがわかった。From the above, it was found that by adjusting the cesium content, the amount of ethylene absorbed could be easily controlled, and the expansion rate could be easily controlled.
【００７７】［第２実施例］エチレングリコールジメチ
ルエーテル１０ｍｌにナフタレンを０．２ｍｏｌ／ｄｍ
3の濃度で溶かした溶液に、金属ナトリウムの塊を１０
０ｍｍ3程度（対黒鉛モル比で大過剰量）加えて溶か
し、反応溶液を作成した。この反応溶液に、第１実施例
で使用したものと同じ黒鉛シート片を数個浸して室温で
１昼夜密閉することにより、ナトリウムイオンとエチレ
ングリコールジメチルエーテル分子を共に層間に保持し
たステージ１構造の層間化合物が得られた。[Second Embodiment] Naphthalene was added at 0.2 mol / dm in 10 ml of ethylene glycol dimethyl ether.
In a solution dissolved at a concentration of 3 , add 10 lump of metallic sodium
About 0 mm 3 (a large excess with respect to graphite molar ratio) was added and dissolved to prepare a reaction solution. By immersing several pieces of the same graphite sheet as used in the first embodiment in this reaction solution and sealing the mixture at room temperature for 24 hours, sodium ion and ethylene glycol dimethyl ether molecules are held between the layers. The compound was obtained.
【００７８】得られた三成分系黒鉛層間化合物を反応溶
液から取り出し、濾紙で余分な液分をすばやく吸い取り
アルミナ製の坩堝に入れ、管状電気炉を用いて１０００
℃で急熱したところ、層間化合物の面と垂直な方向のみ
に膨張した機能性膨張黒鉛が得られた。このステージ１
構造の黒鉛層間化合物の膨張率は最大で約４０倍であ
り、第１実施例の手法では得られない高膨張率の機能性
膨張黒鉛を得ることができた。The obtained ternary graphite intercalation compound was taken out of the reaction solution, excess liquid was quickly sucked off with a filter paper, put into an alumina crucible, and put in a tube electric furnace for 1000 times.
Upon rapid heating at ℃, functional expanded graphite expanded only in the direction perpendicular to the plane of the intercalation compound was obtained. This stage 1
The expansion coefficient of the graphite intercalation compound having the structure is about 40 times at the maximum, and functional expanded graphite having a high expansion coefficient which cannot be obtained by the method of the first embodiment was obtained.
【００７９】[0079]
【発明の効果】以上の説明で明らかなように、本発明に
よれば優れた加工適性と適度な強度を持ち、取扱いが容
易で、しかも側面部だけに黒鉛の端面が広く露出した特
徴的に異方性のある構造の機能性膨張黒鉛を得ることが
できる。As is apparent from the above description, according to the present invention, it has excellent workability and moderate strength, is easy to handle, and has a characteristic feature that the end face of graphite is widely exposed only on the side surfaces. Functional expanded graphite having an anisotropic structure can be obtained.
【図１】機能性膨張黒鉛の模式図FIG. 1 is a schematic view of a functional expanded graphite.
【図２】黒鉛層間化合物のステージ構造の説明図FIG. 2 is an explanatory diagram of a stage structure of a graphite intercalation compound.
【図３】アルカリ金属黒鉛層間化合物の合成に用いる装
置の一例を示す図FIG. 3 is a diagram showing an example of an apparatus used for synthesizing an alkali metal graphite intercalation compound.
【図４】有機分子を導入する工程の一例を示す図FIG. 4 is a diagram showing an example of a step of introducing an organic molecule.
【図５】溶媒を用いた黒鉛層間化合物合成方法の一例を
示す図FIG. 5 shows an example of a method for synthesizing a graphite intercalation compound using a solvent.
【図６】セシウム−エチレン系黒鉛層間化合物の膨張率
と化合物中の黒鉛／セシウム比（モル比）との相関図FIG. 6 is a correlation diagram between the expansion coefficient of a cesium-ethylene-based graphite intercalation compound and the graphite / cesium ratio (molar ratio) in the compound.
１ 黒鉛シート ２ 黒鉛層間化合物 ３ 機能性膨張黒鉛 ４ 黒鉛結晶層 ５ インターカレート ６ 膨張黒鉛粒 ７ マクロ孔 ８ 管状電気炉 ９ ムライト製炉心管 １０ 黒鉛シート １１ アルカリ金属 １２ パイレックス管 １３ ヒーター １４ アルカリ金属層間化合物 １５ 恒温槽 １６ 冷媒 １７ 圧力計 １８ ガスリザーバー １９ コック ２０ インターカレートを溶かした溶媒 ２１ ネジ口瓶 DESCRIPTION OF SYMBOLS 1 Graphite sheet 2 Graphite intercalation compound 3 Functional expanded graphite 4 Graphite crystal layer 5 Intercalate 6 Expanded graphite particles 7 Macropore 8 Tubular electric furnace 9 Mullite furnace tube 10 Graphite sheet 11 Alkali metal 12 Pyrex tube 13 Heater 14 Alkali metal Interlayer compound 15 Constant temperature bath 16 Refrigerant 17 Pressure gauge 18 Gas reservoir 19 Cock 20 Solvent in which intercalate is dissolved 21 Screw bottle
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年１１月１６日（２０００．１１．
１６）[Submission date] November 16, 2000 (200.11.
