JP2530332B2 - Electrode for electrolysis - Google Patents
Electrode for electrolysisInfo
- Publication number
- JP2530332B2 JP2530332B2 JP62094094A JP9409487A JP2530332B2 JP 2530332 B2 JP2530332 B2 JP 2530332B2 JP 62094094 A JP62094094 A JP 62094094A JP 9409487 A JP9409487 A JP 9409487A JP 2530332 B2 JP2530332 B2 JP 2530332B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- electrolysis
- carbon
- powder
- glassy carbon
- 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
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Description
【発明の詳細な説明】 （イ）産業上の利用分野 この発明は、電解用電極に関する。さらに詳しくは水
電解や電気透析等に適用でき、ことに電気透析により脱
イオン水や高濃度イオン水を製造するのに適した電解用
電極に関する。TECHNICAL FIELD The present invention relates to an electrode for electrolysis. More specifically, the present invention relates to an electrode for electrolysis which is applicable to water electrolysis, electrodialysis and the like, and is particularly suitable for producing deionized water or highly concentrated ionic water by electrodialysis.
（ロ）従来の技術 従来から水道水に二本の電解用電極を浸漬すると共に
この間に隔膜を設けた状態で電解を行ない、それにより
一方の電極側に金属イオンの少ない脱イオン水を、他方
の電極側に高濃度イオン水を得る方法が知られている。
そして、この原理を応用して飲料用高濃度カルシウム水
とアストリンゼン液（低濃度イオン水）とを簡便に生成
する家庭用の電気透析器が販売されるに至っている。(B) Conventional technique Conventionally, two electrodes for electrolysis are immersed in tap water and electrolysis is performed with a diaphragm provided between them, whereby deionized water with a small amount of metal ions is provided on one electrode side, and A method for obtaining high-concentration ionized water on the electrode side is known.
Then, by applying this principle, household electrodialyzers that easily generate high-concentration calcium water for beverages and astringent liquid (low-concentration ionized water) have been sold.
このような電解電極としては従来から、白金やチタン
のごとき金属電極、酸化鉄や酸化チタンの焼結体からな
る酸化金属電極（特公昭51−35394,35395号公報）、通
常の炭素粉末を焼結したカーボン電極等が知られてい
る。As such an electrolytic electrode, conventionally, a metal electrode such as platinum or titanium, a metal oxide electrode composed of a sintered body of iron oxide or titanium oxide (Japanese Patent Publication No. 51-35394, 35395), and ordinary carbon powder are burned. Bonded carbon electrodes and the like are known.
（ハ）発明が解決しようとする問題点 しかし、金属を用いた電解電極を用いた場合には、金
属イオンが電極から溶出する問題点があり、とくに飲料
用の電気透析器に適用するのは望ましくない。(C) Problems to be solved by the invention However, when an electrolytic electrode using a metal is used, there is a problem that metal ions are eluted from the electrode, and it is particularly applicable to an electrodialyzer for beverages. Not desirable.
一方、通常の炭素を用いたカーボン電極は抵抗率は低
いが耐食性が低く、かつ機械的強度が小さく炭素片が容
易に脱落したり亀裂が生じる問題点がある。ことに電解
中に電極面でのガス（水素、酵素、塩素等）発明に伴な
って炭素片が剥離・脱落する欠点があり、到底実用に耐
えない。On the other hand, a carbon electrode using ordinary carbon has a problem that it has a low resistivity but a low corrosion resistance, a low mechanical strength, and carbon pieces easily fall off or crack. In particular, during electrolysis, there is a drawback that the carbon pieces are peeled off or dropped off due to the invention of gas (hydrogen, enzyme, chlorine, etc.) on the electrode surface, and it cannot be put to practical use at all.
この発明は、かかる状況に鑑みなされたものであり、
ことに水の電解電圧以上の電圧が印加される電解系にお
いて素材の溶出や脱落が防止され亀裂も生じ難い電解用
電極を提供しようとするものである。The present invention has been made in view of such circumstances,
In particular, it is an object of the present invention to provide an electrode for electrolysis in which a material is prevented from eluting or falling off and cracks hardly occur in an electrolysis system to which a voltage higher than the electrolysis voltage of water is applied.
