JPH0726219B2 - Electrode for electrolysis - Google Patents
Electrode for electrolysisInfo
- Publication number
- JPH0726219B2 JPH0726219B2 JP61189616A JP18961686A JPH0726219B2 JP H0726219 B2 JPH0726219 B2 JP H0726219B2 JP 61189616 A JP61189616 A JP 61189616A JP 18961686 A JP18961686 A JP 18961686A JP H0726219 B2 JPH0726219 B2 JP H0726219B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- electrolysis
- manganese dioxide
- present
- current density
- 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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は電解用電極に関し、詳しくは不動態化するチタ
ンからなる基体の表面に、不動態化しない、電解液に不
溶性の鉛−銀合金を部分的に固定せしめることにより、
生産性、経済性を向上させた二酸化マンガン電解用電極
に関する。Description: TECHNICAL FIELD The present invention relates to an electrode for electrolysis, and more specifically, it is a lead-silver alloy that is not passivated and is insoluble in an electrolytic solution on the surface of a substrate made of passivated titanium. By partially fixing
The present invention relates to an electrode for manganese dioxide electrolysis with improved productivity and economy.
［従来の技術］ 従来、二酸化マンガンを始めとして、スズ、亜鉛、銅、
ニッケル等が電解により採取されている。[Prior Art] Conventionally, starting from manganese dioxide, tin, zinc, copper,
Nickel or the like is collected by electrolysis.
この電解に用いられる電極としては、例えば、二酸化マ
ンガン製造用のアノードとしては、鉛合金や黒鉛等の炭
素材料が用いられていたが、不純物の存在や機械的強度
等の観点から、チタンにほぼ代替されている。しかし、
チタンは電解の進行と共に不動態化現象を起こすため、
電流密度を高くできないという制約がある。従って、従
来は電流密度を約50〜60A/m2程度と低く抑えて、不動態
化現象を最小限にする方法がとられていた。As an electrode used for this electrolysis, for example, a carbon material such as a lead alloy or graphite was used as an anode for producing manganese dioxide, but from the viewpoint of the presence of impurities and mechanical strength, titanium is almost Has been replaced. But,
Since titanium causes a passivation phenomenon with the progress of electrolysis,
There is a restriction that the current density cannot be increased. Therefore, conventionally, a method of suppressing the passivation phenomenon by minimizing the current density to about 50 to 60 A / m 2 has been used.
このように、二酸化マンガンの電解採取は、亜鉛、銅、
ニッケル、錫、アンチモン等の様な他の金属の電解採取
と比較して、電流密度が1/8〜1/10であるため、電極単
位面積当りの生産量が極めて小さく、この点で電解の高
速化およびコストダウンにとって避けることができない
問題点となっていた。Thus, the electrowinning of manganese dioxide involves the extraction of zinc, copper,
Compared with the electrowinning of other metals such as nickel, tin, antimony, etc., the current density is 1/8 to 1/10, so the production amount per unit area of the electrode is extremely small. This has been an unavoidable problem for speeding up and cost reduction.
特に、従来のチタン板アノードを用いた電解操業におい
ては、不動態化するぎりぎりの電流密度で電解を行って
いたため、槽電圧が常に上昇傾向にあることは避けられ
ず、必要に応じてアノードの研磨や逆電解等を行ってチ
タン表面の不動態化膜を除去する必要があり繁雑な操業
を行っていた。In particular, in the conventional electrolytic operation using a titanium plate anode, since the electrolysis was carried out at a current density at the limit of passivation, it was unavoidable that the cell voltage always tended to rise, and if necessary, the anode voltage It is necessary to remove the passivation film on the titanium surface by performing polishing, reverse electrolysis, etc., and a complicated operation has been performed.
このように、二酸化マンガンの電解採取工程において電
流密度を大きくできないということは、生産性の観点か
ら極めて不利なことであった。As described above, the fact that the current density cannot be increased in the electrowinning process of manganese dioxide is extremely disadvantageous from the viewpoint of productivity.
