TWI760564B - Electrode for plating and manufacturing equipment for electrolytic metal foil - Google Patents
Electrode for plating and manufacturing equipment for electrolytic metal foil Download PDFInfo
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- TWI760564B TWI760564B TW107133097A TW107133097A TWI760564B TW I760564 B TWI760564 B TW I760564B TW 107133097 A TW107133097 A TW 107133097A TW 107133097 A TW107133097 A TW 107133097A TW I760564 B TWI760564 B TW I760564B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0657—Conducting rolls
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Description
本發明係關於一種電鍍用電極及電解金屬箔之製造裝置。更詳而言之,本發明係關於用於以電鍍法製造電解金屬箔之電極,且關於具備此電極的電解金屬箔之製造裝置。The present invention relates to an electrode for electroplating and an apparatus for manufacturing electrolytic metal foil. More specifically, the present invention relates to an electrode for producing an electrolytic metal foil by an electroplating method, and relates to an apparatus for producing an electrolytic metal foil provided with the electrode.
金屬箔,既往以來廣泛利用在工業上,在電氣/電子領域作為印刷電路材而使用,在電化學領域作為電池之集電體而使用。作為此金屬箔的種類,除了機械性壓延所獲得之壓延箔以外,尚存在藉由電化學電鍍而獲得之電解金屬箔等。藉由電鍍而製造金屬箔之技術,亦可稱作電氣鑄造(尤其可稱作“電鑄”)。在電鑄中,可較為簡單地獲得連續的金屬箔,且較容易控制表面平滑性等金屬箔之特性,多使用於製造銅箔或銅合金箔等金屬箔。Metal foils have been widely used in industry in the past, used as printed circuit materials in electrical/electronic fields, and used as current collectors of batteries in electrochemical fields. As a kind of this metal foil, in addition to the rolled foil obtained by mechanical rolling, the electrolytic metal foil obtained by electrochemical plating, etc. exist. The technique of producing metal foils by electroplating may also be referred to as electrical casting (in particular, it may be referred to as "electroforming"). In electroforming, continuous metal foil can be obtained relatively easily, and the characteristics of metal foil such as surface smoothness can be easily controlled.
在電解金屬箔的製造中,利用電鍍之原理,使用電鍍用電極。如圖11所示,使用由電鍍用電極520及與其成對的相反電極530構成之電鍍裝置,電鍍用電極520浸漬於電解槽500的電解液510,相反電極530呈滾筒狀。電鍍用電極520,設置為與滾筒狀相反電極530相對向,具有沿著滾筒狀相反電極530之“圓形輪廓”彎曲的形態。若將此等電鍍用電極520與滾筒狀相反電極530之間通電,則可於相反電極530的表面將金屬成分電解析出。因此,使滾筒狀相反電極530對電鍍用電極520旋轉並施行通電,從相反電極530依序剝離因電解析出而形成的金屬層,藉而可連續獲得金屬箔550。
[習知技術文獻]
[專利文獻]In the production of electrolytic metal foil, the principle of electroplating is used, and the electrode for electroplating is used. As shown in FIG. 11 , an electroplating apparatus comprising an
專利文獻1:日本特開平第8-209396號公報 專利文獻2:日本特公平第6-47758號公報 專利文獻3:國際公開(WO)第2010/067754號公報 專利文獻4:日本特許第3468545號公報Patent Document 1: Japanese Patent Application Laid-Open No. 8-209396 Patent Document 2: Japanese Patent Publication No. 6-47758 Patent Document 3: International Publication (WO) No. 2010/067754 Patent Document 4: Japanese Patent No. 3468545
[本發明所欲解決的問題][Problems to be Solved by the Invention]
本申請案發明人,注意到過去電解金屬箔的製造中尚存在應克服之問題,發現必須採取因應該問題之對策。具體而言,本申請案發明人發現下述問題。The inventor of the present application has noticed that there are still problems to be overcome in the production of electrolytic metal foils in the past, and found that countermeasures must be taken to deal with the problems. Specifically, the inventors of the present application found the following problems.
在金屬箔的電鑄製造中,有使用不溶性陽極作為電鍍用電極,將此陽極單片化之方式。於基板安裝複數片之單片化陽極而使用。此一方式中,成為陽極隔著電解液而與陰極滾筒相對向之狀態,而本申請案發明人等,發現若陽極與陰極之間的距離越大,則無法忽略電解槽之電壓變得更高而電力成本上升的問題。此外,亦發現依照現行之電極構造,陽極上的電流分布變得不均勻,亦無法忽略發生電解金屬箔的瑕疵之疑慮。In the electroforming production of metal foil, there is a method of using an insoluble anode as an electrode for electroplating and dividing the anode into a single piece. It is used by mounting a plurality of monolithic anodes on a substrate. In this method, the anode is in a state of facing the cathode roll across the electrolyte, but the inventors of the present application found that the greater the distance between the anode and the cathode, the greater the voltage of the electrolytic cell cannot be ignored. High and rising electricity costs. In addition, it is also found that according to the current electrode structure, the current distribution on the anode becomes uneven, and the possibility of the occurrence of defects in the electrolytic metal foil cannot be ignored.
尤其是,安裝單片狀陽極的基板,有成為電解槽之槽壁的一部分之情況,此時陽極與陰極之間的距離可能取決於該槽壁之位置。在施行連續的金屬箔製造之電鑄中,不僅重視成本及操作性,一般亦重視可彎曲性,故使用“薄型”陽極。因此,電鑄之所屬技術領域中具有通常知識者,一般而言,普遍重視使用適合該彎曲之“薄型”電極,而並未意識到陽極與陰極之間的距離較大。In particular, the substrate on which the monolithic anode is mounted may become part of the cell wall of an electrolytic cell, in which case the distance between the anode and the cathode may depend on the position of the cell wall. In electroforming of continuous metal foil production, not only cost and operability, but also flexibility are generally important, so "thin" anodes are used. Therefore, those skilled in the art of electroforming generally place emphasis on the use of "thin" electrodes suitable for this bending, without realizing that the distance between the anode and the cathode is large.
鑒於上述問題,發明人提出本發明。亦即,本發明之主要目的,係在於提供一種可更為妥善地因應陽極與陰極之間的距離之電鑄技術。 [解決問題之技術手段]In view of the above problems, the inventors propose the present invention. That is, the main purpose of the present invention is to provide an electroforming technique that can more appropriately respond to the distance between the anode and the cathode. [Technical means to solve problems]
本申請案發明人,並未從習知技術之延伸方向上來因應,而係嘗試藉由從新的方向處理,而解決上述問題。此一結果,提出達成上述主要目的的電鍍用電極及電解金屬箔之製造裝置的發明。The inventor of the present application did not respond from the extension direction of the conventional technology, but tried to solve the above-mentioned problems by dealing with it from a new direction. As a result, the invention of the manufacturing apparatus of the electrode for electroplating and electrolytic metal foil which achieves the said main objective is proposed.
本發明提供一種電鍍用電極,使用於製造電解金屬箔,其特徵在於: 該電鍍用電極,至少由電極構件、及安裝該電極構件之基板構成; 該電極構件之與滾筒狀相反電極相對向的面上具備增厚面。The present invention provides an electrode for electroplating, which is used in the manufacture of electrolytic metal foil, and is characterized in that: The electrode for electroplating is composed of at least an electrode member and a substrate on which the electrode member is mounted; The electrode member has a thickened surface on the surface facing the roller-shaped counter electrode.
此外,本發明亦提供一種電解金屬箔之製造裝置,至少具備上述電鍍用電極而構成。 [本發明之效果]Moreover, this invention also provides the manufacturing apparatus of the electrolytic metal foil which is provided with the said electrode for electroplating at least and is comprised. [Effect of the present invention]
本發明的電鍍用電極之安裝在基板之電極構件與滾筒狀相反電極相對向的面上具備增厚面,提供在陽極與陰極之間的電極間距離之觀點上更為適宜的電鑄技術。The electrode for electroplating of the present invention has a thickened surface on the surface of the electrode member mounted on the substrate facing the roller-shaped counter electrode, and provides a more suitable electroforming technique from the viewpoint of the distance between the electrodes between the anode and the cathode.
具體而言,由於電極構件之“增厚面”,可適宜地減少金屬箔製造中的電極間距離,故可在電解槽之電壓較低的狀態下運轉,如此可降低電力成本。此外,本發明,改善電極與基板的接觸面積,故電鍍用電極上之電流分布更容易變得均勻,亦可減少製造之金屬箔的瑕疵發生。Specifically, since the "thickened surface" of the electrode member can appropriately reduce the distance between electrodes in the production of metal foil, it is possible to operate the electrolytic cell at a low voltage, thereby reducing power costs. In addition, according to the present invention, the contact area between the electrode and the substrate is improved, so that the current distribution on the electrode for electroplating is more likely to become uniform, and the occurrence of defects in the manufactured metal foil can also be reduced.
以下,詳細地說明本發明的電鍍用電極及電解金屬箔之製造裝置。因應必要,參考附圖而進行說明,但圖示之內容,僅係為了理解本發明而予以示意並例示而展現,其外觀或尺寸比等可能與實物不同。Hereinafter, the manufacturing apparatus of the electrode for electroplating and electrolytic metal foil of this invention is demonstrated in detail. If necessary, descriptions are made with reference to the accompanying drawings, but the contents of the drawings are only shown for the purpose of understanding the present invention, and their appearance or size ratio may be different from the actual ones.
