WO2010128641A1 - 酸素発生用陽極 - Google Patents
酸素発生用陽極 Download PDFInfo
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- WO2010128641A1 WO2010128641A1 PCT/JP2010/057562 JP2010057562W WO2010128641A1 WO 2010128641 A1 WO2010128641 A1 WO 2010128641A1 JP 2010057562 W JP2010057562 W JP 2010057562W WO 2010128641 A1 WO2010128641 A1 WO 2010128641A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
Definitions
- the present invention relates to an oxygen generating anode used as an insoluble anode in an electrolysis process accompanied by oxygen generation, mainly electroplating of zinc, tin or copper, surface treatment of stainless steel, and electrolytic extraction of metals.
- two anodes are used so as to face both sides of the steel plate in order to plate both sides of the steel plate, and the width of the two anodes arranged facing each other (perpendicular to the traveling direction of the steel strip)
- the dimension in the right direction) is set in accordance with the maximum width of the steel strip because there are many kinds of widths of the steel strip passing between them. For this reason, when a steel strip having a width smaller than the maximum width passes (a portion through which the steel strip passes is referred to as a plate path), the electrodes are directly opposed at the side end portions on both sides of the anode.
- Patent Document 1 In order to extend the life of this type of electrode as a cathode, an electrode in which an intermediate layer of two layers of a platinum layer and an oxide layer is provided between a conductive electrode substrate and an electrode active material layer is disclosed in Patent Document 1. Has been proposed. Although this electrode has an effect of extending the life as a cathode, the platinum layer and the oxide layer have inherently poor adhesion, and the life of the plate path portion of the anode and the outer portion of the plate path in the electroplating of the steel plate is the same. It has not yet reached.
- Patent Document 2 proposes an electrode provided with an upper layer made of iridium oxide. Although an improvement in durability can be seen by providing an upper layer, the significant wear inherent in platinum when acting as an anode cannot be suppressed, and the durability when acting as a cathode intermittently is insufficient.
- the cathode This is to make the thickness of the electrode active material layer thicker than the thickness of other portions in the portion where the crystallization phenomenon occurs (Patent Document 3). While increasing the thickness of the electrode active material layer is effective, increasing the thickness of the electrode active material layer is accompanied by a significant increase in cost. That is, the electrode active material layer is formed in a predetermined layer thickness by repeating so-called baking coating in which an electrode coating solution is applied, dried and baked. In order to increase the layer thickness, it is necessary to increase the number of times the baking coating is repeated, and not only the amount of expensive electrode active material used is increased, but also the number of work steps is remarkable.
- Patent Document 4 has been proposed (Patent Document 4).
- a valve metal such as titanium metal is exposed to a high temperature of 650 ° C. or higher in air for a long time, the titanium substrate is oxidized and the electrode becomes unusable.
- Patent Document 5 proposes a method of forming an electrode active material layer on an electrode substrate in which fine titanium particles are sintered on a titanium plate in a vacuum or in an inert atmosphere as an electrode that can withstand negative polarization. Sintering requires strict temperature control and atmosphere control at high temperatures, and the cost of manufacturing a sintered base becomes very high.
- the object of the present invention is to provide an oxygen generating anode that has sufficient durability not only in anodic polarization but also in electrolysis with negative polarization, thereby extending the use period of the anode, repairing and replacing the anode, etc. This is to reduce the manufacturing cost of the oxygen generating anode.
- the present inventors diligently studied and examined a method for suppressing the consumption of the electrode active substance when used for electrolysis with negative polarization.
- porous metal sheets such as expanded metal (expanded metal) and punched metal (punched metal) are bonded as a physical support for the electrode active substance on the conductive metal that is the electrode structure from the electrode structural surface. It has been found that the use of the electrode substrate is an effective means for extending the lifetime of the portion where negative polarization occurs.
- the porous metal sheet on the conductive metal that is the electrode structure does not affect the life of the anode. That is, the porous metal sheet does not contribute to extending the life of the electrode active material and does not function as a physical holding body.
- the porous metal sheet when used for electrolysis with negative polarization, the porous metal sheet contributes to the extension of the anode life. This fact means that when used for electrolysis with negative polarization, the porous metal sheet contributes to the extension of the life of the electrode active material and functions as a physical holding body or holding accelerator. .
- the oxygen generating anode of the present invention has been completed on the basis of such knowledge, and in the oxygen generating anode formed by coating the surface of the electrode substrate with an electrode active material, the surface of the conductive metal that is an electrode structure is provided.
