JP2018016872A - Method for producing electrode for generating hydrogen, and electrolysis method using the electrode for generating hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an electrode for generating hydrogen, the electrode having excellent durability, wherein the method does not cause poisoning influence due to an iron ion, and does not cause elevation of hydrogen overvoltage and separation of a supporting material during operation, startup and suspension.SOLUTION: An electrode for generating hydrogen is configured by supporting a catalyst layer mainly comprising platinum, nickel, and palladium on a conductive base material. The method for producing the electrode for generating the hydrogen sequentially conducts: a first step of applying a liquid for forming a catalyst layer on a conductive base material, the liquid containing platinum, nickel and palladium, and drying and pyrolyzing the liquid to form the catalyst layer on the conductive base material; and a second step of conduct calcination at 300-500°C.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an electrode for hydrogen generation used for electrolysis of water or electrolysis of an aqueous solution of an alkali metal chloride such as salt, and an electrolysis method using the electrode for hydrogen generation.

  The water or alkali metal chloride aqueous solution electrolysis industry is a power-intensive industry, and various technological developments have been made to save energy. The energy saving means is to reduce power loss generated during electrolysis by reducing electrolysis voltage and / or improving current efficiency. For example, in the salt electrolysis industry, the current efficiency is operated at 95% or more, and there is little room for improvement. On the other hand, the electrolysis voltage is operated at around 3.0 V with respect to the theoretical decomposition voltage of about 2.3 V, and there is a lot of room for voltage reduction, and research and development for reducing the voltage are actively conducted.

  In particular, regarding the reduction of the overvoltage, since the overvoltage value depends on the electrode catalyst material and the morphology of the electrode surface, many researches and developments have been conducted on the improvement thereof. For example, as a result of vigorous research and development for reducing anode overvoltage for the ion exchange membrane salt electrolysis anode, a dimensional stability electrode with low anode overvoltage and excellent durability [eg Denora Permerek Co., Ltd. DSE chlorine-generating electrode (registered trademark)] made commercially available.

  On the other hand, many proposals have been made regarding an electrode for hydrogen generation for reducing cathode overvoltage, so-called active cathode. For example, Patent Document 1 states that “a material containing an organic compound such as an amino acid, a carboxylic acid, or an amine in addition to a combination of nickel, iron, cobalt, and indium is supported on the surface of a conductive substrate by electroplating”. An electrode for hydrogen generation has been proposed.

  As described in Patent Document 1 [0011], the hydrogen generating electrode disclosed in Patent Document 1 is “if the coating layer is too thin, sufficient low hydrogen overvoltage performance cannot be obtained, and if it is too thick, it tends to peel off. 20 μm to 300 μm is suitable ”.

  In recent years, a so-called “zero-gap ion exchange membrane electrolytic cell” in which an anode, an ion exchange membrane and a cathode are brought into close contact with each other has been put into practical use. 0.1 mm to 1.0 mm, the minor axis is 0.5 mm to 5.0 mm, the major axis is 1.0 mm to 10 mm, the plate thickness is 0.1 mm to 1.0 mm, and the aperture ratio is 48 to 48 mm. It has been proposed to use an electrode for hydrogen generation in which an electrode catalyst is supported on 60% expanded metal. When the electrocatalyst is supported on such an expanded metal (also referred to as “expanded mesh”) that is thin and has a small aperture, the coating layer is too thick at 20 μm to 300 μm. These effects may not be exhibited when used in a zero gap electrolytic cell.

In recent years, an electrode for hydrogen generation using a catalyst containing platinum has been proposed. The electrode for hydrogen generation using the catalyst containing platinum is, for example, as described in [0036] of Patent Document 3, “The weight of the catalyst layer is best at about 1 to 15 g / m ² and the optimum thickness. Is about 0.1 to 10 μm ”and can be preferably used in the zero-gap ion exchange membrane electrolytic cell described in Patent Document 2 as well, and research and development has been actively conducted.

  Among them, an electrode for hydrogen generation in which a catalyst layer mainly composed of platinum, nickel and palladium is supported on a conductive substrate is disclosed in, for example, “conventional platinum-based catalyst” as described in Patent Document 4 [0047]. The hydrogen overvoltage does not increase due to the poisoning of iron ions in the electrolyte, which has been regarded as a disadvantage of the above, and the catalyst may be peeled off or dropped due to the reverse current that flows during the electrolysis operation or stop / start operation. "No" excellent performance.

  The electrode for hydrogen generation in which the catalyst layer which has platinum, nickel, and palladium as a main component is carry | supported has a hydrogen overvoltage of 70-80 mV as described in Table 1 of patent document 4, for example. This can be positioned as sufficiently high performance as compared with the prior art, but from the viewpoint of environmental protection, a technology capable of further reducing hydrogen overvoltage is required.

Japanese Patent No. 3319370 Japanese Patent No. 5582002 Japanese Patent No. 5042389 JP2015-143389A

The object of the present invention is that it can be used in the water or alkali metal chloride aqueous solution electrolysis industry, etc., and is not affected by poisoning by iron ions. Platinum, nickel, and an electrode for hydrogen generation excellent in durability with no dropout, and further having a hydrogen overvoltage of less than 70 mV measured at 6 kA / m ² in a 32 wt% sodium hydroxide aqueous solution at 90 ° C. The object is to provide a method for producing an electrode for hydrogen generation in which a catalyst layer mainly composed of palladium is supported.

  In order to solve the above-mentioned problems, the inventor has conducted extensive studies on a method for producing an electrode for hydrogen generation in which a catalyst layer mainly composed of platinum, nickel, and palladium is supported. As a result, platinum, nickel, palladium A catalyst layer forming solution containing a catalyst is applied onto a conductive substrate, dried, thermally decomposed, and subjected to a first step of forming a catalyst layer on the conductive substrate, followed by baking at 300 to 500 ° C. By carrying out the process, it was found that a hydrogen generation electrode in which a catalyst layer mainly composed of platinum, nickel and palladium showing a hydrogen overvoltage of less than 70 mV was supported was obtained, and the present invention has been achieved. . That is, the present invention performs the first step of forming a catalyst layer on a conductive substrate by applying a catalyst layer forming liquid containing platinum, nickel and palladium on the conductive substrate, drying and pyrolyzing the solution. Thereafter, a second step of firing at 300 to 500 ° C. is performed. A hydrogen generating electrode comprising a conductive base material and a catalyst layer mainly composed of platinum, nickel, and palladium supported thereon. A production method and an electrolysis method using an electrode for hydrogen generation.

  Hereinafter, the present invention will be described in detail.

In the method for producing an electrode for hydrogen generation according to the present invention, a catalyst layer forming liquid containing platinum, nickel, and palladium is applied on a conductive substrate, dried, and thermally decomposed to form a catalyst layer on the conductive substrate. After performing the first step, it is essential to perform the second step of baking at 300 to 500 ° C.

  The catalyst layer forming liquid containing platinum, nickel, and palladium used in the method for producing an electrode for hydrogen generation of the present invention can be prepared by dissolving a platinum compound, a nickel compound, and a palladium compound in a solvent.

  Examples of the platinum compound used for preparing the catalyst layer forming liquid include platinum salts such as chloroplatinic acid and dinitrodiamine platinum. In particular, it is preferable to use dinitrodiammine platinum that forms an ammine complex because the crystallite diameter of the platinum alloy after the reduction treatment can be reduced to, for example, 200 angstroms or less to increase the reaction specific surface area. This is because the thermal decomposition temperature of the dinitrodiamine platinum is as high as about 550 ° C., so that aggregation of platinum during thermal decomposition is suppressed, and a film in which platinum, nickel and palladium are uniformly mixed after thermal decomposition is obtained. It is estimated that a fine crystallite-based alloy is obtained by the treatment.

  The nickel compound and palladium compound used for the preparation of the catalyst layer forming liquid are preferably a material that is soluble in a solvent because the composition of the catalyst layer tends to be uniform and the surface area of the support is easily increased. Nickel salt, nickel fine particles, palladium salt, palladium fine particles and the like. Examples of the salt in the nickel salt and the palladium salt include nitrates, sulfates, chlorides, carbonates, acetates, sulfamates, and the like.

  The solvent is preferably one in which a platinum compound, a nickel compound and a palladium compound can be completely dissolved, an inorganic acid such as water, nitric acid, hydrochloric acid, sulfuric acid and acetic acid solution, an organic solvent such as methanol, ethanol, propanol and butanol, or these. It can also be used as a mixture. In addition, the pH of the catalyst layer forming solution may be adjusted and used for the purpose of suppressing dissolution of the base metal in the coating solution, and complex salts such as lysine and citric acid may be added to increase the surface area of the support. Nickel and palladium may be complexed.

  The composition (ratio of platinum, nickel and palladium) of the catalyst layer formed by the method for producing the electrode for hydrogen generation of the present invention is determined by the composition of the catalyst layer forming solution. What is necessary is just to adjust palladium to the same composition as the catalyst layer of the electrode for hydrogen generation desired. Moreover, the metal component concentration of the catalyst layer forming liquid is not particularly limited. For example, if the platinum concentration is 40 to 80 g / L and nickel and palladium are in a desired ratio with respect to platinum. Good.

  In order to express high performance as an electrode for hydrogen generation, it is desirable that platinum, nickel and palladium be appropriately dispersed at the atomic level in the catalyst layer mainly composed of platinum, nickel and palladium. In particular, palladium has a high affinity for platinum and nickel, and therefore plays an important role in appropriately dispersing these three components.

  In order to obtain an appropriate dispersion state, the palladium content in the catalyst layer forming liquid is preferably 1 to 55 mol%.

  Further, in order to obtain a more appropriate dispersed state, it is preferable that the palladium content in the catalyst layer forming liquid is 4 to 48 mol%, the nickel content is 48 to 4 mol%, and the balance is platinum.

  Next, the conductive substrate used in the present invention will be described. Examples of the material of the conductive substrate used include nickel, iron, copper, titanium, and stainless steel alloy, and nickel having excellent corrosion resistance against an alkaline solution is particularly preferable.

  The shape of the conductive substrate is not particularly limited, and may generally be a shape that matches the electrode of the electrolytic cell. For example, a flat plate, a curved plate, or the like can be used.

  In addition, the conductive substrate used is preferably a perforated plate, and for example, expanded metal, punching metal, nets, and the like can be used.

  The conductive substrate is preferably roughened in advance. This is because the contact surface area can be increased by roughening, and the adhesion between the substrate and the support is improved. The surface roughening means is not particularly limited, and a known method such as sand blasting, etching with oxalic acid or hydrochloric acid solution, washing with water, drying and the like can be used.

  In the first step of the present invention, the catalyst layer forming solution is applied on the conductive substrate, dried, and subjected to a series of operations for thermal decomposition to form a catalyst layer on the conductive substrate.

  The method for applying the catalyst layer forming liquid to the conductive base material is, for example, by applying a catalyst layer forming liquid containing a platinum salt, a nickel salt, and a palladium salt to the conductive base material using a brush or the like. Also good. In addition to brush coating, all known methods such as a spray method and a dip coating method can be suitably used.

  What is necessary is just to perform the drying temperature after application | coating at the temperature of 200 degrees C or less for 5 to 60 minutes, for example, and the drying temperature of 150 degrees C or less is preferable.

