KR102605336B1 - Electrode for electrolysis, method for producing the same, and electrochemical cell - Google Patents

Abstract

The present invention relates to an electrode for electrolysis, a method of manufacturing the same, and an electrochemical cell that improve overvoltage caused by the cathode in the electrolysis process and reduce electrode manufacturing costs.

Description

Electrode for electrolysis and method of manufacturing the same {ELECTRODE FOR ELECTROLYSIS, METHOD FOR PRODUCING THE SAME, AND ELECTROCHEMICAL CELL}

The present invention relates to an electrode for electrolysis that improves overvoltage caused by the cathode in the electrolysis process and reduces electrode manufacturing costs, a method of manufacturing the same, and an electrochemical cell for electrolysis of alkali chloride brine.

The Chlor-Alkali (hereinafter referred to as “CA”) process electrolyzes high-concentration brine and water to produce chlorine gas (Cl ₂ ), which is the raw material for producing vinyl chloride monomer (VCM), soap, bleach, etc. This is a process for producing caustic soda (NaOH) and hydrogen gas (H ₂ ).

The CA process is a high energy consumption process in which electricity costs account for approximately 40-60% of the total process operating cost. In order to reduce these electricity costs, it is important to reduce additional voltage (overvoltage) beyond the voltage required for electrolysis. Factors that increase this overvoltage include separator resistance, electrolyte resistance, anode, and cathode, and among these, overvoltage caused by the cathode accounts for a significant portion of the total overvoltage.

Currently, the commercial cathode electrode used in the CA process shows an overvoltage that is significantly higher than the theoretical voltage due to problems such as plating deterioration and coating on the electrode peeling off if the electrolysis process continues.

Therefore, there is a demand for the development of electrodes that have excellent stability and high efficiency compared to existing commercial electrodes.

The present invention is intended to provide an electrode for electrolysis that improves overvoltage caused by the cathode in the electrolysis process and reduces electrode manufacturing costs.

In addition, the present invention is intended to provide a method of manufacturing an electrode for electrolysis that improves overvoltage caused by the cathode in the electrolysis process and reduces electrode manufacturing costs.

Additionally, the present invention is to provide an electrochemical cell for electrolysis of alkali chloride brine.

In this specification, a conductive substrate; and a catalyst layer containing ruthenium (Ru), cobalt (Co), and cerium (Ce).

Additionally, in the present specification, the steps include applying a coating solution containing a ruthenium (Ru) compound or a precursor thereof, a cobalt (Co) compound or a precursor thereof, and a cerium (Ce) compound or a precursor thereof on a conductive substrate; and calcining the coating solution. It provides a method of manufacturing an electrode for electrolysis, including a step.

In addition, the present specification provides an electrochemical cell for electrolysis of alkali chloride brine including the electrolysis electrode as a cathode.

Hereinafter, an electrode for electrolysis, a method of manufacturing an electrode for electrolysis, and an electrochemical cell according to specific embodiments of the invention will be described in more detail.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as “comprise,” “comprise,” or “have” are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and are intended to indicate the presence of one or more other features or It should be understood that this does not exclude in advance the possibility of the presence or addition of numbers, steps, components, or combinations thereof.

Additionally, in the present invention, when each layer or element is referred to as being formed “on” or “on” the respective layers or elements, it means that each layer or element is formed directly on the respective layers or elements, or other This means that layers or elements can be additionally formed between each layer, on the object, or on the substrate.

Since the present invention can be subject to various changes and can take various forms, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

According to one embodiment of the invention, a conductive substrate; and a catalyst layer containing ruthenium (Ru), cobalt (Co), and cerium (Ce). An electrode for electrolysis containing a may be provided.

The present inventors have developed an electrode for electrolysis comprising a conductive substrate and a catalyst layer containing ruthenium (Ru), cobalt (Co), and cerium (Ce), and this electrode is used as a cathode in the electrolysis process. The invention was completed after confirming through experiments that the overvoltage caused by the electrodes can be improved and the manufacturing cost of the electrode can be reduced by relatively reducing the content of ruthenium (Ru) due to the addition of cobalt (Co).

