JPH0371368B2 - - Google Patents
Info
- Publication number
- JPH0371368B2 JPH0371368B2 JP61227434A JP22743486A JPH0371368B2 JP H0371368 B2 JPH0371368 B2 JP H0371368B2 JP 61227434 A JP61227434 A JP 61227434A JP 22743486 A JP22743486 A JP 22743486A JP H0371368 B2 JPH0371368 B2 JP H0371368B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- polymer
- carbon
- platinum
- carbon film
- 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 - Lifetime
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229920006254 polymer film Polymers 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- -1 polyphenylene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FKQOMXQAEKRXDM-UHFFFAOYSA-N [Li].[As] Chemical compound [Li].[As] FKQOMXQAEKRXDM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
〔技術分野〕
本発明は新規な炭素フイルムの製造法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel method for producing a carbon film.
炭素フイルムは電極材料や導電性材料として注
目されている物質である。従来から行われてきた
製造法には、天然黒鉛を強い酸化性溶液中で処理
して生成した酸化黒鉛を基盤に塗布し、乾燥後還
元雰囲気下で炭素化してフイルムを得る方法、天
然黒鉛を硫酸中で電解処理して層間化合物を形成
させ、急熱して得たコロイド状の膨張黒鉛をシー
ト状にして炭素フイルムを製造する方法、炭素や
黒鉛粉を物理的に圧着して賦形する方法、炭素の
蒸着法などがある。また、最近では高分子フイル
ムを出発原料にしてそのまま炭素化したり、可溶
性ポリマーであれば適当な溶剤に溶かしてからガ
ラス板などにキヤストして炭素化する方法が行わ
れている。しかしながら、このような方法ではフ
イルムの厚みを制御することができず、また均一
な膜を得にくいなどの欠点がある。そのため、比
較的薄く、かつ均一な炭素フイルムの工業的な製
造法は確立されていない。
Carbon film is a substance that is attracting attention as an electrode material and conductive material. Conventional manufacturing methods include applying graphite oxide produced by treating natural graphite in a strong oxidizing solution to a substrate, drying it and then carbonizing it in a reducing atmosphere to obtain a film; A method of manufacturing a carbon film by forming a sheet of colloidal expanded graphite obtained by electrolytic treatment in sulfuric acid to form an intercalation compound and rapidly heating it, and a method of shaping carbon and graphite powder by physically compressing them. , carbon vapor deposition method, etc. Recently, methods have been used in which a polymer film is used as a starting material and carbonized as it is, or in the case of a soluble polymer, it is dissolved in an appropriate solvent and then cast onto a glass plate or the like and carbonized. However, this method has drawbacks such as the inability to control the thickness of the film and the difficulty in obtaining a uniform film. Therefore, an industrial method for producing a relatively thin and uniform carbon film has not been established.
本発明は前記従来技術とは異なつた方法による
炭素フイルムの製造方法を提供することを目的と
する。
An object of the present invention is to provide a method for manufacturing a carbon film using a method different from that of the prior art.
本発明はベンゼンを支持電解質を含む溶媒に溶
かし、二つの電極間に電気を流して陽極板上に生
成したポリフエニレンフイルムを炭素化して炭素
フイルムを製造する方法である。この方法では印
加する電気量によつて膜厚を容易に制御すること
ができる上に、生成したポリマーは固相で収率よ
く炭素化されるため、膜の形状をほとんど維持し
たまま厚さ２〜30μｍ程度の炭素フイルムを作る
ことができる。以下に具体的な製造法を述べる。
The present invention is a method for manufacturing a carbon film by dissolving benzene in a solvent containing a supporting electrolyte and passing electricity between two electrodes to carbonize a polyphenylene film formed on an anode plate. In this method, the film thickness can be easily controlled by the amount of electricity applied, and the produced polymer is carbonized in a solid phase with a high yield, so the film thickness can be reduced to 2.0% while maintaining most of the shape of the film. Carbon films with a thickness of ~30 μm can be made. The specific manufacturing method will be described below.
