WO2018074723A1 - 기능성 전극 및 이의 제조방법 - Google Patents

기능성 전극 및 이의 제조방법 Download PDF

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Publication number
WO2018074723A1
WO2018074723A1 PCT/KR2017/009091 KR2017009091W WO2018074723A1 WO 2018074723 A1 WO2018074723 A1 WO 2018074723A1 KR 2017009091 W KR2017009091 W KR 2017009091W WO 2018074723 A1 WO2018074723 A1 WO 2018074723A1
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Prior art keywords
nickel
electrode
metal
particles
metal hydroxide
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English (en)
French (fr)
Inventor
강경수
김종원
박주식
배기광
김창희
조원철
정성욱
조현석
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Korea Institute of Energy Research KIER
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Korea Institute of Energy Research KIER
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Priority to JP2017559858A priority Critical patent/JP2019502016A/ja
Publication of WO2018074723A1 publication Critical patent/WO2018074723A1/ko
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/10—Agitating of electrolytes; Moving of racks
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a functional electrode and a method for manufacturing the same.
  • a composite metal hydroxide having excellent electrochemical activity is firmly bonded to a base material, has an enhanced reaction area, and has a low electrical conductivity of a complex metal hydroxide.
  • the supplementary functional electrode and its manufacturing method are described.
  • Representative methods of hydrolysis include hot water vapor electrolysis, proton exchange membrane electrolysis, and alkali water electrolysis.
  • High temperature water vapor electrolysis is the same as that of a solid oxide fuel cell, its structure and principle allow bidirectional operation. Maintenance and repair are easy. However, as high temperature operating conditions above 700 ° C are required, there are thermal durability problems and additional heat source problems.
  • the proton exchange membrane electrolysis method has high energy efficiency, requires electrolyte and can be made small in size, but the separator used It is very expensive and has a very strong corrosion resistance in itself, which shortens the service life and decreases the commercial viability.
  • the electrodes used in alkaline water electrolysis are mainly nickel plated carbon steel.
  • Nickel has been regarded as an electrode material for hydrolysis because it is relatively inexpensive and resistant to corrosion in alkaline environments and positive voltages.
  • the process used to increase the specific surface area of nickel has a process of forming alloy films and then selectively dealloying other non-alloyed metals, which not only limits the specific surface area but also the process itself. There is a limit to energy consumption.
  • Nickel hydroxides including layered double hydroxide (LDH) have low overvoltage and excellent corrosion resistance during electrolysis, and are suitable for various oxygen generators or water treatment devices such as electrodes in electrolytic baths, electrodes in capacitive desalination devices, and electrodes in ionizers.
  • LDH layered double hydroxide
  • the electrical properties of the electrode are affected by the low electrical conductivity of the hydroxide, with the problem that the binding force between the hydroxide particles and the substrate is very low. There is a problem falling.
  • An object of the present invention is to provide a functional electrode having a good electrochemical activity, which is firmly bonded to a base material, has a high specific surface area, and has an excellent electrical conductivity, and a method of manufacturing the same.
  • Another object of the present invention is to provide a method for producing functional electrodes having excellent electrochemical activity through an extremely simple, low cost and rapid process, and furthermore, to mass produce functional electrodes through energy efficient methods of phase silver and atmospheric pressure. It is to provide a manufacturing method that can be done.
  • a method of manufacturing a functional electrode according to the present invention includes a step of charging and plating a conductive base material into a plating solution containing nickel-metal hydroxide plate-like particles.
  • the plating solution may be a nickel-based plating solution.
  • the plating solution may contain 0.1 to 20 g / L of nickel-metal hydroxide plate-like particles.
  • the metal of the nickel-metal hydroxide plate-shaped particle may be one or a fused metal selected from Fe, Al, Mn, Co, and Cr.
  • the nickel: metal molar ratio of the nickel-metal hydroxide plate-shaped particles may be 1: 0.2 to 0.8.
  • the average diameter of the nickel-metal hydroxide platelet particles may be 0.5 to ⁇ .
  • a manufacturing method comprises a chemical bath comprising the electrolytic plating, nickel silver source, iron ion source, and hydroxyl source.
  • Chemical bath deposition (CBD) by hydrothermal synthesis, may further comprise the step of producing the nickel-metal hydroxide plate-like particles.
