JP2019023349A - Manufacturing method of electrode for water electrolyte - Google Patents

Abstract

To provide an industrially advantageous manufacturing method of an alloy electrode that has high activity for a generation of oxygen when it is used for an electrolysis system of alkaline aqueous solution.SOLUTION: The method includes forming an alloy composed of the composition of Fe-Ni-(Co)-C on an appropriate electrode substrate in an electrodeposition, while maintaining a constant current with an electric current density of 100-300 A/m, using plating solution prepared into pH 2 or lower by adding acids, containing aminocarboxylic acid and boric acid as well as iron soluble salt, nickel soluble salt, and, if necessary, cobalt soluble salt.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing, by electrodeposition, a cathode and an anode used for electrolysis of an alkaline aqueous solution to generate hydrogen and oxygen.

  In order to use renewable energy, technologies such as solar power generation and wind power generation are being developed, but the problem with the power derived from these renewable energy is that the amount of generated power fluctuates every moment. Or to be intermittent. As one measure for coping with this problem, it has been studied that water is electrolyzed using the electric power, in particular, electrolysis of an alkaline aqueous solution to produce hydrogen, which is used as an energy source. In order to efficiently perform electrolysis, a cathode and an anode in which electrolysis of an aqueous solution proceeds with low power consumption is required, and a technique for manufacturing such an electrode is being developed.

  One of the inventors, together with other co-inventors, invented a highly active and durable alloy electrode for hydrogen generation, and the electrodeposition is a simple and low cost electrode manufacturing technique. Invented a method that uses the law and disclosed it at an early stage (Patent Document 1). The alloy electrode for hydrogen generation contains iron: 2.9 to 45 atomic% and carbon: 0.6 to 10 atomic%, with the balance being 5 atomic% or more nickel and 0.1 atomic% or more cobalt. This is an electrode in which an alloy having an occupied composition is formed on the surface of an appropriate electrode base material as an electrode active material. In addition, the method for producing the alloy electrode for hydrogen generation includes an oxycarboxylic acid or an aminocarboxylic acid in addition to a soluble salt of iron, a soluble salt of cobalt and a soluble salt of nickel. Electrolysis is performed using a plating solution prepared as follows, and an Fe—Co—Ni—C alloy is deposited on an appropriate cathode base material.

  The inventors' group has advanced research on the alloy composition of the hydrogen generating alloy electrode, and recently, the electrode having an alloy composition in a region where the concentration of iron is higher than that of the alloy shown in Patent Document 1 is higher. It discovered that it showed activity and it disclosed separately (patent document 2). The alloy electrode for hydrogen generation contains iron: more than 45 atomic% and 65 atomic% or less and carbon: 0.6-10 atomic%, with the balance being 5 atomic% or more nickel and 0.1 atomic% or more cobalt. This is an electrode made of an alloy having a composition occupied by. In the same manner as the above-described alloy electrode manufacturing method, this electrode manufacturing method contains aminocarboxylic acid and boric acid in addition to iron soluble salt, cobalt soluble salt and nickel soluble salt. Electrolysis is performed using a plating solution whose pH is adjusted to 2 or less, and an Fe—Co—Ni—C alloy is deposited on an appropriate cathode substrate.

  The iron content in the alloy electrode of Patent Document 1 is 2.9 to 45 atomic%, but this upper limit is that when a large amount of Fe is added to the Ni—Co alloy, the crystal structure of the alloy is changed from the face-centered cubic crystal. It is determined from the fact that it changes to a body-centered cubic crystal and Fe is easily dissolved from the electrode when electrolysis is interrupted, and the durability of the electrode is impaired. However, this problem was not fatal until the iron content exceeded 65 atomic%, while the presence of iron exceeding 45 atomic% was confirmed to exhibit higher activity against hydrogen generation. It is.

  On the other hand, electrolysis requires an anode as well as a cathode. The present inventors have invented an anode that is highly active and excellent in durability when used for electrolysis of an aqueous solution, and established an advantageous production method thereof and previously disclosed (Patent Document 3). There are two types of oxygen generating anodes. The first one is an electrode active material of an alloy composition containing iron in an amount of 3 to 45 atom%, carbon in an amount of 0.6 to 10 atom%, and the balance being substantially nickel. Is formed on the surface of an appropriate electrode base material, and the second one is obtained by adding 30 atomic% or less of cobalt to this alloy composition. The manufacturing method includes a plating solution containing an aminocarboxylic acid and boric acid in addition to a soluble salt of nickel and a soluble salt of iron, and further containing a soluble salt of cobalt if necessary, and adding an acid to adjust the pH to 2 or less. Electrolysis is performed to deposit a Ni—Fe—C alloy on the electrode substrate.