（ニ）問題点を解決するための手段 この点に関し、本発明者らは、従来のカーボン電極に
用いられている通常の炭素とは性状、物性等が大きく異
なるガラス状炭素の電極を作製することを試みた。(D) Means for Solving the Problems In this regard, the inventors of the present invention produce a glassy carbon electrode having properties and physical properties which are greatly different from those of ordinary carbon used in conventional carbon electrodes. Tried that.
しかしながら、かかるガラス状炭素を焼結して作製し
たカーボン電極においては、従来のカーボン電極に比し
て炭素片等の脱落性がある程度改善されるものの、電解
を長時間（例えば、100時間）続けるとやはり炭素片の
脱落が生じることが分った。However, in the carbon electrode produced by sintering such glassy carbon, the electrolysis is continued for a long time (for example, 100 hours), although the detachability of carbon pieces and the like is improved to some extent as compared with the conventional carbon electrode. After all, it was found that carbon fragments would come off.
そこで更に本発明者らは、ガラス状炭素粉末を種々の
結合剤を用いて電極形状に加熱・加圧成形することにつ
いて鋭意研究を行なった。その結果、ポリエチレン、ポ
リアミド、フェノール、エポキシなどの各樹脂、ニトリ
ルゴム、塩素化ポリエチレン、スチレンゴム、シリコー
ンゴム等の各ゴムの結合剤を用いても上記問題点は解決
されないが、結合剤としてポリテトラフルオロエチレン
等のフッ素系樹脂を用いた場合に、長時間に亘って炭素
片や粉末の脱落が防止され実使用可能な電解用電極が得
られる事実を見出し、この発明を完成するに至った。Therefore, the present inventors further conducted earnest research on heating and press-molding glassy carbon powder into an electrode shape using various binders. As a result, the above problems cannot be solved by using a binder for each resin such as polyethylene, polyamide, phenol, and epoxy, and each rubber such as nitrile rubber, chlorinated polyethylene, styrene rubber, and silicone rubber. When a fluorine-based resin such as tetrafluoroethylene was used, the fact that a carbon electrode or powder was prevented from falling off for a long time and a practically usable electrode for electrolysis was obtained was found, and the present invention was completed. .
かくしてこの発明によれば、ガラス状炭素粉末と、こ
の粉末が少なくとも結合されるに足る量でかつこの粉末
の導電性が阻害されない量のフッ素系樹脂とからなる混
合物が加圧・加熱成形されてなる電解用電極が提供され
る。Thus, according to the present invention, a mixture of glassy carbon powder and a fluorine-based resin in an amount sufficient to at least bind the powder and not impairing the conductivity of the powder is press-heated. An electrode for electrolysis is provided.
この発明に用いるガラス状炭素粉末は、熱硬化性樹脂
やセルロースを高温下で熱処理して得られる非晶質の等
方性炭素からなる粉末であって、通常の炭素粉末にない
耐薬品性、高硬度を有するものである。これらのうち好
ましいのは、既に硬化したフェノール樹脂粉末を、還元
雰囲気中800℃以上の温度で熱処理することにより得ら
れるガラス状炭素粉末である。既に硬化したフェノール
樹脂粉末としては、市販品として入手することが可能で
あり、例えば、ユニチカ株式会社製商品名“ユニベック
ス"C−30,C−50,C−100等が使用される。このフェノー
ル樹脂粉末を炭化して得られるガラス状炭素粉末の粒径
は100μｍ以下が望ましい。100μｍを超える粒径のガラ
ス状炭素粉末を用いると、樹脂との混合状態が若干悪く
なって、導電性が低下することがあるので望ましくな
い。通常20〜80μｍのものを用いるのが好ましい。The glassy carbon powder used in the present invention is a powder made of amorphous isotropic carbon obtained by heat-treating a thermosetting resin or cellulose at a high temperature, and chemical resistance not found in ordinary carbon powder, It has a high hardness. Among these, preferred is a glassy carbon powder obtained by heat-treating an already hardened phenol resin powder in a reducing atmosphere at a temperature of 800 ° C. or higher. As the already hardened phenol resin powder, it is possible to obtain it as a commercial product, and for example, trade name “UNIVEX” C-30, C-50, C-100 manufactured by Unitika Ltd. is used. The glassy carbon powder obtained by carbonizing this phenol resin powder preferably has a particle size of 100 μm or less. It is not preferable to use a glassy carbon powder having a particle size of more than 100 μm because the mixed state with the resin may be slightly deteriorated and the conductivity may be lowered. Usually, it is preferable to use one having a thickness of 20 to 80 μm.
