JPH0741980A - Electrolytic electrode - Google Patents
Electrolytic electrodeInfo
- Publication number
- JPH0741980A JPH0741980A JP5145849A JP14584993A JPH0741980A JP H0741980 A JPH0741980 A JP H0741980A JP 5145849 A JP5145849 A JP 5145849A JP 14584993 A JP14584993 A JP 14584993A JP H0741980 A JPH0741980 A JP H0741980A
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- Prior art keywords
- electrode
- metal
- insoluble
- insoluble metal
- electrolysis
- Prior art date
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、各種の物質の電解製造
や金属の電解採取、メッキ等に使用される電解用電極お
よびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for electrolysis used for electrolytic production of various substances, electrolytic extraction of metals, plating and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】電解用電極としては、古くは炭素質電極
が使用されていたが、近年、チタンに代表される弁金属
を基体とし、その表面に、白金族金属を含む酸化物被覆
を施した、本出願人がＤＳＡ、又はＤＳＥの商品名で提
供している不溶性金属電極が使用されるようになってき
た。これらは、比較的小型軽量であり使用中の寸法変化
は実質的になく、また極めてすぐれた耐食性、耐久性を
有するとともに、電極触媒作用を有する電極物質も用途
に応じて任意に選択できるので広く使用されており、現
在では、最大の工業的な電解分野である食塩の電気分解
ではほとんど全てがこの不溶性金属電極に置き換わって
いる。2. Description of the Related Art As an electrode for electrolysis, a carbonaceous electrode has been used for a long time, but in recent years, a valve metal typified by titanium is used as a substrate, and the surface thereof is coated with an oxide containing a platinum group metal. The insoluble metal electrode provided by the applicant under the trade name of DSA or DSE has come to be used. These are comparatively small and light in weight, do not substantially change in size during use, have extremely excellent corrosion resistance and durability, and the electrode material having an electrocatalytic action can be arbitrarily selected according to the application. It has been used and is now almost entirely replaced by insoluble metal electrodes in the electrolysis of common salt, the largest industrial electrolysis field.
【０００３】一方、酸素発生用の陽極分野においては、
炭素は発生する酸素と反応して急速に消耗するととも
に、電気伝導性が不十分という問題がある。そこで、酸
素発生用には不溶性で安定な鉛や鉛合金が使用されてい
るが、鉛の廃水中への混入、製品中への混入問題といっ
た環境上の問題を有している。すなわち、鉛や鉛合金は
工業用電極として導電性、加工性は満足されているもの
の、電解時の消耗が数ｍｇ／Ａｈと大きく、電解液中へ
溶出した鉛が廃水中あるいは製品中へ混入するのであ
る。これらの解決策として、古くより知られている白金
めっきチタン電極、又は白金めっきニオブ電極が実験室
規模、あるいは特殊な分野では用いられているが、高価
であり、工業用として用いるには耐久性が不十分なこと
から、一般に広く使われるには至っていないし、今後と
も拡大していく可能性はないものとみられる。そこで、
鋼板の連続めっきや、金属採取等の酸素発生用陽極を使
用する分野で現在でも主体となっている鉛や鉛合金陽極
についても、既に食塩電解などにおいて広く用いられて
いるチタン等の弁金属の基体上に電極被覆を形成した不
溶性金属陽極への転換が進むものとみられる。On the other hand, in the field of anodes for oxygen generation,
There is a problem that carbon reacts with generated oxygen and is rapidly consumed, and that electric conductivity is insufficient. Therefore, insoluble and stable lead and lead alloys are used for oxygen generation, but they have environmental problems such as the problem of lead being mixed into waste water and products. In other words, although lead and lead alloys are satisfactory in terms of electrical conductivity and workability as industrial electrodes, the consumption during electrolysis is large at several mg / Ah, and lead dissolved in the electrolytic solution is mixed with waste water or products. To do. As a solution to these problems, platinum-plated titanium electrodes or platinum-plated niobium electrodes that have been known for a long time have been used in a laboratory scale or in special fields, but they are expensive and durable for industrial use. Since it is insufficient, it has not been widely used in general, and it is unlikely that it will be expanded in the future. Therefore,
Lead and lead alloy anodes, which are still mainly used in the field of continuous plating of steel sheets and the use of anodes for oxygen generation for metal extraction, are also widely used in salt electrolysis and other valve metals such as titanium. It is expected that conversion to an insoluble metal anode having an electrode coating formed on the substrate will proceed.
