JPH0135768B2 - - Google Patents
Info
- Publication number
- JPH0135768B2 JPH0135768B2 JP56157807A JP15780781A JPH0135768B2 JP H0135768 B2 JPH0135768 B2 JP H0135768B2 JP 56157807 A JP56157807 A JP 56157807A JP 15780781 A JP15780781 A JP 15780781A JP H0135768 B2 JPH0135768 B2 JP H0135768B2
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- alf
- ternary
- stage
- intercalation compound
- 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.)
- Expired
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 88
- 229910002804 graphite Inorganic materials 0.000 claims description 82
- 239000010439 graphite Substances 0.000 claims description 82
- 150000001875 compounds Chemical class 0.000 claims description 72
- 238000009830 intercalation Methods 0.000 claims description 50
- 230000002687 intercalation Effects 0.000 claims description 49
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 12
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- RGPBQGGBWIMGMA-BJMVGYQFSA-N 5-[(e)-[5-(4-bromophenyl)-6-hydroxy-3,6-dihydro-1,3,4-oxadiazin-2-ylidene]methyl]-1h-pyrimidine-2,4-dione Chemical compound OC1O\C(=C\C=2C(NC(=O)NC=2)=O)NN=C1C1=CC=C(Br)C=C1 RGPBQGGBWIMGMA-BJMVGYQFSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910019080 Mg-H Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Conductive Materials (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Carbon And Carbon Compounds (AREA)
Description
本発明は新規な黒鉛層間化合物に関する。更に
詳細には、本発明は湿気に対して安定であるのみ
ならず優れた電導性を有する黒鉛とフツ化アルミ
ニウム及びフツ素との３成分系黒鉛層間化合物に
関する。本発明は又、黒鉛とフツ化アルミニウム
及びフツ素との３成分系黒鉛層間化合物の製造方
法に関する。本発明は更に又、黒鉛とフツ化アル
ミニウム及びフツ素との３成分系黒鉛層間化合物
から成る電導材料に関する。
近年、フツ化物の黒鉛層間化合物が、その秀れ
た電導性の故に注目されつつある。しかし従来よ
り知られている黒鉛層間化合物の殆どは湿気に対
して不安定であり、従つて空気中に放置するとた
だちに分解する。ゆえに実用に供することが不可
能である。これまで、黒鉛層間化合物を作る侵入
物質として用いられているフツ化物は融点及び沸
点ともに低く、室温ではガス状又は液状である。
ゆえに、一般に侵入物質としてのフツ化物は比較
的低温で高い蒸気圧を持つことが必要であるとい
うことが通念となつていた。そのため、高い融点
乃至沸点を有するフツ化物の黒鉛層間化合物の製
造の試みはなされなかつた。事実、高温でも蒸気
圧を示さないフツ化アルミニウムと黒鉛との２成
分系黒鉛層間化合物は生成しない。
本発明者らは、優れた電導性を有するばかりで
なく湿気に対して極めて安定な、実用に供し得る
フツ化物の黒鉛層間化合物を開発すべく鋭意研究
を重ね、その結果、式CxＦ（AlF3）yで表わされる
黒鉛とフツ化アルミニウム及びフツ素との３成分
系黒鉛層間化合物（以下、しばしば単に“３成分
系黒鉛層間化合物”と略記する）が原料黒鉛に対
して100％の収率で得られることを見出した。得
られた３成分系黒鉛層間化合物は湿気に対して安
定であるのみならず耐熱性も高く、又優れた電導
性を有する。本発明の３成分系黒鉛層間化合物の
電導度は原料黒鉛に較べ一桁高い優れたものであ
る。本発明はこのような新しい知見に基づき成さ
れたものである。
したがつて本発明の目的は、湿気に対して安定
であるのみならず耐熱性も高く、又優れた電導性
を有する新規な３成分系黒鉛層間化合物を提供す
ることにある。
本発明の他の一つの目的は、この新規な３成分
系黒鉛層間化合物の製造方法を提供することにあ
る。
本発明の他の更に一つの目的は、上述の如き新
規な３成分系黒鉛層間化合物から成る新規な電導
材料を提供することにある。
上記及び他の諸目的は、本発明の諸特徴及び諸
利益は、以下に述べる詳細な説明及び添付の図面
から明かになろう。
本発明の一つの態様によれば、式CxＦ（AlF3）y
で表わされる黒鉛とフツ化アルミニウム及びフツ
素との３成分系黒鉛層間化合物が提供される。
一般に、式CxＦ（AlF3）yで表わされる３成分系
黒鉛層間化合物は、原料黒鉛を、フツ素雰囲気下
で温度０〜400℃にて少なくとも該黒鉛に重量増
加を起こさせる時間AlF3と接触させることによ
つて得られる。
以下、本発明を更に詳細に説明する。
式CxＦ（AlF3）yで表わされる本発明の３成分系
黒鉛層間化合物には、第１ステージ、第２ステー
ジ、第３ステージ又は第４ステージもしくはそれ
以上のステージ数のものがある。３成分系黒鉛層
間化合物のステージ数は、Ｘ線回折から得られる
周期距離Icを測定することにより求められる。得
られた３成分系黒鉛層間化合物のステージ数は反
応温度及び時間のみならず原料黒鉛の結晶性及び
厚み（Ｃ軸方向）にも影響される。第１ステージ
のものは、ｘ＝約3.0〜20、ｙ＝約0.03〜0.20であ
る。第２ステージのものは、ｘ＝約11〜50、ｙ＝
約0.01〜0.15である。第３ステージ以上のもの
は、ｘ＝約30〜60、ｙ＝10-4〜10-2である。一般
に式CxＦ（AlF3）yで表わされる３成分系黒鉛層間
化合物において、ｘは約３〜100であり、ｙは約
0.0001〜0.20である。第１ステージ、第２ステー
ジ、第３ステージ及び第４ステージもしくはそれ
以上のステージ数の化合物のそれぞれについて、
ｘとｙの値は、上述の範囲内で、反応温度及び時
間のみならず、原料黒鉛の結晶性及びＣ軸方向の
厚みによつて変化する。
本発明に用いられる黒鉛原材料としては、天然
黒鉛のほか、石油コークスなどを加熱処理して得
られる人造黒鉛も用いることができる。粒径は臨
界的ではなくフレーク状あるいは粉状で、約20〜
50メツシユ又は50〜400メツシユ又は400メツシユ
以上（タイラー）のものを用いることができる。