The catalyst layer containing ruthenium (Ru), cobalt (Co), and cerium (Ce) may function to improve overvoltage caused by the cathode in the electrolysis process. Specifically, the ruthenium (Ru) in the catalyst layer is used to generate electricity. It acts as a catalyst to allow the decomposition reaction to progress better, the cobalt (Co) serves to promote the catalytic action of the ruthenium, and the cerium (Ce) ensures durability by preventing damage to the electrode when the electrolysis process continues. It can play a role in maintaining it.

In addition, as the catalyst layer contains cobalt (Co), the bonding energy between ruthenium (Ru) and oxygen may change, and accordingly, within the catalyst layer, ruthenium (Ru) is greater than ruthenium oxide (Ru oxide). ) It may be a state in which the metal is present in a higher proportion. In this way, ruthenium (Ru) metal is present in a larger proportion than ruthenium oxide (Ru oxide) in the catalyst layer, so that the electrolysis electrode of the above embodiment can realize higher electrolysis efficiency.

Meanwhile, based on the central element in the catalyst layer, the molar ratio of cobalt (Co) to cerium (Ce) may be 0.9 or less, or 0.8 or less, or 0.7 or less, or 0.1 to 0.9. As the molar ratio of cobalt (Co) to cerium (Ce) in the catalyst layer is 0.9 or less, overvoltage can be improved and electrode manufacturing costs can be reduced.

On the other hand, if the molar ratio of cobalt (Co) to cerium (Ce) in the catalyst layer exceeds 0.9, the effect of improving the overvoltage may be minimal, or there may be a problem of the overvoltage increasing.

The catalyst layer may include ruthenium (Ru), cobalt (Co), and cerium (Ce) in the form of individual metal elements or compounds containing the metal elements (e.g., oxides, hydrates, nitrides, etc.), The content of ruthenium (Ru), cobalt (Co), and cerium (Ce) or the ratio (molar ratio) between them in the catalyst layer may be defined based on each metal element (based on the central element).

For example, the molar ratio of cobalt (Co) to cerium (Ce) may be defined as the molar ratio of the cerium (Ce) element and the cobalt (Co) element contained in the catalyst layer, and also a compound containing the cerium (Ce) element. Among compounds containing and cobalt (Co), it can be defined as the molar ratio of the cerium (Ce) element and the cobalt (Co) element, respectively.

Meanwhile, the catalyst layer may include ruthenium (Ru), cobalt (Co), and cerium (Ce) at a molar ratio of 2 to 10:0.1 to 0.9:1 based on the central elements.

At this time, when the molar ratio of ruthenium (Ru), cobalt (Co), and cerium (Ce) in the catalyst layer satisfies the above range, the effect of improving overvoltage is maximized, and the content of ruthenium, a platinum group compound, in the coating solution is reduced to reduce the content of ruthenium, a platinum group compound, in the electrode. It can have the effect of reducing manufacturing costs.

The content of ruthenium (Ru) in the catalyst layer can be expressed based on the content of cerium (Ce). Specifically, the molar ratio of ruthenium (Ru) to cerium (Ce) is 2 to 10, or 2 to 8, or 4. It can be from 8 to 8. If the molar ratio of ruthenium (Ru) to cerium (Ce) in the catalyst layer exceeds 10, it is economically disadvantageous without any particular advantage, and if it is less than 2, there may be a problem of increased overvoltage.

In addition, the content of cobalt (Co) in the catalyst layer can be expressed based on the content of cerium (Ce), where the molar ratio of cobalt (Co) to cerium (Ce) is 0.9 or less, or 0.8 or less, or 0.7 or less, Or it may be 0.1 to 0.9.

As the molar ratio of cobalt (Co) to cerium (Ce) in the catalyst layer is 0.9 or less, it can indicate the role of promoting the catalytic action of ruthenium in the electrolysis reaction, and if it exceeds 0.9, ruthenium in the electrolysis reaction Because it acts to hinder the catalytic action, the effect of improving the overvoltage may be minimal or the overvoltage may increase.