  • the nickel-metal hydroxide plate-like particle manufacturing step includes the steps of: a) providing a nickel silver source and a metal silver bath containing iron and silver sources; and b) Preparing a nickel-iron composite metal hydroxide by introducing and stirring a hydroxyl source into the metal ion bath.
  • the hydroxyl source in step b), may be introduced such that the pH of the metal ion bath is 6.0 to 12.0.
  • the electrode may be an electrode for electrolysis or an electrode for water treatment.
  • the present invention includes a functional electrode manufactured by the above-mentioned manufacturing method.
  • the functional electrode according to the embodiment of the present invention is manufactured by the above-described manufacturing method, and has an irregular protrusion structure due to the conductive base material, nickel-metal hydroxide plate particles by electroplating, and nickel-metal hydroxide plate particles. It may be that a plated layer containing a metal that binds the liver and nickel-metal hydroxide plate-like particles and the base metal is formed.
  • the metal of the plating layer is
  • nickel or metal and nickel selected from one or more of Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu and V.
  • the functional electrode according to the present invention has a large semi-ungular area and is remarkably large as the nickel-metal hydroxide plate-like particles form random surface irregularities and at the same time have a structure bound to the conductive base material by the metal. It has the advantages of excellent durability, and has an improved specific surface area and excellent electrochemical activity by nickel-metal hydroxide plate particles, making it an extremely effective electrode for electrolysis or water treatment.
  • the manufacturing method of the functional electrode according to the present invention has excellent electrochemical activity.
  • It has the advantage of manufacturing a durable and durable electrode, and has the advantage of mass production of a large-area functional electrode through a very simple process of plating by adding nickel-metal hydroxide plate-like particles to a plating solution.
  • Example 1 is a diagram showing the results of X-ray diffraction analysis of the nickel-metal hydroxide powder prepared in Example 1,
  • Example 2 is a scanning electron microscope of nickel-metal hydroxide powder prepared in Example 1
  • Example 3 shows a high magnification of the nickel-metal hydroxide powder prepared in Example 1
  • FIG. 3 is a high magnification scanning electron microscope observation of the functional electrode prepared in Example 1.
  • FIG. 6 is a diagram showing the result of element mapping with the surface area all EDX of the functional electrode prepared in Example 1,
  • FIG. 7 shows a scanning electron micrograph of the surface of the plating layer plated under the conditions of Example 1 using the same plating solution as in Table 1 except that the nickel-metal hydroxide powder was not contained in the plating solution of Table 1.
  • FIG. 9 is a view showing LVS measurement results of the functional electrode manufactured in Example 4
  • FIG. 10 is a view showing CV measurement results of the functional electrode manufactured in Example 3.
  • Nickel-metal hydroxides have a very low OER potential and have high corrosion resistance to alkali electrolytes and are considered as electrode materials (catalysts) for electrolysis or water treatment electrodes.
  • a method of synthesizing particles using a hydrothermal composite column and then coating the conductive substrate is mainly used.
  • this method makes it difficult to strongly adhere the hydroxide to the conductive substrate, and the durability and life of the electrode
  • the conductivity of the hydroxide is lower than that of a metal such as Ni, and thus the characteristics of the electrode are reduced.
  • the present applicant has a long-term study to manufacture functional electrodes that have excellent electrochemical activity of these nickel-metal hydroxides, and which are very firmly bound to nickel-metal hydroxides and can improve their electrical conductivity and specific surface area.
  • nickel-metal hydroxide particles were added to the electrolytic plating solution.
  • nickel-metal hydroxides were also deposited on the substrate together with the metal being plated.
  • the metals to be plated were deposited between the nickel-metal hydroxide particles and between the nickel-metal hydroxide particles and the substrate.
  • the nickel-metal hydroxide particles can be very strongly fixed to the substrate, and also the low electrical conductivity of the nickel-metal hydroxide particles by acting as a conductive material in which the metal to be plated provides a stable conductive path.
  • the present invention was filed by discovering that the irregular chemical structure of nickel-metal hydroxide particles, together with the excellent electrochemical activity of the nickel-metal hydroxide itself, increases the electrochemical reaction area. It came to
  • a method of manufacturing a functional electrode according to the present invention based on the above findings includes the step of electroplating a conductive base material into a plating solution containing nickel-metal hydroxide plate-like particles.