また、不動態化しない白金等の貴金属またはその酸化物
をチタン基板の表面にメッキ等によって被覆して用いる
ことも考えられるが、経済性や機械的強度または被覆
（メッキ）層の剥落等による耐久性の点で問題が生じ
る。It is also possible to coat the surface of the titanium substrate with a noble metal such as platinum that does not passivate or its oxide by plating, etc., but it is economical and mechanical strength or durability due to peeling of the coating (plating) layer etc. There is a problem in terms of sex.
［発明が解決しようとする課題］ 本発明の目的は、このような従来技術の課題を克服し、
経済性や生産性の向上に寄与する電解用電極を提供する
ことにある。[Problems to be Solved by the Invention] An object of the present invention is to overcome the problems of the prior art as described above,
It is to provide an electrode for electrolysis that contributes to the improvement of economic efficiency and productivity.
［課題を解決するための手段および作用］ 本発明者等は、上記の課題を解決するため鋭意研究を重
ねた結果、不動態化するチタンからなる基体の表面に、
不動態化しない、電解液に不溶性の鉛−銀合金を複数箇
所に配置、固定せしめることにより、上記目的が達成で
きることを知見して本発明に至った。[Means and Actions for Solving the Problems] The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, on the surface of the base body made of passivating titanium,
The present invention has been accomplished by finding that the above object can be achieved by arranging and fixing lead-silver alloys that are not passivated and insoluble in an electrolytic solution at a plurality of locations.
すなわち本発明は、チタン基体の表面に、鉛−銀合金を
複数箇所に配置、固定させた電解用電極であって、固体
部全体の表面積が基体の有効表面積に対して0.53〜2.89
％であることを特徴とする二酸化マンガン電解用電極で
ある。That is, the present invention is an electrode for electrolysis in which a lead-silver alloy is arranged and fixed at a plurality of locations on the surface of a titanium substrate, and the surface area of the entire solid part is 0.53 to 2.89 with respect to the effective surface area of the substrate.
% Is the electrode for manganese dioxide electrolysis.
本発明において、基体として用いられるチタンは、電解
液中で分極させたときに不動態化する。この基体の形状
としては、平板、有孔平板、テス状等の任意の形状のも
のが適用される。In the present invention, titanium used as a substrate is passivated when it is polarized in an electrolytic solution. As the shape of the base, any shape such as a flat plate, a perforated flat plate, and a tessed shape is applied.
本発明の電極は、このチタン基体表面上に、電解液中で
分極させたときに不動態化せず、かつ電解液に不溶性の
鉛−銀合金（以下、固定材という）を複数箇所に配置、
固定させる。In the electrode of the present invention, a lead-silver alloy (hereinafter referred to as a fixing material), which is not passivated when polarized in an electrolytic solution and is insoluble in the electrolytic solution, is arranged at a plurality of positions on the surface of the titanium substrate. ,
Fix it.
これら固定材の基体への固定方法としては、クラッド
法、部分メッキ法、溶着法、圧着法、嵌合法、鋲止め法
等が採用される。この場合、固定材は少なくとも基体表
面に露出している必要がある。この固定材の基体への具
体的な固定方法としては、例えば、基体表面にそのまま
上記固定方法により固定材を固定するか、基体の所望部
分を穿孔して貫通孔または閉塞孔を設け、孔表面をメッ
キ法、クラッド法等によって被覆し、あるいは孔に固定
材を溶着、圧着、嵌合、鋲止め等により固定する。As a method of fixing these fixing materials to the substrate, a clad method, a partial plating method, a welding method, a pressure bonding method, a fitting method, a tacking method, or the like is adopted. In this case, the fixing material needs to be exposed at least on the surface of the substrate. As a specific method of fixing the fixing material to the base, for example, the fixing material is fixed to the surface of the base by the fixing method as it is, or a desired portion of the base is perforated to form a through hole or a closed hole, Is coated by a plating method, a clad method or the like, or a fixing material is fixed to the hole by welding, pressure bonding, fitting, tacking or the like.