【０００４】不溶性金属陽極は、液体、気体等の化学物
質を製造する目的の電解槽では、電極には平板状のもの
が一般に用いられており、電極の特性を十分に利用する
ことができた。ところが、鋼板のめっきや金属の採取等
の電解装置に使用する場合には、不溶性金属陽極は陽極
での電解反応は重要ではなく、単に対極としての作用を
果たすのみであるが、めっき鋼板、銅箔等の金属箔等を
製品とするために、対極として使用する陽極の大きさ
は、大型のものが必要となり、形状も平板状に限らず、
曲面状等の電極が必要となる。このため、極めて面積の
大きな各種の形状の電極の電極面全体の形状を安定に保
持し、電極面に均一に、あるいは電極面にそれぞれの部
位に必要な電流を給電するために、電極基体の厚みは厚
いものが必要であるとともに大量の給電体を装備するこ
とが必要となる。その結果、電極の重量が大きくなり、
電極の製造および使用における問題となっている。例え
ば、金属箔の電解製造装置に使用する電極には、基体の
板厚が５０ｍｍ以上のものや、直径３ｍの半円筒状の曲
面の内側に電極被覆を行ったものも使用されており、１
つの電極の重量が５００ｋｇを越えるという巨大なもの
まで現れている。このような大型の電極基体を通常の不
溶性電極の製造において行われているような酸素含有雰
囲気において加熱する熱分解法によって電極触媒被覆を
形成することは、大型の加熱炉が必要となり、また大型
の電極の加熱、冷却の繰り返しには長時間を必要とし
た。The insoluble metal anode is a flat plate type electrode generally used in an electrolytic cell for the purpose of producing chemical substances such as liquid and gas, and the characteristics of the electrode can be fully utilized. . However, when it is used in an electrolysis device such as plating of steel sheet or collecting metal, the insoluble metal anode is not important in the electrolytic reaction at the anode and merely serves as a counter electrode. In order to make a metal foil such as a foil into a product, the size of the anode used as the counter electrode needs to be large, and the shape is not limited to a flat plate.
A curved electrode or the like is required. For this reason, in order to stably maintain the shape of the entire electrode surface of various shapes of electrodes having extremely large areas and to supply the necessary electric current to the electrode surface evenly or to each part of the electrode substrate, It is necessary to have a large thickness and to equip a large number of power feeding bodies. As a result, the weight of the electrode increases,
It is a problem in the manufacture and use of electrodes. For example, as an electrode used in an electrolytic production apparatus for metal foil, a substrate having a plate thickness of 50 mm or more, or an electrode coated inside a semi-cylindrical curved surface having a diameter of 3 m is also used.
Even the huge one with the weight of one electrode exceeding 500 kg has appeared. Forming an electrode catalyst coating by a thermal decomposition method in which such a large electrode substrate is heated in an oxygen-containing atmosphere as is done in the usual production of insoluble electrodes requires a large heating furnace, and It took a long time to repeat heating and cooling of the electrode.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、電極面積が
大きな電極面に、多数の給電体を用いることなくそれぞ
れの部位に好ましい大きさの電流の供給が可能な電極を
提供することを課題とするものであり、また、電極の形
状が平面状ではない場合にも、電極表面に均一もしくは
それぞれの部位で要求される電流の供給が可能な構造が
簡単な電解用電極を提供することを課題とするものであ
る。SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrode capable of supplying a desired amount of electric current to each part on an electrode surface having a large electrode area without using a large number of power feeding bodies. In addition, even when the shape of the electrode is not flat, it is possible to provide an electrode for electrolysis that has a simple structure capable of supplying the current required at each part of the electrode surface evenly. This is an issue.
【０００６】[0006]
【課題を解決するための手段】本発明は、電極基体に、
開口を有する不溶性金属の板状体を電極触媒物質で被覆
した不溶性金属電極を取り付けた電解用電極において、
電流密度が大きな部分には、開口率が小さな不溶性金属
電極を配置し、電流密度が小さな部分には開口率が大き
な不溶性金属電極を配置した電解用電極である。不溶性
金属電極がチタンまたはチタン合金の表面にイリジウム
酸化物を含む電極触媒物質を被覆したものである電解用
電極である。The present invention provides an electrode substrate,
In an electrode for electrolysis equipped with an insoluble metal electrode in which a plate-shaped body of an insoluble metal having an opening is coated with an electrode catalyst substance,
This is an electrode for electrolysis in which an insoluble metal electrode having a small aperture ratio is arranged in a portion having a large current density and an insoluble metal electrode having a large aperture ratio is arranged in a portion having a small current density. The insoluble metal electrode is an electrode for electrolysis in which the surface of titanium or a titanium alloy is coated with an electrode catalyst substance containing iridium oxide.