  • the functional electrode may mean an electrode for electrolysis or an electrode for water treatment.
  • the electrode for electrolysis is a hydrogen-evolution reaction (HER) electrode,
  • OER (oxygen-evolution reaction) electrode can also mean.
  • the electrode for water treatment can also mean an electrode such as a capacitive desalination device or a silver hand. More specifically, the functional electrode of the present invention can be an alkaline water electrolytic electrode. , More than
  • the functional electrode may be an HER electrode for alkali water electrolysis or an OER electrode for alkali water electrolysis.
  • the present invention provides a nickel-metal hydroxide plate particle by adding a nickel-metal hydroxide plate particle having excellent electrochemical activity to the plating solution itself and using an extremely simple and easy method of plating a conductive base material.
  • the self-plating structure of the nickel-metal hydroxide plate particles deposited on the conductive base material together with the self-plating metal (hereinafter, the metal plated with the base metal by electroplating) is deposited on the conductive base material.
  • a plating layer containing a metal that binds all of the nickel-metal hydroxide plate-like particles and between the nickel-metal hydroxide plate-like particles and the base material can be formed.
  • the electrode produced has not only excellent electrochemical activity by the nickel-metal hydroxide platelet particles, but also excellent durability as the nickel-metal hydroxide platelet particles are very strongly bound to the conductive substrate by the plated metal. It is possible to have excellent electrical conductivity by the plated metal.
  • the nickel-metal hydroxide platelet particles are protruded at random positions at different positions by the plated metal at arbitrary positions, and are irregularly shaped. Unevenness can be generated to improve the electrochemically active area of the electrode being manufactured. Furthermore, these irregularly shaped coarse surface irregularities prevent the deposition of oxygen bubbles, which together with the increase in the active area due to the increase of the surface roughness. And desorption induction.
  • the stirring of the plating solution It is known that the plating is performed more densely than when the electrolytic plating is carried out.
  • the stirring of the plating liquid uniformly disperses the nickel-metal hydroxide plate-like particles contained in the plating liquid, and is contained in the plating liquid. This is done to uniformly and effectively deposit the nickel-metal hydroxide platelet particles on the substrate. If the stirring speed of the plating solution is too low, there is a risk that the uniform dispersion of the nickel-metal hydroxide platelet particles in the plating solution will not be guaranteed.
  • the uniformity of nickel-metal hydroxide platelets deposited on the substrate may drop, whereas if the stirring speed is too fast, nickel-nickel-metal hydroxide platelets are subjected to physical shocks caused by stirring before they stably bind to the substrate.
  • the metal hydroxide plate particles will fall back into the plating solution.
  • the plating solution is from 100 to 500rpm, specifically, it is advantageous to be stirred at 200 to 400 rpm, such a stirring condition is maintained it is recommended that the electrolytic plating is performed.
  • the plating be performed for a long time with a current condition that is very low compared to conventional plating conditions. That is, the nickel-metal hydroxide plate-like particles are uniformly deposited on the conductive base material and are deposited more densely, and the plating metal is plated in the form of a binder that binds the nickel-metal hydroxide plate-like particles and the nickel-metal hydroxide plate-shaped particles and the base material.
  • the plating be carried out for a long time at a very low current condition compared to the normal plating conditions.
  • the electroplating is preferably performed at a low current density of 1 to 200 mA / cm 2 , and more preferably 5 to a current density of 50mA / cm 2, better than may be carried out from 5 to 25mA / cm 2 current density at such a nickel - by the random deposition of the metal hydroxide particles, plate-shaped It is a condition under which nickel-metal hydroxide plate-like particles deposited on the base material can be firmly and strongly bound to the substrate and / or neighboring nickel_metal hydroxide plate-like particles by the plating metal without damaging the existing surface irregularities.
  • the density is plated with nickel-metal hydroxide platelets and the plating metals deposited on the substrate are not plated as islands, but in a continuous continuum, which is stable and independent of nickel-metal hydroxide platelets.
  • the electroplating time is sufficient if the plating layer containing nickel-metal hydroxide plate-like particles and the plating metal can be formed to the extent that it can reliably cover the base material. As a specific, non-limiting example, electrolysis may be performed for one to three hours.