- An electrode base is formed by bonding an active substance holding body made of a porous metal sheet or an active substance holding promoting body to an electrode active substance mainly composed of iridium oxide on the holding body bonding surface of the electrode base. Is an anode for oxygen generation that is resistant to cathodic phenomenon.
- the resistance to the cathodic phenomenon is improved by a mechanism different from the conventional method, ie, physical retention of the electrode active material.
- the mechanism is known to be intrinsic to electrolysis with negative polarization, but the details of active substance retention are unknown.
- the catalyst coating liquid is unevenly distributed in the gap of the bonded portion or the intersecting portion of the expanded metal. Is thicker but partially, it is more resistant to cathodicization than a uniformly coated plate-like electrode substrate, which is believed to contribute to the extension of anode life in electrolysis with negative polarization. .
- Examples of the porous metal sheet bonded to the surface of the conductive metal that is the electrode structure can include expanded metal, punching metal, interdigital or net-like metal, bondability to the conductive metal surface, availability, From the viewpoint of mechanical strength and the like, an expanded metal or a punching metal is particularly preferable.
- the material of the conductive metal constituting the electrode substrate and the porous metal sheet bonded thereto is preferably a valve metal such as titanium, tantalum, niobium, tungsten or zirconium, and further titanium-tantalum, titanium-tantalum-niobium, titanium.
- a valve metal such as titanium, tantalum, niobium, tungsten or zirconium
- titanium-tantalum, titanium-tantalum-niobium, titanium -Titanium based alloys such as palladium or tantalum coated titanium are preferred and the surface of the metal substrate may be oxidized, nitrided, borated or carbonized.
- the shape of the conductive metal as the electrode structure can be a desired shape such as a flat plate shape, a net shape, a rod shape, or a porous plate shape, but a flat plate shape or a porous plate shape is particularly preferable.
- the thickness of the porous metal sheet is preferably 0.2 mm or more and 4.0 mm or less.
- the thickness of the porous metal sheet is preferably 0.2 mm or more and 4.0 mm or less.
- the aperture ratio is important together with the thickness.
- the opening ratio that is, the ratio of the opening area to the total area is preferably 5 to 85%, particularly preferably 30 to 50%.
- the aperture ratio is too small, the retention ability of the electrode active material and the effect of extending the anode life due to this decrease.
- the aperture ratio is too large, the ability to hold the electrode active material and the effect of extending the anode life due to this decrease.
- the specifications for each type of porous metal sheet are as follows.
- LW distance between centers in the mesh long direction
- thickness 0.5 to 4.0 mm are desirable, and LW: 8 is more preferable.
- the openings in the punching metal may have a staggered arrangement of 45, 60, and 90 degrees, the ratio of the opening area to the total area is preferably 5 to 85%, and the hole diameter of the opening is 1.5 to 25 mm, particularly 2 ⁇ 10 mm is preferred.
- the oxygen generating catalyst which is the main material is platinum.
- Group metal oxides, particularly iridium oxide, are desirable, and for binders added to the main material, the amount of valve metal oxide, for example tantalum oxide, is reduced from the viewpoint of giving priority to suppression of wear over prevention of embrittlement, It has been found effective to increase the relative amount of iridium oxide as the main material.
- the electrode active material to be coated on the electrode substrate a main material that is an oxygen generation catalyst is used as a main component, and a mixture obtained by adding a binder to this is used.
- a binder an oxide of one or more metals selected from the group consisting of valve metals such as titanium, tantalum, niobium, tungsten, zirconium, and tin is preferable.
- the electrode active material include iridium-tantalum mixed oxide, iridium-tantalum-titanium mixed oxide, iridium-tantalum-niobium mixed oxide, and the like.
- the content of the binder is reduced and the content of the oxygen generating catalyst as the main material is increased from the viewpoint of giving priority to suppression of wear over prevention of embrittlement.
- a mixture of metal oxides containing 50 to 95% by weight of iridium in terms of metal and 50 to 5% by weight of one or more kinds of valve metals in terms of metal is preferable.
- a more preferable electrode active material is a mixture of metal oxides in which one type of valve metal is tantalum and iridium is contained at a weight percentage of at least twice that of tantalum in terms of metal.
- a particularly preferred electrode active material is an iridium-tantalum mixed oxide containing 70% by weight or more of iridium in terms of metal and the remaining metal component being tantalum.