【０００７】すなわち、チタンまたはその合金などの弁
金属又は弁金属合金からなる電極基体上に、エキスパン
デッドメタル等の開口を有する不溶性金属表面に電極触
媒物質を被覆した不溶性金属電極を取り付けた電解用電
極において、電解電流が集中する電流密度が大きな部分
には、開口率が小さく実質的な通電面積が大きな不溶性
金属電極を取り付け、電流密度が小さな部分には開口率
が大きく、実質的な通電面積が小さな不溶性金属電極を
取り付けた電解用電極である。なお、本発明における電
流密度は、電極面の開口部分も含めた単位面積当たりの
電流値をいう。[0007] That is, electrolysis in which an insoluble metal electrode having an insoluble metal surface having an opening such as an expanded metal coated with an electrocatalyst substance is attached to an electrode substrate made of a valve metal or a valve metal alloy such as titanium or its alloy. In the metal electrode, an insoluble metal electrode with a small opening ratio and a large effective current-carrying area is attached to the part where the electrolysis current is concentrated and the current density is large. It is an electrode for electrolysis with an insoluble metal electrode having a small area. The current density in the present invention refers to a current value per unit area including the opening portion of the electrode surface.
【０００８】本発明の電解用電極に使用することが可能
な開口を有する不溶性金属には、薄板に規則的に設けた
切れ目を拡開したエキスパンデッドメタル、薄板にプレ
ス等によって開口を形成したパンチドプレート等を用い
ることができ、開口の形状は任意のものを用いることが
できる。またエキスパンデッドメタルの場合には、拡開
したそのままのものであっても、ロール掛けをして表面
を平坦化したものであってもよい。ロール掛けをする場
合には、完全に平坦にしたものよりも、見かけの厚みが
元の金属の１．２〜２倍程度となるようにロール掛けし
たものの方が電極としての利用部分が多くなるので望ま
しい。The insoluble metal having an opening that can be used in the electrode for electrolysis of the present invention is an expanded metal in which cuts regularly formed on a thin plate are expanded, or an opening is formed on the thin plate by pressing or the like. A punched plate or the like can be used, and any shape of the opening can be used. Further, in the case of expanded metal, it may be expanded as it is or may be rolled to have its surface flattened. In the case of rolling, the rolled part having an apparent thickness of about 1.2 to 2 times that of the original metal is more used as an electrode than the completely flat plate. So desirable.
【０００９】エキスパンデッドメタルの表面積と開口率
の関係について説明すると、例えば、厚さ１ｍｍの板を
エキスパンデッドメタルとした場合の表面積は元の板の
表面積と拡開のために板に形成した切れ目の部分の板の
断面積の和で表され、表面積は開口率を５０％とした
時、すなわち元の板を２倍の長さになるように拡げた場
合には、エキスパンデッドメタルの全表面積は投影面の
約２倍である。また、開口率を小さくすると全表面積は
大きく、開口率を大きくすると全表面積は小さくなる。
なお、実際には金属の塑性加工の点から開口率は制限さ
れてくるが、実用上は開口率は３０％〜７０％位が使用
される。The relationship between the surface area of the expanded metal and the aperture ratio will be described. For example, when a plate having a thickness of 1 mm is used as the expanded metal, the surface area of the original plate is the same as that of the original plate. It is expressed as the sum of the cross-sectional areas of the plates at the cuts, and the surface area is expanded metal when the opening ratio is 50%, that is, when the original plate is expanded to have a double length. Has a total surface area about twice that of the projection surface. Further, when the aperture ratio is reduced, the total surface area is large, and when the aperture ratio is increased, the total surface area is reduced.
Although the aperture ratio is actually limited from the viewpoint of metal plastic working, the aperture ratio of about 30% to 70% is practically used.
