JPS62240782A - Carbon electrode - Google Patents
Carbon electrodeInfo
- Publication number
- JPS62240782A JPS62240782A JP61083900A JP8390086A JPS62240782A JP S62240782 A JPS62240782 A JP S62240782A JP 61083900 A JP61083900 A JP 61083900A JP 8390086 A JP8390086 A JP 8390086A JP S62240782 A JPS62240782 A JP S62240782A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- electrode
- atoms
- fluorine atoms
- ratio
- 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
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 238000001228 spectrum Methods 0.000 claims abstract description 3
- 238000005211 surface analysis Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000004438 BET method Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 150000001721 carbon Chemical class 0.000 abstract 1
- 238000004611 spectroscopical analysis Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は炭素電極に関し、特に安定した反応活性寿命を
有する炭素電極に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a carbon electrode, and particularly to a carbon electrode having a stable reaction activity life.
（従来の技術）
炭素繊維集合体などの炭素多孔質体は、有効表面積が著
しく大きいため、電解槽等の電極として有用である。ま
た該多孔質体の表面に各種の化学処理を施して、反応選
択性や反応速度の増大を図る方法が報告されている（長
哲部、電気化学、５１巻、隘１、（１９８３）、特開昭
５９−１０１７７６号、特開昭５９−１１９６８０号、
特開昭６０−２３２６６９号など）。上記のうち、処理
が容易であり、比較的耐久性にも優れた方法として、炭
素表面への極性元素、例えば塩素や臭素を導入する方法
が知られているが、このようにして得られた電極は、単
なる酸素導入によるものよりも寿命が安定化する。しか
し、強力な還元性物質に常時接するような場合は、臭素
や塩素でさえも液側に移行しやすくなり、電極反応性に
問題の生じる場合もある。(Prior Art) Carbon porous bodies such as carbon fiber aggregates have a significantly large effective surface area and are therefore useful as electrodes for electrolytic cells and the like. In addition, methods have been reported in which various chemical treatments are applied to the surface of the porous material to increase reaction selectivity and reaction rate (Nagatetsube, Electrochemistry, Vol. 51, No. 1, (1983), JP-A-59-101776, JP-A-59-119680,
JP-A No. 60-232669, etc.). Among the above methods, a method of introducing polar elements such as chlorine or bromine to the carbon surface is known as a method that is easy to process and has relatively excellent durability. The lifespan of the electrode is more stable than that achieved by simply introducing oxygen. However, if the electrode is constantly in contact with a strong reducing substance, even bromine and chlorine tend to migrate to the liquid side, which may cause problems with electrode reactivity.
本発明の目的は、上記従来技術の欠点を解消し、より安
定した反応活性寿命を有する炭素電極を提供することに
よる。An object of the present invention is to eliminate the drawbacks of the above-mentioned prior art and provide a carbon electrode having a more stable reaction activity life.
（発明が解決しようとする問題点）
本発明は、炭素原子数に対する水素原子数の比が０．０
１以下の炭素多孔質体にフッ素原子を一次結合させ、そ
の割合がＸ線光電子分光法（ＥＳＣＡ）による表面分析
で該炭素表面のＩｓスペクトルから測定される結合フッ
素原子と炭素の原子数比が０．０１以上であることを特
徴とする。(Problems to be Solved by the Invention) In the present invention, the ratio of the number of hydrogen atoms to the number of carbon atoms is 0.0.
Fluorine atoms are linearly bonded to a carbon porous body of 1 or less, and the atomic ratio of bonded fluorine atoms to carbon is measured from the Is spectrum of the carbon surface by surface analysis using X-ray photoelectron spectroscopy (ESCA). It is characterized by being 0.01 or more.
本発明に用いる電極原料は、有機化合物（ピッチ等の炭
化水素原料）を空気のしゃ断下に加熱炭化して生成した
多孔質体、炭素繊維の繊維集合物（フェルト、クロス、
ランプ等）、積層体等のような空隙を多（有するシート
状物を総称するものである。例えば、これをフン素気流
中等において加熱すれば本発明の電極が得られるが、こ
のとき、炭素に対する水素の原子数比が０．０１以下、
好ましくは０．００５以下で水素が残存しているものが
よい。上記水素の原子数比が０．０１を越えるものは、
炭化が不十分で電導性不良であり、電極として使用する
のは好ましくない。The electrode raw materials used in the present invention are porous bodies produced by heating and carbonizing organic compounds (hydrocarbon raw materials such as pitch) under the exclusion of air, and fiber aggregates of carbon fibers (felt, cloth, etc.).