Meanwhile, as described above, the catalyst layer may include ruthenium (Ru), cobalt (Co), and cerium (Ce). Specifically, the catalyst layer may include ruthenium (Ru), cobalt (Co), and cerium (Ce). It may contain oxides. More specifically, the catalyst layer may include a metal oxide of the following formula (1):

[Formula 1]

(Ru)a(Co)b(Ce)cOx

In Formula 1, a, b, c and x are the molar ratio of each element,

a is a rational number between 2 and 10,

b is a rational number from 0.1 to 0.8,

c is a rational number from 0.8 to 1.2,

x is a rational number from 0.5 to 10.

The electrode for electrolysis of the above embodiment may use a commonly known conductive substrate. The electrode for electrolysis may be a cathode for a chlor-alkali process. Accordingly, preferably, the conductive substrate includes one or more metals selected from the group consisting of nickel, titanium, and tantalum, or an alloy thereof. You can.

At this time, the shape of the conductive substrate is not particularly limited and may be in the form of a rod, sheet, or plate.

Meanwhile, the conductive substrate may have a thickness of 10 to 400 ㎛, specifically 10 to 350 ㎛, 10 to 300 ㎛, or 10 to 250 ㎛.

When the conductive substrate has a thickness in the above range, the catalyst layer formed on the conductive substrate may have a sufficient specific surface area, but when it exceeds 400㎛, the conductive substrate becomes too thick and there is a risk that the performance of the electrode may deteriorate. If it is less than 10㎛, the conductive substrate becomes too thin and the surface area of the conductive substrate is insufficient, which may be disadvantageous for the formation of a catalyst layer.

Additionally, the catalyst layer may have a thickness of 5 to 150 ㎛, specifically 5 to 130 ㎛, 5 to 100 ㎛, or 5 to 50 ㎛.

If the catalyst layer exceeds 150㎛, it is economically disadvantageous without any special advantage and has little effect in reducing electrode manufacturing costs, and if it is less than 5㎛, the effect of improving overvoltage may be insufficient due to the insufficient specific surface area of the catalyst layer.

The electrode for electrolysis of the above embodiment may be a cathode for a chlor-alkali process.

According to another embodiment of the invention, applying a coating solution containing a ruthenium (Ru) compound or a precursor thereof, a cobalt (Co) compound or a precursor thereof, and a cerium (Ce) compound or a precursor thereof on a conductive substrate; A method for manufacturing an electrode for electrolysis can be provided, including the step of calcining the coating solution.

The present inventors manufactured an electrode for electrolysis using a coating solution containing the above-described ruthenium (Ru) compound or its precursor, cobalt (Co) compound or its precursor, and cerium (Ce) compound or its precursor, and provided as such. Electrolysis electrodes can improve the overvoltage caused by the cathode in the electrolysis process, and experiments have shown that the addition of cobalt (Co) can relatively reduce the content of ruthenium (Ru), thereby reducing the manufacturing cost of the electrode. It was confirmed through .

The electrode for electrolysis manufactured by the above manufacturing method includes a conductive substrate; and a catalyst layer containing ruthenium (Ru), cobalt (Co), and cerium (Ce).

As described above in the electrolysis electrode of one embodiment, since the catalyst layer contains ruthenium (Ru), cobalt (Co), and cerium (Ce), it can serve to improve overvoltage caused by the cathode in the electrolysis process. Specifically, in the catalyst layer, the ruthenium (Ru) serves as a catalyst to allow the electrolysis reaction to proceed better, the cobalt (Co) serves to promote the catalytic action of the ruthenium, and the cerium (Ce) serves to promote the catalytic action of the ruthenium. ) can play a role in ensuring that the electrode is not damaged and maintains durability when the electrolysis process continues.

At this time, the ruthenium (Ru) compound, cobalt (Co) compound, and cerium (Ce) compound each include the form of an individual metal element or a compound containing the metal element (e.g., oxide, hydrate, nitride, etc.), The ruthenium (Ru) precursor, cobalt (Co) precursor, and cerium (Ce) precursor are materials at the stage before becoming the final materials that can be obtained: ruthenium (Ru) compound, cobalt (Co) compound, and cerium (Ce) compound. it means.