  The thermal decomposition temperature after drying may be performed for 5 to 60 minutes in the range of over 200 ° C. and 700 ° C. or less, but preferably over 350 ° C. and 500 ° C. or less. For example, when a dinitrodiamine platinum solution is used, the thermal decomposition temperature of dinitrodiamine platinum is 550 ° C., and by performing thermal decomposition at 500 ° C. or less, platinum sintering is suppressed and hydrogen overvoltage is further reduced. A working electrode can be obtained.

In the present invention, the coating amount and the number of coatings of the catalyst layer forming liquid are not particularly limited. For example, the coating is performed by controlling the coating amount to 13 to 31 mL / m ² per projected area of the conductive substrate, and then drying and pyrolyzing The process may be repeated 4 to 8 times, and the final catalyst layer weight may be 10 g / m ² or more. The weight of the catalyst layer is preferably 12 g / m ² or more, and more preferably 14 g / m ² or more.

  Further, the catalyst layer forming solution may be applied only to one side of the substrate, but it is preferably applied to both sides particularly when the substrate is a perforated plate.

  In this invention, after complete | finishing a 1st process, the 2nd process of baking at 300-500 degreeC is performed. If it deviates from this temperature range, an overvoltage of less than 70 mV cannot be obtained. The reason for this is not necessarily clear, but if the firing is performed at a temperature lower than 300 ° C., the effect of the firing is not obtained, and the same as when the second step is not performed. It is presumed that the effects of the present invention cannot be obtained because the platinum component and the like are aggregated and the specific surface area is reduced. In order to obtain a low overvoltage, a preferable firing temperature is 350 to 450 ° C. The firing time is not particularly limited, but can be 0.2 to 8 hours from the viewpoint of workability.

  There is no particular limitation on the period from the end of the first step to the start of the second step. That is, the second step may be performed immediately after the first step is completed, or may be stored after the first step is completed. For example, the second step may be performed after 150 days have elapsed.

  In the second step, the conductive substrate on which the catalyst layer is formed in the first step may be baked at 300 to 500 ° C., and there are no other restrictions. Firing may be performed in air, and a special atmosphere such as nitrogen gas, argon gas, or vacuum is not necessary.

  After the 2nd process is complete | finished, it is preferable to perform the reduction process aiming at reducing and alloying the catalyst layer formed in the electroconductive base material to a metal state. Although the reduction treatment method is not particularly limited, for example, a chemical reduction method by contact with a substance having a strong reducing power such as hydrazine, formic acid or oxalic acid, an electrochemical reduction method for giving a reduction potential to platinum, nickel and palladium, etc. Can be used.

  The period from the end of the second step to the start of the reduction process is not particularly limited. That is, the reduction process may be performed immediately after the second process is completed, or may be stored after the second process is completed, for example, the reduction process may be performed after 150 days.

When the electrode for hydrogen generation obtained by the production method of the present invention is used as a cathode when electrolyzing water or an aqueous alkali metal chloride solution, the reduction of the catalyst layer formed on the conductive substrate is an electrochemical reduction. The method is preferred. The “electrolysis of water” in the present invention means not “electrolysis of pure water” but “electrolysis of water containing an electrolyte such as NaOH, KOH, HCl, H ₂ SO ₄ ”.

  For example, after the second step is completed, if the electrode for hydrogen generation of the present invention is attached as a cathode to an ion exchange membrane salt electrolysis tank and salt electrolysis is started, the catalyst layer on the conductive substrate is electrochemically formed. Reduced.

The electrolysis start conditions are not particularly limited, and the electrolysis start conditions for ion exchange membrane salt electrolysis may be applied as they are. For example, it may be carried out at a temperature of 70 to 90 ° C. and an electrolytic current density of 0.05 to 1 kA / m ² , preferably a temperature of 80 to 88 ° C. and an electrolytic current density of 0.1 to 0.5 kA / m. ² . The time required for the reduction of the catalyst layer is proportional to the electrolysis current density, but in the case of 0.1 to 0.5 kA / m ² , the reduction of the catalyst layer is completed in 1 to 3 minutes, and thereafter, for hydrogen generation Can be used as an electrode.