この発明において、フッ素樹脂は、上記ガラス状炭素
粉末が少なくとも結合されるに足る量用いる必要があ
る。一方、フッ素系樹脂の混合割合の上限は、導電性が
阻害されない量以下とする必要がある。かかる観点か
ら、より具体的には、フッ素系樹脂の添加量は、約10〜
約40重量％が好ましいことが見出された。In the present invention, the fluororesin should be used in an amount sufficient to at least bond the glassy carbon powder. On the other hand, the upper limit of the mixing ratio of the fluorine-based resin needs to be equal to or less than the amount that does not hinder the conductivity. From this viewpoint, more specifically, the addition amount of the fluororesin is about 10 to
It has been found that about 40% by weight is preferred.
かかるフッ素系樹脂としては、四フッ化エチレンや六
フッ化エチレンのホモ又はコポリマーやこのポリマー主
鎖にパーフルオロアルコキシ基やトリフルオロメチル基
等の側鎖を有するパーフルオロアルキル系のものが適し
ている。ただし完全にパーフルオロ系でなくても同等の
耐熱性を有するものであれば使用可能である。As such a fluorine-based resin, a homo- or copolymer of tetrafluoroethylene or hexafluoroethylene or a perfluoroalkyl-based resin having a side chain such as a perfluoroalkoxy group or a trifluoromethyl group in the polymer main chain is suitable. There is. However, even if it is not completely perfluoro-based, it can be used as long as it has the same heat resistance.
この発明の電解用電極は、通常、ガラス状炭素粉末に
上記フッ素系樹脂のエマルジョンを混合し、この混合物
を乾燥後、300〜400℃程度の加熱下でプレス成形するこ
とにより効率良く得ることができる。ただし、上記エマ
ルジョンの代わりにフッ素系樹脂自体をガラス状炭素粉
末に溶解混合させて同様にプラス成形してもよい。この
場合、室温下でプレスしその後300〜400℃で熱処理して
成形することもできる。なお、成形後に所定温度でアニ
ーリング等を行なうことにより成形歪等を除くこともで
きる。The electrode for electrolysis of the present invention can usually be obtained efficiently by mixing glassy carbon powder with an emulsion of the above fluororesin, drying the mixture, and press-molding it under heating at about 300 to 400 ° C. it can. However, instead of the above-mentioned emulsion, the fluorine-based resin itself may be dissolved and mixed in the glassy carbon powder and similarly subjected to the plus molding. In this case, it is also possible to press at room temperature and then heat-treat at 300 to 400 ° C. to mold. The molding strain and the like can be removed by performing annealing or the like at a predetermined temperature after molding.
（ホ）実施例 ガラス状炭素として、粒径30〜50μｍの硬化したフェ
ノール樹脂粉末（ユニチカ株式会社製商品名“ユニベッ
クス"C−50）をアルゴン雰囲気中1000℃で、10時間熱処
理して粒径25〜40μｍのガラス状炭素を調製し、これを
用いて、この発明の電解用電極を作製した。(E) Example As a glassy carbon, a cured phenol resin powder having a particle size of 30 to 50 μm (trade name “UNIVEX” C-50 manufactured by Unitika Ltd.) is heat-treated in an argon atmosphere at 1000 ° C. for 10 hours to give a particle size. Glassy carbon of 25 to 40 μm was prepared, and this was used to prepare an electrode for electrolysis of the present invention.
実施例１及び２におけるフッ素系樹脂としては、ポリ
テトラフルオロエチレン（テフロン 三井デュポンフロ
ロケミカル（株）製）を、エマルジョンの形態で使用し
た。 As the fluorine-based resin in Examples 1 and 2,
Tetrafluoroethylene (Teflon Mitsui DuPont Flo
Rochemical Co., Ltd.) is used in the form of emulsion.
Was.
まず、ガラス状炭素粉末にフッ素系樹脂エマルジョン
を各々下記の割合で添加し、ミキサー、ロール又はニー
ダを用いて室温下で10分間混練した。First, the fluorocarbon resin emulsion was added to the glassy carbon powder in the following proportions, and kneaded for 10 minutes at room temperature using a mixer, roll or kneader.
この混合物を粉砕機で粉砕した後、真空脱水機で充分
に脱水する。次いで、所定形状のプレス成形機に導入し
て350℃下、1000kg/cm2でプレス成形を行なった。この
後、成形体を成形機から取出し、恒温槽中で350℃で30
分、アニーリングすることにより、各々12.5×7.5×12.
5mmの寸法のカーボン電極を得た。 This mixture is pulverized with a pulverizer and then thoroughly dehydrated with a vacuum dehydrator. Then, it was introduced into a press-molding machine having a predetermined shape, and press-molded at 1000 kg / cm 2 at 350 ° C. After this, the molded product was removed from the molding machine and kept in a constant temperature bath at 350 ° C for 30
12.5 x 7.5 x 12 each by annealing for minutes.
A carbon electrode having a size of 5 mm was obtained.
実施例３及び同４におけるフッ素系樹脂としては、実
施例１及び２の重合体の粉末を使用した。この場合の電
極の製造方法は、真空脱水機で脱水するプロセスがない
だけで、実施例１及び２のそれと同様である。As the fluororesin in Examples 3 and 4, the polymer powders of Examples 1 and 2 were used. The manufacturing method of the electrode in this case is the same as that of Examples 1 and 2 except that there is no process of dehydrating with a vacuum dehydrator.
かかるカーボン電極は、いずれも曲げ強度300kg/cm2
以上で導電率は10゜Ωcm以上であった。Each of these carbon electrodes has a bending strength of 300 kg / cm 2
The electrical conductivity was 10 ° Ωcm or more.
上記カーボン電極を水中に各々一対浸漬し、この間に
隔膜を介在させ、電極間距離110mm、電圧110Vで連続的
に直流電解を行なった。この結果いずれの電極において
も200時間を経過しても電極炭素片や粉末の脱落や剥離
は生じないことが判明した。A pair of each of the above carbon electrodes was immersed in water, a diaphragm was interposed therebetween, and direct current electrolysis was carried out at an electrode distance of 110 mm and a voltage of 110V. As a result, it was found that the electrode carbon pieces and powder did not fall off or peel off in any of the electrodes even after 200 hours.
これに対し、通常の炭素を用いる以外同様にして成形
した電極について上記と同様な試験条件で電解を行なっ
たところ、３時間後に亀裂や炭素片の脱落が生じ、実使
用に耐えないものであった。また、フッ素系樹脂を用い
ず、ガラス状炭素のみを焼結して作製した電極について
同様な試験を行なったが、80時間後に炭素片や粉末の脱
落が認められた。さらにフッ素系樹脂のかわりに、ポリ
アミド樹脂，ポリエチレン樹脂，フェノール樹脂を用い
た電極も、２時間後に亀裂や炭素片の脱落が生じた。On the other hand, when an electrode formed in the same manner except that ordinary carbon was used was electrolyzed under the same test conditions as described above, cracks and carbon fragments fell off after 3 hours, and it was not practical. It was In addition, the same test was performed on an electrode prepared by sintering only glassy carbon without using a fluorine-based resin, but it was confirmed that carbon fragments and powder were dropped off after 80 hours. Further, the electrode using a polyamide resin, a polyethylene resin, or a phenol resin instead of the fluorine-based resin also had a crack or a drop of a carbon piece after 2 hours.