Specifically, the ruthenium (Ru) compound or its precursor may include at least one selected from the group consisting of ruthenium fluoride, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium oxide hydrate, ruthenium acetate, and sodium ruthenate, The cobalt (Co) compound or its precursor may include one or more selected from the group consisting of cobalt nitrate, cobalt acetate, and cobalt sulfate, and the cerium (Ce) compound or its precursor may include cerium nitrate, cerium oxide, One or more types selected from the group consisting of cerium chloride and cerium acetate may be mentioned.

Meanwhile, the coating solution may contain 0.9 or less of cobalt (Co) compared to the cerium (Ce) based on the central element, and the coating solution may contain ruthenium (Ru), cobalt (Co), and cerium (Ce) based on the central element. ) may be included in a molar ratio of 2 to 10:0.1 to 0.9:1.

At this time, when the molar ratio of ruthenium (Ru), cobalt (Co), and cerium (Ce) in the coating solution satisfies the above range, the effect of improving overvoltage is maximized by reducing the content of ruthenium, a platinum group compound, in the coating solution. This can have the effect of reducing electrode manufacturing costs.

The content of ruthenium (Ru) and cobalt (Co) in the coating solution can each be expressed based on the content of cerium (Ce), and specifically, the molar ratio of ruthenium (Ru) to cerium (Ce) is 2 to 10, or It may be 2 to 8, or 4 to 8. If the molar ratio of ruthenium (Ru) to cerium (Ce) in the coating solution exceeds 10, it is economically disadvantageous without any particular advantage, and if it is less than 2, there may be a problem of increased overvoltage.

In addition, the coating solution may contain cobalt (Co) to the cerium (Ce) in a molar ratio of 0.9 or less, or 0.8 or less, or 0.7 or less, or 0.1 to 0.9 based on the central element, and the cerium (Ce) in the coating solution. As the molar ratio of cobalt (Co) is less than 0.9, it may play a role in promoting the catalytic action of ruthenium in the electrolysis reaction. If it exceeds 0.9, it may play a role in hindering the catalytic action of ruthenium in the electrolysis reaction. The effect of improving the overvoltage may be minimal, or there may be a problem of the overvoltage increasing.

Meanwhile, before applying a coating solution containing a ruthenium (Ru) compound or a precursor thereof, a cobalt (Co) compound or a precursor thereof, and a cerium (Ce) compound or a precursor thereof on the conductive substrate, the ruthenium (Ru) It may further include dissolving the compound or its precursor, the cobalt (Co) compound or its precursor, and the cerium (Ce) compound or its precursor in an organic solvent, wherein the organic solvent is a carboxylic acid having 1 to 8 carbon atoms, or a carbon number. It may be an alcohol having 1 to 8 carbon atoms, a ketone having 1 to 8 carbon atoms, or a mixture thereof, and specifically, it may be methanol, ethanol, n-propanol, isopropanol, or butanol.

In addition, an amine-based compound may be additionally included along with the organic solvent, and the amine-based compound may be one selected from the group consisting of aliphatic amines having 2 to 20 carbon atoms or a mixture thereof, and specifically, oleylamine, It may be propylamine, butylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, or octadecylamine.

The amine-based compound may be included in an amount of 1 to 10% by weight relative to the total weight of the organic solvent and the amine-based compound. When the amine-based compound is included in this amount, chemical changes or changes in the state of the coating solution are prevented. can do.

At this time, if the amine-based compound exceeds 10% by weight relative to the total weight of the organic solvent and the amine-based compound, the viscosity of the coating solution may increase and the solubility of the coating solution may be impaired, and if it is less than 1% by weight, , the amount of the amine-based compound is so small that there is a risk that it will have little effect in preventing chemical changes in the coating solution.

Meanwhile, before applying the coating solution on the conductive substrate, the step of forming fine irregularities on at least one surface of the conductive substrate may be further included.

The surface of the conductive substrate may be polished, for example, the surface may be physically polished, or specifically, it may be polished by a method such as sand blasting.

By forming fine irregularities on at least one surface of the conductive substrate through the physical surface polishing, the coating solution can be better applied to the conductive substrate, improving adhesion, and forming the catalyst layer more uniformly and closely.