在說明本發明時使用之「在剖面圖中」等表現,相當於沿著電鍍用電極之厚度方向截取的剖面圖,可相當於實質上從側面觀察對象物的圖。從另一觀點而言,「在剖面圖中」,可相當於以使與電鍍用陽極成對之陰極滾筒的旋轉軸成為法線之面截取的圖。此外,對本發明的電鍍用電極直接或間接使用之「上方(或上側)」,係指在使用時更為接近相反電極(亦即滾筒狀之電極)的方向,此外,其相反方向相當於「下方(或下側,抑或底側)」。Expressions such as "in a cross-sectional view" used in describing the present invention correspond to a cross-sectional view taken along the thickness direction of the electrode for electroplating, and can be equivalent to a view in which the object is substantially viewed from the side. From another viewpoint, "in a cross-sectional view" can correspond to a view taken on a plane where the axis of rotation of the cathode roll paired with the anode for electroplating becomes a normal line. In addition, the "upper (or upper side)" used directly or indirectly for the electrode for electroplating of the present invention refers to the direction closer to the opposite electrode (that is, the roller-shaped electrode) during use, and the opposite direction is equivalent to " Below (or underside, or underside)".
《本發明的電鍍用電極》 本發明的電鍍用電極,為製造電解金屬箔所使用之電極。此電鍍用電極,可說是用於電鑄之電極,可稱作“電鑄用電極”等。此外,本說明書所述之「電解金屬箔」等詞彙,實質上係指藉由電鍍的原理製造之金屬箔。作為電解金屬箔,可列舉包含從由銅、鎳及鐵構成的群組中選出之至少1種而形成的金屬箔。若列舉一典型例,則電解金屬箔為銅箔。"The Electrode for Electroplating of the Present Invention" The electrode for electroplating of the present invention is an electrode used for producing electrolytic metal foil. This electrode for electroplating can be said to be an electrode for electroforming, and can be called "electrode for electroforming" or the like. In addition, the term "electrolytic metal foil" mentioned in this specification means the metal foil manufactured by the principle of electroplating substantially. As an electrolytic metal foil, the metal foil formed by containing at least 1 type selected from the group which consists of copper, nickel, and iron is mentioned. If a typical example is given, the electrolytic metal foil is copper foil.
如圖1(A)及1(B)所示,本發明的電鍍用電極100,係與滾筒狀相反電極200相對向地使用之電極。若依製造金屬箔的適宜例,則本發明之電鍍用電極100相當於“陽極”,另一方面,相反電極200相當於“陰極”。在製造電解金屬箔時,藉由將陽極與陰極之電極間通電,由於電解析出,在陰極上形成金屬箔(更正確而言,形成成為金屬箔的前驅物之金屬層)。例如,作為陽極使用之電鍍用電極,宜為所謂之不溶性陽極。為不溶性陽極的情況,並非藉由陽極的溶解供給電鍍金屬成分,而係電解槽的電解液原本含有之成分成為電鍍金屬成分的供給源。As shown in FIGS. 1(A) and 1(B) , the electrode for electroplating 100 of the present invention is an electrode used so as to face the roller-
成為陰極之相反電極,全體具有滾筒狀,設置為可旋轉。此處所述之「滾筒狀」,係指相反電極具有有助於金屬箔的連續製造之圓筒形狀或略圓筒形狀。另一方面,成為陽極之電極,宜配置為與滾筒狀之陰極分隔而包圍其一部分。亦即,本發明的陽極之電鍍用電極,可具有於其剖面圖中沿著滾筒輪廓的至少一部分彎曲之形態。如同從圖示的態樣所得知,電解金屬箔製造用之電極100,在剖面圖中全體呈圓弧形狀。The opposite electrode, which becomes the cathode, has a cylindrical shape as a whole and is rotatably installed. "Roll-shaped" as used herein means that the opposite electrode has a cylindrical shape or a substantially cylindrical shape that facilitates continuous production of the metal foil. On the other hand, it is preferable to arrange|position the electrode which becomes an anode so that it may isolate|separate from the cylindrical cathode and surround part of it. That is, the electrode for electroplating of the anode of the present invention may have a shape curved along at least a part of the outline of the drum in the cross-sectional view. As can be seen from the state shown in the figure, the
本發明的電鍍用電極,至少由電極構件、及安裝該電極構件之基板構成。亦即,如圖1(A)及1(B)所示,電鍍用電極100,具備與相反電極200直接對向之電極構件10,且具備固定電極構件之基板20而構成。電極構件10,係在電鑄時實質上作為陽極作用之構件,宜為作為不溶性陽極作用之構件。The electrode for electroplating of the present invention comprises at least an electrode member and a substrate on which the electrode member is mounted. That is, as shown in FIGS. 1(A) and 1(B) , the
本發明的電鍍用電極,其特徵在於電極構件具備特別的表面高度。具體而言,本發明的電鍍用電極中,電極構件之與滾筒狀相反電極相對向的面上具備增厚面。增厚面為表面高度(亦即電極表面高度)增加的面,而本發明的電鍍用電極,具有下述特徵:電極構件的表面高度,尤其與成對之陰極滾筒直接對向的表面高度(亦即頂面水平)高。The electrode for electroplating of the present invention is characterized in that the electrode member has a special surface height. Specifically, in the electrode for electroplating of the present invention, the surface of the electrode member facing the roller-shaped counter electrode is provided with a thickened surface. The thickened surface is the surface in which the surface height (that is, the electrode surface height) increases, and the electrode for electroplating of the present invention has the following characteristics: the surface height of the electrode member, especially the surface height ( That is, the top surface level) is high.
如同自上述說明所得知,本說明書所述之「增厚面」,廣義而言,實質上係指具有電鍍用電極的表面高度,以更為接近相反電極的方式增加之形態。狹義而言,「增厚面」,實質上係指具有電鍍用電極中之電極構件的上側主面水平(與基板直接對向的底側主面位於相反側之主面的水平),以更為接近相反電極的方式增加之形態。從此一情形來看,本發明之「增厚面」,亦可稱作“表面厚度增加的面”或“提高面”等。若予以例示,則增厚面,在電極構件安裝於基板的狀態,係位於從基板的表面(相對於電極構件更為接近的安裝基板面)算起之分隔距離例如較2mm更大的水平,宜為較3mm更大的水平(作為1例,例示較5mm更大的水平)之面。此一分隔距離的上限值並無特別限制,但例如為30mm、20mm、15mm、10mm、8mm、或5mm等。As can be understood from the above description, the "thickened surface" mentioned in this specification, in a broad sense, substantially refers to a form in which the surface height of the electrode for electroplating is increased so as to be closer to the opposite electrode. In a narrow sense, "thickened surface" essentially refers to the level of the main surface of the upper side of the electrode member in the electrode for electroplating (the level of the main surface of the bottom side directly opposite to the substrate and the main surface of the opposite side), so as to be more A form added to approach the opposite electrode. From this point of view, the "thickened surface" of the present invention may also be referred to as a "surface with an increased surface thickness", a "raised surface", or the like. As an example, the thickened surface is located at a level greater than, for example, 2 mm in separation distance from the surface of the substrate (the mounting substrate surface closer to the electrode member) when the electrode member is mounted on the substrate. The surface of a level larger than 3 mm (as an example, a level larger than 5 mm is shown as an example) is suitable. The upper limit of this separation distance is not particularly limited, but is, for example, 30 mm, 20 mm, 15 mm, 10 mm, 8 mm, or 5 mm.
作為電極構件具備“增厚面”之例示態樣,如圖1(A)所示,列舉電極構件10具有實心之厚壁電極的形態之態樣。或如圖1(B)所示,亦可為電極構件10係薄板電極,該薄板電極具有以變得膨起的方式彎曲之形態的態樣。前者,由於實心之厚壁電極厚度大,該厚壁電極之上側表面相當於“增厚面”;後者,由於薄板電極之膨起的彎曲形態,該薄板電極之上側表面相當於“增厚面”。As an exemplary aspect in which the electrode member has a "thickened surface", as shown in FIG. 1(A) , an aspect in which the
如圖1(A)及1(B)所示,電鍍用電極100,宜進一步具備用於將電極構件10安裝於基板20之螺絲30而構成。亦即,作為將電極構件10固定於基板20的構件,本發明的電鍍用電極100,宜具備螺絲30而構成。另,如圖2(A)及2(B)所示,此一螺絲30宜具備錐狀側面35。此一情況,電極構件10之側面部分12(圖2(A))或增厚面15(圖2(B)),宜具有與螺絲30之錐狀側面35為互補的形狀。藉此,改善電極構件與螺絲之統合性,增加作為電鍍用電極全體之一體性。此外,在一些態樣中,藉由此等互補的關係,提供更無間隙之適宜的電極面,且提供經由螺絲之適宜的散熱(關於“散熱”將於後述內容詳述)。As shown in FIGS. 1(A) and 1(B) , the
螺絲30,如圖3所示,至少由冠部32與螺紋部37構成,此一冠部32之側面35宜呈錐狀。具體而言,螺絲30中,宜成為冠部32朝向下側(亦即,朝向螺紋部37)而寬幅尺寸逐漸減少。電極構件10之側面部分12,相對於具備該錐狀側面35之螺絲冠部32宜呈互補的形狀(參考圖2(A))。更佳態樣為,在將電極構件10安裝於基板20的狀態,電極構件10之側面部分12,並未與螺絲30的螺紋部37接觸,而對螺絲30的冠部32之錐狀側面35互補地密接。同樣地,如圖2(B)所示,電極構件10之增厚面15的一部分15A,相對於具備該錐狀側面35之螺絲冠部32宜呈互補的形狀。更佳態樣為,在將電極構件10安裝於基板20的狀態,電極構件10之增厚面15的一部分15A,並未與螺絲30的螺紋部37接觸,而對螺絲30的冠部32之錐狀側面35互補地密接。As shown in FIG. 3 , the
本發明的電鍍用電極之電極構件,由於“增厚面”,電極表面高度變高。例如,在電極構件中從增厚面至「電極構件與基板之接觸水平面」為止的垂直距離尺寸,成為與螺絲中的錐狀側面之設置部分相當的錐部高度尺寸,或較其更大。以圖4及圖5所示之態樣而言,則可說是以增厚面15為基準,從該處至「電極構件10與基板20之接觸水平面」為止的垂直距離尺寸H1,成為與螺絲30的錐部高度尺寸H2實質上相同,或較其更大。如同自此一說明所得知,關於本說明書所使用之「垂直距離尺寸」等詞彙之“垂直”,係指對增厚面(尤其是非彎曲部分中的厚壁面)成為法線或垂線的方向之意。The electrode member of the electrode for electroplating of the present invention has a high electrode surface height due to the "thickened surface". For example, in the electrode member, the vertical distance dimension from the thickened surface to the "contact level between the electrode member and the substrate" is the height dimension of the taper portion corresponding to the installation portion of the tapered side surface in the screw, or larger. 4 and 5, it can be said that with the thickened
若依據圖4(a)及(b)之態樣予以說明,則從實心的厚壁電極10A之上側表面高度,至該厚壁電極10A與基板20接觸之面為止的最短距離尺寸H1,可成為螺絲30的錐部高度尺寸H2以上。此外,圖5(a)及(b)之態樣中,從具有膨起之彎曲形態的薄板電極10B之上側表面高度,至該薄板電極10B與基板20接觸的點18之水平為止的最短距離尺寸H1,可成為與螺絲30的錐部高度尺寸H2實質上相同。4(a) and (b), the shortest distance dimension H1 from the height of the upper surface of the solid thick-
具有此等尺寸特徵之“增厚面”,更有助於金屬箔製造中之陽極與陰極的電極間距離。亦即,由於電極構件之“增厚面”,可更為減少電極間距離,可在電解槽之電壓較低的狀態下運轉。因此,可降低金屬箔製造時之電力成本。此外,可更為減少電極間距離,故電鍍用電極之電流分布更容易變得均勻,亦可減少製造之金屬箔的瑕疵發生。A "thickened face" with these dimensional features further contributes to the electrode distance between the anode and the cathode in the manufacture of metal foils. That is, due to the "thickened surface" of the electrode member, the distance between electrodes can be further reduced, and the electrolytic cell can be operated with a low voltage. Therefore, the electric power cost at the time of metal foil manufacture can be reduced. In addition, the distance between electrodes can be further reduced, so that the current distribution of the electrodes for electroplating is more likely to be uniform, and the occurrence of defects in the manufactured metal foil can also be reduced.
本發明的電鍍用電極,由於“增厚面”,而可使電極構件之側面部分的剖面輪廓或增厚面的剖面輪廓具有有特徵的形態。在一些適宜態樣,在電極構件的剖面圖中,具有電極構件之側面部分或增厚面之輪廓為彎曲的形態。The electrode for electroplating of the present invention can have a characteristic shape in the cross-sectional profile of the side surface portion of the electrode member or the cross-sectional profile of the thickened surface due to the "thickened surface". In some suitable aspects, in the cross-sectional view of the electrode member, the profile having the side portion or the thickened surface of the electrode member is in a curved configuration.
更具體而言,如同圖4(a)之態樣,可具有實心之厚壁電極10A的側面部分12(尤其是與螺絲直接對向的側面部分12)之剖面輪廓為彎曲的形態。此外,如同圖5(a)之態樣,可具有具備膨起之立體形態的薄板電極10B之增厚面15的剖面輪廓之一部分15’(尤其是與螺絲頂面鄰接之部分15’)彎曲的形態。此等彎曲的形態,係由於水平高的“增厚面”,故可說此特徵在有助於減少金屬箔製造中的陽極與陰極之間的距離上,更為適宜。More specifically, as in the state of FIG. 4( a ), the cross-sectional profile of the side portion 12 (especially the
本發明的電鍍用電極,宜與螺絲一同使用,而對電極構件具有適宜的安裝形態。例如,在藉由螺絲將電極構件安裝於基板的狀態,螺絲之頂面與電極構件之增厚面成為同一面。依圖4所示之態樣予以說明,則實心之厚壁電極10A的上側表面高度與螺絲30的頂面水平(冠部的上側面水平),可實質上成為同一面。此外,圖5所示之態樣中,具有膨起之彎曲形態的薄板電極10B之上側表面高度與螺絲30之頂面水平(冠部的上側面水平),可實質上成為同一面。藉由此“同一面”,可提供更為平滑的電極面。如同自圖4及圖5所得知,本發明中,由於“增厚面”,在電極構件中從增厚面算起至與基板之接觸水平面為止的垂直距離尺寸H1,成為螺絲30的錐部高度尺寸H2,或較其更大,但螺絲30之頂面與電極構件10之增厚面仍成為同一面。此等特徵,進一步亦係由於水平高的“增厚面”,故可說此特徵在有助於減少電鑄時之電極間的距離上,更為適宜。The electrode for electroplating of the present invention is preferably used together with a screw, and has a suitable attachment form to the electrode member. For example, in a state where the electrode member is attached to the substrate by a screw, the top surface of the screw and the thickened surface of the electrode member are the same surface. 4, the height of the upper surface of the solid thick-
對本發明的電鍍用電極之「電極構件」、「基板」及「螺絲」予以詳述。The "electrode member", "substrate" and "screw" of the electrode for electroplating of the present invention will be described in detail.
電極構件,如同上述,係在電鑄時實質上作為陽極作用之部分,宜為不溶性陽極。電極構件之材質並無特別限制,但可為閥金屬。更具體而言,則電極構件,可包含從由鉭、鈮、鈦、鉿、鋯、鎢、鉍及銻構成的群組中選擇之至少1種金屬而形成。雖僅為例示,但從耐蝕性及/或通用性等觀點來看,依據一些適宜態樣之電極構件,包含鈦或鈦合金而構成。The electrode member, as described above, is the part that essentially functions as an anode during electroforming, and is preferably an insoluble anode. The material of the electrode member is not particularly limited, but may be valve metal. More specifically, the electrode member may be formed by including at least one metal selected from the group consisting of tantalum, niobium, titanium, hafnium, zirconium, tungsten, bismuth, and antimony. Although it is only an example, from the viewpoints of corrosion resistance and/or versatility, etc., according to some suitable aspects, the electrode member is composed of titanium or a titanium alloy.
電極構件,具有“增厚面”,而從該增厚面至與基板之接觸面或接觸水平面為止的垂直距離尺寸(亦即,圖4及圖5的“H1”),宜較2mm更大,更宜較3mm更大。此一垂直距離尺寸之上限值並無特別限制,但例如從防止短路等的觀點來看,可為30mm、20mm、15mm、10mm、8mm、或5mm。The electrode member has a "thickened surface", and the vertical distance dimension from the thickened surface to the contact surface with the substrate or the contact surface (that is, "H1" in Fig. 4 and Fig. 5) is preferably larger than 2mm , preferably larger than 3mm. The upper limit value of this vertical distance dimension is not particularly limited, but may be 30 mm, 20 mm, 15 mm, 10 mm, 8 mm, or 5 mm, for example, from the viewpoint of preventing short circuits.
另,電極構件的表面可包含電極觸媒。例如,可於電極構件的表面塗布鉑族金屬或其氧化物。亦即,可對電極構件之增厚面設置電極觸媒,該電極觸媒至少包含從由鈀、銠、釕、鉑、銥及鋨構成的群組中選擇之至少1種鉑族金屬,及/或此等鉑族金屬之氧化物而形成。設置此等電極觸媒層之情況,觸媒層可實質上成為增厚面的表面。雖僅為一例,但在依據一些適宜態樣之電極構件,使用包含銥元素及鉭元素而構成的觸媒。In addition, the surface of the electrode member may contain an electrode catalyst. For example, a platinum group metal or an oxide thereof may be coated on the surface of the electrode member. That is, an electrode catalyst may be provided on the thickened surface of the electrode member, the electrode catalyst containing at least one platinum group metal selected from the group consisting of palladium, rhodium, ruthenium, platinum, iridium and osmium, and and/or oxides of these platinum group metals. When these electrode catalyst layers are provided, the catalyst layer can be substantially the surface of the thickened surface. Although it is only an example, according to some suitable aspects of the electrode member, a catalyst composed of iridium element and tantalum element is used.