  Before the electrolytic cell is mounted, the catalyst layer may be reduced by any method, and in that case, the effect of the present invention is sufficiently exhibited. However, as described above, it is preferable that the battery is mounted in an electrolytic cell and reduced at the start of electrolysis because no extra cost is generated.

  The electrode for hydrogen generation of the present invention thus obtained is obtained by electrolyzing water or an aqueous alkali metal chloride solution to produce hydrogen gas and an aqueous alkali metal hydroxide solution from above the cathode, and oxygen gas or from above the anode. When used as an electrode for hydrogen generation in electrolysis characterized by producing chlorine gas, i.e., in an electrolytic cell in which an anode is placed with a diaphragm in between, electrolysis of an aqueous solution of alkali metal chloride such as water or salt In addition to providing a low hydrogen overvoltage, the low overvoltage characteristics can be maintained stably for a long time without special measures to prevent iron ions from being mixed into the catholyte, and the catalyst can be peeled off or dropped during a stop or restart operation. This is an electrode for hydrogen generation that does not occur, that is, extremely excellent in hydrogen overvoltage performance and durability. Here, the diaphragm typically includes a cation exchange membrane that selectively permeates cations.

  Therefore, in the field of electrolysis industry of an aqueous solution of alkali metal chloride such as water or salt, the energy required for the electrolysis industry can be reduced only by changing the electrode for hydrogen generation to the electrode for hydrogen generation provided by the present invention. Become.

  According to the present invention, it is possible to easily obtain an electrode for hydrogen generation in which the initial hydrogen overvoltage is sufficiently low and the durability is excellent.

  The hydrogen generating electrode of the present invention does not increase the hydrogen overvoltage due to iron ion poisoning in the electrolytic solution, which has been regarded as a drawback of the conventional platinum-based catalyst. The catalyst does not peel off or fall off due to the reverse current flowing inside. Therefore, the low hydrogen overvoltage characteristic inherent in platinum can be stably maintained over a long period of time, and in particular, water or alkali that is forced to contain iron in the catholyte and reverse current that flows several times a year during shutdown and restart. The energy required for the electrolysis industry of metal aqueous solutions can be greatly reduced.

  The present invention will be specifically described by the following examples, but the present invention is not limited to the examples.

<Conductive substrate>
Nickel expanded metal was used as the conductive substrate. Nickel expanded metal was etched as a pretreatment using a 10 wt% hydrochloric acid solution at a temperature of 50 ° C. for 10 minutes, and then washed with water and dried.

<Preparation of catalyst layer forming liquid>
Dissolve 8.94 g of nickel nitrate hexahydrate and 0.82 g of palladium nitrate dihydrate (manufactured by Kojima Chemical) in 60 ml of dinitrodiammine platinum nitrate solution (manufactured by Tanaka Kikinzoku) with a platinum content of 100 g / L, The solution was made up to 100 ml with water to prepare a catalyst layer forming liquid containing platinum, nickel and palladium (platinum: 48 mol%, nickel: 48 mol%, palladium: 4 mol%).

<Measurement of hydrogen overvoltage>
Water electrolysis was performed for 10 minutes under the conditions of Ni, temperature 88 ° C., and current density 6.0 kA / m ² using an electrolytic solution of 32 wt% sodium hydroxide aqueous solution (capacity: about 1 L) by the current interrupter method. The hydrogen overvoltage was measured.

Example 1
The 1st process was implemented with the method shown below.

Using a roller, the catalyst layer forming solution containing platinum, nickel and palladium (platinum: 48 mol%, nickel: 48 mol%, palladium: 4 mol%) prepared in <Preparation of catalyst layer forming solution> , Applied to one side of a 1.2 m × 0.4 m nickel expanded metal at a coating amount of 10 mL / m ² , then applied to the other side of the nickel expanded metal at a coating amount of 10 mL / m ² and dried with hot air After drying in the machine at 80 ° C. for 10 minutes, the mixture was pyrolyzed at 400 ° C. for 10 minutes under an air flow using a box-type baking furnace. This series of operations was repeated 6 times to form a catalyst layer on the conductive substrate.