- the content of iridium oxide in the electrode active material is reduced, there is a disadvantage that the oxygen generation capacity of the electrode active layer becomes insufficient and becomes porous. Moreover, the content of the binder is relatively increased, and the resistance to the cathodic phenomenon is lowered. On the other hand, when the iridium oxide content in the electrode active material is excessive, the content of the binder is relatively reduced, and from this point, the electrode active material is dropped, and the performance deterioration due to this becomes remarkable.
- the electrode active substance coating method a conventionally used thermal decomposition method, powder sintering method, or the like can be applied, but the thermal decomposition method is preferable. That is, these metal salt solutions are applied, dried, and fired in air at a temperature of 410 ° C. to 550 ° C. Application, drying, and baking operations are performed several to several tens of times to form a necessary amount of the electrode active layer.
- the oxygen generating anode of the present invention has a portion that is off the plate path of the anode due to the negative polarization phenomenon when zinc metal or the like is plated on the both sides of the steel plate with different coating widths for various plate widths.
- the problem that the life is shorter than the part that always faces the steel plate at the center is that by bonding a porous metal sheet such as expanded metal or punching metal on the conductive metal that is the electrode structure as a support for the electrode active material
- This can be effectively solved by constituting an electrode substrate and coating it with an electrode active substance mainly composed of a platinum group metal, particularly iridium.
- the manufacturing cost can be kept low.
- the anode for oxygen generation according to the present invention is particularly suitable for use in an insoluble anode for electroplating in which a cathodic phenomenon occurs or a portion in which an insoluble anode for electroplating occurs.
- An electrode substrate is constructed by joining an active substance holding body made of a porous metal sheet to one or both sides of the working surface of a flat conductive metal that is an electrode structure.
- the active substance holding body is for physically holding the electrode active substance on the surface of the electrode substrate, which is an electrode structure. More precisely, the electrode active substance is applied to the surface of the electrode base in electrolysis with negative polarization. By physically holding, it contributes to the extension of anode life.
- the porous metal sheet is made of expanded metal, punching metal, interdigital or net-like metal, and is joined to the surface of the conductive metal by welding or the like. These materials are made of valve metal, and titanium is preferable in terms of price and performance.
- the electrode active substance is coated on the active substance holding member bonding surface.
- the electrode active substance is a mixture of an oxygen generation catalyst as a main material and a binder, and specifically, a mixed oxide mainly composed of iridium as an oxygen generation catalyst. Specifically, the iridium content is 50% by weight or more, preferably 70% by weight or more in terms of metal.
- the metal component of the binder is a valve metal, preferably tantalum.
- the method for coating the electrode active material is the same as in the past.
- the produced oxygen generating anode is used in an insoluble anode in an electroplating line of a steel strip, particularly an insoluble anode in which a cathodic phenomenon occurs at the side edge, or a side edge in which the cathodic phenomenon of the insoluble anode occurs. Its durability is remarkably superior to conventional insoluble anodes that do not have an active substance holder.
- Example 1 An electrode structure composed of a 30 mm ⁇ 30 mm ⁇ 10 mm flat plate made of titanium and an expanded metal made of titanium (30 mm ⁇ 30 mm square plate, LW is 8.0 mm, SW (mesh short) The distance between the centers in the eye direction) was 3.6 mm, the thickness was 1.2 mm), and the titanium base material was joined by spot welding. A titanium round bar having a diameter of 8 mm was welded perpendicularly to the center of the back surface of the titanium base material to obtain a power supply lead for energization.
- An electrode active substance coating solution having the following liquid composition was prepared and applied to the expanded metal joint surface of the produced electrode substrate. After coating, the coating was dried at 100 ° C. for 10 minutes and then baked in an electric furnace maintained at 450 ° C. for 20 minutes. This electrode active material coating operation (coating, drying, and firing) was repeated 10 times to produce an oxygen generating anode having iridium oxide as the electrode active material on the electrode substrate surface.
- the electrode active material coating layer formation surface (30 mm ⁇ 30 mm) in this oxygen generating anode was left and the other part sealed was used as an anode for polarity reversal life test.
- forward and reverse energization is repeated by repeating forward energization (positive polarization) for 10 minutes at a current density of 100 A / dm 2 and reverse energization (negative polarization) for 10 minutes at 30 A / dm 2.
- the electrode life was defined as when the cell voltage increased by 5 V compared to the starting voltage.