固定材による固定部全体の表面積が大きい程、低い電極
電位で高い電流密度がとれる。しかしながら固定部があ
まり大きすぎると、電着生成物を削ぎ落とすときの機械
的衝撃に耐えきれず、固定材が基体より外れる恐れがあ
る。従って、固定部表面の大きさは、基体自体の機械的
強度を損わないことはもちろんのこと、固定材が外れな
い程度の大きさに制限すべきである。このような見地か
ら、固定部全体の表面積が基体の有効表面積に対して0.
53〜2.89％であることが有効である。ここでいう有効表
面積とは、電極であるカソードとアノードが相対する面
の面積をいう。The larger the surface area of the entire fixing portion made of the fixing material, the higher the current density can be obtained at the lower electrode potential. However, if the fixing portion is too large, the fixing material may not be able to withstand mechanical shock when the electrodeposition product is scraped off, and the fixing material may come off from the base body. Therefore, the size of the surface of the fixing portion should be limited not to impair the mechanical strength of the substrate itself, but also to such a size that the fixing material does not come off. From this point of view, the total surface area of the fixed part is 0 relative to the effective surface area of the substrate.
It is effective to be 53 to 2.89%. The term "effective surface area" as used herein means the area of the surface where the cathode and the anode, which are electrodes, face each other.
本発明の電極が不動態化を起こさない理論的機構は未だ
明らかではないが、本発明の電極を分極させたときの基
体表面の電位が、従来の基体のみからなる電極が不動態
化するときの電位以上に上昇することがなく、この不動
態化するときの電流値をオーバーする分の電流はすべて
不動態化することのない固定部を通して電解液中に流れ
ているためと推量される。従って、固定部が不動態化を
起こしたり、あるいは電解液中に溶出してそれが消滅し
ない限り、本発明の電極は不動態化することはあり得
ず、事実、実装テストにより確認された。Although the theoretical mechanism by which the electrode of the present invention does not passivate is not yet clear, the potential of the surface of the substrate when the electrode of the present invention is polarized is such that when the electrode consisting only of the conventional substrate is passivated. It is presumed that the electric current which does not rise above the electric potential of the above and exceeds the current value at the time of passivation flows in the electrolytic solution through the fixed portion which does not passivate. Therefore, the electrode of the present invention cannot be passivated unless the fixed part is passivated or is dissolved in the electrolytic solution and disappears, and in fact, it was confirmed by the mounting test.
本発明の電解用電極をアノードとして用い、二酸化マン
ガンの電解に使用した場合、電流密度を大きくすると陽
極酸化された二酸化マンガンが自動的に剥離することも
あるので、その場合は従来の剥ぎ取り工程を省略するこ
とができる。すなわち、電解の高速化、生産性の向上を
図るには、電流密度は大きい程好ましいことは自明の理
であるが、これまでの実験結果では、従来のように電着
状態の緻密な二酸化マンガンを得るためには、アノード
電流密度は300A/m2ぐらいに制限する必要があった。そ
れ以上になると電着応力が大きくなり電着二酸化マンガ
ン層にクラックが入り電着層崩落の原因となる。しかし
ながら、本発明の電極を用いることにより、アノード電
流密度を極端に大きくし、電着二酸化マンガンを槽底に
剥落させ、それを別の方法により回収することにより、
電着二酸化マンガンの極板からの剥ぎ取り工程を省くこ
とができる。When the electrode for electrolysis of the present invention is used as an anode and used for the electrolysis of manganese dioxide, the anodized manganese dioxide may be automatically peeled off when the current density is increased. Can be omitted. That is, in order to speed up electrolysis and improve productivity, it is self-evident that a larger current density is more preferable, but the experimental results so far show that dense manganese dioxide in an electrodeposited state as in the past is used. In order to obtain the above, the anode current density had to be limited to about 300 A / m 2 . If it is more than that, the electrodeposition stress becomes large and cracks occur in the electrodeposited manganese dioxide layer, which causes the electrodeposition layer to collapse. However, by using the electrode of the present invention, the anode current density is extremely increased, the electrodeposited manganese dioxide is peeled off to the bottom of the tank, and it is recovered by another method.
