JPH0631455B2 - Oxygen generating anode and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an insoluble anode used for an electrolysis step involving oxygen generation, particularly for electroplating of tin, zinc, chromium or the like.

[Problems to be solved with conventional technology]

Lead or lead alloy is currently used as an anode for electroplating continuous strip steel such as tin, zinc, chromium, etc. However, lead is relatively quickly consumed, and lead dissolves in the plating solution, resulting in contamination of the plating solution. There was a problem such as deterioration of the plating film. Platinum-plated anodes and platinum foil clad anodes have been studied as alternative anodes, but the platinum consumption is large and has not been solved yet. Therefore, various insoluble anodes with less consumption have been proposed.

For example, in JP-A-59-38394, at least one metal oxide selected from titanium and tin having a valence of 4 and tantalum and niobium having a valence of 5 are formed on a conductive metal substrate. An electrode has been proposed in which an intermediate coating layer made of a mixed oxide with at least one selected metal oxide is provided to impart conductivity, and an electrode active material is coated on the intermediate coating layer. This intermediate coating layer contains a mixture of tetravalent metal and pentavalent metal, and is considered to be an N-type semiconductor based on the generally known valence control principle, but it still has sufficient electric conductivity. Not obtained.

In Japanese Patent Publication No. 51-19429, an oxygen impermeable layer made of a platinum-iridium alloy or an oxide of cobalt, manganese, palladium, lead or platinum is provided on the intermediate layer between the conductive substrate and the electrode active material coating, and further on that. In addition, an electrode composed of a solid solution type outer coating having corrosion resistance to an electrolytic solution has been proposed. According to this, the catalyst of the intermediate layer is itself catalytically active for oxygen generation, and the solid solution type outer coating (a solid solution of ruthenium oxide and titanium oxide as judged from the examples) has more catalytic activity. is there. However, among the intermediate layers, cobalt, manganese, palladium, lead, and platinum oxides are relatively exhausted in a sulfuric acid acidic solution. Further, a solid solution of ruthenium oxide and titanium oxide also has poor durability in a sulfuric acid acidic solution, and is difficult to industrially use.

Further, JP-A-59-150091 discloses JP-A-59-38.
No. 394, an electrode in which platinum is dispersed in an intermediate coating layer is proposed. That is, since the carrier concentration of the semiconductor intermediate layer is limited, it imparts further conductivity, but platinum itself gradually dissolves during electrolysis in an electrolytic solution, especially a sulfuric acid acidic solution, and there is a limit for long-term use. is there.

JP-A-60-184691 discloses that an intermediate layer between a conductive metal substrate and an electrode active material is provided with an oxide of a metal selected from titanium and tin, aluminum, potassium, iron, cobalt,
An intermediate layer has been proposed in which platinum is dispersed in a mixed oxide with an oxide of at least one metal selected from nickel and thallium. This intermediate layer is composed of a tetravalent metal and a divalent or trivalent metal.
Platinum is dispersed in a mixed oxide with a valent metal, and this oxide becomes a P-type semiconductor based on the valence control principle, has good conductivity, and has a high electron conductivity due to the dispersed platinum. It was considered to add degrees.
However, platinum itself gradually dissolves in a sulfuric acid acidic electrolyte solution, and dissolution is accelerated during electrolysis, so a sufficient life cannot be expected.

In JP-A-62-174394, a porous platinum layer is provided on a conductive substrate by electroplating, and at least one oxide layer selected from ruthenium oxide, palladium oxide and iridium oxide by thermal decomposition is provided thereon. It is proposed that the platinum-plated layer and the oxide layer are repeatedly formed in the electrode provided with. In this case as well, the problem that the platinum porous layer gradually dissolves in the sulfuric acid acidic electrolyte during electrolysis has not been solved.

[Means for Solving the Problems]

In the insoluble anode used in the sulfuric acid acidic electrolyte, the present inventors impart corrosion resistance to the oxygen-impermeable intermediate layer and enhance conductivity, and impart oxygen generating catalytic activity to the surface layer to provide mechanical resistance to gas generation. We have developed a long-life electrode that can prevent damage.

That is, the present invention provides a mixed oxide of a) 85 to 95 mol% of at least one metal oxide selected from titanium, tantalum, tin, niobium and zirconium and 5 to 15 mol% of palladium oxide on a conductive metal substrate. An intermediate coating layer comprising b) titanium, tantalum,
At least 1 selected from tin, niobium, and zirconium
20-70 mol% of oxides of certain metals and 30-80 of iridium oxide
An oxygen-evolving anode and a method for producing the same are characterized in that a surface coating layer having an oxygen-evolving catalytic ability composed of a mixed oxide with mol% is formed.