- This polarity reversal electrode life acceleration test evaluates the durability of the electrode against cathodic phenomenon. The test results are shown in Table 1.
- Example 2 An oxygen generating anode was prepared in the same manner as in Example 1 except that the composition of the electrode active material coating solution was as follows.
- the amount of iridium metal was 30 g / m 2 .
- a polarity reversal electrode life acceleration test similar to that in Example 1 was performed. The test results are shown in Table 1.
- Example 3 Titanium punching metal (30 mm x 30 mm square plate, opening at 60 degrees staggered, hole diameter, 30 mm x 30 mm x 10 mm titanium flat plate, which is an electrode structure, as a porous metal sheet for the active substance holder Of 3.0 mm, the hole center pitch of 5.5 mm, and the thickness of 1.5 mm) were joined by spot welding to obtain a titanium base material.
- a titanium round bar having a diameter of 8 mm was welded perpendicularly to the center of the back surface of the titanium base material to obtain a power supply lead for energization. Subsequent treatment of the titanium base material and formation of the electrode active material coating layer were performed in the same manner as in Example 1.
- the amount of iridium metal was 30 g / m 2 .
- a polarity reversal electrode life acceleration test similar to that in Example 1 was performed. The test results are shown in Table 1.
- Example 4 A 30 mm ⁇ 30 mm ⁇ 10 mm titanium flat plate, which is an electrode structure, and a titanium expanded metal (30 mm ⁇ 30 mm square plate, LW is 10.0 mm, SW is 5. 5 mm) as a porous metal sheet for an active substance holder.
- a titanium electrode substrate was prepared in the same manner as in Example 1 except that 0 mm and a thickness of 0.5 mm were joined by spot welding.
- An electrode active material coating layer having the same composition and coating amount as in Example 1 was formed on the surface of the produced electrode substrate, and then a polarity reversal electrode life acceleration test similar to that in Example 1 was performed. The test results are shown in Table 1.
- Example 5 A 30 mm ⁇ 30 mm ⁇ 10 mm titanium flat plate, which is an electrode structure, and a titanium expanded metal (30 mm ⁇ 30 mm square plate, LW is 10.0 mm, SW is 5. 5 mm) as a porous metal sheet for an active substance holder.
- a titanium electrode substrate was prepared in the same manner as in Example 1 except that 0 mm and a thickness of 1.5 mm were joined by spot welding.
- An electrode active material coating layer having the same composition and coating amount as in Example 1 was formed on the surface of the produced electrode substrate, and then a polarity reversal electrode life acceleration test similar to that in Example 1 was performed. The test results are shown in Table 1.
- Comparative Example 1 A titanium electrode substrate was prepared in the same manner as in Example 1 except that a titanium flat plate of 30 mm ⁇ 30 mm ⁇ 10 mm was used as the titanium substrate material. An electrode active material coating layer having the same composition and coating amount as in Example 1 was formed on this surface, and then the polarity inversion electrode life acceleration test similar to that in Example 1 was performed. The test results are shown in Table 1.
- the oxygen generating anodes of Examples 1 to 5 using an electrode base body in which a titanium expanded metal and a punching metal are joined to a titanium plate as an electrode structure are used for oxygen generation using simple plate-like titanium as an electrode base body.
- the electrode life was extremely excellent in the polarity reversal electrode life acceleration test.
- Reference Examples 1-6 Oxygen generating anodes similar to those prepared in Examples 1 to 5 and Comparative Example 1 were prepared, and an electrode life acceleration test was performed on these. These are designated as Reference Examples 1 to 6, respectively.
- a zirconium plate was used for the counter electrode.
- the current density was 200 A / dm 2 continuous positive energization (positive polarization), and when the cell voltage increased by 5 V compared to the starting voltage, the electrode life was defined. The results are shown in Table 2.