【００１０】また、本発明の電解用電極は、チタン又は
チタン合金製のエキスパンデッドメタルの表面をブラス
ト、酸洗等によって表面処理した後、白金族の金属化合
物を含む溶液を塗布した後に酸素含有雰囲気において、
熱分解し電極触媒物質の被覆を形成することによって得
られた不溶性金属電極を、弁金属又は弁金属基合金から
なる電極基体表面に溶接等の手段によって固定すること
ができる。不溶性金属電極の基材とするエキスパンデッ
ドメタルは、厚みが０．２〜１．５ｍｍの板を材料とし
たものが好ましく、０．５〜１ｍｍの厚みのものがとく
に好ましい。板の厚みが０．２ｍｍより薄いと、その物
理強度が不足すると共にエキスパンデッドメタルを製造
することが困難となる。一方、１．５ｍｍより厚くなる
と、エキスパンデッドメタルの見かけ上の厚みが大きく
なり、電極表面に大きな凹凸を有する電極が形成される
こととなり特殊な用途を除いて好ましくない。In the electrode for electrolysis of the present invention, the surface of an expanded metal made of titanium or a titanium alloy is surface-treated by blasting, pickling, etc., and then a solution containing a platinum group metal compound is applied and then oxygen is applied. In the contained atmosphere,
The insoluble metal electrode obtained by pyrolyzing to form a coating of the electrocatalyst material can be fixed to the surface of an electrode substrate made of a valve metal or a valve metal-based alloy by welding or the like. The expanded metal used as the base material of the insoluble metal electrode is preferably made of a plate having a thickness of 0.2 to 1.5 mm, particularly preferably 0.5 to 1 mm. If the thickness of the plate is less than 0.2 mm, its physical strength will be insufficient and it will be difficult to manufacture an expanded metal. On the other hand, if it is thicker than 1.5 mm, the apparent thickness of the expanded metal becomes large, and an electrode having large unevenness is formed on the electrode surface, which is not preferable except for special applications.
【００１１】不溶性金属電極の製造は、電極の製造にお
いて通常採用されている方法によって行うことができ、
微細粒による低圧ブラストで表面組織の調整を行い、さ
らに酸洗等によって表面清浄を行う。表面の調整方法の
一例を示せば、直径０．１ｍｍの炭化ケイ素粒子を用い
て低圧ブラストを行い、表面を均質にした後にシュウ酸
によって酸洗を行い、表面粗度の調整を行うと共に、表
面を活性化する方法が挙げられる。この表面処理を施し
たエキスパンデッドメタル表面に白金族金属化合物を含
有する溶液を塗布し、酸素含有雰囲気にて焼成して電極
触媒被覆物質を形成するが、塗布−乾燥−焼成炉による
焼成の工程を繰り返し行って所望の厚さの被覆を形成す
る。焼成の条件は、電極触媒被覆の成分によって異なる
が、４５０〜５５０℃とすることが好ましい。また、厚
さが０．２〜０．４ｍｍ程度の薄い基材の場合は１ｍｍ
以上の物に比較して５〜１０℃温度を低下させた方が有
効である。電極触媒物質としては、硫酸、硝酸、または
それらの両者を含む電解液中において使用する陽極のよ
うに酸素発生陽極とする場合には酸化イリジウムと酸化
タンタルからなる電極触媒物質が好ましい。The production of the insoluble metal electrode can be carried out by a method usually adopted in the production of the electrode,
The surface texture is adjusted by low pressure blasting with fine particles, and the surface is further cleaned by pickling. As an example of the surface adjustment method, low-pressure blasting is performed using silicon carbide particles having a diameter of 0.1 mm, and the surface is homogenized and then pickled with oxalic acid to adjust the surface roughness. The method of activating is mentioned. A solution containing a platinum group metal compound is applied to the surface of the expanded metal subjected to this surface treatment and fired in an oxygen-containing atmosphere to form an electrode catalyst coating material. The process is repeated to form a coating of desired thickness. The firing conditions differ depending on the components of the electrode catalyst coating, but are preferably 450 to 550 ° C. In addition, in the case of a thin base material with a thickness of about 0.2 to 0.4 mm, 1 mm
It is more effective to lower the temperature by 5 to 10 ° C. as compared with the above. The electrode catalyst substance is preferably an electrode catalyst substance composed of iridium oxide and tantalum oxide when used as an oxygen generating anode such as an anode used in an electrolytic solution containing sulfuric acid, nitric acid, or both.
【００１２】このようにして作製した電極触媒被覆を有
する不溶性金属電極を電極上での電流の分布に応じて電
流の大きな部分は開口率の小さなものを、電流の小さな
部分は開口率の大きなものを取り付けるが、曲面を有す
る板状体を電極基体とする場合には、曲面状の電極基体
に直接に取り付けても良いが、基体上に結合したリブに
不溶性金属電極を取り付けても良い。不溶性金属電極の
取り付けは、機械的な固着手段、あるいはＴＩＧ溶接や
抵抗溶接等の溶接によって行うことができるが、溶接に
よる場合には、ＴＩＧ溶接や抵抗溶接では、溶接箇所が
大きく溶融し、電極としての作用を果たさない部分の面
積が大きくなるので、溶接部分の局部的な加熱溶融が可
能なレーザービームによって溶接することが望ましい。
また、取付箇所の間隔は不溶性金属電極の大きさ、電極
の使用電流の大小によって決めるが、通常は２０〜３０
ｍｍ間隔で行う。According to the current distribution on the electrode, the insoluble metal electrode having an electrocatalyst coating produced in this way has a small aperture ratio at a large current portion and a large aperture ratio at a small current portion. When a plate-shaped body having a curved surface is used as the electrode base, the electrode base may be directly mounted, or the insoluble metal electrode may be mounted on a rib connected to the base. The insoluble metal electrode can be attached by mechanical fixing means or welding such as TIG welding or resistance welding. However, in the case of welding, in TIG welding or resistance welding, the welded portion largely melts and the electrode Since the area of the portion which does not function as the above becomes large, it is desirable to perform welding by a laser beam capable of locally heating and melting the welded portion.