又、ブロツク状の黒鉛が望まれる場合には、メタ
ン、プロパン、ベンゼン及びないし又はアセチレ
ンなどの炭化水素を約2100℃に加熱された基材
（一般に人造黒鉛から成る）に接触させて炭化水
素を熱分解し、得られた黒鉛材料を基材上に沈積
し、その後沈積した黒鉛材料を熱処理して得られ
たものを用いることができる。その場合、熱処理
温度に応じて黒鉛化度の異なつたブロツク状黒鉛
が得られる。約2400℃で熱処理を行なうと、パイ
ロテイツクカーボンが得られる。約2600℃〜3000
℃で熱処理を行なうとパイロテイツクカーボンに
比べて高い結晶性を有するパイロテイツク グラ
フアイトが得られる。
原料黒鉛をフツ素雰囲気下で温度０〜400℃に
て少なくとも該黒鉛に重量増加を起こさせる時間
AlF3と接触させることによつて行なわれる、式
CxＦ（AlF3）yで表わされる３成分系黒鉛層間化合
物の製造に関し、望ましい反応条件は下記の通り
である。フツ素圧は特に臨界的ではないが、通常
0.5〜10atm位が用いられる。反応温度は０〜400
℃、好ましくは15〜370℃である。前述したよう
に、望ましいｘ値及びｙ値を有する、式CxＦ
（AlF3）yで表わされる化合物を得るための反応時
間は、原料黒鉛の結晶性及びＣ軸方向の厚み、且
つ反応温度とに依存する。しかし、反応時間は一
般に１時間〜10日、更に一般には１日〜８日であ
る。原料黒鉛のAlF3に対する重量比は３成分系
黒鉛層間化合物の望ましいステージ数に依存する
が、通常１：0.4〜１：10である。反応条件に関
して注目すべきことは、反応系の温度が100℃よ
り高い温度まで上げられた場合、いつたん加熱し
た反応系を冷却する過程において、温度が100℃
を下回つた時点で黒鉛に重量増加が認められると
いう点である。原料黒鉛のＣ軸方向の厚みが１mm
より厚い場合、生成物は第１ステージ化合物であ
る第２ステージもしくは第１ステージよりむしろ
高いステージ数の化合物である場合が多い。第１
ステージ化合物を得るためには、通常、厚み（Ｃ
軸方向）が0.8mmまでの黒鉛材料を用いるのが好
ましい。
反応終了後、反応系の温度が室温より高い温度
にまで上げられていた場合、反応系の温度は室温
にまで下げられる。未反応のAlF3はシーブかピ
ンセツトによつて分離され、式CxＦ（AlF3）yで表
わされる所望の３成分系黒鉛層間化合物が得られ
る。
CxＦ（AlF3）yの周期距離Icは、第１ステージの
ものについては9.4〜9.5Å、第２ステージのもの
については12.8〜12.9Å、第３ステージのものに
ついては16.1〜16.2Å、そして第４ステージのも
のについては19.5〜19.6Åである。式CxＦ（AlF3）
yで表わされる３成分系黒鉛層間化合物の場合、
第１ステージ化合物は青黒色から黒色を呈し、第
２、第３、及び第４ステージ化合物は黒色を呈す
る。式CxＦ（AlF3）yで表わされる本発明による３
成分系黒鉛層間化合物は全て、湿気に対して非常
に安定であるため、数週間空気中に放置したり、
１晩水に浸しておいてもそのＸ線回折図には何の
変化も見られない。
式CxＦ（AlF3）yで表わされる本発明の３成分系
黒鉛層間化合物のいくつかの例について、元素分
析及びＸ線回折を行なつた結果を第１表に示す。
The present invention relates to a novel graphite intercalation compound. More particularly, the present invention relates to a ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine, which is not only stable against moisture but also has excellent electrical conductivity. The present invention also relates to a method for producing a ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine. The present invention also relates to a conductive material comprising a ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine. In recent years, fluoride graphite intercalation compounds have been attracting attention because of their excellent electrical conductivity. However, most of the conventionally known graphite intercalation compounds are unstable to moisture and therefore decompose immediately when left in air. Therefore, it is impossible to put it into practical use. Fluorides, which have been used as intercalating substances to create graphite intercalation compounds, have low melting and boiling points and are gaseous or liquid at room temperature.
Therefore, it has been generally accepted that fluoride as an interstitial substance needs to have a relatively low temperature and high vapor pressure. Therefore, no attempt has been made to produce a fluoride graphite intercalation compound having a high melting point or boiling point. In fact, a binary graphite intercalation compound of aluminum fluoride and graphite, which exhibits no vapor pressure even at high temperatures, is not produced. The present inventors have conducted extensive research to develop a practically usable fluoride graphite intercalation compound that not only has excellent conductivity but is also extremely stable against moisture, and as a result, has the formula C x F ( AlF 3 ) A ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine (hereinafter often simply referred to as "ternary graphite