Japanese Patent No. 4561149 Japanese Patent Application No. 2014-57227 Japanese Patent Application No. 2013-135650

  The electrodes for aqueous solution electrolysis disclosed in Patent Documents 1 to 3 contain either a predetermined metal salt or an aminocarboxylic acid as a carbon source, and add an additive and an acid. An electrode active material made of Fe—Co—Ni—C alloy or Ni—Fe—C alloy can be formed on a suitable electrode substrate by electrodeposition using an aqueous solution having a pH of 2 or less as a plating solution. This is a common operation.

  In such an electrode, it is desirable that the layer of the electrode active material is thick from the viewpoint of durability. However, since the formation of the thick layer reflects the manufacturing cost, an appropriate compromise is required. Another factor related to the manufacturing cost is the condition of the electrodeposition work. Needless to say, in order to form an electrode active material of a certain thickness on a substrate, it is necessary to energize a corresponding amount of electricity, but when energizing a certain amount of electricity, the current density is increased. If this is done, the time required for the production can be shortened. In view of these reasons, the inventors have sought appropriate conditions for electrodeposition during electrode production.

  In the process of determining appropriate conditions for manufacturing such an electrode, the inventors tried to perform electrodeposition at a high current density. Needless to say, if the current density is increased, electrodeposition can be completed in a short time, which is advantageous for the production of electrodes. In the process, we experienced that when the current density was excessively high, the alloy composition of the electrode varied depending on the position on the electrode. Mild non-uniformity does not affect the generation of hydrogen or oxygen, but excessive non-uniformity causes bias in the electrolysis current, which adversely affects electrode durability. The inventors conducted electrodeposition by changing the current density, and examined the influence of the current density on the composition of the electrode active material. As a result, we learned the fact that non-uniformity does not become a problem up to a certain limit, but excessive non-uniformity occurs when the limit is exceeded.

  The purpose of the present invention is to ensure the durability of the electrode in a method for producing an electrode used for electrolysis of an aqueous solution to generate oxygen and hydrogen by utilizing the knowledge obtained by the above-described inventors. An object of the present invention is to provide an industrially adoptable manufacturing method that realizes such a uniform composition of the electrode active material and does not lengthen the time required for electrodeposition, and therefore does not disadvantageize the manufacturing cost.

A first method for producing an electrode of the present invention that achieves the above object is a method for producing an electrode for generating hydrogen by electrolyzing an alkaline aqueous solution, which comprises a soluble salt of iron, a soluble salt of nickel, cobalt In addition to the soluble salt, a plating solution containing aminocarboxylic acid and boric acid, adjusted to pH 2 or less by adding acid, with a current density of 500 A / m ² or less and maintaining a constant current By performing the electrodeposition, iron: 2.9 to 65 atomic% and carbon: 0.6 to 10 atomic%, with the balance being nickel or 5 atomic% or more nickel and 0.1 atomic% or more cobalt. An alloy having a uniform composition is formed on an appropriate electrode substrate.

The second method for producing an electrode of the present invention is a method for producing an electrode for electrolyzing an alkaline aqueous solution to generate oxygen, and in addition to a soluble salt of nickel and a soluble salt of iron, an aminocarboxylic acid and boron. By using a plating solution containing an acid and adjusting the pH to 2 or less by adding an acid, by performing electrodeposition while maintaining a constant current at a current density of 500 A / m ² or less, iron: 3 to 3 An alloy having a uniform composition consisting of 45 atomic%, carbon: 0.6 to 10 atomic%, and the balance substantially consisting of nickel is formed on an appropriate electrode substrate.

The third method for producing an electrode according to the present invention is a method for producing an electrode for generating oxygen by electrolyzing an alkaline aqueous solution. The method comprises producing a soluble salt of nickel, a soluble salt of iron, and a soluble salt of cobalt. In addition, using a plating solution containing aminocarboxylic acid and boric acid and adjusting the pH to 2 or less by adding acid, electrodeposition is performed at a current density of 500 A / m ² or less and while maintaining a constant current. Thus, an alloy having a uniform composition consisting of iron: 3 to 45 atomic%, carbon: 0.6 to 10 atomic%, cobalt: 30 atomic% or less, and the balance substantially consisting of nickel is formed on an appropriate electrode substrate. Consisting of forming.