  • the concentration of nickel-metal hydroxide platelet particles in the plating solution does not increase the liquid-resistance of the plating solution excessively and does not cause a negative effect on the plating of the metal. It is advantageous to have a concentration such that a sufficient amount of nickel-metal hydroxide platelet particles can be supplied to the base material.
  • the plating solution may contain 1 to 20 g / L nickel-metal hydroxide tubular particles, more specifically 1 to I5 g / L nickel-metal hydroxide platy particles. Such concentrations may be achieved even when the above agitation is performed.
  • the plating solution may be used if the plating solution is used for electroplating conventional metals (including acidic, neutral or alkaline plating solutions).
  • the plating solution is preferably a plating solution of a metal which is active for water treatment or electrolysis.
  • the plating solution may be a nickel plating solution, and the nickel plating solution may be a nickel plating solution or
  • the plating solution of metal and nickel may be selected from one or more of Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu, and V.
  • the nickel plating solution may be an acidic plating solution, a neutral plating solution, or a basic plating solution.
  • the plating metal and the plate-shaped particles may be plated simultaneously regardless of the pH of the plating solution.
  • the nickel-based plating solution may be a solution containing an ion of a metal to be plated including nickel.
  • Plating metal ion sources supplying silver of the metal to be plated are not particularly limited, but sulfates, tetrachlorides, boron chlorides, chlorides, carbonates, pyrophosphates, sulfamate, chlorides, oxides and alkanesulfonates of the metals to be plated are not particularly limited. (Such as methanesulfonate, propanesulfonate), alkanolsulfonates (such as
  • concentration of is not particularly limited, but may be in the range of 100 to 200 g / L.
  • the pH may be controlled by basic substances such as ammonia, sodium hydroxide and potassium hydroxide.
  • ⁇ is a 2 to 6 phosphate plating solution
  • its pH can be adjusted by an acidic substance such as sulfuric acid, nitric acid or hydrochloric acid.
  • nickel plating solution can be present in the liquid phase and chloride as a source of chlorine Chlorides may include metal chlorides including sodium chloride or ammonium chloride, and the plating solution may contain 5 to 15 g / L of chloride, but not limited thereto.
  • the plating solution may further comprise a sorbent commonly used in acidic, thickening or basic plating solutions, which may be organic acid salts such as citrates, inorganic acids such as boric acid or
  • Carbonates such as sodium carbonate are not limited to these.
  • These buffers can be used in plating solutions in amounts known in the metal plating sector.
  • the plating solution is optionally used to improve the stability of the bath, the deposition behavior of the metal, the quality of the deposited metal and the current flow. Accelerators, polishes, leveling agents, wetting agents, conductive salts, and / or stress relief agents commonly used in plating solutions may be further included.
  • the inhibitor may include an oxygen-containing chain type polymer, and in one embodiment,
  • Polyoxypropylene glycol Polypropylene glycol, polypropylene glycol, polyvinyl alcohol, stearic acid polyglycol ester, stearyl alcohol polyglycol ether,
  • the leveling agent may be a nitrogen-containing organic material, specific examples,
  • 2-mercaptobenzothiazole ethylene thiourea, thiourea, thiadiazole, imidazole, monoethane amine, diethan amine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, acetamide, propyl Amide, benzamide, ac3 ⁇ 4amide, methacrylamide, ⁇ , ⁇ -dimethylacrylamide, lauryldimethylbetaine,
  • Lauramidopropylbetaine 1- (3—sulfopropyl) pyridiniumbetaine (PPS) or
  • the potentiating agents are naphthalene, saccharin, sodium sulfonate, sulfonamide, gelatin, butenediol, coumarin, Formalin. These additives can be used in the plating solution in amounts known in the metal plating field.
  • the plating can be carried out at a temperature of from room temperature to 70 ° C, in which the phase does not apply artificial thermal energy to the plating solution from outside. It can mean the temperature of, and in particular, it can mean 15 to 30 ° C, more specifically 20 to 25 ° C. More specifically, the electroplating can be carried out at room temperature when using alkaline plating solution, and the electroplating can be carried out at 30 to 70 ° C silver when using acidic plating solution.
  • Nickel-metal hydroxide may be any nickel hydroxide used as an electrode (or catalyst) material of conventional electrolytic or water treatment electrodes.
  • Nickel-metal hydroxide may include a layered double hydroxide (LDH) structure.
  • the metal of the nickel-metal hydroxide may be one or more metals selected from Fe, Al, Mn, Co, and Cr, and specific examples of the metal of the nickel-metal hydroxide are It may include Fe, but is not limited to it.
  • the nickel-metal hydroxide plate-like particles contained in the plating solution may have a molar ratio of nickel: metal of 1: 0.2 to 0.8.
  • the initiation of the oxygen evolution reaction is based on the occurrence of overvoltage, the nickel: metal contained in the nickel-iron composite metal hydroxide.
  • the molar ratio of 1: 0.2 to 0.8, preferably 1: 0.2 to 0.5 can be.
  • Nickel-metal hydroxide platelet particles in the plating solution have an average diameter of 0.5 to
  • Nickel-metal hydroxide plaque particles of this size can be deposited and bound to the base metal together with the plated metal, while effectively forming irregular shaped structures by the nickel-metal hydroxide plaque particles themselves.
  • a uniform protrusion structure can be formed throughout the substrate surface, which is advantageous for improving the specific surface area.
  • Nickel-metal hydroxide plate-like particles may be manufactured using conventional coprecipitation or hydrothermal synthesis, but are not limited thereto.
  • nickel-iron hydroxide sheet particles manufactured using chemical solution growth, can be mass-produced in a simple, inexpensive and rapid process, and at room temperature and atmospheric pressure as described in the following paragraph. This makes it possible to produce hydroxide platelets efficiently and energy-efficiently. As the plate-shaped hydroxides are produced by spontaneous nucleation and growth in the chemical bath, it is possible to produce platelets that are very coarse and have a specific surface area and are improved.
  • the manufacturing method the growth of the chemical solution using a chemical bath (CBD), including electrolytic plating, nickel ion source, iron ion source and hydroxyl group source (CBD; Bath deposition may further comprise the step of producing nickel-hydroxide platelet particles, wherein the iron ion source and the nickel ion source in the chemical bath are nickel sulfate-iron chloride ( ⁇ ) or nickel chloride ( ⁇ ). It is advantageous to be iron sulfate (II).
  • CBD chemical bath
  • Bath deposition may further comprise the step of producing nickel-hydroxide platelet particles, wherein the iron ion source and the nickel ion source in the chemical bath are nickel sulfate-iron chloride ( ⁇ ) or nickel chloride ( ⁇ ). It is advantageous to be iron sulfate (II).
  • the hydroxyl source may be a basic substance, ie nickel-ferrous metal hydroxides.
  • Base material can be used as a source of hydroxyl radicals.
  • the basic substance as a hydroxyl source may be ammonia, wherein the ammonia hydroxyl source should be interpreted as containing ammonia water, if the solvent of the chemical bath is a water.
  • the manufacturing step of the nickel-metal hydroxide platelet particles comprises the steps of: a) providing a metal ion bath containing a nickel ion source and an iron ion source; and b) introducing and stirring a hydroxyl source into the metal ion bath. To prepare the nickel-hydroxide platelet particles.
  • the metal ion bath may be prepared by mixing a nickel ion solution in which the nickel ion source is dissolved in the water and an iron aqueous solution in which the iron ion source is dissolved in the water.
  • a chemical bath is prepared, from the manufactured chemical bath. It is possible to voluntarily produce nucleated and grown nickel-hydroxide platelets.
  • the molar ratio of nickel silver and iron to silver contained in the nickel-iron composite metal hydroxide can be controlled, i.e., nickel-iron hydroxide sheet particles produced by chemical solution growth by controlling the molar ratio of nickel and iron ions in the chemical bath.
  • the nickel and iron ions can be directly controlled.
  • the molar ratio of nickel ions to nickel ions by the source of iron ions can be from 1: 0.2 to 0.8.
  • a nickel ion source and an iron ion source may be included.
  • the hydroxyl source can be introduced such that the pH of the metal ion bath is between 6.0 and 12.0, but is not limited thereto.
  • the nickel-iron hydroxide plate-shaped particles produced by the above-described chemical solution growth may be complex particles of a composite of plate-shaped granulated particles having an average diameter of 1 to 5 ⁇ and plate-shaped fine particles having an average diameter of 50 to 200 nm.
  • the aggregates of the plate-like fine particles can have an extended structure from the granulated particles, i.e., nickel-hydroxide platelet particles synthesized by the chemical solution growth method described above are physically independent of the aggregates of the granulated particles and the fine particles.
  • the plate-shaped granules having an average diameter of 1 to 5 ⁇ and the plate-like granules having an average diameter of 50 to 200nm are formed.
  • active material such as oxygen generating electrode, hydrolysis electrode or water treatment electrode
  • nickel-metal hydroxide plate-like particles The aggregate is very effective.
  • the nickel-metal hydroxide platy particles produced by the above-described chemical solution growth method, while causing very large surface irregularities by the granulated particles, are present in the granulated particles themselves. They can have a high specific surface area, which may be a collection of plate-like particulates with an average diameter of 50 to 200 nm.
  • the aggregate may be a combination of several plate-like particulates at different angles, and irregular polygonal pores may be formed.Agglomerate polygonal pores are formed by the plate-like particulates extending from the granulated particles, Forming a random angle that is not parallel to the plate of the granulated particles
  • It may be a randomly elongated, shaped plate of elongated particulates that come into contact with each other.
  • Polygonal pores of the agglomerate induce the deposition and desorption of oxygen bubbles that occur along with the enhancement of the active area by an increase in specific surface area. Very effective.
  • Nickel-hydroxide platelets produced by the chemical solution growth method described above may have a very high specific surface area due to the coarse particles of fine particles.
  • the BET specific surface area of the aggregate may be 20 mVg or more, specifically 20 to 20 It can be 100m 2 / g.
  • the conductive base material may be used as long as it is a material capable of serving as a current collector and a physical cognitive retardant.
  • the material may be any material used to support the electrode material (active material, catalyst material) and to ensure the stable movement of current.
  • the current collector may be a nickel plate material, Not limited by substance.
  • the present invention includes a functional electrode manufactured by the above-mentioned manufacturing method, wherein the functional electrode may be an electrode for electrolysis or an electrode for water treatment.
  • the electrode for electrolysis may be a hydrogen-evolution reaction (HER) electrode or an OER. It may be an oxygen-evolution reaction electrode, and the electrode for water treatment may be a capacitive desalination device or a silver electrode. More specifically, the functional electrode of the present invention may be an alkaline electrolytic OER electrode.
  • the functional electrode is a nickel-metal contained in the plating solution itself during electroplating.
  • the functional electrode is composed of a base metal and a metal and nickel-metal hydroxide by the electroplating. Simultaneous deposition of plate-like particles leads to an irregular structure of base metal, nickel-metal hydroxide plate-like particles, and a plating layer containing metals that bind between nickel-metal hydroxide plate-like particles and nickel-metal hydroxide plate-like particles and the base material.
  • the metal of the plating layer may be a nickel-based metal
  • the nickel-based metal is nickel, or one or more of nickel and Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu, and V. It may be a solid solution, an alloy, or a solid of the metal selected.
  • the metal of the plating layer is nickel and dissimilar metals (metals selected from one or more of Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu and V). If it contains, the metal of the plating layer is increased by 50% or more Specifically 60 to
  • nickel It may contain 95% by weight nickel, but this invention is not limited by the nickel content in the metal of the plating layer.
  • Ni-plating solution according to Table 1 was prepared using hydroxide plate-shaped particles and water as a solvent, followed by electroplating Ni on the positive electrode and nickel plate material, the conductive base material, on the negative electrode to produce a functional electrode. Electroplating
  • NiFe 0 . 25 hydroxide plate-shaped particles were prepared, and then Ni-Mo plating solution was prepared using water as a solvent according to Table 2. Then, Ni-Mo alloy (Mo 25 ⁇ %) was used as the positive electrode and the nickel plate material, which was the conductive base material, was obtained as the negative electrode. The electroplating was carried out. The electroplating was carried out for 90 minutes at a current density of 10 mA / cm 1 at 50 ° C. by stirring the plating solution at 200 rpm.
  • NiFe 0 prepared in Example 2. 25 Use hydroxide platelets, label water as solvent
  • Nickel plating solution was prepared according to 3.
  • the electroplating was carried out using Ni as the positive electrode and nickel plated as the conductive base material as the negative electrode.
  • Electroplating was carried out for 50 minutes at a current density of 5 mA / cm 2 at room temperature by stirring the plating solution at 200 rpm.
  • the powder prepared in Example 1 contained 21.6 atomic Ni and 16.5 atomic% Fe.
  • the elemental mapping it was confirmed that Ni and Fe were homogeneously distributed, and that a powdery composition of a homogeneous composition was prepared.
  • nickel-metal hydroxides were prepared.
  • FIG. 2 is a photograph observed with a scanning electron microscope of a powder prepared in Example 1. As shown in FIG. 2, aggregates in which plate-like granules and plate-like fine particles bound to the plate-like granules are aggregated are shown. Scanning electron microscopic observation revealed that together with the plate-like granulated particles having a size of 1 to 5 ⁇ , the plate-like fine particles having a size of 50 nm to 150 nm were aggregated and the size was 200 to 800 nm. It confirmed that the assembly was manufactured.
  • 3 is a high magnification scanning electron microscope for observing the aggregates of the particulate particles on the plate
  • Example 4 is a scanning electron microscope image of the functional electrode manufactured in Example 1.
  • Ni-Fe hydroxide tubular particles and Ni are simultaneously plated on the conductive base material (Ni plate material), thereby conducting conductivity.
  • the base material surface is uniformly covered by Ni-Fe hydroxide plate-like particles and a plated layer with large surface irregularities is formed.
  • the Ni-Fe hydroxide plate-like particles injected into the plating solution are randomly located on the surface of the conductive base material, and are strongly bound by nickel, a plated metal. .
  • Example 1 The surface of the functional electrode prepared in Example 1 was subjected to energy dispersive fluorescence X-ray analysis (EDX) in a 25 ⁇ 20 ⁇ region, indicating that the prepared electrode contained 43.24 atomic% Ni and 2.89 atomic% Fe.
  • EDX energy dispersive fluorescence X-ray analysis
  • FIGS. 4 to 5 show that Ni-Fe hydroxide plate particles injected into the plating solution are simultaneously plated with Ni, which is a plating metal. Ni-Fe hydroxide plate particles As Ni is plated together, nickel is plated on the surface and the content of Fe is platelet. It can be seen that it is lower than itself.
  • FIG. 6 is a result of element mapping of the surface area of the functional electrode prepared in Example 1 with EDX
  • FIG. 6 (a) shows scanning electron microscopy of the surface to be mapped
  • FIG. 6 (b) shows The mapping results of Fe Kal (black) and Ni Kal (grey) are shown.
  • Fig. 6 it can be seen that as a result of elemental mapping for each region, the nickel components are distributed evenly and the iron components are concentrated and detected on the plate-like protrusion structure.
  • the structural characteristics of the hydroxide plate-like particles are shown, but it can be seen that a functional electrode having the hydroxide plate-like particles strongly bound to the conductive base material by the plating metal is produced.
  • the plated layer of the functional electrode is not a form in which Ni-Fe hydroxide plate-like particles are randomly embedded in the nickel plated film, but in which Ni-Fe hydroxide plate-like particles are bound to the conductive base material by Ni metal. will be.
  • the oxygen generation reaction was performed by performing linear scan voltammetry (LVS) with a 1 M KOH aqueous solution at room temperature using an electrolyte and a scanning speed of 5 mV / min. OER) activity was measured.
  • the counter electrode was Ni and the reference electrode was Hg / HgO.
  • Example 8 is a functional electrode manufactured in Example 1 (NiFe 0.5 + Ni of FIG. 8), a functional electrode prepared in Example 2 (NiFe 0.25 + Ni of FIG. 8), manufactured in Example 3
  • the plating solution of Table 1 plating was carried out under the conditions of Example 1 using the same plating solution as in Table 1, except that Ni-Fe hydroxide plate-shaped particles were not contained.
  • the LVS results of the Ni electrode of Comparative Example 1 (Ni in Fig. 8) and the electrode of Comparative Example 2 (Raney Ni in Fig. 8) using the nickel electrode as the electrode were measured. Raney nickel was prepared using (atmospheric plasma spraying).
  • the functional electrode has an oxygen generating reaction voltage of 595 mV (vs. Hg / HgO) at a current density of 100 mA / cm 2, which is 80% less than that of Raen nickel (749.3 mV).