16)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図５[Correction target item name] Fig. 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図５】 FIG. 5
【手続補正２】[Procedure amendment 2]
【補正対象書類名】図面[Document name to be amended] Drawing
【補正対象項目名】図６[Correction target item name] Fig. 6
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【図６】 FIG. 6
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 32/00 Ｂ０１Ｊ 32/00 Ｈ０１Ｍ 4/58 Ｈ０１Ｍ 4/58 Ｆターム(参考） 4G046 EA05 EB04 EC01 EC08 4G066 AA02D AA04B AA09D AB01D AB03D AB05D BA02 BA21 BA38 FA17 FA22 FA25 FA38 FA40 4G069 AA01 AA08 BA08A BA08B BA12A BA12B BA21A BA21B BC01A BC02A BC02B BC03A BC04A BC05A BC06A BC06B BE02A EA11 FA01 FB29 FB66 5H050 AA19 BA15 CB08 EA06 EA21 GA02 GA03 GA08 GA10 GA12 GA27 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 32/00 B01J 32/00 H01M 4/58 H01M 4/58 F-term (Reference) 4G046 EA05 EB04 EC01 EC08 4G066 AA02D AA04B AA09D AB01D AB03D AB05D BA02 BA21 BA38 FA17 FA22 FA25 FA38 FA40 4G069 AA01 AA08 BA08A BA08B BA12A BA12B BA21A BA21B BC01A BC02A BC02B BC03A BC04A BC05A BC06A BC06B GA02 EA11 GA01 GA03 FB11
Claims (6)
ートを再膨張させてなる機能性膨張黒鉛。1. A functional expanded graphite obtained by reexpanding a graphite sheet formed by pressing an expanded graphite powder under pressure.
レートを保持させた後、該インターカレートを熱分解さ
せることにより、黒鉛材料全体を膨張させて機能性膨張
黒鉛を得る機能性膨張黒鉛の製造方法において、 前記原料となる黒鉛材料として、膨張黒鉛粉末を加圧成
形してなる黒鉛シートを用いることを特徴とする機能性
膨張黒鉛の製造方法。2. Functionally expanded graphite in which the intercalate is thermally decomposed after the intercalate is held between layers of a graphite material as a raw material, whereby the entire graphite material is expanded to obtain a functionally expanded graphite. The method for producing functional expanded graphite, wherein a graphite sheet obtained by press-molding expanded graphite powder is used as the raw material graphite material.
ルカリ金属を用いることを特徴とする請求項２に記載の
機能性膨張黒鉛製造方法。3. The method for producing expanded functional graphite according to claim 2, wherein at least an alkali metal is used as the intercalate.
合を持つ炭化水素を用いることを特徴とする請求項３に
記載の機能性膨張黒鉛製造方法。4. The method for producing a functional expanded graphite according to claim 3, wherein a hydrocarbon having an unsaturated bond is further used as the intercalate.
を酸素過剰雰囲気中で行うことを特徴とする請求項２乃
至４のいずれかに記載の機能性膨張黒鉛製造方法。5. The method for producing a functional expanded graphite according to claim 2, wherein heating for expanding the graphite intercalation compound is performed in an oxygen-excess atmosphere.
いて、 前記三成分系黒鉛層間化合物は黒鉛原料とアルカリ金属
と不飽和結合を持つ炭化水素とから成り、 前記三成分系黒鉛層間化合物の製造方法は、黒鉛原料の
層間にアルカリ金属を挿入させてアルカリ金属層間化合
物を生成する第１の過程と、前記アルカリ金属層間化合
物に不飽和結合を持つ炭化水素を挿入させて三成分系黒
鉛層間化合物を生成する第２の過程からなり、 前記第１の過程は、黒鉛原料とアルカリ金属との配合比
を調整し、アルカリ金属黒鉛層間化合物中に第１ステー
ジ構造と第２ステージ構造が任意の割合で混在するよう
にしたものであることを特徴とする、三成分系黒鉛層間
化合物の製造方法。6. The method for producing a ternary graphite intercalation compound, wherein the ternary graphite intercalation compound comprises a graphite raw material and a hydrocarbon having an unsaturated bond with an alkali metal, and the ternary graphite intercalation compound is produced. The method comprises a first step of forming an alkali metal intercalation compound by inserting an alkali metal between layers of graphite raw material, and a ternary graphite intercalation compound by inserting a hydrocarbon having an unsaturated bond into the alkali metal intercalation compound. The first step is to adjust the compounding ratio of the graphite raw material and the alkali metal, and the first stage structure and the second stage structure can have any ratio in the alkali metal graphite intercalation compound. A method for producing a ternary graphite intercalation compound, characterized in that the ternary graphite intercalation compound is mixed.
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| JP2000349819A JP2002154814A (en) | 2000-11-16 | 2000-11-16 | Functional expanded graphite and method for producing the same |
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| JP2000349819A JP2002154814A (en) | 2000-11-16 | 2000-11-16 | Functional expanded graphite and method for producing the same |
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| JP2002154814A true JP2002154814A (en) | 2002-05-28 |
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