The interval between the attachment points is determined by the size of the insoluble metal electrode and the magnitude of the current used by the electrode, but it is usually 20-30.
Perform at mm intervals.
【００１３】電極基体には、各種の金属を用いることが
できるが、陽極として使用する場合に、耐食性のあるチ
タンあるいはその合金などの弁金属、あるいは弁金属合
金を電極基体とすることが好ましい。そして、電極基体
上には、直接に電極触媒被覆を形成しないので、電極基
体の形状、構造を熱処理を考慮して決定する必要はな
い。また、電極基体には、既に電極として使用して電極
活性の低下した部材を使用し、不溶性金属電極を溶接等
の手段によって取付けることにより、電極基体の熱処理
等を行わずに電極の再生が可能である。さらに、電極基
体は清浄にするのみで良いので、溶接の障害となるよう
な酸洗処理や活性化処理を行わなくてもよい。Various metals can be used for the electrode base, but when used as an anode, it is preferable to use a valve metal such as titanium or its alloy having corrosion resistance, or a valve metal alloy as the electrode base. Since the electrode catalyst coating is not directly formed on the electrode base, it is not necessary to determine the shape and structure of the electrode base in consideration of heat treatment. Also, the electrode base is made of a material that has already been used as an electrode and has reduced electrode activity, and the insoluble metal electrode is attached by means such as welding, so that the electrode can be regenerated without heat treatment of the electrode base. Is. Further, since the electrode base body only needs to be cleaned, it is not necessary to perform the pickling treatment or the activation treatment that may hinder welding.
【００１４】[0014]
【作用】電極基体上に開口率の異なる開口部を有する不
溶性金属電極を取りつけた電解用電極において、電流が
集中する部分にはその他の部分に比較して開口率の小さ
な不溶性金属電極を取付けて、電流が集中する部分での
電極として作用する面積を増大させて電流集中部分での
実質的な電流密度を低下させることができ、電極基体と
不溶性金属電極を別個に製造することができるので、任
意の形状あるいは大きさの電極を製造することができ
る。[Function] In an electrode for electrolysis in which an insoluble metal electrode having openings having different opening ratios is mounted on an electrode substrate, an insoluble metal electrode having a smaller opening ratio is attached to a portion where current concentrates compared to other portions. Since the area acting as an electrode in the portion where the current is concentrated can be increased to reduce the substantial current density in the portion where the current is concentrated, the electrode substrate and the insoluble metal electrode can be manufactured separately. Electrodes of any shape or size can be manufactured.
【００１５】[0015]
【実施例】以下、実施例によりさらに詳細に説明する。
本発明の１実施例を図面を用いて説明する。図１は、銅
箔製造用の電解装置において、回転する円筒状陰極に対
向して用いられる陽極として用いる電極である。電極１
は円筒の曲面の一部からなり、通常の電解装置では円筒
の４分の１の大きさのものを２個用いている。チタン等
の弁金属からなる電極基体２に電極触媒物質を被覆した
エキスパンデッドメタルの不溶性金属電極３を溶接によ
って取りつけたものであるが、エキスパンデッドメタル
として、開口率が大きな不溶性金属電極３１と開口率が
中間の電極３２、および開口率が小さな電極３３を配置
している。EXAMPLES The present invention will be described in more detail below with reference to examples.
An embodiment of the present invention will be described with reference to the drawings. FIG. 1 shows an electrode used as an anode used so as to face a rotating cylindrical cathode in an electrolytic apparatus for producing a copper foil. Electrode 1
Consists of a part of a curved surface of a cylinder, and in an ordinary electrolysis apparatus, two one-quarter-sized cylinders are used. An insoluble metal electrode 3 made of expanded metal in which an electrode catalyst material is coated on an electrode substrate 2 made of a valve metal such as titanium is attached by welding. As the expanded metal, an insoluble metal electrode 31 having a large aperture ratio is used. An electrode 32 having an intermediate aperture ratio and an electrode 33 having a small aperture ratio are arranged.