基板,係固定電極構件之電鑄構件,宜由金屬材質構成。例如,此等電極基板可包含閥金屬而構成。亦即,固定電極構件之基板,可包含從由鉭、鈮、鈦、鉿、鋯、鎢、鉍及銻構成的群組中選擇之至少1種金屬而形成。雖僅為例示,但依據一些適宜態樣之基板,係包含鈦或鈦合金而構成。此係因鈦或鈦合金,從耐蝕性等觀點來看較為適宜。基板的厚度,若為有助於在電鑄所使用的電極構件之固定者,即無特別限制,例如可為10mm~40mm程度。另,如同自圖9所示之態樣所得知,基板20可構成電解槽50之槽壁的至少一部分。例如,可使直接有助於貯存電解液的槽內壁具有彎曲形態(尤其在剖面圖中呈圓弧狀),該彎曲形態之槽內壁的至少一部成為基板。The base plate, which is the electroformed member for fixing the electrode member, should be made of metal material. For example, these electrode substrates may include valve metal. That is, the substrate to which the electrode member is fixed may contain at least one metal selected from the group consisting of tantalum, niobium, titanium, hafnium, zirconium, tungsten, bismuth, and antimony. Although it is only an example, according to some suitable aspects, the substrate is composed of titanium or titanium alloy. This is because titanium or a titanium alloy is suitable from the viewpoint of corrosion resistance and the like. The thickness of the substrate is not particularly limited as long as it contributes to the fixation of the electrode member used in electroforming, and may be, for example, about 10 mm to 40 mm. In addition, as can be seen from the aspect shown in FIG. 9 , the
螺絲,用於電極構件與基板之相互的固定,可由金屬材質構成。例如,螺絲可包含閥金屬而構成。亦即,螺絲,可包含從由鉭、鈮、鈦、鉿、鋯、鎢、鉍及銻構成的群組中選擇之至少1種金屬而形成。雖僅為例示,但依據一些適宜態樣之螺絲,從耐蝕性及/或通用性等觀點來看,包含鈦或鈦合金而構成。The screw is used for mutual fixation between the electrode member and the substrate, and can be made of a metal material. For example, the screw may be constructed to contain valve metal. That is, the screw may be formed by including at least one metal selected from the group consisting of tantalum, niobium, titanium, hafnium, zirconium, tungsten, bismuth, and antimony. Although it is only an example, according to some suitable types of screws, from the viewpoint of corrosion resistance and/or versatility, etc., it is constituted by including titanium or a titanium alloy.
如圖3所示,螺絲30,至少由冠部32與螺紋部37構成,此一冠部32之側面35宜呈錐狀。圖3所示的錐部角度α,宜為10°~80°,更宜為20°~70°,進一步宜為30°~60°。此錐狀側面,例如可藉由機械加工而設置。抑或直接使用市售之設有錐狀部的螺絲亦可。設置錐狀側面35之冠部32的高度尺寸H2(參考圖3),應助於實現本發明的增厚面之實現,可較習知的尺寸更大。亦即,依據一些適宜態樣之螺絲,可說是具備「在所屬技術領域中具有通常知識者(尤其是電解金屬箔的製造業者)之一般認知中係高度尺寸為大的冠部」。例如,冠部32的高度尺寸H2,較2mm更大,宜較3mm更大。此一螺絲之冠部的高度尺寸之上限值,並無特別限制,但例如可為30mm、20mm、15mm、10mm、8mm、或5mm。As shown in FIG. 3 , the
本發明的電鍍用電極,可藉由各種態樣具體實現。代表性地,可具體實現為上述「厚壁電極之態樣」及「提供膨起之彎曲的薄板電極之態樣」。The electrode for electroplating of the present invention can be embodied in various aspects. Representatively, it can be embodied as the above-mentioned "the aspect of the thick-walled electrode" and the "the aspect of the curved thin-plate electrode that provides bulging".
(厚壁電極之態樣)
此一態樣中,如圖4所示,電極構件10成為實心之厚壁電極10A。亦即,並非為對電鑄(尤其是電解金屬箔的製造)之所屬技術領域中具有通常知識者而言認為係薄層之電極厚度,而係在其等之認知上一般認為係厚層之厚度的電極,構成電極構件。例如,實心之厚壁電極10A,其厚度可成為與螺絲中的錐狀側面之設置部分相當的錐部高度尺寸,或較其更大。換而言之,實心之厚壁電極的厚度,可成為螺絲之冠部的高度尺寸以上。進一步而言,厚壁電極的厚度,可成為具有藉由螺絲的錐狀側面之設置部分而固定於基板的強度。此係指,為了具備藉由螺絲之錐狀側面的設置部往基板固定所用之強度,實心之厚壁電極的厚度,例如宜為螺絲冠部32的高度尺寸H2之50%以上。亦即,實心之厚壁電極,可成為具有藉由螺絲之錐狀側面所產生的支持而能夠將厚壁電極往基板固定或安裝之強度的厚度(此一情況,實心之厚壁電極的厚度,例如可成為螺絲冠部32的高度尺寸H2之50%以上)。(Condition of thick-walled electrode)
In this aspect, as shown in FIG. 4 , the
此等厚壁電極的厚度,有助於電極構件之“增厚面”的實現,更有助於金屬箔製造中之陽極與陰極的電極間距離。亦即,由於此厚壁電極的厚度,可更為減少電極間距離,可在電解槽之電壓較低的狀態下運轉。藉此,可降低金屬箔製造時之電力成本。此外,不僅更為減少電極間距離,藉由增加電極的厚度,而使通電時的電鍍用電極上之電流分布更容易變得均勻,亦可減少製造之金屬箔的瑕疵發生。The thickness of these thick-walled electrodes is helpful to the realization of the "thickened surface" of the electrode member, and also to the electrode distance between the anode and the cathode in the manufacture of metal foils. That is, due to the thickness of the thick-walled electrodes, the distance between the electrodes can be further reduced, and the electrolytic cell can be operated at a low voltage. Thereby, the electric power cost at the time of metal foil manufacture can be reduced. In addition, not only the distance between electrodes is further reduced, but also by increasing the thickness of the electrodes, the current distribution on the electrode for electroplating during energization can be more easily made uniform, and the occurrence of defects in the manufactured metal foil can also be reduced.
雖僅為例示,但實心之厚壁電極的具體厚度,例如較2mm更大,宜較3mm更大。此一實心之厚壁電極之上限值並無特別限制,但例如可為30mm、20mm、15mm、10mm、8mm、或5mm等。鑒於所屬技術領域中具有通常知識者(尤其是電解金屬箔的製造業者)的一般認知,此等厚度,作為製造電解金屬箔所使用之陽極為大厚度。習知的電極厚度為約1mm程度,而本發明的實心之厚壁電極,可說是較習知之電鍍電極的至少2倍更大,宜為較3倍更大,簡而言之,成為習知的電極厚度之2倍~30倍,宜為3倍~20倍(例如3倍~10倍、3倍~8倍、或3倍~5倍)等。此等較習知更厚的電極,對所屬技術領域中具有通常知識者而言,認為通常不易加工(尤其是用在螺絲用孔的加工),過去並未實際作為電解金屬箔之陽極電極使用。在此點上,本發明並未囿於此等習知常識,可說是刻意積極地使用由大的電極厚度構成者。Although it is only an example, the specific thickness of the solid thick-walled electrode is, for example, larger than 2 mm, preferably larger than 3 mm. The upper limit of the solid thick-walled electrode is not particularly limited, but may be, for example, 30 mm, 20 mm, 15 mm, 10 mm, 8 mm, or 5 mm. In view of the general knowledge of those skilled in the art (especially the manufacturers of electrolytic metal foils), these thicknesses, as anodes used in the manufacture of electrolytic metal foils, are large. The thickness of the conventional electrode is about 1 mm, and the solid thick-walled electrode of the present invention can be said to be at least 2 times larger than the conventional electroplating electrode, preferably larger than 3 times, in short, it becomes the conventional electrode. The known electrode thickness is 2 to 30 times, preferably 3 to 20 times (for example, 3 to 10 times, 3 to 8 times, or 3 to 5 times) and the like. These thicker electrodes than conventional ones are generally considered difficult to process (especially for screw holes) by those with ordinary knowledge in the art, and have not been actually used as anode electrodes for electrolytic metal foils in the past. . In this regard, the present invention is not limited to such conventional knowledge, and it can be said that the electrode having a large thickness is deliberately and actively used.
一些適宜態樣中,在藉由螺絲30將厚壁電極10A安裝於基板20的狀態下,厚壁電極10A與基板20全表面接觸,尤其使其等彼此密接(參考圖4)。如同自圖4所得知,厚壁電極10A具有非彎曲形態,而此一厚壁電極10A的下側主面與基板20的上側主面密接。較佳態樣中,厚壁電極的下側主面與基板的上側主面實質上無間隙地以液密狀態彼此密接。相較於電極構件為薄型電極的情況,此點為可展現之特徵。針對此一特徵予以詳述。假設電極構件並非為厚壁而係薄型電極之情況,在以螺絲將電極構件往基板固定時,由於螺絲固定的點狀鎖緊而使薄型電極構件有差別程度地撓曲之疑慮(參考圖6的“薄型電極之情況”)。因此,安裝於基板之薄型電極構件中,可能在其與基板之間形成微小的間隙(一般圖示之態樣中,即便描繪為密接,實際上仍為產生微小間隙,或容易產生間隙的狀態)。此點,本發明中,由於厚壁電極之大厚度,亦對電極構件提供更高的剛性,變得不易因螺絲固定的點狀鎖緊而使電極構件撓曲(參考圖6的“本發明”)。藉此,可將厚壁電極10的下側主面與基板20的上側主面彼此妥善地密接,較佳態樣中,其等可實質上無間隙地以液密方式密接。此係指,若使用本發明的電鍍用電極,則電流分布更容易變得均勻,容易減少製造之金屬箔的瑕疵發生。此外,厚壁電極10A之情況,首先由於大的電極厚度(較習知之薄型電極更厚的電極)而使通電時之電流分布變佳,故可成為更為均勻的電鍍。進一步,厚壁電極10A之情況,在將電極構件安裝於基板的狀態,厚壁電極之厚度側面與螺絲之冠部側面可成為彼此密接的狀態(參考圖6的“本發明”),故在此點上,變得容易使通電時之電流分布變佳而達成均勻的電鍍。In some suitable aspects, when the thick-
此外,電極構件為實心之厚壁電極的情況,由於其厚壁,而可使電極側面與螺絲具有特別的形狀關係。具體而言,如圖4所示,厚壁電極10A之厚壁側面12,可包含與螺絲30之錐狀側面35為互補的形狀。亦即,有助於具有非彎曲形態之厚壁電極10A的厚壁化之側面,與螺絲30的冠部之側面,彼此具有互補的形狀,在將電極構件安裝於基板的狀態,此等厚壁電極之厚度側面與螺絲之冠部側面成為彼此密接的狀態。此等形態,在經由厚壁電極之側面進行適宜的散熱之點上,可獲得有利的效果。具體而言,可追求抑制在電鑄時由於通電而使電解液的溫度上升所導致之該升溫,而本發明中,可經由厚壁電極、及與其側面密接之螺絲,往槽外適宜地散熱。In addition, when the electrode member is a solid thick-walled electrode, the side surface of the electrode and the screw can have a special shape relationship due to the thick wall. Specifically, as shown in FIG. 4 , the thick-
本發明的電鍍用電極所使用之厚壁電極,在使用鹼或有機溶劑將導電性母材予以脫脂清洗後,經由藉由噴砂清理等機械性的表面處理、或使用酸或鹼之化學性的表面處理、或將機械性處理與化學性處理雙方組合的表面處理,對基板施行電極觸媒之塗布鍛燒。此電極觸媒之構成,宜為鉑族金屬或其氧化物、與從由閥金屬(鈦、鉭、鈮、鎢、鋯)及錫所構成的群組中選出之1種以上的金屬氧化物之混合氧化物。代表例可列舉銥-鉭混合氧化物,銥-鉭-鈦混合氧化物等。電極活性物質的被覆,可藉由將包含如上所述之電極活性物質的溶液以塗布、乾燥、鍛燒之順序施行而製作,可藉由重複此一從塗布至鍛燒為止的步驟直至既定觸媒量為止,而獲得不溶性陽極。對如此地獲得之厚壁電極,藉由機械加工或化學蝕刻等設置螺絲用孔,經由該孔以螺絲將厚壁電極安裝於基板,藉而可獲得供電解金屬箔的製造所用之電鍍用電極。此外,亦可在塗布包含如上所述之電極活性物質的溶液前,對厚壁電極之導電性母材,藉由機械加工或化學蝕刻等設置螺絲孔用的孔。For the thick-walled electrode used in the electrode for electroplating of the present invention, after degreasing and cleaning the conductive base material with alkali or organic solvent, mechanical surface treatment such as sandblasting, or chemical treatment with acid or alkali is performed. Surface treatment, or surface treatment combining both mechanical treatment and chemical treatment, is applied to the substrate by coating and calcining the electrode catalyst. The electrode catalyst is preferably composed of platinum group metals or oxides thereof, and one or more metal oxides selected from the group consisting of valve metals (titanium, tantalum, niobium, tungsten, zirconium) and tin of mixed oxides. Representative examples include iridium-tantalum mixed oxide, iridium-tantalum-titanium mixed oxide, and the like. The coating of the electrode active material can be prepared by applying the solution containing the electrode active material as described above in the order of coating, drying, and calcining, and can be prepared by repeating the steps from coating to calcining until a predetermined contact is made. The amount of the medium is reached to obtain an insoluble anode. The thick-walled electrode thus obtained is provided with holes for screws by machining or chemical etching, and the thick-walled electrodes are attached to the substrate with screws through the holes, whereby an electrode for electroplating for producing electrolytic metal foil can be obtained. . In addition, before applying the solution containing the electrode active material as described above, holes for screw holes may be provided in the conductive base material of the thick-walled electrode by machining, chemical etching, or the like.
參考圖7,說明電極構件成為實心之厚壁電極的情況之較佳具體例。此一具體例中,對基板20設置沉頭孔26。沉頭孔26可具有錐狀凹部之形態,因此,如同圖示,可於基板20設置全體具有與螺絲同樣之形態的凹部(本說明書之「沉頭孔」可稱作“基板凹部”或“錐狀凹部”等)。如此地,即便設置沉頭孔26,由於“實心之厚壁電極”,螺絲30並未完全填入沉頭孔26。亦即,在一些適宜的例子中,以螺絲冠部32勾卡在電極構件10之錐狀側面的形態,將螺絲30從基板20的沉頭孔面26’(形成沉頭孔26的底面26’)分隔而配置。此係指,在將電極構件10安裝於基板20的狀態,於螺絲30(尤其是螺絲冠部32)、電極構件10、基板20所包圍的領域設置空間28(尤其是源自於錐狀沉頭孔的錐形空間28)。如同自圖示之態樣所得知,彼此密接之螺絲冠部32與電極構件10的組合,在沉頭孔之形成區域留下或供給空間28(此外,在基板的螺紋孔之領域亦留下或供給空間29),並與基板20一體化。此等態樣,亦宜使螺絲30之頂面與電極構件10之增厚面15成為同一面。此外,厚壁電極10A之厚壁側面12可包含與螺絲30之錐狀側面35為互補的形狀。實心之厚壁電極10A,其厚度可成為與螺絲中的錐狀側面之設置部分相當的錐部高度尺寸,或較其更大(然則,實心之厚壁電極10A,若如同上述地成為螺絲冠部勾卡在電極之錐狀側面的形態,則如圖7的下側括弧內所示,厚壁電極10A亦可成為未滿錐部高度尺寸。另,如同自此等附圖所得知,若沉頭孔為錐狀,則可適宜避免與螺絲冠部的干涉,故可將螺絲配合電極構件厚度而配置於更往下方的位置)。雖僅為例示,但依據圖7的態樣之電極構件10的厚度,例如可為3~8mm程度。Referring to FIG. 7 , a preferred specific example of the case where the electrode member is a solid thick-walled electrode will be described. In this specific example, the
茲就於基板20設置有沉頭孔26的態樣之本發明的優點,與薄型電極構件之情況比較而予以說明。如圖8所示,相對較薄的電極構件11(例如,由鈦構成的1mm程度厚度之電極構件),實際上在不易在螺絲卡合部彎曲為銳角狀,有其接點受限之疑慮。亦即,此等帶有彎曲之薄型電極構件11,有螺絲卡合部的接點受到限定之情況(例如有限定在圖8所示之虛線包圍的部分之情況),在與基板接觸之觀點中,有無法說是變得理想之情況。從此一情形來看,薄型電極構件,可說在通電時之電流分布的觀點上,尚有追求進一步改善的餘地。關於此點,本發明的實心之厚壁電極的情況,如同自圖7所示之態樣所得知,螺絲卡合部的接點實質上變得一樣,故在通電時之電流分布的觀點上可成為適宜狀態。The advantages of the present invention in the aspect in which the countersunk
此外,換而言之,如圖7所示之本發明的態樣,在電極構件10與基板20之彼此安裝的點上為適宜態樣。具體而言,將空間28配置於螺絲30(尤其是螺絲冠部32)之下方,故可為了使螺絲往更下方位移而更強力地鎖緊,可將厚壁電極10的下側主面與基板20的上側主面彼此更為強力地密接。較佳態樣中,可將其等無間隙地以液密方式密接(如同參考圖6所說明,厚壁電極,由於其大厚度,而對電極構件提供更高的剛性,故即便更強力地鎖緊,電極構件本身仍不易撓曲)。因此,在此點中,電流分布容易更為均勻,結果容易減少製造之金屬箔的瑕疵發生。In addition, in other words, the aspect of the present invention shown in FIG. 7 is a suitable aspect at the point where the
(提供膨起之彎曲的薄板電極之態樣)
如圖5所示,此態樣之電極構件10,成為薄板電極10B,尤其具有以變得膨起的方式彎曲之薄板電極10B的形態。亦即,藉由將厚度實質上為一定之薄板電極10B彎曲而使電極構件全體變得膨起(亦即,可說是一定厚度之電極構件彎曲而使電鍍用電極變得膨起)。此一態樣中,係對電鑄(尤其是電解金屬箔的製造)之所屬技術領域中具有通常知識者而言認為薄的電極厚度,但成為該薄型電極以變得立體地膨起的方式部分地彎曲之形態。薄板電極10B的厚度本身,由於係“薄板”,故為3mm以下,宜為2mm以下,例如為1.5mm以下或1.0mm以下(下限值並無特別限制,但例如可為0.2mm、0.5mm、0.7mm程度)。如此地,儘管厚度薄,以變得立體地膨起的方式部分地彎曲之薄板電極,其最上水平與最下水平之間的尺寸宜成為螺絲的錐部高度尺寸,或較其更大。簡而言之,以全體變得膨起的方式彎曲之薄板電極的最大立體厚度,可成為螺絲之冠部的高度尺寸以上。(Provide the form of a bulging and curved sheet electrode)
As shown in FIG. 5, the
由於以變得立體地膨起的方式部分彎曲,在電極構件藉由螺絲安裝於基板的狀態,於薄板電極與基板之間形成分隔空間。如同自圖5所示之形態所得知,成為薄板電極10B的非彎曲部與基板20彼此分隔之狀態,藉此提供電極構件10的“增厚面”。換而言之,以立體地全體變得膨起的方式彎曲之薄板電極中,薄板電極與基板之間的空間係對於“增厚面”的實現有所助益,對於金屬箔製造的陽極與陰極之間的距離產生顯著的功效。因此,圖5所示之態樣,亦可更為減少電極間距離,可在電解槽之電壓較低的狀態下運轉。亦即,可降低金屬箔製造時之電力成本。Since the part is bent so as to bulge three-dimensionally, a partition space is formed between the thin-plate electrode and the substrate in a state where the electrode member is attached to the substrate with a screw. As can be understood from the form shown in FIG. 5 , the non-bent portion of the thin-
由於“增厚面”,亦即,由於薄板電極之立體地膨起的彎曲形態,在藉由螺絲將電極構件安裝於基板的狀態,薄板電極的厚度(薄板電極本身的厚度)與分隔空間的厚度之和,宜成為與螺絲中的錐狀側面之設置部分相當的錐部高度尺寸,或較其更大。此一情形,亦可說是具有立體地膨起的彎曲形態之薄板電極的厚度(薄板電極本身的厚度)與分隔空間的厚度之和,成為螺絲之冠部的高度尺寸以上。Due to the "thickened surface", that is, due to the three-dimensionally bulging curved shape of the thin-plate electrode, the difference between the thickness of the thin-plate electrode (thickness of the thin-plate electrode itself) and the separation space in the state where the electrode member is attached to the substrate with screws The sum of the thicknesses should preferably be the height dimension of the taper portion corresponding to the set portion of the tapered side surface in the screw, or larger. In this case, it can be said that the sum of the thickness of the sheet electrode having the three-dimensionally bulging curved shape (thickness of the sheet electrode itself) and the thickness of the partition space is equal to or greater than the height dimension of the crown of the screw.
雖僅為例示,但立體地膨起彎曲的薄板電極之態樣中,基板的表面與薄板電極的增厚面(亦即,電極的上側主面)之間的距離,例如較2mm更大,宜較3mm更大。此一距離之上限值並無特別限制,例如可為30mm、20mm、15mm、10mm、8mm、或5mm。雖僅為例示,但在薄板電極本身的厚度例如為1mm以下之情況,薄板電極與基板間之分隔空間中的間隙尺寸(沿著電極之非彎曲部分的厚度之方向的尺寸),可為1mm以下,宜為2mm以下(其上限值,例如可為29mm、19mm、14mm、9mm、7mm、或4mm)。Although it is only an example, in the form of the three-dimensionally bulging and curved thin-plate electrode, the distance between the surface of the substrate and the thickened surface of the thin-plate electrode (that is, the upper main surface of the electrode) is, for example, greater than 2 mm. Should be larger than 3mm. The upper limit of the distance is not particularly limited, for example, it can be 30mm, 20mm, 15mm, 10mm, 8mm, or 5mm. Although it is only an example, when the thickness of the sheet electrode itself is, for example, 1 mm or less, the size of the gap in the space between the sheet electrode and the substrate (the size in the direction of the thickness of the non-bending portion of the electrode) may be 1 mm. Below, it is preferable that it is 2 mm or less (the upper limit value may be, for example, 29 mm, 19 mm, 14 mm, 9 mm, 7 mm, or 4 mm).
本發明的電鍍用電極所使用之立體地膨起的薄板電極,例如可藉由將經常作為電解金屬箔的陽極電極使用之厚度小的電極,利用外力形成局部的彎曲或局部的凹部而獲得。對如此地獲得之膨起的薄板電極,藉由機械加工或化學蝕刻等設置螺絲用孔(尤其是在局部的彎曲部・凹部處設置螺絲用孔),經由該孔以螺絲將薄板電極安裝於基板,則可獲得供電解金屬箔的製造所用之本發明的電鍍用電極。另,在螺絲用孔的形成伴隨有局部外力之情況,亦可在形成螺絲用孔時形成局部的彎曲或凹部。The three-dimensionally bulging thin-plate electrode used in the electrode for electroplating of the present invention can be obtained, for example, by using an electrode with a small thickness, which is often used as an anode electrode of an electrolytic metal foil, to form a local curvature or a local concave portion by an external force. The thus obtained bulging sheet electrode is provided with holes for screws by machining or chemical etching (particularly, holes for screws are provided in local bent parts and recesses), and the sheet electrode is attached to the electrode with screws through the holes. substrate, the electrode for electroplating of the present invention for use in the production of electrolytic metal foil can be obtained. In addition, in the case where the formation of the screw hole is accompanied by a local external force, a local curvature or a concave portion may be formed when the screw hole is formed.
立體地膨起彎曲的薄板電極之態樣,可在分隔空間40具備間隔件60(參考圖5(b))。亦即,在藉由螺絲30將電極構件10安裝於基板20的狀態,可設置間隔件60,其部分地佔據薄板電極10B的非彎曲部與基板20之間的空間40。藉由設置此一間隔件,更容易在電鑄時隨著時間適宜地維持薄板電極之膨起的形態。In the form of the thin-plate electrode that is three-dimensionally swollen and curved, the
間隔件之材質,若為可供維持“分隔空間”者則無特別限制。因此,間隔件,可為包含金屬材、樹脂材及/或陶瓷材而構成者。從容易適宜地維持“分隔空間”的點來看,宜具有某程度的剛性。若顯示一例,則間隔件可為實心之金屬塊。此外,間隔件,可為具有所謂的“金屬刷”之形態者,可使間隔件具有適度的彈性。間隔件之材質為金屬材的情況,可適宜形成通過薄板構件、間隔件、基板的散熱路徑,可將電鑄時因電解液產生的熱經由間隔件而往槽外逸散。間隔件的固定手法並無特別限制。可藉由其他手段固定,但可藉由因螺絲對薄板電極的非彎曲部與基板之間提供的夾持力,將間隔件固定。The material of the spacer is not particularly limited as long as it can maintain the "separated space". Therefore, the spacer may be composed of a metal material, a resin material, and/or a ceramic material. From the viewpoint of easily maintaining the "partitioned space" appropriately, it is desirable to have a certain degree of rigidity. If an example is shown, the spacer may be a solid metal block. In addition, the spacer may have the form of a so-called "metal brush", and the spacer may have appropriate elasticity. When the material of the spacer is a metal material, the heat dissipation path through the thin plate member, the spacer, and the substrate can be appropriately formed, and the heat generated by the electrolyte during electroforming can be dissipated out of the tank through the spacer. The fixing method of the spacer is not particularly limited. It can be fixed by other means, but the spacer can be fixed by the clamping force provided by the screw between the non-bent part of the thin plate electrode and the substrate.
在藉由螺絲將電極構件安裝於基板的狀態,立體地膨起彎曲的薄板電極,其非彎曲部分與基板分隔,但彎曲部宜與基板接觸。此外,例如如同自圖5(b)所示之態樣所得知,立體地膨起彎曲的薄板電極10B之彎曲部10B彎曲
,宜與螺絲之錐狀側面35彼此密接。尤其是,有助於立體地膨起的薄板電極10B之彎曲部10B彎曲
,與螺絲30的冠部32之側面35,宜成為以液密狀態彼此密接的狀態。此係因在可經由薄板電極之彎曲部進行適宜的散熱之點上獲得有利的效果之緣故。具體而言,追求抑制電鑄時由於通電而使電解液的溫度上升而導致之升溫,而經由薄板電極之彎曲部、及與該彎曲部密接之螺絲,可使熱適宜地往槽外逸散。另,此薄板電極之彎曲部10B彎曲
,如圖5(b)所示,與螺絲30接觸且亦與基板20接觸。因此,薄板電極之彎曲部,亦可不僅經由螺絲,而亦經由基板使電鑄時因電解液產生的熱適宜地往外部逸散。鑑於此點,薄板電極之彎曲部,亦可稱作電鍍散熱部。In a state where the electrode member is attached to the substrate with screws, the thin-plate electrode that is three-dimensionally bulged and bent is separated from the substrate by the non-bent portion, but the bent portion is preferably in contact with the substrate. In addition, as is known from the state shown in FIG. 5( b ), for example, the
本發明的電鍍用電極,無論為上述「厚壁電極之態樣」及「提供膨起之彎曲的薄板電極之態樣」之任一,電極構件皆可具有單片化之形態。亦即,可為由複數片單片化之子電極10’的組合構成電極構件10,該子電極10’分別安裝於基板20的形態(參考圖9)。此一情況,該子電極10’分別藉由螺絲30固定於基板20。Regardless of whether the electrode for electroplating of the present invention is in any of the above-mentioned "the form of the thick-walled electrode" and the "the form of the thin-plate electrode that provides the bulge and the curvature", the electrode member may have a form of singulation. That is, the
此等子電極之態樣中,在發生電極之觸媒失去活性或剝離,抑或電極構件腐蝕或損傷等缺陷時,可僅更換成為其對象之子電極。亦即,單片化之子電極的態樣中,在電鍍用電極的保養或修護等觀點上,便利性增加。In the form of these sub-electrodes, in the event of a defect such as deactivation or peeling of the catalyst of the electrode, or corrosion or damage of the electrode member, only the sub-electrode that is the target can be replaced. That is, in the aspect of the sub-electrode that is singulated, the convenience is increased from the viewpoint of maintenance and repair of the electrode for electroplating.