The conductive substrate used in the present invention includes titanium, tantalum,
Materials that form a passive film such as niobium, zirconium and alloys thereof can be mentioned. Usually, titanium and / or its alloys are used in terms of economic efficiency, electromechanical properties, workability, and the like. The electrode may have various shapes such as a plate shape, a rod shape, an expanded shape, and a perforated plate shape.

The intermediate coating layer is a mixed oxide layer composed of 85 to 95 mol% of one or more oxides of titanium, tantalum, tin, niobium, and zirconium and 5 to 15 mol% of palladium oxide, and has a palladium oxide content of 5%. If it is less than the molar amount, the electric conductivity is small and the intermediate coating layer functions as a resistor to increase the voltage during electrolysis, which is not preferable. If it exceeds 15 mol%, the catalytic activity of oxygen generation is strongly exhibited and the oxygen impermeable function is impaired, so that the life of the electrode is shortened. This is because even if a surface coating layer is formed on the intermediate coating layer, a film without pinholes cannot be completely formed, so that the electrolytic solution can permeate and oxygen can be generated in the intermediate coating layer itself. This is because the permeation of the generated oxygen to the surface of the substrate occurs. Palladium oxide content 15
Oxygen overvoltage of the intermediate coating layer
Oxidation of one or more of titanium, tantalum, tin, niobium and zirconium without adding palladium oxide to the intermediate coating layer which can be 0.90 V (50 ° C., 10% H ₂ SO ₄ , 20 A / dm ² ) or more. When a physical layer film is formed, the life of the accelerated electrolysis test is rather shortened. Although the cause is not clear, in this case, even if the intermediate coating layer can sufficiently prevent oxygen permeation, the potential barrier between the substrate and the intermediate coating layer becomes high, and therefore the voltage rises quickly in the electrolytic life test. it is conceivable that.

The surface coating layer is a mixed oxide layer consisting of 20 to 70 mol% of one or more oxides of titanium, tantalum, tin, niobium, and zirconium and 30 to 80 mol% of iridium oxide. The catalytic ability of oxygen generation deteriorates, and when it exceeds 80 mol%, the adhesion of the film is impaired.

Oxygen overvoltage of the surface coating layer is 0.35-0.50V (50 ℃, 10% H
₂ SO ₄ , 20-100 A / dm ² ), and due to the low oxygen overvoltage, oxygen generation occurs only in the surface coating layer, and the intermediate coating layer acts only as an electric conductor.

The coating layer of the electrode of the present invention is shaped as follows.

The surface of the conductive metal substrate is subjected to etching by a method such as acid treatment or blast treatment to roughen the surface, and metal salts such as titanium chloride, tantalum chloride, stannous chloride, niobium chloride, zirconium oxychloride and palladium chloride are added. Dissolve in a solvent such as ethyl alcohol or butyl alcohol to make a mixed solution of a predetermined composition, and then apply by brush, roll, spray method,
Apply by a method such as a dipping method. After application, the coating is dried at 100 to 150 ° C for several tens of minutes to evaporate the solvent, and then subjected to thermal decomposition treatment at 300 to 700 ° C for 10 to 20 minutes in an electric furnace in an air or oxygen atmosphere. If the heat treatment temperature is less than 300 ° C, thermal decomposition does not completely occur, and if it exceeds 700 ° C, oxidation of the metal substrate proceeds and the substrate is damaged. In order to have the oxygen permeation preventive ability of the intermediate coating layer, the coating amount is preferably 3.0 g / m ² or more, and the effect is small when it is less than that.

The surface coating layer is prepared by dissolving a metal salt of iridium chloride and titanium chloride, butyl titanate, tantalum chloride, niobium chloride, zirconium oxychloride, stannous chloride or the like in a solvent such as ethyl alcohol or butyl alcohol to prepare a mixed solution having a predetermined composition. The coating is carried out in the same manner as the intermediate layer.
When the amount of catalyst in the coating layer is 10 g / m ² or more in terms of metal iridium, both the catalytic ability for oxygen generation and the life are good.

The present invention will be described in detail below with reference to examples. All compositional percentages in the examples are on a molar basis unless otherwise specified.

Example 1 Comparative Examples 1 and 2 Commercially available titanium plates (1 × 10 × 0.1 cm) were degreased with acetone and then etched in a 10 wt% hot oxalic acid solution to apply a solution having the following composition below the surface thereof.

TaC ₅ 2.0g Butyl titanate 3.9g PdC ₂ 0.5g Concentrated HC 1.0m n-Butyl alcohol 20m This is dried at 120 ° C for 20 minutes and then in an electric furnace at 500 ° C.
By firing for 10 minutes, Ta ₂ O ₅ 30%, TiO ₂ 60
%, PdO 10% mixed oxide film was obtained. This operation was repeated 4 times to obtain an intermediate coating layer of 3.0 g / m ² .
Next, a solution having the following composition was applied onto this intermediate coating layer.