The step of stripping the electrodeposited manganese dioxide from the electrode plate can be omitted.
このような本発明の電解用電極は、二酸化マンガン電解
の際のアノードとして用いられるのみならず、例えばス
ズ、亜鉛、銅、ニッケル等の電解用のアノードまたはカ
ソードとして用いられる。Such an electrode for electrolysis of the present invention is used not only as an anode in electrolysis of manganese dioxide, but also as an anode or cathode for electrolysis of tin, zinc, copper, nickel or the like.
［実施例］ 以下、本発明を実施例および比較例によりさらに具体的
に説明する。[Examples] Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
実施例１〜３および比較例１〜２ 20mm×200mm×5mm厚のチタン板４枚に対し、第１図に示
すように、それぞれ7mmφのPb-Ag（１重量％）合金をチ
タン板の３ケ所に固定したもの:A（実施例1:固定部面積
2.89％）、同じく5mmφの合金を３ケ所に固定したもの:
B（実施例2:固定部面積1.47％）、同じく3mmφの合金を
３ケ所に固定したもの:C（実施例3:固定部面積0.53
％）、残りの一枚は固定しないそのままのもの:D（比較
例１）を準備し、第１表に示す電解条件でそれぞれの電
極について、二酸化マンガンを製造した。第２表に各電
極の電流効率および得られた電着二酸化マンガンの結晶
形を示す。さらに、第２図に各４枚の電極の槽電圧の経
日変化を示す。Examples 1 to 3 and Comparative Examples 1 to 2 As shown in FIG. 1, Pb-Ag (1% by weight) alloy of 7 mmφ was used for each of the titanium plates of 20 mm × 200 mm × 5 mm thickness. Fixed in place: A (Example 1: Fixed part area
2.89%), also with 5mmφ alloy fixed in 3 places:
B (Example 2: Fixed part area 1.47%), similarly fixed with 3 mmφ alloy in 3 places: C (Example 3: Fixed part area 0.53)
%), The remaining one was not fixed and was used as it was: D (Comparative Example 1), and manganese dioxide was produced for each electrode under the electrolysis conditions shown in Table 1. Table 2 shows the current efficiency of each electrode and the crystal form of the obtained electrodeposited manganese dioxide. Furthermore, FIG. 2 shows the change over time in the cell voltage of each of the four electrodes.
第２表および第２図より明らかなように、アノードＤの
場合、つまり固定していないチタン板の場合120A/m2の
高電流密度においては２日目で不動態化し、通電不能と
なった。また、実操業と同じ60A/m2のときは不動態化は
しないものの電圧は2.4V〜3.0Vに上昇した。一方、本発
明の固定電極であるＡ、Ｂ、Ｃは、120A/m2の高電流密
度においても不動態化せず、槽電圧の上昇も僅かであっ
た。 As is clear from Table 2 and FIG. 2, in the case of the anode D, that is, in the case of the titanium plate not fixed, at the high current density of 120 A / m 2 , it was passivated on the second day and the current flow became impossible. . At 60 A / m 2 , which is the same as the actual operation, the voltage did not passivate but increased to 2.4 V to 3.0 V. On the other hand, the fixed electrodes A, B, and C of the present invention did not passivate even at a high current density of 120 A / m 2 , and the increase in cell voltage was slight.
電流効率については従来法と同程度で、得られた二酸化
マンガンの結晶形は全てγ型であった（γ−MnO2は主に
乾電池用に使用される）。また、電着二酸化マンガンの
性状も従来法により製造されたものと同様緻密なもので
あった。The current efficiency was similar to that of the conventional method, and the crystal form of the obtained manganese dioxide was all γ type (γ-MnO 2 is mainly used for dry batteries). In addition, the properties of electrodeposited manganese dioxide were as dense as those produced by the conventional method.