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Abstract
Description
実施例1
30mm×30mm×10mmのチタン製平板からなる電極構造体に、活性物質保持体用の多孔金属シートとしてチタン製のエキスパンド金属(30mm×30mmの角板で、LWは8.0mm、SW(メッシュ短目方向の中心間距離)は3.6mm、厚さは1.2mm)をスポット溶接法で接合してチタン基体材とした。チタン基体材の裏面中央に垂直に直径8mmのチタン製丸棒を溶接して通電のための給電リードとした。これをアセトン中で超音波洗浄により脱脂した後、24番のアランダムを用い、0.6MPaで約10分間エキスパンド金属面にブラスト処理を施した。ブラスト処理後のチタン基体材を流水中で一昼夜洗い、乾燥したものを電極基体として用いた。
H2IrCl6・6H2O: 10.0g
35%HCl: 10ml
n-CH3(CH2)3OH: 100ml
電極活性物質塗布液の組成を下記とした以外は、実施例1と全く同様にして酸素発生用陽極を作製した。電極活性物質被覆層の金属重量組成比はIr/Ta/Nb=6.3/2.6/1.1、であり、イリジウムの含有比は63重量%であるが、タンタルの含有比(26重量%)の2倍以上である。イリジウム金属量は30g/m2 であった。実施例1と同様の極性反転電極寿命加速試験を行った。試験結果を表1に示す。
H2IrCl6・6H2O: 32.5g
NbCl5: 6.3g
35%HCl: 15ml
n-CH3(CH2)3OH: 240ml
電極構造体である30mm×30mm×10mmのチタン製平板に、活性物質保持体用の多孔金属シートとしてチタン製のパンチング金属(30mm×30mmの角板で、開口部は60度千鳥、孔の直径は3.0mm、孔のセンターピッチは5.5mm、厚さは1.5mm)をスポット溶接法で接合してチタン基体材とした。チタン基体材の裏面中央に垂直に直径8mmのチタン製丸棒を溶接して通電のための給電リードとした。チタン基体材に対する以後の処理および電極活性物質被覆層の形成は実施例1と同様に行った。電極活性物質被覆層の金属重量組成比はIr/Ta=7/3であり、イリジウムの含有比は70重量%で、タンタルの含有比(30重量%)の2倍以上である。イリジウム金属量は30g/m2 であった。実施例1と同様の極性反転電極寿命加速試験を行った。試験結果を表1に示す。
電極構造体である30mm×30mm×10mmのチタン製平板に、活性物質保持体用の多孔金属シートとしてチタン製のエキスパンド金属(30mm×30mmの角板で、LWは10.0mm、SWは5.0mm、厚さは0.5mm)をスポット溶接法で接合した以外は、実施例1と同様の処理を施したチタン電極基体を作製した。作製した電極基体の表面に実施例1と同じ組成、被覆量の電極活性物質被覆層を形成した後、実施例1と同様の極性反転電極寿命加速試験を行った。試験結果を表1に示す。
電極構造体である30mm×30mm×10mmのチタン製平板に、活性物質保持体用の多孔金属シートとしてチタン製のエキスパンド金属(30mm×30mmの角板で、LWは10.0mm、SWは5.0mm、厚さは1.5mm)をスポット溶接法で接合した以外は、実施例1と同様の処理を施したチタン電極基体を作製した。作製した電極基体の表面に実施例1と同じ組成、被覆量の電極活性物質被覆層を形成した後、実施例1と同様の極性反転電極寿命加速試験を行った。試験結果を表1に示す。
30mm×30mm×10mmのチタン製平板単体をチタン基体材とした以外は、実施例1と同様の処理を施したチタン電極基体を作製した。この表面に実施例1と同じ組成、被覆量の電極活性物質被覆層を形成した後、実施例1と同様の極性反転電極寿命加速試験を行った。試験結果を表1に示す。
実施例1~5および比較例1で作製したものと同様の酸素発生用陽極を作製し、これらについて電極寿命加速試験を行った。各々を参考例1~6とする。
Claims (9)
- 電極基体の表面に電極活性物質を被覆してなる酸素発生用陽極において、電極構造体である導電性金属の表面に多孔金属シートからなる活性物質保持体を接合することにより電極基体が構成されており、該電極基体における保持体接合面に酸化イリジウムを主成分とする電極活性物質が被覆されている、陰極化現象に耐性を示す酸素発生用陽極。
- 多孔金属シートがエキスパンド金属、パンチング金属、すだれ状または網状金属である請求項1に記載の酸素発生用陽極。
- 電極活性物質が金属換算でイリジウムを50~95重量%を含有し、且つ金属換算でバルブ金属の1種以上を50~5重量%を含有する金属酸化物の混合物である請求項1または2に記載の酸素発生用陽極。
- バルブ金属の1種がタンタルであり、金属換算でのイリジウム含有量(重量%)がタンタル含有量(重量%)の2倍以上である請求項3に記載の酸素発生用陽極。
- 電極活性物質中の酸化イリジウム含有量が金属換算で70重量%以上であり、残りの金属酸化物がタンタル酸化物である請求項4に記載の酸素発生用陽極。
- 陰極化現象が生じる電気めっき用不溶性陽極として使用される請求項1~5の何れかに記載の酸素発生用電極。
- 電気めっき用不溶性陽極の陰極化現象が生じる部分に使用される請求項1~5の何れかに記載の酸素発生用電極。
- 導電性金属及び多孔金属シートがバルブ金属よりなることを特徴とする請求項1~7の何れかに記載の酸素発生用陽極。
- バルブ金属がチタン、タンタル、ニオブ、タングステン、ジルコニウムから選ばれた金属である請求項8に記載の酸素発生用陽極。
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JP2011512344A JPWO2010128641A1 (ja) | 2009-05-07 | 2010-04-28 | 酸素発生用陽極 |
US13/319,115 US20120091007A1 (en) | 2009-05-07 | 2010-04-28 | Anode for oxygen generation |
EP10772160A EP2428595A1 (en) | 2009-05-07 | 2010-04-28 | Anode for oxygen generation |
CN2010800114534A CN102348837A (zh) | 2009-05-07 | 2010-04-28 | 氧产生用阳极 |
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US11668017B2 (en) | 2018-07-30 | 2023-06-06 | Water Star, Inc. | Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS59200781A (ja) * | 1983-02-01 | 1984-11-14 | Ishifuku Kinzoku Kogyo Kk | 電解用電極 |
JPH02285098A (ja) * | 1989-04-27 | 1990-11-22 | Japan Carlit Co Ltd:The | クロムメッキ用電極の保護方法 |
JPH05230682A (ja) | 1992-02-25 | 1993-09-07 | Permelec Electrode Ltd | 電解用電極 |
JPH10287998A (ja) | 1997-04-17 | 1998-10-27 | Daiso Co Ltd | 不溶性陽極 |
JPH11302892A (ja) | 1998-04-24 | 1999-11-02 | Tdk Corp | 電解用電極およびその製造方法 |
JP2002275697A (ja) | 2001-03-15 | 2002-09-25 | Daiso Co Ltd | 酸素発生用陽極 |
JP2004238697A (ja) * | 2003-02-07 | 2004-08-26 | Daiso Co Ltd | 酸素発生用電極 |
JP2006188742A (ja) | 2005-01-07 | 2006-07-20 | Daiso Co Ltd | 不溶性陽極 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0310099A (ja) * | 1989-06-07 | 1991-01-17 | Permelec Electrode Ltd | 電気メッキ用不溶性電極とその製造方法 |
-
2010
- 2010-04-28 EP EP10772160A patent/EP2428595A1/en not_active Withdrawn
- 2010-04-28 WO PCT/JP2010/057562 patent/WO2010128641A1/ja active Application Filing
- 2010-04-28 JP JP2011512344A patent/JPWO2010128641A1/ja active Pending
- 2010-04-28 CN CN2010800114534A patent/CN102348837A/zh active Pending
- 2010-04-28 US US13/319,115 patent/US20120091007A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59200781A (ja) * | 1983-02-01 | 1984-11-14 | Ishifuku Kinzoku Kogyo Kk | 電解用電極 |
JPH02285098A (ja) * | 1989-04-27 | 1990-11-22 | Japan Carlit Co Ltd:The | クロムメッキ用電極の保護方法 |
JPH05230682A (ja) | 1992-02-25 | 1993-09-07 | Permelec Electrode Ltd | 電解用電極 |
JPH10287998A (ja) | 1997-04-17 | 1998-10-27 | Daiso Co Ltd | 不溶性陽極 |
JPH11302892A (ja) | 1998-04-24 | 1999-11-02 | Tdk Corp | 電解用電極およびその製造方法 |
JP2002275697A (ja) | 2001-03-15 | 2002-09-25 | Daiso Co Ltd | 酸素発生用陽極 |
JP2004238697A (ja) * | 2003-02-07 | 2004-08-26 | Daiso Co Ltd | 酸素発生用電極 |
JP2006188742A (ja) | 2005-01-07 | 2006-07-20 | Daiso Co Ltd | 不溶性陽極 |
Also Published As
Publication number | Publication date |
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US20120091007A1 (en) | 2012-04-19 |
CN102348837A (zh) | 2012-02-08 |
JPWO2010128641A1 (ja) | 2012-11-01 |
EP2428595A1 (en) | 2012-03-14 |
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