JP3089682B2 - Graphite intercalation compound - Google Patents
Graphite intercalation compoundInfo
- Publication number
- JP3089682B2 JP3089682B2 JP03063508A JP6350891A JP3089682B2 JP 3089682 B2 JP3089682 B2 JP 3089682B2 JP 03063508 A JP03063508 A JP 03063508A JP 6350891 A JP6350891 A JP 6350891A JP 3089682 B2 JP3089682 B2 JP 3089682B2
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- intercalation compound
- titanium
- graphite intercalation
- oxyfluoride
- 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 - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸化フッ化チタン−黒
鉛層間化合物に関する。The present invention relates to a titanium oxyfluoride-graphite intercalation compound.
【０００２】[0002]
【従来の技術】従来、黒鉛層間化合物として数多くの化
合物が合成され、導電材料、電池材料、触媒、潤滑材等
の種々の用途に用いられ、もしくは利用の可能性が検討
されている。しかしながら、酸化フッ化遷移金属につい
ては、その低揮発性等のために層間化合物の生成が困難
であるため、ＶＯＦ3 ，ＣｒＯ2 Ｆ2 ，ＭｏＯＦ4 ，Ｗ
ＯＦ 4 ，ＷＯ2 Ｆ2 等の限定された元素についてしか得
られていない。2. Description of the Related Art Conventionally, many compounds have been used as graphite intercalation compounds.
Compounds are synthesized, conductive materials, battery materials, catalysts, lubricants, etc.
Is used for various purposes or the possibility of use is examined
Have been. However, transition metal oxyfluoride
The formation of intercalation compounds due to its low volatility
, So VOFThree, CrOTwoFTwo, MoOFFour, W
OF Four, WOTwoFTwoOnly for limited elements such as
Not been.
【０００３】[0003]
【発明が解決しようとする課題】そこで、本発明者ら
は、新規な酸化フッ化遷移金属を得るために種々検討を
行ない、本発明に到達した。すなわち、本発明の要旨
は、酸化フッ化チタンが、黒鉛の層間に取り込まれてな
る酸化フッ化チタン−黒鉛層間化合物にある。The present inventors have made various studies to obtain a novel transition metal oxyfluoride metal, and have reached the present invention. That is, the gist of the present invention lies in a titanium oxyfluoride-graphite intercalation compound in which titanium oxyfluoride is taken in between graphite layers.
【０００４】[0004]
【課題を解決するための手段】以下、本発明を詳細に説
明する。本発明に係る層間化合物は、酸化フッ化チタン
が黒鉛の層間に取り込まれてなる。このような黒鉛層間
化合物は、たとえば、次のような方法によって得ること
ができる。 ［Ａ］酸化チタンと黒鉛をフッ素ガスと反応させる方
法。 まず、酸化チタンとしては、アナターゼ型、ルチル型又
は無定形のいずれも用いることができる。また、黒鉛と
しては、特に制限されず天然黒鉛、人造黒鉛、キッシュ
黒鉛、熱分解黒鉛もしくは炭素繊維等、またはそれらの
混合物が用いられる。製法の一例を挙げると、黒鉛と酸
化チタンを別々のニッケル製皿に入れ、これらを反応管
内に設置し、真空排気しながら反応温度まで昇温し、フ
ッ素ガス又はアルゴン等の不活性ガスで希釈したフッ素
ガスを導入し（通常０．１〜１ａｔｍ程度）、系内を所
定圧に保つ。反応温度は１００〜２５０℃程度が一般的
であり、好適には１５０〜２００℃程度から選ばれる。
反応時間は通常数時間〜数日間程度である。Hereinafter, the present invention will be described in detail. The interlayer compound according to the present invention is obtained by incorporating titanium oxyfluoride between layers of graphite. Such a graphite intercalation compound can be obtained, for example, by the following method. [A] A method of reacting titanium oxide and graphite with fluorine gas. First, any of anatase type, rutile type and amorphous type can be used as titanium oxide. The graphite is not particularly limited, and natural graphite, artificial graphite, quiche graphite, pyrolytic graphite, carbon fiber, or the like, or a mixture thereof is used. As an example of the production method, graphite and titanium oxide are placed in separate nickel dishes, placed in a reaction tube, heated to the reaction temperature while evacuating, and diluted with an inert gas such as fluorine gas or argon. Fluorine gas is introduced (usually about 0.1 to 1 atm), and the inside of the system is maintained at a predetermined pressure. The reaction temperature is generally about 100 to 250 ° C, and is preferably selected from about 150 to 200 ° C.
The reaction time is usually about several hours to several days.
【０００５】このようにして得られる本発明の層間化合
物の組成は、ＣｘＴｉＯＦｙで表わされ、通常、ｘは６
〜６０、ｙは２〜６である。反応を加圧系（たとえば〜
数気圧）で行うことにより、ｙが６より大きいものを得
ることもできるが、フッ素が離脱しやすくなり一般にあ
まり好適ではない。本発明における上記黒鉛層間化合物
においては、酸化フッ化チタンが炭素平面一層ごとに入
ったステージ１型、二層ごとに入ったステージ２型、さ
らに高次のステージ型、のいずれも得ることができる。[0005] The composition of the intercalation compound of the present invention thus obtained is represented by CxTiOFy.
６０60, y is 2-6. The reaction is performed in a pressurized system (eg, ~
By performing the reaction at a pressure of several atmospheres, it is possible to obtain a material having y larger than 6, but fluorine is easily released, which is not generally preferable. In the graphite intercalation compound of the present invention, any of stage 1 type in which titanium oxyfluoride is contained in each carbon layer, stage 2 type in which every two layers are contained, and a higher-order stage type can be obtained. .
【０００６】［Ｂ］酸化フッ化チタンと黒鉛に強酸化性
物質を反応させる方法。 酸化フッ化チタンとしては、ＴｉＯＦ2 が好適に用いら
れる。また、強酸化性物質としては、フッ素ガス以外
に、塩素ガス、ＨＦ等のフッ化物を用いることができ
る。この［Ｂ］法によっても、［Ａ］法で得られる層間
化合物と同一の前記組成を有するものが得られる。[B] A method of reacting a titanium oxide fluoride and graphite with a strongly oxidizing substance. As the titanium oxyfluoride, TiOF 2 is preferably used. Further, as the strongly oxidizing substance, a fluoride such as chlorine gas or HF can be used in addition to the fluorine gas. According to the method [B], a compound having the same composition as the intercalation compound obtained by the method [A] can be obtained.
【０００７】[0007]
【発明の効果】本発明により、容易に酸化フッ化チタン
−黒鉛層間化合物を得ることができる。According to the present invention, a titanium oxyfluoride-graphite intercalation compound can be easily obtained.
【０００８】[0008]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明は以下の実施例に限定されるものではな
い。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.
【０００９】実施例１ 約１ｇの酸化チタン（アナターゼ）粉末を入れたニッケ
ル製皿を水平型反応器の中央に置く。高配向性熱分解黒
鉛試料（幅及び長さ１〜７ｍｍ及び０．５〜２ｍｍ厚さ
の平行六面体状）を２〜３個、別々に置き、真空排気し
ながら３〜４時間で１８０℃まで昇温し、フッ素ガスを
１ａｔｍ（Ｆ2 ）又は０．５ａｔｍ（Ｆ 2 ：Ａｒ＝１：
１）で導入し、系内を所定圧に保持した。温度は反応管
内の酸化チタンの温度を１７５〜１７０℃、黒鉛試料の
温度を１６５〜１４０℃とし、４８〜１６０時間の反応
の後、室温まで反応器を冷却し、過剰のフッ素ガスをＡ
ｒガスで除去し、活性アルミナに固定した。生成物につ
き重量測定、Ｘ線回折（ＣｕＫα）及びＥＳＣＡ測定を
行った。フッ素分圧（ＰＦ2 ）が１ａｔｍのとき、ステ
ージ２及び３、０．５ａｔｍでさらに高次（４、５及び
７）のステージが得られた。反応条件及び結果を表１に
示す。表中、ｄｉは挿入物質の厚み、Ｔｈは反応管内の
酸化チタンの温度、Ｔｌは黒鉛試料の温度を表わす。Example 1 Nickel containing about 1 g of titanium oxide (anatase) powder
Place the pan in the center of the horizontal reactor. Highly oriented pyrolytic black
Lead sample (width and length 1-7mm and 0.5-2mm thickness
2 to 3 pieces are placed separately and evacuated.
While raising the temperature to 180 ° C in 3 to 4 hours,
1 atm (FTwo) Or 0.5 atm (F Two: Ar = 1:
The system was introduced in 1), and the inside of the system was maintained at a predetermined pressure. Temperature is the reaction tube
The temperature of the titanium oxide inside is 175-170 ° C,
Temperature of 165-140 ° C, reaction for 48-160 hours
After that, the reactor is cooled to room temperature, and
It was removed with r gas and fixed on activated alumina. About the product
Weight measurement, X-ray diffraction (CuKα) and ESCA measurement
went. Fluorine partial pressure (PFTwo) Is 1 atm,
Pages 2 and 3, higher order at 0.5 atm (4, 5 and
Stage 7) was obtained. Table 1 shows the reaction conditions and results.
Show. In the table, di is the thickness of the insertion material, and Th is the inside of the reaction tube.
The temperature of the titanium oxide, Tl, represents the temperature of the graphite sample.
【００１０】[0010]
【表１】 [Table 1]
【００１１】図１は実施例１で得られた層間化合物のＸ
線回折パターンを示す（ステージ２、３、４、５及び
７）。また、図２〜５は上記ステージ２の層間化合物に
ついて得られたＥＳＣＡスペクトルを示す（Ｆ1s，
Ｏ1S，Ｃ1S及びＴｉ2p）。図２のＦ 1sピークは酸化フッ
化チタンポリマーの生成を示し、６８５．３±０．２ｅ
Ｖ及び６８３．６±０．２ｅＶにおける２つのピークは
Ｔｉ−Ｆイオン結合の２つの形態を示す。前者はＴｉ−
Ｆ結合、後者はＴｉ−Ｆ−Ｔｉ結合を示し、挿入された
酸化フッ化チタンがグラファイト層間で、架橋状態にあ
ることを示す。図３の５３２．２±０．１ｅＶにおける
Ｏ1Sピークは、ＣｘＴｉＯＦｙにおける酸素の存在を意
味し、更に図４のＣ1sピーク及び図５のＴｉ2P 3/2〜1/
2 ピークは、ＴｉＯＦ2 のイオン結合性層間化合物の生
成を示すものである。FIG. 1 shows X of the intercalation compound obtained in Example 1.
Shows the line diffraction patterns (stages 2, 3, 4, 5, and
7). FIGS. 2 to 5 show the intercalation compounds of the above stage 2.
The ESCA spectrum obtained for (F)1s,
O1S, C1SAnd Ti2p). F in FIG. 1sThe peak is oxidized fluorine.
Showing the formation of titanium halide polymer, 685.3 ± 0.2 e
V and two peaks at 683.6 ± 0.2 eV
2 shows two forms of Ti-F ionic bonding. The former is Ti-
F bond, the latter showing a Ti-F-Ti bond and inserted
Titanium oxyfluoride is cross-linked between graphite layers
To indicate that At 532.2 ± 0.1 eV in FIG.
O1SThe peak indicates the presence of oxygen in CxTiOFy.
Taste, and C in Fig. 41sPeak and Ti in FIG.2P 3/2 ~ 1 /
2 Peak is TiOFTwoOf Ion-Binding Intercalation Compounds in Water
It shows the result.
【図１】実施例で得られた層間化合物のＸ線回折パター
ンFIG. 1 is an X-ray diffraction pattern of an intercalation compound obtained in an example.
【図２】ＥＳＣＡスペクトルを示すFIG. 2 shows an ESCA spectrum
【図３】ＥＳＣＡスペクトルを示すFIG. 3 shows an ESCA spectrum.
【図４】ＥＳＣＡスペクトルを示すFIG. 4 shows an ESCA spectrum.
【図５】ＥＳＣＡスペクトルを示すFIG. 5 shows an ESCA spectrum.
フロントページの続き (56)参考文献 特開 昭51−65092（ＪＰ，Ａ) 特開 平４−202006（ＪＰ，Ａ) 特開 平３−187909（ＪＰ，Ａ) Ｓｙｎｔｈ．Ｍｅｔ 40［３］（1991 −４−15）ｐ387−392 (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 31/00 C01B 31/04 101 H01B 1/04 H01M 4/58 Continuation of front page (56) References JP-A-51-65092 (JP, A) JP-A-4-202006 (JP, A) JP-A-3-187909 (JP, A) Synth. Met 40 [3] (1991-4-15) p387-392 (58) Fields investigated (Int. Cl. 7 , DB name) C01B 31/00 C01B 31/04 101 H01B 1/04 H01M 4/58
Claims (1)
込まれてなる酸化フッ化チタン−黒鉛層間化合物。1. A titanium oxyfluoride-graphite intercalation compound in which titanium oxyfluoride is taken in between graphite layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03063508A JP3089682B2 (en) | 1991-03-27 | 1991-03-27 | Graphite intercalation compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03063508A JP3089682B2 (en) | 1991-03-27 | 1991-03-27 | Graphite intercalation compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04300205A JPH04300205A (en) | 1992-10-23 |
| JP3089682B2 true JP3089682B2 (en) | 2000-09-18 |
Family
ID=13231241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03063508A Expired - Fee Related JP3089682B2 (en) | 1991-03-27 | 1991-03-27 | Graphite intercalation compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3089682B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5208244B2 (en) * | 2011-05-06 | 2013-06-12 | 株式会社豊田自動織機 | Negative electrode active material for lithium ion secondary battery and method for producing the same, lithium ion secondary battery and method for producing the same |
-
1991
- 1991-03-27 JP JP03063508A patent/JP3089682B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ｓｙｎｔｈ．Ｍｅｔ ４０［３］（１９９１−４−１５）ｐ３８７−３９２ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04300205A (en) | 1992-10-23 |
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