intercalation compound") represented by y has a yield of 100% relative to the raw material graphite. I found that it can be obtained at a lower rate. The obtained three-component graphite intercalation compound is not only stable against moisture but also has high heat resistance and excellent electrical conductivity. The electrical conductivity of the ternary graphite intercalation compound of the present invention is one order of magnitude higher than that of the raw material graphite. The present invention has been made based on this new knowledge. Therefore, an object of the present invention is to provide a novel three-component graphite intercalation compound that is not only stable against moisture but also has high heat resistance and excellent electrical conductivity. Another object of the present invention is to provide a method for producing this novel ternary graphite intercalation compound. Another object of the present invention is to provide a novel electrically conductive material comprising the novel ternary graphite intercalation compound as described above. These and other objects, features and advantages of the present invention will become apparent from the following detailed description and accompanying drawings. According to one embodiment of the invention, the formula C x F(AlF 3 ) y
A ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine is provided. In general, a ternary graphite intercalation compound represented by the formula C x F (AlF 3 ) y is prepared by treating raw graphite in a fluorine atmosphere at a temperature of 0 to 400°C for at least a period of time to cause the graphite to increase in weight . obtained by contacting with. The present invention will be explained in more detail below. The ternary graphite intercalation compound of the present invention represented by the formula C x F (AlF 3 ) y may have a first stage, a second stage, a third stage, a fourth stage, or more. The number of stages of the ternary graphite intercalation compound is determined by measuring the periodic distance I c obtained from X-ray diffraction. The number of stages of the obtained ternary graphite intercalation compound is influenced not only by the reaction temperature and time but also by the crystallinity and thickness (in the C-axis direction) of the raw graphite. For the first stage, x=about 3.0-20 and y=about 0.03-0.20. For the second stage, x=about 11-50, y=
It is approximately 0.01-0.15. For the third stage and above, x=approximately 30 to 60 and y=10 -4 to 10 -2 . In the ternary graphite intercalation compound generally represented by the formula C x F(AlF 3 ) y , x is about 3 to 100 and y is about
It is 0.0001 to 0.20. For each compound of the first stage, second stage, third stage, and fourth stage or more stages,
The values of x and y vary within the above-mentioned ranges depending not only on the reaction temperature and time but also on the crystallinity of the raw graphite and the thickness in the C-axis direction. As the graphite raw material used in the present invention, in addition to natural graphite, artificial graphite obtained by heat treating petroleum coke or the like can also be used. Particle size is not critical, flake-like or powder-like, approximately 20 to
50 meshes, 50 to 400 meshes, or more than 400 meshes (Tyler) can be used.
Alternatively, if block-shaped graphite is desired, hydrocarbons such as methane, propane, benzene, and/or acetylene are brought into contact with a substrate (generally made of artificial graphite) heated to about 2100°C. The graphite material obtained by thermal decomposition is deposited on a base material, and then the deposited graphite material is heat-treated, which can be used. In that case, block-shaped graphite having different degrees of graphitization can be obtained depending on the heat treatment temperature. Pyrotechnic carbon is obtained by heat treatment at approximately 2400°C. Approximately 2600℃~3000℃
When heat treated at 0.degree. C., pyrotechnic graphite having higher crystallinity than pyrotechnic carbon can be obtained. At least a period of time to cause the graphite to increase in weight at a temperature of 0 to 400°C in a fluorine atmosphere.
By contacting with AlF 3 , the formula
Regarding the production of a ternary graphite intercalation compound represented by C x F (AlF 3 ) y , desirable reaction conditions are as follows. Fluorine pressure is not particularly critical, but usually
Approximately 0.5 to 10 atm is used. Reaction temperature is 0~400
℃, preferably 15 to 370℃. As mentioned above, the formula C x F with desired x and y values
The reaction time to obtain the compound represented by (AlF 3 ) y depends on the crystallinity and thickness of the raw graphite in the C-axis direction, and the reaction temperature. However, reaction times generally range from 1 hour to 10 days, more typically from 1 day to 8 days. The weight ratio of raw graphite to AlF 3 depends on the desired number of stages of the ternary graphite intercalation compound, but is usually 1:0.4 to 1:10. Regarding the reaction conditions, it should be noted that if the temperature of the reaction system is raised to a temperature higher than 100℃, the temperature will rise to 100℃ in the process of cooling the heated reaction system.
The point is that an increase in weight of graphite is observed when the weight drops below . The thickness of raw graphite in the C-axis direction is 1mm.
When thicker, the product is often a higher stage number compound rather than a second stage or first stage compound. 1st
To obtain a stage compound, the thickness (C
It is preferable to use graphite material with a diameter of up to 0.8 mm (in the axial direction). After the reaction is completed, if the temperature of the reaction system has been raised to a temperature higher than room temperature, the temperature of the reaction system is lowered to room temperature. Unreacted AlF 3 is separated using a sieve or tweezers to yield the desired ternary graphite intercalation compound having the formula C x F (AlF 3 ) y . The periodic distance I c of C x F (AlF 3 ) y is 9.4 to 9.5 Å for the first stage, 12.8 to 12.9 Å for the second stage, and 16.1 to 16.2 Å for the third stage. , and 19.5-19.6 Å for the fourth stage. Formula C x F( AlF3 )
In the case of a ternary graphite intercalation compound represented by y ,
The first stage compounds exhibit a blue-black to black color, and the second, third, and fourth stage compounds exhibit a black color. 3 according to the invention with the formula C x F(AlF 3 ) y
All component-based graphite intercalation compounds are very stable to moisture, so they can be left in the air for several weeks,
Even after soaking in water overnight, no change was observed in its X-ray diffraction pattern. Table 1 shows the results of elemental analysis and X-ray diffraction of some examples of the ternary graphite intercalation compound of the present invention represented by the formula C x F (AlF 3 ) y .
【表】
第１図には、C6F（AlF3）0.15のＸ線回折図（Cu
−K〓）を、（C2F）o71重量％及び（CF）o29重量％
から成るフツ化黒鉛のそれと対比して示す。上述
の３成分系黒鉛層間化合物のＸ線回折パターンを
考察すると、ブロードな回折線が時々観察され
る。第１図に示されるCxＦ（AlF3）yで表わされる
化合物の内の一種についての周期距離Icは、00l
回折線から計算され、9.4Åである。
第２図には、C11F（AlF3）0.09のDTA曲線（昇
温速度20℃／分にて、空気中にて測定）を示す。
第２図においては、C11F（AlF3）0.09の発熱のブロ
ードなピークが230℃の附近で最初に開始するの
が認められる。ESCAは、ホスト黒鉛と侵入物質
の間の化学結合に関する貫重な情報を得るための
最も有用な手段の一つである。第３図には第１ス
テージ化合物〔C6F（AlF3）0.15〕及びCxＦ（AlF3）
yの第２ステージ化合物のESCAスペクトルを、
（C2F）o71重量％及び（CF）o29重量％から成るフ
ツ化黒鉛のそれと対比して示す。（C2F）o型のフ
ツ化黒鉛については、コンタミネーシヨン炭素の
1sピークが284.0eVのところに観察されるのに対
し、炭素の1sピークが289.0eVと287.0eVのとこ
ろに２個観察される。289.0eVのところに観察さ
れるC1SピークはＣ−Ｆ結合に由来するものであ
り、287.0eVのところに観察されるC1SピークはＣ
−Ｆ結合に隣接するＣ−Ｃ結合に由来するもので
ある。（CF）o型のフツ化黒鉛はＣ−Ｃ結合のみし
か有していないため、ESCAスペクトルは
289.0eVのところにC1Sピークを１個有するのみで
ある。第２ステージ化合物については、284.0eV
のところに強いピークが観察され、286eVから
291eVの範囲にわたつて広いシヨルダーが見られ
る。後者は、ホスト黒鉛の炭素原子に化学的に吸
着し且つ共有結合したフツ素原子が存在すること
を示唆するものである。F1Sスペクトルも又、
687.6eVのところに比較的ブロードなピークを持
つ。
C6F（AlF3）0.15によるC1Sピークはフツ化黒鉛と
同じ位置に観察されるが、これはホスト黒鉛と侵
入したフツ素との間の化学結合が殆ど（C2F）oの
それに類似した共有結合であることを示してい
る。
ESCA考察において、各原子の内殻から発する
光電子のエネルギーが測定される。固体における
光電子の平均自由行程はせいぜい数十Å程度であ
るため、黒鉛層間化合物においては僅か数層の黒
鉛層が分析できるにすぎない。よつて、化合物の
表面附近の化学結合がESCAスペクトルにおいて
は強く出てくる。分析した化学組成物のピークの
強さを比較すると、第１ステージ化合物の表面附
近には少量のフツ化黒鉛が生成されていることが
分る。
式CxＦ（AlF3）yで表わされる３成分系黒鉛層間
化合物の生成については、下記のことが考えられ
る。気体種（AlF3）n・（F2）oが次式によつて表わ
されるAlF3とフツ素との反応によつて最初に生
成する。
mAlF3＋nF2（AlF3）n・（F2）o
上述の気体種は次に黒鉛に侵入する。温度上昇
と共に化学的平衡は左に移動し、気体状の錯化合
物には高温において分解する。
上述の如く、本発明による３成分系黒鉛層間化
合物を数週間空気中に放置し、その後Ｘ線回折法
による分析を行なつても、空気中に放置しなかつ
たものと殆ど同じＸ線回折パターンが得られる。
本発明による３成分系黒鉛層間化合物は、空気中
に放置するとただちに分解してしまう従来のフツ
化物−黒鉛層間化合物とは異なり、湿気に対して
安定である。
本発明による３成分系黒鉛層間化合物のａ軸方
向（黒鉛層に対して平行な方向）における電導度
について、一般に当業者には、第２ステージ化合
物と第３ステージ化合物との間には実質上電導度
における差異はないこと、及び第２ステージ、第
３ステージ化合物の電導度は他のステージの化合
物のそれに比べて優れていることが知られている
〔デイー・ビランド、エー・エロルド及びエフ・
フオーゲル、シンセテイツク メタルス第３号
（1981）、第279〜288頁（D.Billand、A.He´rold
and F.Vorgel、SYNTHETIC METALS、３
（1981）279−288）を参照〕。本発明による３成分
系黒鉛層間化合物は湿気に対して安定であるのみ
ならず高い電導度を有する。本発明による３成分
系黒鉛層間化合物は、銅箔に包みこんだり、エポ
キシなどに含入せしめることによつて電導材料と
して用いることができる。本発明による３成分系
黒鉛層間化合物は電導材料として有用であるのみ
ならず、各種の有機反応における触媒としても用
いることができる。
次に本発明の実施例を挙げるが、本発明の範囲
は実施例に限定されるものではない。
実施例
マダガスカル産フレーク状天然黒鉛（297〜
840μｍ）0.3ｇと粉末状AlF30.6ｇを混合し、Ni製
反応管に入れ真空排気する。これに温度25℃でフ
ツ素ガスを導入して１気圧とし、30分間放置後
350℃まで４℃／分の昇温速度で昇温し、30時間
反応させた。次に反応管を25℃まで冷却した。フ
ツ素ガスをチツ素で置換した。反応終了後、生成
物と未反応のAlF3を297μｍのシーブを用いて分
離し、青黒色の黒鉛層間化合物C6F（AlF3）0.15を
得た。
ところでここに記載のESCA考察は、デユポン
社製650B電子分光計を用いて、Mg−H〓線で行
なつたものである。DTAについては、空気中に
てα−Al2O3を対照として行なつた。Alの分析は
原子吸収法によつて行なつた。
上述の実施例より、本発明が式CxＦ（AlF3）yで
表わされ、優れた特性を有する新規な黒鉛層間化
合物及びその製造方法を提供するものであること
が明らかである。又、本発明の諸特徴及び諸利益
は前述した詳細な説明において挙げられた多くの
実験データより明らかである。[Table] Figure 1 shows the X-ray diffraction diagram of C 6 F (AlF 3 ) 0.15 (Cu
−K〓), (C 2 F) o 71% by weight and (CF) o 29% by weight
This is shown in comparison with that of graphite fluoride, which consists of fluorinated graphite. When considering the X-ray diffraction pattern of the above-mentioned ternary graphite intercalation compound, broad diffraction lines are sometimes observed. The periodic distance I c for one of the compounds represented by C x F (AlF 3 ) y shown in Figure 1 is 00l