【００１６】通常、このような円筒状の電極を使用した
電解装置によって、銅箔を製造する場合には、円筒の下
部より電解液を陰極と陽極の電極間隔に供給し、電解液
を上方から排出しながら電解をする。陽極では酸素が発
生し気泡となって電解液中を上昇する。電解液の流速に
よって異なるが、電解槽の上部ほど気泡の量および気泡
の大きさが大きくなり電解槽の下部と上部では電流密度
の差が生じる。そこで、電解槽の下部の電極の開口率を
他の部分の電極の開口率よりも小さくすることによっ
て、それぞれの部分の電流密度に対応した電流を供給す
ることが可能となり、安定な電解を行うことができる。Usually, when a copper foil is manufactured by an electrolysis apparatus using such a cylindrical electrode, the electrolytic solution is supplied from the lower part of the cylinder to the electrode gap between the cathode and the anode, and the electrolytic solution is supplied from above. Electrolyze while discharging. Oxygen is generated at the anode to form bubbles and rise in the electrolytic solution. Although it depends on the flow rate of the electrolytic solution, the amount of bubbles and the size of bubbles increase toward the upper part of the electrolytic cell, resulting in a difference in current density between the lower part and the upper part of the electrolytic cell. Therefore, by making the aperture ratio of the electrode in the lower part of the electrolytic cell smaller than the aperture ratio of the electrodes in other parts, it becomes possible to supply a current corresponding to the current density of each part, and perform stable electrolysis. be able to.
【００１７】実施例１ 銅箔製造用試験電解槽として、直径１ｍの円筒状の陰
極、および陰極の下部の半分を取り囲むようにした半円
筒状の陽極を使用して電解試験を行った。電極間距離は
１０ｍｍであった。陰極には、ステンレス鋼にクロムめ
っきを行ったドラムを使用し、陽極には曲面状に加工し
たチタン板上に板厚１．０ｍｍのチタンで作ったエキス
パンデッドメタルを基材とする不溶性金属電極を溶接し
たものを使用した。なお、ここで用意したエキスパンデ
ッドメタルは３種類であり、これらは図２のエキスパン
デッドメタルを説明する図におけるＬＷを１０ｍｍで共
通とし、ＳＷを変えて開口率４０％、５０％、及び６０
％としたものを用意した。拡開後、ロールによって厚み
を１．２ｍｍに調整した。これら３種のエキスパンデッ
ドメタルを、開口率の小さいもの（４０％）を下方に、
中間（５０％）を真中に、大きいもの（６０％）を上部
に抵抗溶接により取りつけた。Example 1 As a test electrolytic cell for producing a copper foil, an electrolytic test was conducted using a cylindrical cathode having a diameter of 1 m and a semi-cylindrical anode surrounding the lower half of the cathode. The distance between the electrodes was 10 mm. An insoluble metal whose base is an expanded metal made of titanium with a thickness of 1.0 mm on a titanium plate that has been processed into a curved surface for the anode, using a drum made of chrome-plated stainless steel for the cathode Welded electrodes were used. Note that there are three types of expanded metal prepared here, and these have a common LW of 10 mm in the diagram for explaining the expanded metal of FIG. 2 and change SW to have aperture ratios of 40%, 50%, and 60
% Prepared. After the expansion, the thickness was adjusted to 1.2 mm with a roll. For these three types of expanded metal, the one with a small aperture ratio (40%) is
The middle (50%) was attached to the middle and the larger one (60%) was attached to the top by resistance welding.
【００１８】電解液として銅イオンを５０ｇ／ｌ、硫酸
を２００ｇ／ｌ含む水溶液を用い、添加剤としてゼラチ
ンを５０ｍｇ／ｌの濃度となるように加えたものを使用
し、電解槽下方から流速２０ｃｍ／秒の速度で電解液を
上方に供給した。電解液温度は６０℃であり、電流密度
を１００Ａ／ｃｍ2 とした。なお、実質電流分布を測定
するためドラムの回転は行わなかった。その結果、陰極
のドラム状の電極上に析出した銅の厚さには分布が生
じ、液入口の銅の厚さに対して液出口の銅の厚さは約３
０％薄いものであった。本実施例における下部と上部と
の電極の表面積比は約１：０．６５であり、この電流密
度の分布にほぼ対応するもので、陽極表面当たりの電流
負荷はほぼ同じになることが予想された。An aqueous solution containing 50 g / l of copper ions and 200 g / l of sulfuric acid was used as an electrolytic solution, and gelatin was added as an additive to a concentration of 50 mg / l. The electrolyte was fed upward at a rate of / sec. The electrolyte temperature was 60 ° C. and the current density was 100 A / cm 2 . The drum was not rotated in order to measure the actual current distribution. As a result, there is a distribution in the thickness of the copper deposited on the cathode drum-shaped electrode, and the thickness of the copper at the liquid outlet is about 3 with respect to the thickness of the copper at the liquid inlet.