The conductive substrate may be additionally etched after the surface polishing. The etching may be a chemical etching using a strong base and/or acid. The etching method is not particularly limited, but for example, the conductive substrate is etched at a temperature of 40°C to 100°C for 10 to 120 minutes using an alkali hydroxide such as NaOH, KOH, or a strong base such as an alkaline earth metal hydroxide, or etching with HCl or HF. , HBr, oxalic acid, etc. may be used to etch for 10 to 120 minutes at a temperature of 40°C to 100°C, and etching using the strong base and etching using the acid may be performed sequentially.

Meanwhile, the coating liquid is applied to the conductive substrate. At this time, the application method is not particularly limited, and may be, for example, applied using a brush (brushing method).

The coating solution is applied on the conductive substrate and then fired. The firing step may be performed at a temperature of 300°C or higher, and specifically, may be performed at a temperature of 300°C or higher, 400°C or higher, or 300°C to 800°C. .

At this time, if the firing step is performed below 300°C, there is a risk that the ruthenium compound or its precursor may remain without being completely oxidized.

Meanwhile, before the step of baking the coating solution, the step of drying the conductive substrate to which the coating solution is applied may be further included.

Methods and conditions usable in the drying step are not greatly limited. For example, the drying may be performed at a temperature of 50°C to 200°C, and specifically, may be performed at a temperature of 100°C to 200°C.

These coating liquid application, drying, and firing steps may be repeated several times, for example, 2 to 20 times.

According to another embodiment of the invention, an electrochemical cell for electrolysis of alkali chloride brine can be provided, including the electrolysis electrode of the above-described embodiment as a cathode.

The specific structure of the electrochemical cell is not limited, and as commonly known, it includes an aqueous electrolyte containing an alkali metal chloride; anode; The electrolysis electrode of the above-described embodiment as a cathode; and a separator located within the aqueous electrolyte and between the anode and the cathode. It may include configurations such as:

The present invention improves the overvoltage caused by the cathode in the electrolysis process and manufactures an electrolysis electrode that reduces electrode manufacturing costs and improves the overvoltage caused by the cathode in the electrolysis process and reduces electrode manufacturing costs. We can provide a way to do this.

In addition, the present invention can provide an electrochemical cell for electrolysis of alkali chloride brine including the electrolysis electrode as a cathode.

Figure 1 is a graph showing surface condition analysis (XPS) of the electrolysis electrode prepared in Example 1.
Figure 2 is a graph showing surface condition analysis (XPS) of the electrode for electrolysis manufactured in Comparative Example 1.

The invention is explained in more detail in the following examples. However, the following examples only illustrate the present invention, and the content of the present invention is not limited by the following examples.

In the following examples or comparative examples, a product from Ildong Gold Mesh (200 μm, Ni purity of 99% or higher) was used as the conductive substrate (nickel substrate), and as the ruthenium (Ru) compound, Ruthenium Chloride Hydrate from Heraeus was used. ), Cobalt Acetate Tetrahydrate from Deoksan Pharmaceutical Co., Ltd. was used as a cobalt (Co) compound, and Cerium Nitrate Hexahydrate from Sigma-Aldrich was used as a cerium (Ce) compound.

In addition, isopropyl alcohol and 2-butoxyethanol from Daejung Chemical were used as solvents, and n-Octylamine from Daejung Chemical was used as an amine compound.

[Example 1]

The surface of the nickel base was processed into an uneven structure by sandblasting, a physical surface polishing, with aluminum oxide (120 mesh) under 0.4 MPa conditions. Afterwards, the nickel substrate was placed in a 5M sulfuric acid aqueous solution at 80°C and treated for 3 minutes to complete the pretreatment process for the conductive substrate.

RuCl ₃ ·nH ₂ O, Co(CH 3 CO 2 ) ₂ ·4H ₂ O, and Ce(NO ₃ ) ₂ ·6H ₂ O as _ruthenium (Ru) compound, cobalt (Co) compound, and cerium (Ce) _compound . It was mixed at a molar ratio of 4.5: 0.5: 1.0 based on the central element. After dissolving the mixture in an alcohol-based solvent mixed with isopropyl alcohol (IPA) and 2-butoxy ethanol (2-butoxy EtOH) in a 1:1 volume ratio for more than 30 minutes, the amine-based compound n -Octylamine was added at 5% by weight compared to the alcohol-based mixed solvent. Afterwards, the mixture was stirred for 24 hours at 50°C and 300RPM to prepare a coating solution with a ruthenium (Ru) concentration of 90 g/L.