The difference in weight before and after the first step was 16.4 g / m ² .

Next, 0.1 m × 0.1 m was cut out from the mesh after completion of the first step, and baked at 300 ° C. for 8 hours under an air flow using a box-type baking furnace, and the second step was performed. There was no change in weight before and after the second step, and the weight of the catalyst layer was determined to be 16.4 g / m ² . The remaining mesh cut out in Example 1 was used in other examples and comparative examples.

Next, the electrolysis of the mesh after the completion of the second step is performed using water electrolyte of 32 wt% sodium hydroxide aqueous solution under the conditions of Ni, temperature 88 ° C., current density 0.3 kA / m ^{2 on} the counter electrode, The catalyst layer of the electrode was subjected to electrochemical reduction treatment. At the beginning of water electrolysis, gas generation was not observed from the electrode, and generation of hydrogen gas from the electrode was visually observed 1 minute and 35 seconds after the start of water electrolysis. From the state of hydrogen gas generation from the electrode, it was determined that the reduction of the catalyst layer was completed in 1 minute 35 seconds from the start of water electrolysis.

After the electrochemical reduction treatment was completed, the current density of water electrolysis was increased to 6 kA / m ² and the hydrogen overvoltage was measured to be 65 mV. The electrode manufactured by performing the first and second steps was hydrogen. It was confirmed that the generated overvoltage was an excellent performance of less than 70 mV.

Example 2
A 0.1 m × 0.1 m piece was cut out from the mesh after completion of the first step in Example 1, and as a second step, it was fired at 450 ° C. for 1 hour under an air flow using a box-type firing furnace. There was no change in weight before and after the second step, and the weight of the catalyst layer was determined to be 16.4 g / m ² .

  Thereafter, reduction treatment was performed under the same conditions as in Example 1, and then the hydrogen overvoltage was measured under the same conditions as in Example 1. The measured hydrogen overvoltage was 65 mV.

Comparative Example 1
Cut out 0.1 m × 0.1 m from the mesh after the completion of the first step of Example 1, perform the reduction treatment under the same conditions as in Example 1 without performing the second step, and then perform the same as in Example 1. The hydrogen overvoltage was measured under the following conditions. The measured hydrogen overvoltage was 71 mV, indicating a hydrogen overvoltage of 70 mV or higher.

Example 3
A 0.1 m × 0.1 m piece was cut out from the mesh after completion of the first step of Example 1, and as a second step, it was fired at 400 ° C. for 0.5 hours under an air flow using a box-type firing furnace. There was no change in weight before and after the second step, and the weight of the catalyst layer was determined to be 16.4 g / m ² .

  Thereafter, reduction treatment was performed under the same conditions as in Example 1, and then the hydrogen overvoltage was measured under the same conditions as in Example 1. The measured hydrogen overvoltage was 67 mV.

Example 4
A 0.1 m × 0.1 m piece was cut out from the mesh after completion of the first step in Example 1, and as a second step, it was fired at 350 ° C. for 1 hour under an air flow using a box-type firing furnace. There was no change in weight before and after the second step, and the weight of the catalyst layer was determined to be 16.4 g / m ² .

  Thereafter, reduction treatment was performed under the same conditions as in Example 1, and then the hydrogen overvoltage was measured under the same conditions as in Example 1. The measured hydrogen overvoltage was 64 mV.

Example 5
A 0.1 m × 0.1 m piece was cut out from the mesh after completion of the first step in Example 1, and as a second step, it was fired at 450 ° C. for 0.5 hours under an air flow using a box-type firing furnace. There was no change in weight before and after the second step, and the weight of the catalyst layer was determined to be 16.4 g / m ² .