較佳態樣中,子電極10’分別具有沿著基板之彎曲形狀的形態。換而言之,子電極10’,宜分別具有固定於基板時(或安裝於基板的情況)沿著基板彎曲之形態。將複數子電極彼此組合而獲得之電極構件,全體宜具有將相反電極之滾筒輪廓與陽極的分隔距離維持為相等之形態。藉由使將厚壁電極10A單片化之子電極10’具有沿著基板的彎曲形狀之形態(參考圖9),若藉由螺絲30將子電極10’固定於基板20,則可將子電極10’與基板20無間隙地密接。然則,子電極10’厚度小之薄板電極10B中,在將子電極10’藉由螺絲30往基板20固定以使可子電極10’追蹤基板形態而變形的情況,亦可不具有預先沿著彎曲形狀之形態(例如,子電極亦可分別具備非彎曲形態或平坦形態)。In a preferred form, the sub-electrodes 10' respectively have a shape along the curved shape of the substrate. In other words, each of the sub-electrodes 10' preferably has a shape that bends along the substrate when it is fixed to the substrate (or when it is mounted on the substrate). The electrode member obtained by combining a plurality of sub-electrodes with each other should preferably have a form in which the separation distance between the roller profile of the opposite electrode and the anode is kept equal. Since the sub-electrode 10 ′ obtained by dividing the thick-
《本發明的電解金屬箔之製造裝置》
本發明的裝置,係用於製造電解金屬箔的裝置,至少具備上述電鍍用電極而構成。亦即,本發明之電解金屬箔的裝置,具備作為陽極的上述電鍍用電極100、及作為陰極的滾筒狀相反電極200而構成(參考圖9)。"Production Apparatus of Electrolytic Metal Foil of the Present Invention"
The apparatus of the present invention is an apparatus for producing an electrolytic metal foil, and includes at least the electrode for electroplating described above. That is, the apparatus for electrolyzing metal foil according to the present invention includes the above-described electrode for electroplating 100 as an anode and a roller-shaped
本發明的裝置中,作為陽極使用之電鍍用電極,至少由電極構件與安裝該電極構件之基板構成;此一陽極之電極構件之與陰極的滾筒狀相反電極相對向的面具備“增厚面”。In the device of the present invention, the electrode for electroplating used as the anode is composed of at least an electrode member and a substrate on which the electrode member is mounted; the surface of the electrode member of the anode facing the roller-shaped opposite electrode of the cathode has a "thickened surface". ".
本發明之製造裝置,由於“增厚面”,而具有陽極之電鍍用電極對陰極之相反電極更接近的位置關係或更靠近的位置關係。因此,若使用本發明之製造裝置,則可在電解槽之電壓較低的狀態下運轉,可降低電力成本。此外,藉由增加作為陽極之導電性母材的厚度,在通電時電鍍用電極上之電流分布更容易變得均勻,亦可減少製造之金屬箔的瑕疵發生。雖僅為例示,但本發明的電解金屬箔之裝置中,陽極與陰極之間的分隔距離(兩電極之接近面間的距離)宜為5~25mm,更宜為5~20mm,進一步宜為6~15mm(例如,6mm~10mm程度)。The manufacturing apparatus of the present invention has a closer positional relationship or a closer positional relationship between the electrode for electroplating of the anode and the opposite electrode of the cathode due to the "thickened surface". Therefore, when the manufacturing apparatus of this invention is used, it becomes possible to operate in the low voltage state of an electrolytic cell, and it becomes possible to reduce electric power cost. In addition, by increasing the thickness of the conductive base material used as the anode, the current distribution on the electrode for electroplating during energization is more likely to become uniform, and the occurrence of defects in the manufactured metal foil can also be reduced. Although it is only an example, in the device for electrolytic metal foil of the present invention, the separation distance between the anode and the cathode (the distance between the surfaces of the two electrodes) is preferably 5 to 25 mm, more preferably 5 to 20 mm, and further preferably 5 to 20 mm. 6 to 15 mm (for example, about 6 mm to 10 mm).
在製造金屬箔時施行電鍍。因此,本發明的裝置,進一步具備電解槽而構成。於此一電解槽內,將「作為陽極的電鍍用電極」及「作為陰極的滾筒狀相反電極」彼此隔著一定距離而配置。電解槽50之槽壁的至少一部可成為電鍍用電極之基板20。亦即,電解槽之槽壁的一部分圓弧狀地彎曲,如此地彎曲的槽壁亦可兼作電鍍用電極之基板。Electroplating is performed in the manufacture of metal foils. Therefore, the apparatus of the present invention is further provided with an electrolytic cell. In this electrolytic cell, the "electrode for electroplating as the anode" and the "roller-shaped counter electrode as the cathode" are arranged at a certain distance from each other. At least a part of the cell wall of the
電解槽中,將作為陰極的滾筒狀相反電極以可任意旋轉的方式設置。亦即,將陰極作為旋轉滾筒而設置於電解槽。具體而言,宜設置為陰極的旋轉滾筒之略下半部以上浸漬於電解槽的電解液(即電鍍液)。滾筒狀之陰極本身,可常見於電解金屬箔的製造。在製造金屬箔時,陰極的滾筒旋轉,在其接觸電解液時產生電沉積。由於滾筒的旋轉,接觸到電解液之陰極滾筒的一部分往空氣中露出,而此時電沉積層從滾筒表面機械性地剝離。藉此,可獲得期望的金屬箔。金屬箔可連續獲得,故可設置用於將其捲取之適宜的捲筒手段。In the electrolytic cell, a roller-shaped counter electrode serving as a cathode was installed so as to be rotatable arbitrarily. That is, the cathode is installed in the electrolytic cell as a rotating drum. Specifically, it is preferable to set it as the electrolytic solution (that is, the electroplating solution) immersed in the electrolytic bath above the slightly lower half of the rotating drum of the cathode. The cylindrical cathode itself is commonly used in the manufacture of electrolytic metal foils. In the manufacture of metal foils, the drum of the cathode rotates, causing electrodeposition as it contacts the electrolyte. Due to the rotation of the drum, a part of the cathode drum that came into contact with the electrolyte was exposed to the air, and at this time, the electrodeposited layer was mechanically peeled off from the drum surface. Thereby, a desired metal foil can be obtained. Since the metal foil can be obtained continuously, suitable roll means for winding it can be provided.
本發明之製造裝置,進一步具備用於往電極供電之匯流排(busbar)而構成。例如,匯流排,可對電鍍用電極之電極構件及/或基板安裝。藉由此等匯流排,可使直流電流往陽極與陰極之間流通,可實施期望的電鑄。此外,基板等,可具備用於供給電解液之供給口(例如間隙部)。經由此一供給口,可適宜補充消耗的電鍍成分。The manufacturing apparatus of this invention is further provided with the busbar for supplying electric power to an electrode, and is comprised. For example, the bus bar can be mounted on the electrode member and/or the substrate of the electrode for electroplating. With these bus bars, a direct current can be made to flow between the anode and the cathode, and desired electroforming can be performed. In addition, the substrate or the like may be provided with a supply port (eg, a gap portion) for supplying the electrolyte. Through this supply port, the consumed electroplating components can be appropriately replenished.
本發明之製造裝置的更詳細之事項、更具體的態樣等其他事項,於上述《本發明的電鍍用電極》說明,為了避免重複故省略其說明。Other matters such as more detailed matters and more specific aspects of the manufacturing apparatus of the present invention are described in the above-mentioned "electrode for electroplating of the present invention", and the description thereof is omitted in order to avoid repetition.
以上,雖說明本發明的各種態樣,但本發明並未限定於此等態樣,應理解在不脫離發明申請專利範圍所規定之發明範疇,可由所屬技術領域中具有通常知識者具體實現各種態樣。Although various aspects of the present invention have been described above, the present invention is not limited to these aspects, and it should be understood that various aspects can be specifically realized by those with ordinary knowledge in the technical field without departing from the scope of the invention defined in the scope of the patent application for the invention. manner.