In actual electrode production, the current density within the above-mentioned limit, for example, 350 A / m ² or less, further 300 A / m ² is considered in consideration of the balance between the uniformity of the desired electrode alloy composition and the efficiency of electrode production. Of course, electrodeposition may be performed at the following current density. If the discussed lower limit of the current density, the industrial practice conditions, a value of greater than 50A / ^{m 2,} for example, a 100A / ^{m 2} or more is practical, 200A / ^{m 2} or more.

  By performing electrodeposition under the conditions according to the present invention, an electrode for aqueous solution electrolysis having an alloy electrode on the electrode substrate can be produced in a short industrially advantageous electrodeposition time, and on the surface of the electrode. It is possible to obtain an electrode having a uniform composition of the formed electrode active material and no variation depending on the position, and thus excellent durability.

Shown in the inset of the electrode surface when an electrode active material made of a Fe-Co-Ni-C alloy is formed on a nickel substrate having an area of 1 cm ² by electrodeposition of a certain amount of electricity at various current densities. It is a graph which shows the Fe density | concentration in an electrode active material measured in each position of the numbers 1-9. The horizontal axis of the graph is the measurement positions 1 to 9, the vertical axis is the Fe concentration, and the numerical value across the graph is the current density during electrodeposition. In the electrodeposition shown in FIG. 1, it is the graph which showed the thickness of the deposit which was computed from the mass of the deposit and the mass assuming that the deposit was all nickel. The current density is plotted on the horizontal axis, and the mass of the deposit and the calculated thickness are plotted on the vertical axis. The upper part of the graph shows the time required for electrodeposition.

The electrodeposition shown in FIG. 1 and FIG. 2 uses an aqueous solution having the following composition as a basic bath,
NiSO ₄ · 6H ₂ O 1.14 mol NiCl ₂ · 6H ₂ O 0.19 mol H ₃ BO ₃ 0.49 mol C ₁₂ H ₂₅ NaSO ₄ 0.104 mmol This also contains FeSO ₄ as an iron source and carbon source This was carried out using a plating bath prepared by adding lysine hydrochloride C ₆ H ₁₄ N ₂ O ₂ HCl, which is a long chain amino acid.

A nickel plate having an area (single side) of 1 cm ² was prepared as an electrodeposition substrate, and etching was performed by immersing in a 1: 1 mixture of concentrated sulfuric acid and concentrated hydrochloric acid for 30 seconds as a pretreatment. This electrodeposition substrate is arranged between two anodes provided at an interval of 10 cm so as to face the anode, and the current density is set to 50, 100, 150, 200, 250, 300, 350 or 500 A / m ² . The current and energization time are 180, 90, 60, 45, 36, 30, 25.7, 22.5, 20 or 18 minutes, and the amount of electrodeposition is 540 kC / m ² so that the amount is almost constant. Carried out. EPMA was used to analyze the metal component formed on the electrode surface, and the carbon content was analyzed by the combustion-infrared absorption method.

As shown in FIG. 1, the iron concentration in the electrode active material increases as the current density during electrodeposition increases. Therefore, the current density should be selected according to the alloy composition desired to be formed on the electrode substrate. Even when electrodeposition is performed with the same amount of electricity, the composition of the electrode active material varies not only with the iron concentration but also with the current density. On the other hand, the uniformity of the composition of the electrode active material examined using the iron concentration as a scale seemed to decrease as the current density was increased, but it can be regarded as almost uniform up to 300 A / m ² . There was a tendency for the composition variation to become remarkable up to 350 A / m ^2, and at a current density of 500 A / m ² , the variation of the iron concentration in the electrode alloy reached ± 20%. Although there is no problem in the performance of the electrode itself even with this degree of non-uniformity in the alloy composition, this current density was determined to be the upper limit from the viewpoint of durability. In view of obtaining high uniformity, it is preferably 300 A / m 2 or less as described above. Of course, the value of the current density to be selected should be determined taking into account the alloy composition desired to be formed on the electrode substrate.