  Thereafter, reduction treatment was performed under the same conditions as in Example 1, and then the hydrogen overvoltage was measured under the same conditions as in Example 1. The measured hydrogen overvoltage was 64 mV.

Example 6
A 0.1 m × 0.1 m piece was cut out from the mesh after completion of the first step of Example 1, and as a second step, it was fired at 500 ° C. for 0.2 hours under an air flow using a box-type firing furnace. There was no change in weight before and after the second step, and the weight of the catalyst layer was determined to be 16.4 g / m ² .

  Thereafter, reduction treatment was performed under the same conditions as in Example 1, and then the hydrogen overvoltage was measured under the same conditions as in Example 1. The measured hydrogen overvoltage was 64 mV.

Comparative Example 2
A 0.1 m × 0.1 m piece was cut out from the mesh after completion of the first step in Example 1, and as a second step, it was fired at 575 ° C. for 0.1 hour under an air flow using a box-type firing furnace. There was no change in weight before and after the second step, and the weight of the catalyst layer was determined to be 16.4 g / m ² .

  Thereafter, reduction treatment was performed under the same conditions as in Example 1, and then the hydrogen overvoltage was measured under the same conditions as in Example 1. The measured hydrogen overvoltage was 72 mV, indicating a hydrogen overvoltage of 70 mV or higher.

  From the results of Examples and Comparative Examples, when the production method of the present invention is applied, a low value of hydrogen overvoltage of less than 70 mV is obtained. However, if the production method of the present invention is deviated, the hydrogen overvoltage becomes 70 mV or more. I understood that.

  The electrode for hydrogen generation obtained by the production method of the present invention can be used for electrolysis of water or electrolysis of an aqueous solution of alkali metal chloride such as sodium chloride, and can be used in a wide range of electrolysis industries including the salt electrolysis industry. Have sex.

Claims (8)

After performing the 1st process which apply | coats the liquid for catalyst layer formation containing platinum, nickel, and palladium on an electroconductive base material, drys and thermally decomposes and forms a catalyst layer on an electroconductive base material, 300-500 degreeC A method for producing an electrode for hydrogen generation in which a catalyst layer mainly composed of platinum, nickel and palladium is supported on a conductive base material, wherein the second step of firing is performed. The method for producing an electrode for hydrogen generation according to claim 1, wherein the palladium content in the catalyst layer forming liquid is 1 to 55 mol%. 2. The production of an electrode for hydrogen generation according to claim 1, wherein the catalyst layer forming liquid has a palladium content of 4 to 48 mol%, a nickel content of 48 to 4 mol%, and the balance being platinum. Method. In performing the first step, the step of applying the catalyst layer forming liquid by controlling the coating amount of the liquid for forming the catalyst layer to 13 to 31 mL / m ² per projected area of the conductive substrate, followed by drying and pyrolysis is performed in 4 to 8 steps. The method for producing an electrode for hydrogen generation according to any one of claims 1 to 3, wherein the method is repeated twice. The method for producing an electrode for hydrogen generation according to any one of claims 1 to 4, wherein after the second step is performed, the catalyst layer on the conductive substrate is subjected to a reduction treatment. 6. The method for producing an electrode for hydrogen generation according to claim 5, wherein the reduction treatment is an electrochemical reduction treatment in electrolysis of water or an aqueous alkali metal chloride solution. The electrode for hydrogen generation obtained by the method for producing an electrode for hydrogen generation according to any one of claims 1 to 6 is used as a cathode, and water or alkali metal is used in an electrolytic cell in which the anode is arranged with a diaphragm interposed therebetween. An electrolysis method comprising electrolyzing an aqueous chloride solution to produce hydrogen gas and an alkali metal hydroxide aqueous solution from above the cathode, and producing oxygen gas or chlorine gas from above the anode. The electrolysis method according to claim 7, wherein the diaphragm is a cation exchange membrane.