（ヘ）発明の効果 この発明の電解用電極は、良好な導電性を有しかつ長
時間に亘る水電解中においても炭素片の脱落、剥離さら
には亀裂が生じることなく電解を効率良く行なうことが
できる。(F) Effects of the Invention The electrode for electrolysis of the present invention has good conductivity and can efficiently perform electrolysis without dropping, peeling, or cracking of carbon pieces even during water electrolysis for a long time. You can
そして、金属を用いていないため金属溶出等の問題が
なく、耐食性、耐熱性、耐薬品性にも優れた耐久性の優
れたものである。Further, since no metal is used, there is no problem of metal elution and the like, and corrosion resistance, heat resistance, and chemical resistance are excellent and durability is excellent.
しかも、かかる利点を備えているうえ、その成形性、
加工性が良く、シート状、板状、棒状等の所望形状のも
のを簡便に作製することができる。Moreover, in addition to having such advantages, its moldability,
It has good workability and can be easily formed into a desired shape such as a sheet, plate or rod.
従って、ことに水電解用や電気透析用の電極としてそ
の価値は著しく高いものである。Therefore, its value is extremely high especially as an electrode for water electrolysis or electrodialysis.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 垣生 茂 鹿沼市茂呂1211番地５ (56)参考文献 特開 昭61−48586（ＪＰ，Ａ) 特開 昭58−9989（ＪＰ，Ａ) 特公 昭58−48036（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigeru Kakio 1211-5 Mororo, Kanuma City (56) References JP-A-61-48586 (JP, A) JP-A-58-9989 (JP, A) JP-B 58-48036 (JP, B2)
Claims (3)
なる混合物が加圧・加熱成形されてなり、前記フッ素系
樹脂が混合物に対して10〜40重量％からなる電解用電
極。1. An electrode for electrolysis comprising a mixture of glassy carbon powder and a fluororesin, which is pressed and heat-molded, and the fluororesin is 10 to 40% by weight of the mixture.
下である特許請求の範囲第１項記載の電解用電極。2. The electrode for electrolysis according to claim 1, wherein the glassy carbon powder has a particle size of 100 μm or less.
炭化して得られるものである特許請求の範囲第１項記載
の電解用電極。3. The electrode for electrolysis according to claim 1, wherein the glassy carbon powder is obtained by carbonizing a phenolic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62094094A JP2530332B2 (en) | 1987-04-15 | 1987-04-15 | Electrode for electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62094094A JP2530332B2 (en) | 1987-04-15 | 1987-04-15 | Electrode for electrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63259092A JPS63259092A (en) | 1988-10-26 |
| JP2530332B2 true JP2530332B2 (en) | 1996-09-04 |
Family
ID=14100864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62094094A Expired - Lifetime JP2530332B2 (en) | 1987-04-15 | 1987-04-15 | Electrode for electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2530332B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006292519A (en) * | 2005-04-08 | 2006-10-26 | Kawamura Electric Inc | Tap plug socket |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4375395A (en) * | 1981-05-21 | 1983-03-01 | Foller Peter C | Process for producing ozone |
| JPS5848036A (en) * | 1981-09-18 | 1983-03-19 | Fuji Photo Film Co Ltd | Camera processor |
| DE3429768A1 (en) * | 1984-08-13 | 1986-02-20 | Siemens AG, 1000 Berlin und 8000 München | METHOD FOR PRODUCING GLASS CARBON ELECTRODES |
-
1987
- 1987-04-15 JP JP62094094A patent/JP2530332B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63259092A (en) | 1988-10-26 |
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