It is a general term for sheet-like materials having a large number of voids, such as lamps, etc.), laminates, etc. For example, the electrode of the present invention can be obtained by heating this in a fluorine gas stream. The atomic ratio of hydrogen to is 0.01 or less,
Preferably, hydrogen remains at 0.005 or less. The above hydrogen atomic ratio exceeds 0.01,
Carbonization is insufficient and conductivity is poor, making it undesirable to use as an electrode.
このような多孔質体の炭素原子にフッ素原子を１％以下
導入するには、例えば前記原料をフッ素含有気流中で数
百℃〜約千℃で焼成すればよい。In order to introduce 1% or less of fluorine atoms into the carbon atoms of such a porous body, for example, the raw material may be fired at several hundred degrees Celsius to about 1,000 degrees Celsius in a fluorine-containing air stream.
本発明の炭素電極は多孔質状であり、これを電極として
用いる方法の一つとして隔膜と電極とが密着した、いわ
ゆるゼロギャップ方式の電極が挙げられる。このような
方式を採用することにより、電解時に浴電圧を上昇させ
る要因の−っである溶液抵抗と気泡効果、すなわち発生
する気泡によって溶液の電気抵抗が上昇する現象を除去
することができる。The carbon electrode of the present invention is porous, and one method of using it as an electrode is a so-called zero-gap type electrode in which a diaphragm and an electrode are in close contact with each other. By adopting such a method, it is possible to eliminate the solution resistance and bubble effect, which are factors that increase the bath voltage during electrolysis, that is, the phenomenon in which the electrical resistance of the solution increases due to generated bubbles.
本発明の炭素電極を電解槽に通用した例を第１図に示す
。第１図に示す電解槽は、隔膜４の両側に設けられた陽
極１および陰極２と、該陽極１および陰極２の外側にそ
れぞれ設けられた集電板３と、前記陽極１および陰極２
に陽極液５および陰極液６をそれぞれ流通させるための
大口５Ａおよび６Ｂ、出口５Ｂ、６Ｂとから構成される
。本発明の炭素電極は陽極１および陰極２として使用さ
れるが、複極式構造を取る場合には、図面のような単電
解槽を直列に積層し、集電板３の代わりに複極仕切り板
を設ければよい。FIG. 1 shows an example in which the carbon electrode of the present invention is used in an electrolytic cell. The electrolytic cell shown in FIG. 1 includes an anode 1 and a cathode 2 provided on both sides of a diaphragm 4, a current collector plate 3 provided on the outside of the anode 1 and the cathode 2, and an anode 1 and a cathode 2.
It is comprised of large ports 5A and 6B and outlets 5B and 6B for flowing the anolyte 5 and catholyte 6, respectively. The carbon electrode of the present invention is used as an anode 1 and a cathode 2, but when a bipolar structure is adopted, single electrolytic cells are stacked in series as shown in the drawing, and a bipolar partition is used instead of the current collector plate 3. Just set up a board.
（実施例） 以下、本発明を実施例によりさらに詳細に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
石油系重質残油を蒸留、水素化処理、接触分解、蒸留、
溶融紡糸、不溶化処理および積層加工を行い、最後に炭
素化したカーボンフェルトを５％フッ素を含有する窒素
ガス中で８００℃で焼成した。Example 1 Distillation, hydrogenation treatment, catalytic cracking, distillation,
Melt spinning, insolubilization treatment and lamination processing were performed, and finally the carbonized carbon felt was fired at 800° C. in nitrogen gas containing 5% fluorine.
比較のためにそれぞれ５％酸素および５％塩素を含有す
る窒素ガス中で同様に焼成して酸素導入および塩素導入
したフェルトも製作した。これらのＸ線光電子分光法（
ＥＳＣＡ）等の測定結果は第１表のとおりであった。For comparison, felts were also produced in which oxygen and chlorine were introduced by firing in nitrogen gas containing 5% oxygen and 5% chlorine, respectively. These X-ray photoelectron spectroscopy (
The results of measurements such as ESCA) are shown in Table 1.
以下余白
第１表に示した各サンプルａ ％ ｈを陰極および陽極
の各材料として用い、第２図に示す電極ホルダー１１に
支持し、３％食塩水溶液に浸漬して電解実験を行った。Each sample a % h shown in Table 1 below was used as the material for the cathode and anode, supported on the electrode holder 11 shown in FIG. 2, and immersed in a 3% saline solution for electrolysis experiments.
結果を第２表に示す。表中の数値の単位はボルト（対せ
永電極）である。The results are shown in Table 2. The units of numerical values in the table are volts (paired permanent electrodes).
第２表
本実施例および比較例の結果より、本発明による電極は
水素過電圧が大きく、またハロゲン発生のための良好な
機能を有しており、かつこのような特性を長時間保持し
、長寿命を有することがわかった。Table 2 From the results of this example and comparative example, the electrode according to the present invention has a large hydrogen overvoltage, has a good function for halogen generation, maintains these characteristics for a long time, and has a long lifespan. It was found that it has a long lifespan.