Calculated from the diffraction line, it is 9.4 Å. FIG. 2 shows the DTA curve of C 11 F(AlF 3 ) 0.09 (measured in air at a heating rate of 20° C./min).
In FIG. 2, it can be seen that a broad exothermic peak of C 11 F(AlF 3 ) 0.09 first starts around 230°C. ESCA is one of the most useful tools to obtain thorough information on the chemical bonding between host graphite and interloping substances. Figure 3 shows the first stage compounds [C 6 F (AlF 3 ) 0.15 ] and C x F (AlF 3 ).
The ESCA spectrum of the second stage compound of y is
It is shown in comparison with that of fluorinated graphite consisting of 71% by weight of (C 2 F) o and 29% by weight of (CF) o . (C 2 F) For o- type graphite fluoride, contamination carbon
The 1s peak is observed at 284.0eV, while two carbon 1s peaks are observed at 289.0eV and 287.0eV. The C 1S peak observed at 289.0eV originates from the C-F bond, and the C 1S peak observed at 287.0eV originates from the C-F bond.
It originates from the C--C bond adjacent to the -F bond. (CF) O -type graphite fluoride has only C-C bonds, so the ESCA spectrum is
It has only one C 1S peak at 289.0eV. For second stage compounds, 284.0eV
A strong peak was observed at 286 eV
A broad shoulder can be seen over the 291eV range. The latter suggests the presence of fluorine atoms chemically adsorbed and covalently bonded to the carbon atoms of the host graphite. The F 1S spectrum is also
It has a relatively broad peak at 687.6eV. The C 1S peak due to C 6 F (AlF 3 ) 0.15 is observed at the same position as that of fluorinated graphite, but this is because most of the chemical bonds between the host graphite and the penetrating fluorine are similar to those of (C 2 F) o. This indicates a similar covalent bond. In ESCA considerations, the energy of photoelectrons emitted from the inner shell of each atom is measured. Since the mean free path of photoelectrons in a solid is approximately several tens of angstroms at most, only a few graphite layers can be analyzed in graphite intercalation compounds. Therefore, chemical bonds near the surface of a compound appear strongly in the ESCA spectrum. A comparison of the peak intensities of the analyzed chemical compositions reveals that a small amount of graphite fluoride is produced near the surface of the first stage compound. Regarding the formation of the ternary graphite intercalation compound represented by the formula C x F (AlF 3 ) y , the following may be considered. The gaseous species (AlF 3 ) n ·(F 2 ) o is first generated by the reaction between AlF 3 and fluorine as expressed by the following equation. mAlF 3 +nF 2 (AlF 3 ) n ·(F 2 ) o The above gaseous species then penetrate the graphite. As the temperature increases, the chemical equilibrium shifts to the left, and gaseous complexes decompose at high temperatures. As mentioned above, even if the ternary graphite intercalation compound according to the present invention is left in the air for several weeks and then analyzed by X-ray diffraction, the X-ray diffraction pattern is almost the same as that obtained when it was not left in the air. is obtained.
The ternary graphite intercalation compound according to the present invention is stable against moisture, unlike conventional fluoride-graphite intercalation compounds which decompose immediately when left in air. Regarding the electrical conductivity in the a-axis direction (direction parallel to the graphite layer) of the ternary graphite intercalation compound according to the present invention, it is generally known to those skilled in the art that there is a substantial difference between the second stage compound and the third stage compound. It is known that there is no difference in conductivity, and that the conductivities of the second and third stage compounds are superior to those of other stage compounds [D. Billand, A. Herold and F.
Fogel, Synthetic Metals No. 3 (1981), pp. 279-288 (D. Billand, A. Her´rold
and F.Vorgel, SYNTHETIC METALS, 3
(1981) 279-288)]. The ternary graphite intercalation compound according to the invention is not only stable against moisture but also has high electrical conductivity. The ternary graphite intercalation compound according to the present invention can be used as a conductive material by wrapping it in copper foil or incorporating it into epoxy or the like. The ternary graphite intercalation compound according to the present invention is not only useful as a conductive material, but also can be used as a catalyst in various organic reactions. Next, examples of the present invention will be described, but the scope of the present invention is not limited to the examples. Example Flake natural graphite from Madagascar (297~
840 μm) and 0.6 g of powdered AlF 3 were mixed, placed in a Ni reaction tube, and evacuated. Fluorine gas was introduced into this at a temperature of 25℃ to create a pressure of 1 atm, and after leaving it for 30 minutes.
The temperature was raised to 350°C at a rate of 4°C/min, and the reaction was carried out for 30 hours. The reaction tube was then cooled to 25°C. Fluorine gas was replaced with nitrogen. After the reaction was completed, the product and unreacted AlF 3 were separated using a 297 μm sieve to obtain a blue-black graphite intercalation compound C 6 F (AlF 3 ) 0.15 . By the way, the ESCA study described here was conducted using the Mg-H ray using a DuPont 650B electron spectrometer. DTA was performed in air using α-Al 2 O 3 as a control. Analysis of Al was performed by atomic absorption method. From the above examples, it is clear that the present invention provides a novel graphite intercalation compound represented by the formula C x F (AlF 3 ) y and having excellent properties, and a method for producing the same. The features and benefits of the present invention are also apparent from the extensive experimental data set forth in the foregoing detailed description.
第１図に本発明による３成分系黒鉛層間化合物
の一例であるC6F（AlF3）0.15のＸ線回折図をフツ
化黒鉛のそれと対比して示す。
第２図に本発明による３成分系黒鉛層間化合物
の他の一つの例であるC11F（AlF3）0.09のDTA曲
線を示す。第３図にフツ化金属としてAlF3をそ
れぞれ含有する本発明の第１ステージ化合物及び
第２ステージ化合物のESCAスペクトルをフツ化
黒鉛のそれと対比して示す。
FIG. 1 shows the X-ray diffraction pattern of C 6 F (AlF 3 ) 0.15 , which is an example of the ternary graphite intercalation compound according to the present invention, in comparison with that of graphite fluoride. FIG. 2 shows the DTA curve of C 11 F (AlF 3 ) 0.09, which is another example of the ternary graphite intercalation compound according to the present invention. FIG. 3 shows the ESCA spectra of the first stage compound and second stage compound of the present invention, each containing AlF 3 as the metal fluoride, in comparison with that of graphite fluoride.
Claims (1)
ルミニウム及びフツ素との３成分系黒鉛層間化合
物。 ２ ｘが約３〜100でｙが約0.0001〜0.20である
ことを特徴とする特許請求の範囲第１項に記載の
３成分系黒鉛層間化合物。 ３ 該３成分系黒鉛層間化合物が、第１ステージ
化合物、第２ステージ化合物、第３ステージ化合
物及び第４ステージ化合物より成る群から選ばれ
た少なくとも２種より成る混合ステージ化合物で
あることを特徴とする特許請求の範囲第１項に記
載の３成分系黒鉛層間化合物。 ４ 原料黒鉛をフツ素雰囲気下に０〜400℃の温
度で少なくとも該黒鉛に重量増加を起こさせる時
間AlF3と接触せしめることを特徴とする式CxＦ
（AlF3）yで表わされる黒鉛とフツ化アルミニウム
及びフツ素との３成分系黒鉛層間化合物の製造方
法。 ５ 原料黒鉛とフツ化アルミニウムの重量比が
１：0.4〜１：10であることを特徴とする特許請
求の範囲第４項に記載の方法。 ６ 温度が15〜370℃であることを特徴とする特
許請求の範囲第４項に記載の方法。 ７ フツ素雰囲気のフツ素圧が0.5〜10atmであ
ることを特徴とする特許請求の範囲第４項に記載
の方法。 ８ 式CxＦ（AlF3）yで表わされる黒鉛とフツ化ア
ルミニウム及びフツ素との３成分系黒鉛層間化合
物より成る電導材料。[Claims] 1. A ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine represented by the formula C x F (AlF 3 ) y . 2. The ternary graphite intercalation compound according to claim 1, wherein x is about 3 to 100 and y is about 0.0001 to 0.20. 3. The ternary graphite intercalation compound is a mixed stage compound consisting of at least two types selected from the group consisting of a first stage compound, a second stage compound, a third stage compound and a fourth stage compound. A ternary graphite intercalation compound according to claim 1. 4 Formula C x F characterized in that the raw graphite is brought into contact with AlF 3 in a fluorine atmosphere at a temperature of 0 to 400°C for at least a period of time to cause the graphite to increase in weight.