The prepared coating solution was applied to the surface-treated nickel substrate using a brush, dried in a convection drying oven at 180°C for 10 minutes, and then placed in an electric heating furnace at 500°C and fired for 10 minutes.

The application, drying, and firing processes of this coating solution were performed an additional 9 times, and finally heat treatment was performed at 500°C for 1 hour to prepare an electrode for an electrolytic cell.

[Example 2]

In Example 1, the ruthenium (Ru) compound, cobalt (Co) compound, and cerium (Ce) compound were RuCl ₃ ·nH ₂ O, Co(CH ₃ CO ₂ ) ₂ ·4H ₂ O, and Ce(NO ₃ ) ₂ ·An electrode for an electrolytic battery was prepared in the same manner as in Example 1, except that 6H ₂ O was mixed at a molar ratio of 4.8: 0.2: 1.0 based on the central element to prepare a coating solution with a ruthenium (Ru) concentration of 96 g/L. was manufactured.

[Comparative Example 1]

In Example 1, the ruthenium (Ru) compound, cobalt (Co) compound, and cerium (Ce) compound were RuCl ₃ ·nH ₂ O, Co(CH ₃ CO ₂ ) ₂ ·4H ₂ O, and Ce(NO ₃ ) ₂ Electrode for electrolytic battery in the same manner as in Example 1, except that 6H ₂ O was mixed at a molar ratio of 5.0: 0: 1.0 based on the central element to prepare a coating solution with a ruthenium (Ru) concentration of 100 g/L. was manufactured.

Experimental Example 1: Voltage measurement after activation

To confirm the performance of the electrolytic cell electrodes prepared in Examples 1 to 2 and Comparative Example 1, a cathode voltage measurement experiment using a half cell in chlor-alkali electrolysis was performed.

An electrode activation experiment was performed under the current density of -0.62 A/cm ² using linear sweep voltammetry to optimize the electrode condition.

A 32% NaOH aqueous solution was used as the electrolyte, a Pt wire was used as the counter electrode, and an Hg/HgO electrode was used as the reference electrode. The prepared electrode was immersed in the electrolyte solution and treated for 1 hour under a current density of -6 A/cm ² .

Using the activated electrode, the voltage was measured at a current density of 0.62 A/cm ² using the linear scanning potential method, and the results are summarized in Table 1 below.

Example 1 Example 2 Comparative Example 1 Coating liquid (Ru:Co:Ce) composition ratio 4.5: 0.5: 1.0 4.8: 0.2: 1.0 5.0: 0: 1.0 Ru concentration (g/L) 90 96 100 Solvent composition ratio (IPA: 2-Butoxy EtOH: Octylamine) 1.0: 1.0: 0.1 1.0: 1.0: 0.1 1.0: 1.0: 0.1 Drying temperature (℃) 180 180 180 Firing temperature (℃) 500 500 500 Final firing temperature (℃) 500 500 500 Number of coated liquid applications 10 times 10 times 10 times Voltage after activation (V) (@ 0.62 A/cm ² ) 1.086 1.094 1.099

As a result of the experiment, in Examples 1 and 2 where a coating solution containing a ruthenium (Ru) compound or a precursor thereof and a cerium (Ce) compound or a precursor thereof was applied in addition to a cobalt (Co) compound or a precursor thereof, the ruthenium (Ru) compound Alternatively, it was confirmed that the overvoltage was improved by 5 to 13 mV compared to Comparative Example 1 in which a coating solution containing only its precursor and a cerium (Ce) compound or its precursor was applied.

Additionally, by reducing the concentration of ruthenium (Ru) in the coating solution to 10 wt%, it was predicted that manufacturing costs would be reduced when manufacturing electrodes.

Experimental Example 2: Surface condition analysis (XPS)

Surface condition analysis (XPS) was performed to confirm the metal oxidation state of the electrodes prepared in Example 1 and Comparative Example 1.