実施例 １
50mlの三ツ口フラスコの中央に20×20mmの白金
およびニツケルの平板電極を吊るし、窒素ガスを
流しながら塩化アルミニウム４ｇと塩化テトラー
ｎ−ブチルアンモニウム0.5ｇを35mlのニトロメ
タンまたはニトロベンゼンに溶かす。これにベン
ゼン２mlを加え、白金極をプラス、ニツケル極を
マイナスとして48ｍＡの直流定電流を印加する。
0.5〜３時間後白金板上のポリマーをアセトン、
加熱した希塩酸で洗い100℃で乾燥する。0.5時間
程度で約10μｍ、１〜２時間で20μｍ以上になる。
得られたフイルムを白金か石英ボート上に置き、
アルゴンガスを流しながら３℃／minの昇温速度
で800または1000℃で１時間熱処理することによ
つて所望の炭素フイルムを得る。膜収率としては
75〜80％で、多少収縮するが膜の形状は保たれ
る。Example 1 A 20 x 20 mm platinum and nickel plate electrode is suspended in the center of a 50 ml three-necked flask, and 4 g of aluminum chloride and 0.5 g of tetra-n-butylammonium chloride are dissolved in 35 ml of nitromethane or nitrobenzene while nitrogen gas is flowing. Add 2 ml of benzene to this, and apply a constant DC current of 48 mA with the platinum electrode as positive and the nickel electrode as negative.
After 0.5 to 3 hours, the polymer on the platinum plate was washed with acetone.
Wash with heated dilute hydrochloric acid and dry at 100℃. It becomes about 10 μm in about 0.5 hours and more than 20 μm in 1 to 2 hours.
Place the obtained film on a platinum or quartz boat,
A desired carbon film is obtained by heat treatment at 800 or 1000° C. for 1 hour at a heating rate of 3° C./min while flowing argon gas. As membrane yield
At 75-80%, the membrane retains its shape although it shrinks somewhat.
実施例 ２
１と同じ反応容器に白金、ニツケル電極を吊る
し、塩化第二銅0.5ｇ、リチウム六フツ化ヒ素0.7
ｇを35mlのニトロベンゼンに懸濁させる。これに
ベンゼン約４mlを加え、白金極をプラス、ニツケ
ル極をマイナスとして８ｍＡの定電流を印加す
る。１時間後、白金極板上のポリマーをアセトン
で洗つてポリフエニレンフイルムを得る。ポリマ
ー中にドープされたアニオンは、反応後極性を逆
にするかアンモニア水に浸して除く。膜の厚さは
１時間で10〜12μｍである。次に前記と同様に得
られたフイルムを炭素化する。収率は800℃処理
で約85％と実施例１よりも高い。Example 2 Platinum and nickel electrodes were suspended in the same reaction vessel as in 1, and 0.5 g of cupric chloride and 0.7 g of lithium arsenic hexafluoride were added.
suspend g in 35 ml of nitrobenzene. Approximately 4 ml of benzene was added to this, and a constant current of 8 mA was applied with the platinum electrode set as positive and the nickel electrode set as negative. After 1 hour, the polymer on the platinum electrode plate is washed with acetone to obtain a polyphenylene film. Anions doped into the polymer are removed by reversing the polarity after the reaction or by soaking the polymer in aqueous ammonia. The thickness of the film is 10-12 μm in 1 hour. Next, the obtained film is carbonized in the same manner as above. The yield is about 85% when treated at 800°C, which is higher than in Example 1.
本発明によつて得られた薄くて均一な炭素フイ
ルムは、電池用電極や各種エレクトロニクス材料
への用途が期待される。
The thin and uniform carbon film obtained by the present invention is expected to be used in battery electrodes and various electronic materials.
Claims (1)
た高分子フイルムを炭素化して炭素フイルムを製
造する方法。1. A method of producing a carbon film by carbonizing a polymer film synthesized from benzene using an electrolytic oxidation polymerization method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61227434A JPS6385010A (en) | 1986-09-26 | 1986-09-26 | Production of carbon film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61227434A JPS6385010A (en) | 1986-09-26 | 1986-09-26 | Production of carbon film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6385010A JPS6385010A (en) | 1988-04-15 |
| JPH0371368B2 true JPH0371368B2 (en) | 1991-11-13 |
Family
ID=16860798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61227434A Granted JPS6385010A (en) | 1986-09-26 | 1986-09-26 | Production of carbon film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6385010A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01282111A (en) * | 1988-05-06 | 1989-11-14 | Toshiba Ceramics Co Ltd | Production of carbonaceous raw material |
| JP2011195432A (en) * | 2010-02-26 | 2011-10-06 | Sekisui Chem Co Ltd | Method for producing flaky graphite and flaky graphite |
-
1986
- 1986-09-26 JP JP61227434A patent/JPS6385010A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6385010A (en) | 1988-04-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |