JPH0660427B2 - Oxygen generating electrode and method for manufacturing the same - Google Patents
Oxygen generating electrode and method for manufacturing the sameInfo
- Publication number
- JPH0660427B2 JPH0660427B2 JP63131374A JP13137488A JPH0660427B2 JP H0660427 B2 JPH0660427 B2 JP H0660427B2 JP 63131374 A JP63131374 A JP 63131374A JP 13137488 A JP13137488 A JP 13137488A JP H0660427 B2 JPH0660427 B2 JP H0660427B2
- Authority
- JP
- Japan
- Prior art keywords
- iridium
- tantalum
- oxide
- mol
- platinum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、新規な酸素発生用電極及びその製造方法に関
するものである。さらに、詳しくいえば、本発明は、所
望の水溶液を電解して、陽極で酸素を発生させる反応に
好適に用いられる、優れた耐久性及び低い酸素過電圧を
有する酸素発生用電極及びこれを製造するための方法に
関するものである。TECHNICAL FIELD The present invention relates to a novel oxygen generating electrode and a method for producing the same. More specifically, the present invention produces an oxygen generating electrode having excellent durability and a low oxygen overvoltage, which is preferably used for a reaction in which a desired aqueous solution is electrolyzed to generate oxygen at an anode. It is about the method for.
従来の技術 従来、金属チタンを導電性基体とし、その上に白金族金
属やその酸化物の被覆層を設けた金属電極は、種々の電
解工業の分野において使用されている。2. Description of the Related Art Conventionally, a metal electrode in which metallic titanium is used as a conductive substrate and a coating layer of a platinum group metal or its oxide is provided thereon has been used in various fields of the electrolytic industry.
例えば、チタン基板上に、ルテニウムとチタンの酸化物
や、ルテニウムとスズの酸化物の被覆を施した電極が食
塩電解による塩素発生用陽極として知られている(特公
昭46−21844号公報、特公昭48−3954号公報、特公昭50
−11330号公報)。For example, an electrode obtained by coating a ruthenium-titanium oxide or a ruthenium-tin oxide on a titanium substrate is known as an anode for chlorine generation by salt electrolysis (Japanese Patent Publication No. 46-21844, Japanese Patent Publication No. Japanese Patent Publication No. 48-3954, Japanese Patent Publication No. 50
-11330 publication).
ところで、電解工業においては、前記の食塩電解の場合
のように塩素発生を伴う電解のほかに、酸、アルカリ又
は塩の回収、銅、亜鉛などの金属の採取、めっき、陰極
防食など酸素発生を伴う場合がある。By the way, in the electrolysis industry, in addition to electrolysis accompanied by chlorine generation as in the case of the above-mentioned salt electrolysis, recovery of acid, alkali or salt, collection of metals such as copper and zinc, plating, and oxygen generation such as cathodic protection. May be accompanied.
そして、このような酸素発生を伴う電解に、塩素発生用
として慣用されている電極、例えば前記したチタン基板
上に、ルテニウムとチタンの酸化物やルテニウムとスズ
の酸化物の被覆を施した電極を用いると、短期間で腐食
し、電解が不能になるため、特に酸素発生用として構成
された電極が用いられている。このような電極として
は、酸化イリジウム−白金系電極、酸化イリジウム−酸
化スズ系電極、白金めっきチタン電極などが知られてい
るが、最も一般的に使用されているのは鉛系電極や可溶
性亜鉛陽極である。Then, in the electrolysis involving the generation of oxygen, an electrode that is commonly used for generating chlorine, for example, the above-described titanium substrate, an electrode that is coated with an oxide of ruthenium and titanium or an oxide of ruthenium and tin is used. If it is used, it corrodes in a short period of time and electrolysis becomes impossible. Therefore, an electrode configured especially for oxygen generation is used. As such electrodes, iridium oxide-platinum-based electrodes, iridium oxide-tin oxide-based electrodes, platinum-plated titanium electrodes, etc. are known, but the most commonly used are lead-based electrodes and soluble zinc. It is an anode.
しかしながら、これらの公知の電極は、その使用目的に
よっては種々のトラブルを生じ、必ずしも適当なものと
はいえない。例えば亜鉛めっき用の陽極として可溶性亜
鉛陽極を用いると、陽極の溶解が著しいので、極間距離
の調節を頻繁に行わなければならないし、また鉛系の不
溶性陽極を用いると、電解液中に混入した鉛の影響によ
りめっき不良を生じる。また、白金めっきチタン電極
は、１００Ａ/dm2以上の高電流密度で、いわゆる高速亜
鉛めっきを行う場合には、消耗が激しく使用することが
できない。However, these known electrodes are not always suitable because they cause various troubles depending on the purpose of use. For example, if a soluble zinc anode is used as the zinc plating anode, the anode will be significantly dissolved, so the distance between the electrodes must be adjusted frequently, and if a lead-based insoluble anode is used, it will be mixed in the electrolyte. Plating failure occurs due to the effect of lead. In addition, the platinum-plated titanium electrode has a high current density of 100 A / dm 2 or more, and is highly consumed and cannot be used when so-called high-speed zinc plating is performed.
したがって、酸素発生を伴う電解用として、なんら障害
を伴わずに、広い分野に普遍的に適用できる電極の開発
が、電極製造技術における重要な課題の１つになってい
る。Therefore, the development of an electrode that can be universally applied to a wide field without any trouble for electrolysis involving oxygen generation has become one of the important issues in the electrode manufacturing technology.
他方、一般に被覆層を有するチタン基板電極を陽極と
し、酸素発生を伴う電解を行うと、基板と被覆層との間
に酸化チタン層を生じ、次第に陽極電位が高くなり遂に
は被覆層が剥離して陽極が不働態化することがしばしば
みられ、このような中間に形成される酸化チタンを抑制
し、陽極の不働態化を防止するために、適当な中間層を
設けることが行われている(特公昭60−21232号公報、特
開昭60−22074号公報、特開昭57−116786号公報、特開
昭60−184690号公報)。On the other hand, in general, when a titanium substrate electrode having a coating layer is used as an anode and electrolysis involving oxygen generation is performed, a titanium oxide layer is formed between the substrate and the coating layer, the anode potential gradually increases, and the coating layer eventually peels off. It is often observed that the anode becomes passivated, and in order to suppress the titanium oxide formed in the middle and prevent the passivation of the anode, an appropriate intermediate layer is provided. (JP-B-60-21232, JP-A-60-22074, JP-A-57-116786, JP-A-60-184690).
しかしながら、このようにして設けられた中間層は、一
般に被覆層よりも導電性が低いため、高電流密度で電解
を行う場合には、期待するほどの効果が得られないのが
実状である。また、卑金属酸化物に金属を分散させた中
間層を設けること(特開昭60−184691号公報)や、バルブ
金属酸化物と貴金属から成る中間層を設けること(特開
昭57−73193号公報)も提案されているが、白金はそれ自
体耐食性が低いため、中間層としての効果が不十分であ
るし、またバルブ金属酸化物を混合する場合には、その
種類や配合量におのずから制約があり、所期の効果を奏
することが困難である。However, since the intermediate layer thus provided generally has lower conductivity than the coating layer, it is the actual situation that the expected effect cannot be obtained when electrolysis is performed at a high current density. Further, providing an intermediate layer in which a metal is dispersed in a base metal oxide (JP-A-60-184691) or providing an intermediate layer composed of a valve metal oxide and a noble metal (JP-A-57-73193). ) Has been proposed, platinum itself has a low corrosion resistance, so the effect as an intermediate layer is insufficient, and when mixing valve metal oxides, there are naturally restrictions on the type and blending amount. Yes, it is difficult to achieve the intended effect.
そのほか、導電性金属基体の上に酸化イリジウムと酸化
タンタルを含む中間層を介して二酸化鉛被覆を施した電
極も知られているが（特開昭56−123388号公報、特開昭
56−123389号公報）、この中間層は単に金属基体と二酸
化鉛被覆との間の密着性を改善し、ピンホールなどに起
因する腐食を防止する効果があるだけで、これを酸素発
生を伴う電解に用いた場合、酸化チタンの生成抑制の効
果が不十分な上に、電解液中に鉛が混入するのを避けら
れないという欠点がある。In addition, there is also known an electrode in which a lead dioxide coating is formed on a conductive metal substrate through an intermediate layer containing iridium oxide and tantalum oxide (JP-A-56-123388, JP-A-56-123388).
56-123389), this intermediate layer merely has the effect of improving the adhesion between the metal substrate and the lead dioxide coating and preventing corrosion due to pinholes, etc. When it is used for electrolysis, it has a drawback that the effect of suppressing the production of titanium oxide is insufficient and that lead is inevitably mixed in the electrolytic solution.
発明が解決しようとする課題 本発明は、チタン基板上に酸化イリジウム被覆を有する
電極において、中間に酸化チタンが生成するのを効果的
に抑制し、酸素発生を伴う電解に用いた場合にも、長期
間にわたって、なんの支障もなく使用することができ、
しかも高電流密度での電解においても低い陽極電位を示
す電極を提供することを目的としてなされたものであ
る。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention, in an electrode having an iridium oxide coating on a titanium substrate, effectively suppresses the formation of titanium oxide in the middle, even when used for electrolysis involving oxygen generation, It can be used for a long time without any trouble,
Moreover, the purpose of the invention is to provide an electrode exhibiting a low anode potential even in electrolysis at high current density.
課題を解決するための手段 本発明者らは、優れた耐久性を有し、長期間にわたって
使用可能な酸素発生用電極を開発するために種々研究を
重ねた結果、チタンのような導電性基体上の酸化イリジ
ウムと酸化タンタル被覆層に、白金金属を特定割合添加
することにより電気抵抗を低下させうる上に、電極の消
耗劣化を抑制しうることを見出し、また、この白金金属
の添加された被覆層の上にさらに酸化イリジウム層又は
酸化イリジウム−酸化タンタル層を設けることにより電
気抵抗の増大を伴うことなく中間被覆層部における劣化
を抑制しうることを見出し、これらの知見に基づいて本
発明をなすに至った。Means for Solving the Problems The present inventors have conducted various studies to develop an oxygen generating electrode having excellent durability and usable for a long period of time, and as a result, a conductive substrate such as titanium has been obtained. It was found that by adding a specific proportion of platinum metal to the above iridium oxide and tantalum oxide coating layer, it is possible to reduce the electrical resistance and also to suppress the wear and deterioration of the electrode, and this platinum metal was added. By further providing an iridium oxide layer or an iridium oxide-tantalum oxide layer on the coating layer, it was found that deterioration in the intermediate coating layer portion can be suppressed without increasing the electric resistance, and the present invention is based on these findings. Came to make.
すなわち、本発明は、導電性基体上にイリジウム４０〜
９０モル％、白金０．１〜３０モル％及びタンタル５０
〜１０モル％を含有する、酸化イリジウム、白金金属及
び酸化タンタルから成る層を設けたことを特徴とする酸
素発生用電極、及び導電性基体上にイリジウム４０〜９
０モル％、白金０．１〜３０モル％及びタンタル５０〜
１０モル％を含有する、酸化イリジウム、白金金属及び
酸化タンタルから成る下地層を介して、酸化イリジウム
層又は多くとも５０モル％のタンタルを含有する酸化イ
リジウム−酸化タンタル層を上地層として設けたことを
特徴とする酸素発生用電極を提供するものである。That is, the present invention relates to iridium 40-
90 mol%, platinum 0.1-30 mol% and tantalum 50
An electrode for oxygen generation, which is provided with a layer composed of iridium oxide, platinum metal and tantalum oxide containing 10 to 10 mol%, and iridium 40 to 9 on a conductive substrate.
0 mol%, platinum 0.1-30 mol% and tantalum 50-
An iridium oxide layer or an iridium oxide-tantalum oxide layer containing at most 50 mol% tantalum oxide was provided as an overlayer through an underlayer containing iridium oxide, platinum metal and tantalum oxide containing 10 mol%. An electrode for oxygen generation is provided.
この酸素発生用電極は、例えば導電性基体上に、イリジ
ウム化合物と白金化合物とタンタル化合物とを含有する
溶液を塗布したのち、酸化性雰囲気中に熱処理して、イ
リジウム４０〜９０モル％、白金０．１〜３０モル％及
びタンタル５０〜１０モル％を含有する、酸化イリジウ
ム、白金金属及び酸化タンタルから成る層を形成させる
か、あるいは導電性基体上に、まずイリジウム化合物と
白金化合物とタンタル化合物とを含有する溶液を塗布し
たのち、酸化性雰囲気中に熱処理して、イリジウム４０
〜９０モル％、白金０．１〜３０モル％及びタンタル５
０〜１０モル％を含有する、酸化イリジウム、白金金属
及び酸化タンタルから成る下地層を形成させ、次いで、
この上にイリジウム化合物又はイリジウム化合物及びタ
ンタル化合物を含有する溶液を塗布したのち、酸化性雰
囲気中で熱処理して、酸化イリジウム層又は多くとも５
０モル％のタンタルを含有する酸化イリジウム−酸化タ
ンタル層を形成させることによって、製造することがで
きる。This electrode for oxygen generation has, for example, a conductive substrate on which a solution containing an iridium compound, a platinum compound and a tantalum compound is applied, followed by heat treatment in an oxidizing atmosphere to obtain 40 to 90 mol% of iridium and 0% platinum. 1 to 30 mol% and 50 to 10 mol% of tantalum to form a layer composed of iridium oxide, platinum metal and tantalum oxide, or to form an iridium compound, a platinum compound and a tantalum compound on a conductive substrate. After applying a solution containing iridium, iridium 40 is heat-treated in an oxidizing atmosphere.
~ 90 mol%, platinum 0.1-30 mol% and tantalum 5
Forming an underlayer of iridium oxide, platinum metal and tantalum oxide containing 0 to 10 mol%;
An iridium compound or a solution containing an iridium compound and a tantalum compound is applied thereon, and then heat-treated in an oxidizing atmosphere to form an iridium oxide layer or at most 5
It can be produced by forming an iridium oxide-tantalum oxide layer containing 0 mol% tantalum.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明の電極に用いられる導電性基体としては、例えば
チタン、タンタル、ジルコニウム、ニオブなどのバルブ
金属又はこれらのバルブ金属の中から選ばれた２種以上
の金属の合金が挙げられる。Examples of the conductive substrate used for the electrode of the present invention include valve metals such as titanium, tantalum, zirconium, and niobium, or alloys of two or more metals selected from these valve metals.
本発明の電極においては、これらの導電性基体上に、酸
化イリジウム、白金金属及び酸化タンタルから成る層が
設けられており、この層のイリジウム、白金及びタンタ
ルの割合は、イリジウムが４０〜９０モル％、白金が
０．１〜３０モル％及びタンタルが５０〜１０モル％の
範囲にあることが必要である。この範囲内においては、
酸化イリジウムの割合が少ない方が良好な結果が得られ
るが、白金が多すぎると白金の酸素過電圧の特性に近づ
き、過電圧特性が高くなるし、酸化タンタルが多すぎる
と被覆の電気抵抗が増大し、過電圧の増加を招き、十分
な効果が発揮されない。また、上層に酸化イリジウム−
酸化タンタル層を設けることにより、電極の消耗度の減
少がみられ、寿命が延びるが、下地層に白金ならびに酸
化タンタルが多すぎると過電圧の増加を招き、上地層と
の密着強度が低下する。さらに上地層のタンタルが50モ
ル％以上の酸化イリジウム−酸化タンタル層では酸化タ
ンタルが増加するため電気抵抗が増大し、過電圧が上昇
して電極寿命が短くなり、十分な効果が発揮されない。
所期の効果を十分達成するには、該被覆層において酸化
イリジウムをイリジウム換算で０．１mg／cm2以上の割
合で施すのが好ましい。In the electrode of the present invention, a layer composed of iridium oxide, platinum metal and tantalum oxide is provided on these conductive substrates, and the ratio of iridium, platinum and tantalum in this layer is 40 to 90 mol of iridium. %, Platinum 0.1 to 30 mol%, and tantalum 50 to 10 mol%. Within this range,
The smaller the proportion of iridium oxide, the better the results obtained.However, if the amount of platinum is too large, it approaches the oxygen overvoltage characteristic of platinum, and the overvoltage characteristic becomes high.If the amount of tantalum oxide is too large, the electrical resistance of the coating increases. However, it causes an increase in overvoltage and the sufficient effect is not exhibited. In addition, iridium oxide-
By providing the tantalum oxide layer, the degree of wear of the electrode is reduced and the life is extended, but if the base layer contains too much platinum and tantalum oxide, the overvoltage is increased and the adhesion strength with the upper layer is lowered. Further, in the iridium oxide-tantalum oxide layer in which the tantalum of the upper ground layer is 50 mol% or more, the tantalum oxide increases, so that the electric resistance increases, the overvoltage increases, the electrode life shortens, and the sufficient effect cannot be exhibited.
In order to achieve the desired effect sufficiently, it is preferable to apply iridium oxide in the coating layer at a rate of 0.1 mg / cm 2 or more in terms of iridium.
また、該被覆層を下地層として酸化イリジウム層又は酸
化イリジウム−酸化タンタル層から成る上地層が設けら
れるが、この被覆層はイリジウム換算で０．０２〜５mg
／cm2の割合で施すのが好ましい。この被覆層がイリジ
ウム換算で０．０２mg／cm2未満では電解時の電極消耗
量が多く、耐久性が低下するし、また５mg／cm2を越え
ると密着強度が低下する。Further, an upper layer composed of an iridium oxide layer or an iridium oxide-tantalum oxide layer is provided with the coating layer as a base layer, and the coating layer is 0.02 to 5 mg in terms of iridium.
It is preferably applied at a ratio of / cm 2 . If this coating layer is less than 0.02 mg / cm 2 in terms of iridium, the amount of electrode consumption during electrolysis is large and the durability is reduced, and if it exceeds 5 mg / cm 2 , the adhesion strength is reduced.
次に、この酸素発生用電極を製造するための好適な実施
態様を説明すると、導電性基体上に、イリジウム化合
物、白金化合物及びタンタル化合物を含有する溶液を塗
布したのち、酸化雰囲気中で熱処理して、イリジウム４
０〜９０モル％、白金０．１〜３０モル％及びタンタル
５０〜１０モル％を含有する、酸化イリジウム、白金金
属及び酸化タンタルから成る被覆層を設ける。この際使
用する塗布液は、熱分解によって酸化イリジウムになる
化合物、例えば塩化イリジウム酸(H2IrCl6・６H2O)、塩
化イリジウムなどのイリジウム化合物と、熱分解によっ
て白金金属になる化合物、例えば塩化白金酸(H2PtCl6・
６H2O)、塩化白金などの白金化合物と、熱分解によって
酸化タンタルになる化合物、例えば塩化タンタルのよう
なハロゲン化タンタルやエトキシタンタルのようなタン
タルアルコキシドなどのタンタル化合物とを、所定の割
合で適当な溶媒に溶解することによって調製することが
できる。Next, a description will be given of a preferred embodiment for producing this oxygen generating electrode. A conductive substrate is coated with a solution containing an iridium compound, a platinum compound and a tantalum compound, and then heat-treated in an oxidizing atmosphere. Iridium 4
A coating layer comprising iridium oxide, platinum metal and tantalum oxide containing 0 to 90 mol%, 0.1 to 30 mol% platinum and 50 to 10 mol% tantalum is provided. The coating liquid used at this time is a compound that becomes iridium oxide by thermal decomposition, for example, an iridium compound such as iridium chloride (H 2 IrCl 6 · 6H 2 O) or iridium chloride, and a compound that becomes platinum metal by thermal decomposition, such as Chloroplatinic acid (H 2 PtCl 6
6H 2 O), a platinum compound such as platinum chloride, and a compound that becomes tantalum oxide by thermal decomposition, for example, a tantalum halide such as tantalum chloride or a tantalum compound such as tantalum alkoxide such as ethoxy tantalum, in a predetermined ratio. It can be prepared by dissolving in a suitable solvent.
また、酸化性雰囲気中での熱処理は、前記塗布液を導電
性基体上に塗布し、乾燥したのち、酸素の存在下に、好
ましくは４００〜５５０℃の範囲の温度において焼成す
ることによって行われる。この操作は必要な担持量にな
るまで複数回繰り返され、本発明の電極が得られる。The heat treatment in an oxidizing atmosphere is carried out by applying the coating solution on a conductive substrate, drying, and then firing in the presence of oxygen, preferably at a temperature in the range of 400 to 550 ° C. . This operation is repeated a plurality of times until the required loading amount is obtained, and the electrode of the present invention is obtained.
また、上記のように作成された酸化イリジウム、白金金
属及び酸化タンタルから成る被覆層を所望の担持量とし
た下地層の上に、さらに熱分解によって酸化イリジウム
になる化合物、例えば塩化イリジウム酸などのイリジウ
ム化合物、又は熱分解によって酸化イリジウムになるイ
リジウム化合物と熱分解によって酸化タンタルになる化
合物、例えば塩化タンタル、タンタルアルコキシドなど
のタンタル化合物とを、所定の割合で適当な溶媒に溶解
することによって調製した塗布液を塗布したのち、酸化
性雰囲気中で熱処理することにより、所望の担持量の上
地層が施される。In addition, iridium oxide prepared as described above, a coating layer consisting of platinum metal and tantalum oxide on the underlying layer having a desired supporting amount, a compound which becomes iridium oxide by thermal decomposition, such as iridium chloride Prepared by dissolving an iridium compound, or an iridium compound that becomes iridium oxide by thermal decomposition and a compound that becomes tantalum oxide by thermal decomposition, for example, tantalum compound such as tantalum chloride or tantalum alkoxide, in a suitable solvent at a predetermined ratio. After applying the coating solution, a heat treatment is performed in an oxidizing atmosphere to apply a desired amount of the upper layer.
また酸化性雰囲気中での熱処理は、この塗布液を該下地
層の上に塗布し、乾燥したのち、酸素の存在下、好まし
くは４００〜５５０℃の範囲の温度において、焼成する
ことによって行われる。この操作は必要な担持量に達す
るまで複数回繰り返される。このようにして、該下地層
の上に所望の担持量を有する酸化イリジウム層又は酸化
イリジウム−酸化タンタル層が施され、本発明の電極が
得られる。下地層及び上地層を形成するための熱処理を
酸化性雰囲気中で行わない場合には、酸化が不十分にな
り、金属が遊離状態で存在するので得られる電極の耐久
性が低下する。The heat treatment in an oxidizing atmosphere is carried out by applying the coating solution on the underlayer, drying it, and baking it in the presence of oxygen, preferably at a temperature in the range of 400 to 550 ° C. . This operation is repeated multiple times until the required loading amount is reached. In this way, the iridium oxide layer or the iridium oxide-tantalum oxide layer having a desired loading amount is applied on the underlayer, and the electrode of the present invention is obtained. If the heat treatment for forming the underlayer and the overlayer is not performed in an oxidizing atmosphere, the oxidation is insufficient and the metal is present in a free state, so that the durability of the obtained electrode is reduced.
発明の効果 本発明の電極は、酸素発生を伴う電解において陽極とし
て使用する場合、低い槽電圧で長期間の使用に耐える
上、100Ａ／dm2以上の高電流密度で電解を行っても、耐
久性に優れ、長期間の使用が可能である。Effect of the Invention When the electrode of the present invention is used as an anode in electrolysis involving oxygen generation, it withstands long-term use at a low cell voltage and is durable even when electrolysis is performed at a high current density of 100 A / dm 2 or more. It has excellent properties and can be used for a long time.
このように、本発明の電極は、酸素発生用電極として、
好適である。Thus, the electrode of the present invention, as an oxygen generating electrode,
It is suitable.
実施例 次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によってなんら限定されるものではな
い。Examples Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例１〜７、比較例１〜５ 所定の塩化イリジウム酸(H2IrCl6・６H2O)、塩化白金酸
(H2PtCl6・６H2O)およびタンタルエトキシド(Ta(OC2H5)
5)をブタノールに溶解して、イリジウム／白金／タンタ
ルの組成比を変化させた金属換算濃度８０ｇ／の下地
用塗布液を調整した。Examples 1 to 7, Comparative Examples 1 to 5 Predetermined iridium chlorochloride (H 2 IrCl 6 · 6H 2 O), chloroplatinic acid
(H 2 PtCl 6・ 6H 2 O) and tantalum ethoxide (Ta (OC 2 H 5 ))
5 ) was dissolved in butanol to prepare an undercoating coating solution having a metal-equivalent concentration of 80 g / in which the composition ratio of iridium / platinum / tantalum was changed.
別に、熱シュウ酸でエッチングしたチタン基体上に、前
記下地用塗布液を刷毛で塗布し、乾燥した後、電気炉に
入れて空気を吹き込みながら500 ℃で焼付けた。この塗
布、乾燥、焼付けの操作を適当な回数所定の担持量にな
るまで繰返して、酸化イリジウムと白金金属と酸化タン
タルの被覆層の電極試料を作成した。Separately, the above-mentioned base coating liquid was applied onto a titanium substrate etched with hot oxalic acid with a brush, dried, and then placed in an electric furnace and baked at 500 ° C. while blowing air. This coating, drying, and baking operations were repeated an appropriate number of times until the predetermined loading amount was reached to prepare an electrode sample of a coating layer of iridium oxide, platinum metal, and tantalum oxide.
次に、この作成した電極について、酸素過電圧を測定し
た。測定方法は電位走査法により、３０℃、１モル／
硫酸水溶液中で電流密度２０Ａ/dm2における値を求め
た。その結果を第１表に示す。Next, the oxygen overvoltage was measured about this produced electrode. The measuring method is a potential scanning method at 30 ° C., 1 mol /
The value at a current density of 20 A / dm 2 was obtained in a sulfuric acid aqueous solution. The results are shown in Table 1.
また、この電極について６０℃、１モル／硫酸水溶液
中で寿命試験を行った。陰極には白金を用い、電流密度
２００Ａ/dm2で、前記No.1〜No.１２の電極を陽極とし
て電解を行った。その結果を第１表に示した。Further, a life test was conducted on this electrode at 60 ° C. in a 1 mol / sulfuric acid aqueous solution. Platinum was used as the cathode, and electrolysis was performed at a current density of 200 A / dm 2 using the No. 1 to No. 12 electrodes as the anode. The results are shown in Table 1.
この結果から明らかなように、本発明の電極は低い酸素
過電圧を示し、著しく長い寿命を有する。As is apparent from these results, the electrode of the present invention exhibits low oxygen overvoltage and has a significantly long life.
なお、電極の寿命は○:2000時間以上、△:1000〜2000時
間、×：1000時間以下で表示してあり、電解可能時間を
示している。The electrode life is indicated by ◯: 2000 hours or more, Δ: 1000 to 2000 hours, and ×: 1000 hours or less, which indicates the electrolyzable time.
実施例８〜１３，比較例６〜８ 前記実施例又は比較例と同様に作成した酸化イリジウム
と白金金属と酸化タンタルの被覆層を下地層として設
け、この上に酸化イリジウム又は酸化イリジウムと酸化
タンタルの上層被覆用の塗布液を、金属換算濃度８０ｇ
／の濃度になるように、酸化イリジウム又は塩化イリ
ジウム酸とタンタルエトキシド(Ta(OC2H5)5)あるいはタ
ンタブトキシド(Ta(OC4H9)5)をブタノールに溶解するこ
とによって調整した。 Examples 8 to 13 and Comparative Examples 6 to 8 A coating layer of iridium oxide, platinum metal, and tantalum oxide prepared in the same manner as in the above Examples or Comparative Examples was provided as an underlayer, and iridium oxide or iridium oxide and tantalum oxide was formed on this layer. The coating solution for coating the upper layer of 80g
The concentration of / was adjusted by dissolving iridium oxide or iridium chloride and tantalum ethoxide (Ta (OC 2 H 5 ) 5 ) or tantabutoxide (Ta (OC 4 H 9 ) 5 ) in butanol. .
この塗布液を刷毛で、該下地層に塗布し、乾燥した後、
電気炉に入れて空気を吹き込みながら、５００℃で焼付
けた。この塗布、乾燥、焼付けの操作を繰り返して、下
地層の上に酸化イリジウム又は酸化イリジウムと酸化タ
ンタル上層を被覆した本発明の電極を作成した。After applying this coating liquid to the underlayer with a brush and drying,
It was put in an electric furnace and baked at 500 ° C. while blowing air. By repeating the coating, drying and baking operations, an electrode of the present invention was prepared in which the underlayer was covered with iridium oxide or an iridium oxide and tantalum oxide upper layer.
次に、この作成した電極について前記実施例又は比較例
と同様に酸素過電圧測定、寿命試験を行い、その結果を
第２表に示した。この結果から明らかなように本発明の
電極は低い酸化過電圧を示し、著しく長い寿命を有す
る。Next, the oxygen overvoltage measurement and the life test were performed on the thus-prepared electrodes in the same manner as in the above-mentioned Examples or Comparative Examples, and the results are shown in Table 2. As is clear from this result, the electrode of the present invention exhibits low oxidative overvoltage and has a remarkably long life.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−150091（ＪＰ，Ａ) 特開 昭56−123388（ＪＰ，Ａ) 特開 昭59−38394（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-59-150091 (JP, A) JP-A-56-123388 (JP, A) JP-A-59-38394 (JP, A)
Claims (4)
％、白金０．１〜３０モル％及びタンタル５０〜１０モ
ル％を含有する、酸化イリジウム、白金金属及び酸化タ
ンタルから成る層を設けたことを特徴とする酸素発生用
電極。1. A layer of iridium oxide, platinum metal and tantalum oxide containing 40 to 90 mol% of iridium, 0.1 to 30 mol% of platinum and 50 to 10 mol% of tantalum is provided on a conductive substrate. An electrode for oxygen generation characterized by the above.
％、白金０．１〜３０モル％及びタンタル５０〜１０モ
ル％を含有する、酸化イリジウム、白金金属及び酸化タ
ンタルから成る下地層を介して、酸化イリジウム層又は
多くとも５０モル％のタンタルを含有する酸化イリジウ
ム−酸化タンタル層を上地層として設けたことを特徴と
する酸素発生用電極。2. An underlayer comprising iridium oxide, platinum metal and tantalum oxide containing 40 to 90 mol% of iridium, 0.1 to 30 mol% of platinum and 50 to 10 mol% of tantalum on a conductive substrate. And an iridium oxide layer or an iridium oxide-tantalum oxide layer containing at most 50 mol% of tantalum as an upper layer, the oxygen generating electrode.
化合物とタンタル化合物とを含有する溶液を塗布後、酸
化性雰囲気中で熱処理して、イリジウム４０〜９０モル
％、白金０．１〜３０モル％及びタンタル５０〜１０モ
ル％を含有する、酸化イリジウム、白金金属及び酸化タ
ンタルから成る層を形成させることを特徴とする酸素発
生用電極の製造方法。3. A solution containing an iridium compound, a platinum compound and a tantalum compound is applied onto a conductive substrate and then heat-treated in an oxidizing atmosphere to give 40 to 90 mol% of iridium and 0.1 to 30 platinum. A method for producing an electrode for oxygen generation, which comprises forming a layer composed of iridium oxide, platinum metal and tantalum oxide containing 50% to 10% by mol of tantalum.
白金化合物とタンタル化合物とを含有する溶液を塗布
後、酸化性雰囲気中で熱処理して、イリジウム４０〜９
０モル％、白金０．１〜３０モル％及びタンタル５０〜
１０モル％を含有する、酸化イリジウム、白金金属及び
酸化タンタルから成る下地層を形成させ、次いで、この
上にイリジウム化合物又はイリジウム化合物及びタンタ
ル化合物を含有する溶液を塗布後酸化性雰囲気中で熱処
理して、酸化イリジウム層又は多くとも５０モル％のタ
ンタルを含有する酸化イリジウム−酸化タンタル層を形
成させることを特徴とする酸素発生用電極の製造方法。4. A conductive substrate is first coated with a solution containing an iridium compound, a platinum compound, and a tantalum compound, and then heat-treated in an oxidizing atmosphere to form iridium 40-9.
0 mol%, platinum 0.1-30 mol% and tantalum 50-
An underlayer made of iridium oxide, platinum metal and tantalum oxide containing 10 mol% is formed, and then an iridium compound or a solution containing an iridium compound and a tantalum compound is applied thereon and heat-treated in an oxidizing atmosphere. And an iridium oxide layer or an iridium oxide-tantalum oxide layer containing at most 50 mol% of tantalum is formed.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63131374A JPH0660427B2 (en) | 1988-05-31 | 1988-05-31 | Oxygen generating electrode and method for manufacturing the same |
| CA000577350A CA1335496C (en) | 1988-05-31 | 1988-09-14 | Oxygen-generating electrode and method for the preparation thereof |
| EP88308794A EP0344378B1 (en) | 1988-05-31 | 1988-09-22 | Oxygen-generating electrode and method for the preparation thereof |
| DE8888308794T DE3872228T2 (en) | 1988-05-31 | 1988-09-22 | ELECTRODE FOR THE DEVELOPMENT OF OXYGEN AND THEIR PRODUCTION PROCESS. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63131374A JPH0660427B2 (en) | 1988-05-31 | 1988-05-31 | Oxygen generating electrode and method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01301876A JPH01301876A (en) | 1989-12-06 |
| JPH0660427B2 true JPH0660427B2 (en) | 1994-08-10 |
Family
ID=15056447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63131374A Expired - Lifetime JPH0660427B2 (en) | 1988-05-31 | 1988-05-31 | Oxygen generating electrode and method for manufacturing the same |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0344378B1 (en) |
| JP (1) | JPH0660427B2 (en) |
| CA (1) | CA1335496C (en) |
| DE (1) | DE3872228T2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2713788B2 (en) * | 1989-12-22 | 1998-02-16 | ティーディーケイ株式会社 | Oxygen generating electrode and method for producing the same |
| JP3212327B2 (en) * | 1991-08-30 | 2001-09-25 | ペルメレック電極株式会社 | Electrode for electrolysis |
| JP3212334B2 (en) * | 1991-11-28 | 2001-09-25 | ペルメレック電極株式会社 | Electrode substrate for electrolysis, electrode for electrolysis, and methods for producing them |
| KR100196094B1 (en) * | 1992-03-11 | 1999-06-15 | 사토 히로시 | Oxygen generating electrode |
| US5503663A (en) * | 1994-11-30 | 1996-04-02 | The Dow Chemical Company | Sable coating solutions for coating valve metal anodes |
| US6217729B1 (en) * | 1999-04-08 | 2001-04-17 | United States Filter Corporation | Anode formulation and methods of manufacture |
| US6572758B2 (en) | 2001-02-06 | 2003-06-03 | United States Filter Corporation | Electrode coating and method of use and preparation thereof |
| JP5037133B2 (en) * | 2003-10-08 | 2012-09-26 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Electrode preparation method and electrode |
| JP4734664B1 (en) * | 2010-09-17 | 2011-07-27 | 田中貴金属工業株式会社 | Electrode for electrolysis, anode for electrolysis of ozone, anode for electrolysis of persulfate, and anode for chromium electrooxidation |
| CN116219470B (en) * | 2023-03-28 | 2024-04-02 | 广东卡沃罗氢科技有限公司 | Membrane electrode with double-layer anode coating and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123388A (en) * | 1980-02-29 | 1981-09-28 | Asahi Chem Ind Co Ltd | Lead dioxide electrode |
| JPS6021232B2 (en) * | 1981-05-19 | 1985-05-25 | ペルメレツク電極株式会社 | Durable electrolytic electrode and its manufacturing method |
| JPS6022074B2 (en) * | 1982-08-26 | 1985-05-30 | ペルメレツク電極株式会社 | Durable electrolytic electrode and its manufacturing method |
| JPS6022075B2 (en) * | 1983-01-31 | 1985-05-30 | ペルメレック電極株式会社 | Durable electrolytic electrode and its manufacturing method |
| DE3776187D1 (en) * | 1986-04-17 | 1992-03-05 | Eltech Systems Corp | ELECTRODE WITH PLATINUM METAL CATALYST IN THE SURFACE LAYER AND THEIR USE. |
| JPS63286198A (en) * | 1987-05-19 | 1988-11-22 | 松下電器産業株式会社 | Steam iron |
| JP2679282B2 (en) * | 1989-08-04 | 1997-11-19 | 松下電器産業株式会社 | Cordless steam iron |
| JPH03106339A (en) * | 1989-09-19 | 1991-05-02 | Hitachi Medical Corp | Magnetic resonance imaging device |
-
1988
- 1988-05-31 JP JP63131374A patent/JPH0660427B2/en not_active Expired - Lifetime
- 1988-09-14 CA CA000577350A patent/CA1335496C/en not_active Expired - Fee Related
- 1988-09-22 EP EP88308794A patent/EP0344378B1/en not_active Expired
- 1988-09-22 DE DE8888308794T patent/DE3872228T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3872228T2 (en) | 1992-12-03 |
| EP0344378B1 (en) | 1992-06-17 |
| DE3872228D1 (en) | 1992-07-23 |
| JPH01301876A (en) | 1989-12-06 |
| EP0344378A1 (en) | 1989-12-06 |
| CA1335496C (en) | 1995-05-09 |
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