_{TaC 5 0.47g H 2 IrC 6 ·} 6H 2 O 1.0g of concentrated HC 1.0 m n-butyl alcohol 15m which was dried at 120 ° C. 20 min, in an electric furnace of subsequent 500 ° C.
By firing for 10 minutes, Ta ₂ O ₅ 40%, IrO ₂ 60
% Of mixed oxide was obtained. This operation was repeated 10 times to obtain a surface coating layer of 10.0 g / m ² .

This electrode was used as an anode in 100g / sulfuric acid solution at 50 ° C, a platinum wire was used as the cathode, and the distance between the electrodes was about 4 cm and the current density was
An accelerated electrolysis test was performed at 0 A / dm ² . The initial voltage is 8V, and it gradually rises, but after 320 hours, it rapidly increases to about 10V.
Rose to. This time is the life of the electrode. On the other hand, as a comparison, an accelerated electrolysis test was conducted under the same conditions as above using an anode prepared in the same manner except that TaC ₅ was not added to the coating liquid for the surface coating layer, and an anode prepared in the same manner except that the intermediate coating layer was omitted. The electrode life was 110 hours and 35 hours, respectively.

Examples 2 to 4 Comparative Examples 3 and 4 The surface coating layer (10 times coating, 10.0 g / m ² ) of Example 1 was similarly adjusted to the composition ratio of the intermediate coating layer (4 times coating, 3.0 g / m ² ). An anode was produced in the same manner as in Example 1 except that the anode was changed as shown in Table 1. The results of an accelerated electrolysis test conducted under the same conditions as in Example 1 are also shown in Table 1.

As described above, the PdO content of the intermediate coating layer is 3%, 20%
In the case of 1, the life of the electrode was short and the effect of including the intermediate coating layer was not obtained.

Examples 5 to 8 Comparative Examples 5 and 6 The intermediate coating layer was the same as in Example 1 except that the composition ratio of the surface coating layer (10 coatings, 10.0 g / m ² ) was changed as shown in Table 2. An anode was prepared in the same manner as in 1. The results of an accelerated electrolysis test conducted under the same conditions as in Example 1 are also shown in Table 2.

As described above, the IrO ₂ content of the surface coating layer is preferably 30% or more, and when it is 90% or more, the life is shortened.

Examples 9 to 12 Comparative Examples 7 to 10 Intermediate coating layer (4 times coating, 3.0 g)
/ M ² ) and the surface coating layer (10 times coating, 10.0 g / m ² ) were changed as shown in Table 3 to prepare an anode, and an accelerated electrolysis test was conducted under the same conditions as in Example 1. went. The results are also shown in Table 3.

As described above, it can be seen that the electrode of the present invention provided with the intermediate coating layer containing PdO is superior in durability to the electrode provided with the intermediate coating layer containing no PdO.

〔The invention's effect〕

The anode of the present invention is provided with a mixed oxide layer of palladium oxide having oxygen permeation preventing ability and one or more kinds of oxides of titanium, tantalum, tin, zirconium and niobium as an intermediate coating layer, and as a surface coating layer against oxygen generation. Since a mixed oxide layer of iridium oxide that is catalytically active and hardly dissolved by electrolysis in a sulfuric acid solution and one or more kinds of oxides of the following titanium or lower metals is provided, durable oxygen generation is achieved. It is useful as an anode.

Claims (4)

[Claims] 1. A) on a conductive metal substrate, a) 85 to 95 mol% of an oxide of at least one metal selected from titanium, tantalum, tin, niobium and zirconium and palladium oxide 5.
To 15 mol% mixed oxide, and b) at least one metal oxide selected from titanium, tantalum, tin, niobium, and zirconium on the intermediate coating layer.
An oxygen generating anode comprising a surface coating layer having an oxygen generating catalytic ability formed of a mixed oxide of 20 to 70 mol% and iridium oxide of 30 to 80 mol%. 2. The anode according to claim 1, wherein the conductive metal substrate is a metal selected from titanium, tantalum, niobium, zirconium or an alloy thereof. 3. A conductive metal substrate is coated with a solution containing at least one metal salt selected from titanium, tantalum, tin, niobium and zirconium and a metal salt of palladium,
At least one metal oxide selected from titanium, tantalum, tin, and niobium by heat treatment in an oxidizing atmosphere 85
-95 mol% and 5-15 mol% of palladium oxide are mixed to form an intermediate coating layer, and at least one selected from titanium, tantalum, tin, niobium, and zirconium is formed in the same manner as above. A method for producing an oxygen generating anode, which comprises forming a surface coating layer made of a mixed oxide of 20 to 70 mol% of metal oxide and 30 to 80 mol% of iridium oxide. 4. The heat treatment temperature in an oxidizing atmosphere is 300 to 7
The method according to claim 3, wherein the method is 00 ° C.