（発明の効果）
本発明によれば、多孔質炭素電極にフッ素原子を所定量
導入することにより、従来の酸素導入電極、臭素導入電
極寿命特性を著しく向上させることができる。(Effects of the Invention) According to the present invention, by introducing a predetermined amount of fluorine atoms into a porous carbon electrode, the life characteristics of conventional oxygen-introducing electrodes and bromine-introducing electrodes can be significantly improved.
本発明によるフッ素導入炭素電極は、例えばガス発生極
やレドックスメディエータ再生極として広い通用分野を
有する。The fluorine-introduced carbon electrode according to the present invention has a wide range of applications, such as as a gas generating electrode or a redox mediator regeneration electrode.
【図面の簡単な説明】
第１図は、本発明による炭素電極が適応される単電解槽
の説明図、第２図は、本発明の実施例に用いた実験装置
の説明図、第３図は、本発明の実施例１に用いた電極の
ＥＳＣＡの分析結果（Ｗｉｄｅ Ｓｃａｎｎｉｎｇ）
を示す図である。
ｌ・・・陽極、２・・・陰極、３・・・集電板、４・・
・隔膜、５・・・陽極液、６・・・陰極液、５Ａ、６Ａ
・・・入口、５Ｂ、６Ｂ・・・出口、７・・・押えネッ
ト、８・・・参照極、９・・・プラスチック筒、１０・
・・リード線、１１・・・電極ホルダー。
代理人 弁理士 川 北 武 長
第１図
第２図[Brief Description of the Drawings] Fig. 1 is an explanatory diagram of a single electrolytic cell to which the carbon electrode according to the present invention is applied, Fig. 2 is an explanatory diagram of an experimental apparatus used in an example of the present invention, and Fig. 3 is an explanatory diagram of an experimental apparatus used in an example of the present invention. is the ESCA analysis result (Wide Scanning) of the electrode used in Example 1 of the present invention.
FIG. l... Anode, 2... Cathode, 3... Current collector plate, 4...
・Diaphragm, 5...Anolyte, 6...Catholyte, 5A, 6A
... Inlet, 5B, 6B... Outlet, 7... Holder net, 8... Reference electrode, 9... Plastic cylinder, 10...
... Lead wire, 11... Electrode holder. Agent Patent Attorney Takenaga Kawakita Figure 1 Figure 2
Claims (2)
下の炭素多孔質体にフッ素原子を一次結合させ、その割
合がＸ線光電子分光法（ＥＳＣＡ）による表面分析で該
炭素表面の１Ｓスペクトルから測定される結合フッ素原
子と炭素の原子数比が０．０１以上であることを特徴と
する炭素電極。(1) Fluorine atoms are linearly bonded to a carbon porous body in which the ratio of the number of hydrogen atoms to the number of carbon atoms is 0.01 or less, and the ratio is determined by surface analysis using X-ray photoelectron spectroscopy (ESCA). A carbon electrode characterized in that the atomic ratio of bonded fluorine atoms to carbon as measured from a spectrum is 0.01 or more.
体の表面積が窒素ガス吸着によるＢＥＴ法表面積測定値
で１ｍ＾２／ｇ以上あることを特徴とする炭素電極。(2) The carbon electrode according to claim (1), wherein the carbon porous body has a surface area of 1 m^2/g or more as measured by the BET method using nitrogen gas adsorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61083900A JPS62240782A (en) | 1986-04-11 | 1986-04-11 | Carbon electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61083900A JPS62240782A (en) | 1986-04-11 | 1986-04-11 | Carbon electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62240782A true JPS62240782A (en) | 1987-10-21 |
Family
ID=13815502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61083900A Pending JPS62240782A (en) | 1986-04-11 | 1986-04-11 | Carbon electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62240782A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02133593A (en) * | 1988-11-11 | 1990-05-22 | Mitsui Eng & Shipbuild Co Ltd | Carbonaceous electrode |
| CN113874554A (en) * | 2019-12-27 | 2021-12-31 | 昭和电工株式会社 | Method for producing fluorine gas and apparatus for producing fluorine gas |
-
1986
- 1986-04-11 JP JP61083900A patent/JPS62240782A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02133593A (en) * | 1988-11-11 | 1990-05-22 | Mitsui Eng & Shipbuild Co Ltd | Carbonaceous electrode |
| CN113874554A (en) * | 2019-12-27 | 2021-12-31 | 昭和电工株式会社 | Method for producing fluorine gas and apparatus for producing fluorine gas |
| CN113874554B (en) * | 2019-12-27 | 2024-01-05 | 株式会社力森诺科 | Method and apparatus for producing fluorine gas |
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