As shown in the data of FIG. 2, even when electrodeposition of the same amount of electricity is performed, if the current density is high, the thickness of the electrode active material layer formed increases accordingly. For example, when electrodeposition is performed for 30 minutes at a current density of 300 A / m ² with high uniformity of composition, the thickness of the electrodeposit exceeds 6 μm. This thickness can be said to be sufficient from the viewpoint of durability required for a normal electrode. If the electrode active material has a thickness of 1 μm, when a plating bath having the above-described composition is used, electrodeposition can be performed at a current density of 300 A / m ² for 10 minutes and 180 kC / m ^2. It will be good.

Prepare an aqueous solution with the following composition:
NiSO ₄ · 6H ₂ O 1.14 mol NiCl ₂ · 6H ₂ O 0.19 mol CoSO ₄ · 7H ₂ O 0.01 mol FeSO ₄ · 7H ₂ O 0.108 mol H ₃ BO ₃ 0.49 mol C ₁₂ H ₂₅ NaSO ₄ 0.104 mmol C ₆ H ₁₄ N ₂ O ₂ HCl 0.4 mol sulfuric acid was added to adjust the pH to 1.5 to obtain a plating bath. This is for forming an electrode for hydrogen generation having the alloy composition of Patent Document 2 described above.

A nickel substrate was plated with a current density of 300 A / m ² for 10 minutes and an electric quantity of 180 kC / m ² to produce an electrode for hydrogen generation. The obtained electrode active material had a thickness of 1.8 μm, and the alloy composition was 48.0 atomic% Fe-42.3 atomic% Ni-2.8 atomic% Co-6.9 atomic% C. . Using this electrode, 30% by weight KOH aqueous solution at a temperature of 90 ° C. was electrolyzed, and the hydrogen generation performance was examined. The Tafel gradient was about 36 mV / decade, and the highest activity in the reaction mechanism was maintained up to a high current density, and it was confirmed that the hydrogen overvoltage was 0.104 V at a current density of 1,250 A / m ² . .

An aqueous solution containing a soluble salt and an organic substance having the following composition was prepared, and sulfuric acid was added to adjust the pH to 1.5 to obtain a plating bath. This is for forming an electrode for oxygen generation having the alloy composition of Patent Document 3 described above.
NiSO ₄ · 6H ₂ O 1.14 mol NiCl ₂ · 6H ₂ O 0.19 mol FeSO ₄ · 7H ₂ O 0.036 mol H ₃ BO ₃ 0.49 mol C ₁₂ H ₂₅ NaSO ₄ 0.104 mmol C ₆ H ₁₄ N ₂ O ₂ HCl 0.2 mol A nickel base was plated at an electric density of 540 kC / m ² for 18 minutes at a current density of 500 A / m ² to produce an oxygen generating electrode. The obtained electrode active material had a thickness of 8.2 μm, and the alloy composition was 70.3 atomic% Ni-29.7 atomic% Fe-6.1 atomic% C.

Using this electrode, electrolysis of a 30 wt% KOH aqueous solution at a temperature of 90 ° C. was performed, and the oxygen generation performance was examined. The Tafel gradient is about 36 mV / decade, and the highest activity in the reaction mechanism is maintained up to a high current density, and the oxygen overvoltage at a current density of 1,250 A / m ² is a highly active electrode of 0.134 V. It was.

Claims (3)

A method for producing an electrode for electrolyzing an alkaline aqueous solution to generate oxygen, comprising a soluble salt of nickel, a soluble salt of iron, an aminocarboxylic acid and boric acid, and adding an acid to a pH of 2 or less By using the prepared plating solution and carrying out electrodeposition while maintaining a constant current at a current density in the range of 100 to 300 A / m ² , iron: 3 to 45 atomic%, carbon: 0.6 to 10 A method for producing an electrode comprising forming an alloy having a composition consisting of atomic% and the balance substantially consisting of nickel on an appropriate electrode substrate. A method for producing an electrode for electrolyzing an alkaline aqueous solution to generate oxygen, comprising a soluble salt of nickel, a soluble salt of iron, a soluble salt of cobalt, an aminocarboxylic acid and boric acid, and adding an acid By using a plating solution whose pH is adjusted to 2 or less and performing electrodeposition while maintaining a constant current at a current density in the range of 100 to 300 A / m ² , iron: 3 to 45 atomic%, carbon: An electrode manufacturing method comprising forming an alloy having a composition of 0.6 to 10 atomic%, cobalt: 30 atomic% or less, and the balance being substantially nickel on an appropriate electrode substrate. The process according to claim 1 or 2 electrodes carried by performing range electrodeposition current density 200~300A / ^{m 2.}

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