It was 0% thin. The surface area ratio between the lower electrode and the upper electrode in this example is about 1: 0.65, which almost corresponds to this current density distribution, and it is expected that the current load per anode surface will be almost the same. It was
【００１９】比較例１ 陽極として、厚さ３ｍｍの曲面状のチタン板に実施例１
と同様の電極被覆を形成した点を除いて、実施例１と同
様の条件で電解したところ、陰極のドラム状電極の銅の
厚みは実施例１と同様に電解液の入口部の厚みに対して
液出口の銅の厚みは３０％薄いものであり、陽極の電極
としての表面積分布には起因していないことがわかっ
た。なお、この分布は電解液中に混入した陽極より発生
した酸素ガス気泡によるものであり、上部ほど気泡率が
高くなり、液の実質的な抵抗が増大したためと考えられ
る。Comparative Example 1 A curved titanium plate having a thickness of 3 mm was used as the anode in Example 1.
Electrolysis was performed under the same conditions as in Example 1 except that the same electrode coating as in Example 1 was formed, and the copper thickness of the cathode drum electrode was the same as that in Example 1 with respect to the thickness of the electrolyte inlet. As a result, it was found that the thickness of copper at the liquid outlet was 30% thinner and was not caused by the surface area distribution of the anode electrode. This distribution is due to oxygen gas bubbles generated from the anode mixed in the electrolytic solution, and it is considered that the bubble ratio becomes higher toward the upper part and the substantial resistance of the liquid increases.
【００２０】実施例２ 無水硫酸ナトリウム１６０ｇ／ｌ、硫酸２０ｇ／ｌ、並
びに添加剤としてゼラチンを５０ｍｇ／ｌ含む電解液を
使用し、実施例１と同様に電極寿命試験を行った。試験
した電極は３７００時間で寿命に達したが、その時には
ほぼ電解面全面にわたって活性が低下していた。Example 2 An electrode life test was conducted in the same manner as in Example 1 using an electrolytic solution containing anhydrous sodium sulfate of 160 g / l, sulfuric acid of 20 g / l and gelatin of 50 mg / l as an additive. The tested electrode reached the end of its life at 3700 hours, at which time the activity was reduced over almost the entire electrolytic surface.
【００２１】比較例２ 比較例１の電極を用いた点を除いて実施例２と同一の条
件で電極寿命の試験をお行ったところ、電極下部は１６
００時間で活性を失ってしまった。Comparative Example 2 An electrode life test was conducted under the same conditions as in Example 2 except that the electrode of Comparative Example 1 was used.
I lost activity at 00 hours.
【００２２】[0022]
【発明の効果】本発明の電極は、電極基体上に取り付け
る開口を有する電極触媒被覆を形成した不溶性金属電極
の開口率を、電流の大小に応じて部分的に変更したの
で、電極の一部分における電流密度の上昇を防止するこ
とができ、電極を長寿命化させることが可能となる。ま
た、電極被覆を電極基体上に直接に形成していないの
で、大型の電極であっても製造が容易となり、また性能
の低下した電極の再活性化にはこの電極基体上の不溶性
金属電極を取り替えるのみで、再活性化を短時間に容易
に行うことが可能となった。In the electrode of the present invention, the aperture ratio of the insoluble metal electrode having the electrocatalyst coating having the opening to be mounted on the electrode substrate is partially changed according to the magnitude of the electric current. It is possible to prevent an increase in current density and prolong the life of the electrode. In addition, since the electrode coating is not directly formed on the electrode base, it is easy to manufacture even a large size electrode, and the insoluble metal electrode on this electrode base is used to reactivate the electrode with degraded performance. Only by replacing, it became possible to reactivate easily in a short time.
【図１】本発明の電極を説明する図である。FIG. 1 is a diagram illustrating an electrode of the present invention.
【図２】エキスパンデッドメタルを説明する図である。FIG. 2 is a diagram illustrating an expanded metal.