例如,本發明中,如圖10(a)~(c)所示,可將用於電極構件10之固定或穩定的溝25,設置於基板20。亦即,在將電極構件10安裝於基板20的狀態,可將嵌入電極構件10中的“螺絲孔之鄰近部分19”的溝25設置於基板20。此一情況,電極構件10(尤其是薄板電極10B)之鄰近部分19夾持在螺絲30與基板20之間,故對安裝於基板的電極構件之固定或穩定有所助益。另,如同自圖示之態樣所得知,溝25,在一些態樣中對於基板20相當於沉頭孔,故圖10(a)~(c)所示之態樣,亦可說是將沉頭孔適宜利用在電極構件10(尤其是薄板電極10B)之固定或穩定的態樣。For example, in the present invention, as shown in FIGS. 10( a ) to ( c ),
如圖10(c)所示,螺絲30的冠部可包含非錐狀部分。此一情況,可更容易增加在螺絲30與基板20之間夾持的電極構件10(尤其是薄板電極10B)之部分(亦即,如同自圖示之態樣所得知,可更容易增加在在螺絲30與基板20之間夾持的電極構件10(10B)之鄰近部分19)。因此,此點亦對安裝於基板的電極構件之固定或穩定有所助益。
[產業上利用性]As shown in Figure 10(c), the crown of the
本發明的電鍍用電極,可利用在實施電鍍之各式各樣的領域。尤其是,可適宜利用在藉由電鍍製造金屬箔之電鑄。雖僅為例示,但作為製造印刷電路材或二次電池之電極集電體所使用的金屬箔之電解裝置的陽極,可適宜利用本發明的電鍍用電極。The electrode for electroplating of the present invention can be used in various fields in which electroplating is performed. In particular, it can be suitably used for electroforming for producing metal foil by electroplating. Although it is only an illustration, the electrode for electroplating of this invention can be utilized suitably as an anode of the electrolysis apparatus of the metal foil used for manufacturing the electrode collector of a printed circuit material or a secondary battery.
10‧‧‧電極構件
10’‧‧‧子電極
10A‧‧‧厚壁電極
10B‧‧‧薄板電極
10B彎曲‧‧‧彎曲部
11‧‧‧薄型電極構件
12‧‧‧電極構件之側面部分
15‧‧‧增厚面
15’、15A‧‧‧部分
18‧‧‧點
19‧‧‧鄰近部分
20‧‧‧基板
25‧‧‧溝
26‧‧‧沉頭孔
26’‧‧‧沉頭孔面(形成沉頭孔底面)
28、29‧‧‧空間
30‧‧‧螺絲
32‧‧‧冠部
35‧‧‧錐狀側面
37‧‧‧螺紋部
40‧‧‧空間(分隔空間)
50‧‧‧電解槽
60‧‧‧間隔件
100‧‧‧電鍍用電極
200‧‧‧相反電極
500‧‧‧電解槽
510‧‧‧電解液
520‧‧‧電鍍用電極
530‧‧‧相反電極
550‧‧‧金屬箔
H1‧‧‧從增厚面至與基板之接觸水平面為止的垂直距離尺寸
H2‧‧‧螺絲的錐部高度尺寸10‧‧‧Electrode member 10'‧‧‧
圖1係本發明的電鍍用電極之示意剖面圖(圖1(A):使用厚壁電極;圖1(B):使用薄板電極)。 圖2係本發明的電鍍用電極之示意剖面圖(圖2(A):使用厚壁電極;圖2(B):使用薄板電極)。 圖3係螺絲之示意剖面圖。 圖4係用於說明“厚壁電極之態樣”中的增厚面之示意剖面圖(圖4(a):電極厚度為沉頭螺絲的冠部尺寸以上;圖4(b):電極厚度與沉頭螺絲的冠部尺寸相同)。 圖5係用於說明“提供膨起之彎曲的薄板電極之態樣”中的增厚面之示意剖面圖(圖5(a):電極的膨起與沉頭螺絲的冠部尺寸相同;圖5(b):電極的膨脹度與沉頭螺絲的冠部尺寸相同,附設間隔件)。 圖6係用於將本發明的源自於增厚之適宜的密接狀態與“薄型電極”對比說明之示意剖面圖。 圖7係關於“厚壁電極之態樣”的較佳具體例之示意剖面圖。 圖8係用於說明圖7之具體例的意義之示意剖面圖。 圖9係本發明之製造裝置的例示態樣之示意立體圖。 圖10係本發明的電鍍用電極之具備有助於電極構件的對於基板之固定或穩定的溝之態樣的示意剖面圖(圖10(a):不具備間隔件;圖10(b):具備間隔件;圖10(c):使用特殊形狀之沉頭螺絲)。 圖11係用於說明藉由電鍍製造連續的金屬箔之態樣的示意剖面圖。Fig. 1 is a schematic cross-sectional view of the electrode for electroplating of the present invention (Fig. 1(A): using a thick-walled electrode; Fig. 1(B): using a thin-plate electrode). Fig. 2 is a schematic cross-sectional view of the electrode for electroplating of the present invention (Fig. 2(A): using a thick-walled electrode; Fig. 2(B): using a thin-plate electrode). FIG. 3 is a schematic cross-sectional view of the screw. Fig. 4 is a schematic cross-sectional view for explaining the thickened surface in "Condition of thick-walled electrode" (Fig. 4(a): the thickness of the electrode is above the crown size of the countersunk head screw; Fig. 4(b): the thickness of the electrode The same size as the crown of the countersunk head screw). Fig. 5 is a schematic cross-sectional view for explaining the thickened surface in "Condition of the curved sheet electrode provided with bulge" (Fig. 5(a): the bulge of the electrode is the same as that of the crown of the countersunk head screw; Fig. 5(a)) 5(b): The expansion of the electrode is the same as the coronal dimension of the countersunk screw, with spacers attached). FIG. 6 is a schematic cross-sectional view for explaining a suitable close contact state derived from thickening of the present invention in comparison with a “thin electrode”. FIG. 7 is a schematic cross-sectional view of a preferred specific example of "a form of a thick-walled electrode". FIG. 8 is a schematic cross-sectional view for explaining the meaning of the specific example of FIG. 7 . 9 is a schematic perspective view of an exemplary aspect of the manufacturing apparatus of the present invention. 10 is a schematic cross-sectional view of a state in which the electrode for electroplating of the present invention is provided with grooves that contribute to fixing or stabilizing the electrode member to the substrate ( FIG. 10( a ): no spacer is provided; FIG. 10( b ): With spacers; Fig. 10(c): Use special shaped countersunk head screws). FIG. 11 is a schematic cross-sectional view for explaining a state of manufacturing a continuous metal foil by electroplating.
10‧‧‧電極構件 10‧‧‧Electrode components
15‧‧‧增厚面 15‧‧‧Thickening surface
20‧‧‧基板 20‧‧‧Substrate
30‧‧‧螺絲 30‧‧‧Screw
100‧‧‧電鍍用電極 100‧‧‧electrode for electroplating
200‧‧‧相反電極 200‧‧‧Reverse electrode
Claims (11)
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JP2017191163A JP6946911B2 (en) | 2017-09-29 | 2017-09-29 | Manufacturing equipment for plating electrodes and electrolytic metal leaf |
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CN112251780B (en) * | 2020-09-07 | 2021-11-05 | 浙江大学 | Improved preparation method of flat electro-deposition copper foil |
KR20240057678A (en) | 2022-10-25 | 2024-05-03 | 주식회사 웨스코일렉트로드 | Method for removing lead materials on anode of electrolytic copper foil |
KR102538289B1 (en) * | 2023-02-07 | 2023-05-31 | 주식회사 웨스코일렉트로드 | Anode assembly for manufacturing electrolytic copper foil |
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TW273578B (en) * | 1992-01-28 | 1996-04-01 | Berumerekku Denkyoku Kk | |
JP2013204042A (en) * | 2012-03-27 | 2013-10-07 | Daiso Co Ltd | Insoluble electrode structural body and method of repairing the insoluble electrode structural body |
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JP2675219B2 (en) * | 1991-12-26 | 1997-11-12 | ペルメレック電極株式会社 | Method for reactivating anode for continuous production of metal foil |
JPH0647758A (en) | 1992-07-31 | 1994-02-22 | Olympus Optical Co Ltd | Method and apparatus for producing composite optical element |
JP3468545B2 (en) | 1993-04-30 | 2003-11-17 | ペルメレック電極株式会社 | Electrode for electrolysis |
JP3207973B2 (en) * | 1993-06-10 | 2001-09-10 | ティーディーケイ株式会社 | Electroplating method and split type insoluble electrode for electroplating |
JP3606932B2 (en) * | 1994-12-30 | 2005-01-05 | 石福金属興業株式会社 | Electrode composite electrode |
JP2002038291A (en) * | 2001-09-03 | 2002-02-06 | Daiso Co Ltd | Anode for manufacturing metallic foil |
JP5414257B2 (en) | 2008-12-08 | 2014-02-12 | 株式会社昭和 | Electrode for electrolysis |
JP4642120B2 (en) * | 2009-04-01 | 2011-03-02 | 三井金属鉱業株式会社 | Electrolytic metal foil manufacturing apparatus, method for manufacturing thin plate insoluble metal electrode used in electrolytic metal foil manufacturing apparatus, and electrolytic metal foil obtained using the electrolytic metal foil manufacturing apparatus |
CN202482454U (en) * | 2012-02-07 | 2012-10-10 | 宝鸡天邦钛镍有限公司 | Dimensionally stable anode (DSA) integrated titanium anode for electrolytic copper foil manufacturing machine |
CN205088315U (en) * | 2015-09-16 | 2016-03-16 | 沈阳中科惠友科技发展有限责任公司 | Thickening arc titanium anode board |
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JP2013204042A (en) * | 2012-03-27 | 2013-10-07 | Daiso Co Ltd | Insoluble electrode structural body and method of repairing the insoluble electrode structural body |
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CN109576739A (en) | 2019-04-05 |
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