実施例４〜６ 実施例１において使用した電極Ｂを使用して、アノード
電流密度をそれぞれ240A/m2、120A/m2、60A/m2と変化さ
せ、その他は実施例１と同一条件で電解テストを行っ
た。（但し電解日数10日間）その結果を第３表に示す。Examples 4 to 6 Using the electrode B used in Example 1, the anode current density was changed to 240 A / m 2 , 120 A / m 2 and 60 A / m 2 , respectively, and other conditions were the same as in Example 1. An electrolytic test was conducted. (However, the number of electrolysis days is 10 days.) The results are shown in Table 3.
第３表より明らかなように、本発明の電極は、電流密度
を従来の２〜４倍に変化させても不動態化せず、槽電圧
の上昇も僅かであった。また、電流効率は従来法と同程
度の値を示し、得られた二酸化マンガンの結晶形は全て
γ型で、その性状も緻密なものであった。 As is clear from Table 3, the electrode of the present invention did not passivate even when the current density was changed to 2 to 4 times that of the conventional electrode, and the increase in cell voltage was slight. Moreover, the current efficiency showed a value similar to that of the conventional method, and the crystal form of the obtained manganese dioxide was all γ type, and its properties were also dense.
［発明の効果］ 以上の説明から明らかなように、本発明の電解用電極
は、経済性、生産性や作業性の向上に寄与することか
ら、二酸化マンガンの電解用のアノード等として好適に
用いられる。[Effects of the Invention] As is clear from the above description, the electrode for electrolysis of the present invention contributes to the improvement of economic efficiency, productivity and workability, and thus is suitably used as an anode for electrolysis of manganese dioxide and the like. To be
第１図は、本発明の電解用電極の一例を示す斜視図、 第２図は、本発明の電解用電極を使用して二酸化マンガ
ンの電解採取を行ったときの槽電圧と電解日数との関係
を示すグラフである。 1:基体、2:固定材。FIG. 1 is a perspective view showing an example of the electrode for electrolysis of the present invention, and FIG. 2 is a diagram showing the cell voltage and the number of electrolysis days when electrolytically collecting manganese dioxide using the electrode for electrolysis of the present invention. It is a graph which shows a relationship. 1: Base, 2: Fixing material.
Claims (1)
所に配置、固定させた電解用電極であって、固定部全体
の表面積が基体の有効表面積に対して0.53〜2.89％であ
ることを特徴とする二酸化マンガン電解用電極。1. An electrode for electrolysis in which a lead-silver alloy is arranged and fixed at a plurality of positions on a surface of a titanium substrate, and the total surface area of the fixed portion is 0.53 to 2.89% of the effective surface area of the substrate. An electrode for manganese dioxide electrolysis, which is characterized in that
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61189616A JPH0726219B2 (en) | 1986-08-14 | 1986-08-14 | Electrode for electrolysis |
| GR871281A GR871281B (en) | 1986-08-14 | 1987-08-13 | Electrodes for electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61189616A JPH0726219B2 (en) | 1986-08-14 | 1986-08-14 | Electrode for electrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6347390A JPS6347390A (en) | 1988-02-29 |
| JPH0726219B2 true JPH0726219B2 (en) | 1995-03-22 |
Family
ID=16244281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61189616A Expired - Lifetime JPH0726219B2 (en) | 1986-08-14 | 1986-08-14 | Electrode for electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0726219B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820820B (en) * | 2014-03-03 | 2017-05-24 | 湘潭安拓机电科技有限公司 | An environment-friendly type automatic passivation cleaning plate-arranging machine for an electrolytic manganese metal pole plate |
| CN109385645B (en) * | 2018-12-06 | 2021-05-11 | 普瑞斯矿业(中国)有限公司 | Treatment method for improving conductivity of anode plate for electrolytic manganese dioxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0137911B1 (en) * | 1983-06-28 | 1988-07-27 | BBC Brown Boveri AG | Process for manufacturing a depassivating layer and depassivating layer on an electrode for an electrochemical cell |
-
1986
- 1986-08-14 JP JP61189616A patent/JPH0726219B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6347390A (en) | 1988-02-29 |
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