１…電極、２…電極基体、３…不溶性金属電極、３１…
開口率が大きな不溶性金属電極、３２…中間の開口率の
不溶性金属電極、３３…開口率が小さな不溶性金属電極1 ... Electrode, 2 ... Electrode base, 3 ... Insoluble metal electrode, 31 ...
Insoluble metal electrode with large aperture ratio, 32 ... Insoluble metal electrode with intermediate aperture ratio, 33 ... Insoluble metal electrode with small aperture ratio
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２５Ｄ 21/12 Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C25D 21/12 E
Claims (2)
板状体を電極触媒物質で被覆した不溶性金属電極を取り
付けた電解用電極において、電流密度が大きな部分に
は、開口率が小さな不溶性金属電極を配置し、電流密度
が小さな部分には開口率が大きな不溶性金属電極を配置
したことを特徴とする電解用電極。1. An electrode for electrolysis in which an electrode substrate is provided with an insoluble metal electrode in which a plate-shaped body of insoluble metal having openings is coated with an electrocatalyst substance is attached. An electrode for electrolysis, wherein an electrode is arranged, and an insoluble metal electrode having a large aperture ratio is arranged in a portion having a small current density.
金の表面にイリジウム酸化物を含む電極触媒物質を被覆
したものであることを特徴とする請求項１記載の電解用
電極。2. The electrode for electrolysis according to claim 1, wherein the insoluble metal electrode is titanium or a titanium alloy having a surface coated with an electrode catalyst substance containing iridium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14584993A JP3332264B2 (en) | 1993-06-17 | 1993-06-17 | Electrode for electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14584993A JP3332264B2 (en) | 1993-06-17 | 1993-06-17 | Electrode for electrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0741980A true JPH0741980A (en) | 1995-02-10 |
| JP3332264B2 JP3332264B2 (en) | 2002-10-07 |
Family
ID=15394521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14584993A Expired - Fee Related JP3332264B2 (en) | 1993-06-17 | 1993-06-17 | Electrode for electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3332264B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1063322A3 (en) * | 1999-06-22 | 2001-08-22 | Ga-Tek, Inc. (dba Gould Electronics, Inc.) | Anode structure for manufacture of metallic foil |
| JP2002513860A (en) * | 1998-05-06 | 2002-05-14 | エルテック・システムズ・コーポレーション | Improved lead electrode |
| CN100418695C (en) * | 2004-09-20 | 2008-09-17 | 长春石油化学股份有限公司 | Method for mfg. copper foil |
| JP2009127068A (en) * | 2007-11-21 | 2009-06-11 | Akita Prefectural Univ | Cathode for electrolytic treatment, and electrolytic cell |
| WO2015151665A1 (en) * | 2014-03-31 | 2015-10-08 | 株式会社シンク・ラボラトリー | Cylinder plating apparatus and method |
| US9777382B2 (en) | 2015-06-03 | 2017-10-03 | Kabushiki Kaisha Toshiba | Electrochemical cell, oxygen reduction device using the cell and refrigerator using the oxygen reduction device |
-
1993
- 1993-06-17 JP JP14584993A patent/JP3332264B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002513860A (en) * | 1998-05-06 | 2002-05-14 | エルテック・システムズ・コーポレーション | Improved lead electrode |
| EP1063322A3 (en) * | 1999-06-22 | 2001-08-22 | Ga-Tek, Inc. (dba Gould Electronics, Inc.) | Anode structure for manufacture of metallic foil |
| KR100356308B1 (en) * | 1999-06-22 | 2002-10-18 | 가-텍 인코포레이티드 | Anode structure for manufacture of metallic foil |
| CN100418695C (en) * | 2004-09-20 | 2008-09-17 | 长春石油化学股份有限公司 | Method for mfg. copper foil |
| JP2009127068A (en) * | 2007-11-21 | 2009-06-11 | Akita Prefectural Univ | Cathode for electrolytic treatment, and electrolytic cell |
| WO2015151665A1 (en) * | 2014-03-31 | 2015-10-08 | 株式会社シンク・ラボラトリー | Cylinder plating apparatus and method |
| JP6062600B2 (en) * | 2014-03-31 | 2017-01-18 | 株式会社シンク・ラボラトリー | Cylinder plating apparatus and method |
| US10041185B2 (en) | 2014-03-31 | 2018-08-07 | Think Laboratory Co., Ltd. | Cylinder plating apparatus and method |
| US9777382B2 (en) | 2015-06-03 | 2017-10-03 | Kabushiki Kaisha Toshiba | Electrochemical cell, oxygen reduction device using the cell and refrigerator using the oxygen reduction device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3332264B2 (en) | 2002-10-07 |
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