(AlF 3 ) A method for producing a ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine represented by y . 5. The method according to claim 4, wherein the weight ratio of raw material graphite to aluminum fluoride is 1:0.4 to 1:10. 6. The method according to claim 4, wherein the temperature is 15 to 370°C. 7. The method according to claim 4, wherein the fluorine pressure of the fluorine atmosphere is 0.5 to 10 atm. 8 A conductive material made of a ternary graphite intercalation compound of graphite, aluminum fluoride, and fluorine represented by the formula C x F (AlF 3 ) y .
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56157807A JPS5860607A (en) | 1981-10-03 | 1981-10-03 | Interlaminar compound in graphite of aluminum fluoride and fluorine and its preparation |
| US06/394,530 US4477374A (en) | 1981-10-03 | 1982-07-02 | Ternary intercalation compound of a graphite with a metal fluoride and fluorine, a process for producing the same, and an electrically conductive material comprising the ternary intercalation compound |
| GB08219748A GB2107296B (en) | 1981-10-03 | 1982-07-08 | A ternary intercalation compound of graphite with a metal fluoride and fluorine a process for producing the same and an electrically conductive material comprising the ternary intercalation compound |
| IT22633/82A IT1152305B (en) | 1981-10-03 | 1982-07-29 | GRAPHITE INTERCALAR TERNARY COMPOUND WITH A METALLIC FLUORIDE AND FLUOR, PROCEDURE FOR ITS PRODUCTION AND ELECTRICALLY CONDUCTING MATERIAL INCLUDING THE INTERCALAR TERNARY COMPOUND |
| NL8203056A NL8203056A (en) | 1981-10-03 | 1982-07-30 | NEW INTERCALAR JOINT OF GRAPHITE. |
| FR8213413A FR2513981B1 (en) | 1981-10-03 | 1982-07-30 | TERNARY COMPOUND OF INTERCALATION OF A GRAPHITE WITH A FLUORIDE OF A METAL AND FLUOR, METHOD FOR THE PRODUCTION THEREOF AND ELECTRICALLY CONDUCTIVE MATERIAL CONTAINING THE SAME |
| DE3235596A DE3235596A1 (en) | 1981-10-03 | 1982-09-25 | TERNAERE STORAGE LINK, METHOD FOR THEIR PRODUCTION AND ELECTRICALLY CONDUCTIVE MATERIAL, CONTAINING THE LINK |
| NL8603066A NL8603066A (en) | 1981-10-03 | 1986-12-01 | NEW INTERCALATION JOINTS OF GRAPHITE. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56157807A JPS5860607A (en) | 1981-10-03 | 1981-10-03 | Interlaminar compound in graphite of aluminum fluoride and fluorine and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5860607A JPS5860607A (en) | 1983-04-11 |
| JPH0135768B2 true JPH0135768B2 (en) | 1989-07-27 |
Family
ID=15657711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56157807A Granted JPS5860607A (en) | 1981-10-03 | 1981-10-03 | Interlaminar compound in graphite of aluminum fluoride and fluorine and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5860607A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6287407A (en) * | 1985-10-12 | 1987-04-21 | Res Dev Corp Of Japan | Filmy graphite interlaminar compound and production thereof |
| JP7695997B2 (en) * | 2020-12-15 | 2025-06-19 | ロベルト・ボッシュ・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング | Method for producing an electrically conductive conductor strand having at least one carbon conductor |
-
1981
- 1981-10-03 JP JP56157807A patent/JPS5860607A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5860607A (en) | 1983-04-11 |
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