Analysis was performed using ThermoFisher Scientific's VG Scientific ESCALAB 250 equipment under ultra-high vacuum conditions of less than 10 ^-9 Torr.

X-rays were incident on the surface of the sample and the energy of emitted photoelectrons was measured to confirm the composition and chemical bonding state of the sample surface.

Figure 1 is a graph showing the surface state analysis (XPS) of the electrolysis electrode prepared in Example 1, and Figure 2 is a graph showing the surface state analysis (XPS) of the electrolysis electrode prepared in Comparative Example 1.

According to Figure 1, in Example 1, in which a coating solution was applied that additionally contains a cobalt (Co) compound or a precursor thereof in addition to a ruthenium (Ru) compound or a precursor thereof and a cerium (Ce) compound or a precursor thereof, ruthenium (Ru) and It was confirmed that the binding energy between oxygens changed, and the amount of ruthenium (Ru) metal increased relatively compared to ruthenium oxide (Ru oxide).

Claims (17)

conductive substrate; and
It includes a catalyst layer containing ruthenium (Ru), cobalt (Co), and cerium (Ce),
The catalyst layer includes ruthenium (Ru), cobalt (Co), and cerium (Ce) at a molar ratio of 2 to 10:0.1 to 0.9:1 based on each metal element.
delete delete delete According to paragraph 1,
The conductive substrate is a cathode for electrolysis comprising at least one metal selected from the group consisting of nickel, titanium, and tantalum, or an alloy thereof.
According to paragraph 1,
The conductive substrate has a thickness of 10 to 400 μm,
The catalyst layer has a thickness of 5 to 150㎛, a cathode for electrolysis.
According to paragraph 1,
The cathode for electrolysis is a cathode for electrolysis, which is a cathode for a chlor-alkali process.
Applying a coating solution containing a ruthenium (Ru) compound or a precursor thereof, a cobalt (Co) compound or a precursor thereof, and a cerium (Ce) compound or a precursor thereof on a conductive substrate; and
It includes the step of baking the coating liquid,
The coating liquid includes ruthenium (Ru), cobalt (Co), and cerium (Ce) at a molar ratio of 2 to 10:0.1 to 0.9:1 based on each metal element.
According to clause 8,
The ruthenium (Ru) compound or its precursor is at least one selected from the group consisting of ruthenium fluoride, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium oxide hydrate, ruthenium acetate, and sodium ruthenate,
The cobalt (Co) compound or its precursor is at least one selected from the group consisting of cobalt nitrate, cobalt acetate, and cobalt sulfate,
A method of manufacturing a cathode for electrolysis, wherein the cerium (Ce) compound or its precursor is at least one selected from the group consisting of cerium nitrate, cerium oxide, cerium chloride, and cerium acetate.
delete delete According to clause 8,
Before applying a coating solution containing a ruthenium (Ru) compound or a precursor thereof, a cobalt (Co) compound or a precursor thereof, and a cerium (Ce) compound or a precursor thereof on the conductive substrate,
A method of manufacturing a cathode for electrolysis, further comprising dissolving the ruthenium (Ru) compound or its precursor, the cobalt (Co) compound or its precursor, and the cerium (Ce) compound or its precursor in an organic solvent.
According to clause 12,
A method for producing a cathode for electrolysis, further comprising an amine-based compound along with the organic solvent.
According to clause 13,
A method of manufacturing a cathode for electrolysis, wherein the amine-based compound is contained in an amount of 1 to 10% by weight based on the total weight of the organic solvent and the amine-based compound.
According to clause 8,
Before applying a coating solution containing a ruthenium (Ru) compound or a precursor thereof, a cobalt (Co) compound or a precursor thereof, and a cerium (Ce) compound or a precursor thereof on the conductive substrate,
A method of manufacturing a cathode for electrolysis, further comprising forming fine irregularities on at least one surface of the conductive substrate.
According to clause 8,
A method of manufacturing a cathode for electrolysis, wherein the step of baking the coating liquid is performed at a temperature of 300° C. or higher.
An electrochemical cell for electrolysis of alkali chloride brine comprising the cathode for electrolysis of claim 1.