  • a Ni-Mo electrode prepared by performing plating under the conditions of Example 3 using the same plating solution as in Table 2, except that Ni-Fe hydroxide plate-shaped particles were not contained When the OER characteristics of the electrode of Comparative Example 3) and the electrode manufactured in Example 3 were examined, the Ni-Mo electrode (the electrode of Comparative Example 3) had an oxygen generation reaction voltage of 1085.3 mV, but the electrode manufactured in Example 3 In this case, it has an oxygen generation reaction voltage of 681.8mV, and it has a remarkably improved reaction characteristic to about 62% of the Ni-Mo electrode (Comparative Example 3).
  • the drawing shows the LVS results of Ni electrodes (Ni in FIG. 9) manufactured by plating under the conditions of Example 3 using the same plating solution as in Table 3.
  • FIG. 9 the functional electrode prepared according to Example 4 can also be found to have significantly improved OER reactivity characteristics. Specifically, for the functional electrode manufactured in Example 4, it is 650 mV at a current density of 100 mA / cm 2 . It can be seen that it has an oxygen evolution reaction voltage (vs. Hg HgO)
  • FIG. 10 is a diagram showing the results of performing cyclic voltammetry with a 1 M KOH aqueous solution at room temperature with a scan rate of 50 mV / min.
  • the counter electrode was N and the reference electrode was Hg / HgO.
  • FIG. 10 (a) shows the same limit as Table 2 except that the plating solution of Table 2 does not contain Ni-Fe hydroxide plate-like particles.
  • Fig. 10 shows the CV measurement result of the Ni-Mo electrode manufactured by plating under the conditions of Example 3 using the amount of money
  • Fig. 10 (b) shows the CV measurement result of the functional electrode produced in Example 3; It's a limit.
  • the HER test also showed better activity of the electrode plated with Ni-Fe hydroxide plate-like particles, and as shown in FIG. 10, the electrode prepared in Example 3 was considerably wider and the oxidation reaction was performed.
  • the amount of current flowing in the electrode was also increased by 10 times compared to the electrode of Comparative Example 3.
  • the current density of 100 mA / cm 2 was measured in a 1 M KOH aqueous solution with an electrolyte and a scan rate of 0.1 mV / min.
  • the electrode of Comparative Example 3 (Ni-Mo electrode) has a hydrogen generation reaction voltage of -1.190V (vs.
  • the Ni electrode of Comparative Example 1 has a hydrogen generation reaction voltage of -1.490V.
  • the electrode manufactured in Example 3 had a hydrogen generating reaction voltage of -1.168V
  • the electrode manufactured in Example 2 had a hydrogen generating reaction voltage of -1.396V
  • the Ni-Fe hydroxide It can be seen that the activity of HER reaction is better when the plate-like particle and the plated metal are simultaneously plated. The.

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Abstract

본 발명은, 전기분해용 또는 수처리용 전극인 기능성 전극의 제조방법을 제공하며, 상세하게, 본 발명에 따른 기능성 전극의 제조방법은 니켈-금속 수산화물 판상 입자를 함유하는 도금액에 전도성 모재를 장입하여 전해 도금하는 단계를 포함한다.

Description

명세서
발명의명칭:기능성전극및이의제조방법 기술분야
[1] 본발명은기능성전극및이의제조방법에관한것으로,상세하게，전기화학적 활성이우수한복합금속수산화물이모재에견고하게결합되고,증진된반웅 면적을가지며,복함금속수산화물의낮은전기전도도가보완된기능성전극및 이의제조방법에관한것이다.
배경기술
[2] 수전해의대표적인방법으로고온수증기전해법,양성자교환막전해법및 알칼리수전해법을들수있다.고온수증기전해법은고체산화물연료전지와그 구조및원리가동일하여양방향운전이가능하고，유지및보수가용이하다. 그러나， 700°C이상의고온작동조건이요구됨에따라,열적내구성문제및추가 열원의문제등을갖는다.양성자교환막전해법은높은에너지효율을가지며 전해액이블필요하고작은크기로제작가능하나，사용되는분리막이매우 고가이며그자체로매우강한부식성을가져수명이짧고상업성이떨어지는 문제점이 있다.알칼리수전해법은알칼리전해액을이용하는물의
전기분해법으로,제조와유지보수가용이하고， 90°C이하의낮은온도에서운전 가능하며，에너지효율이높고설비구축비용또한작아가장상업성이우수한 방법이다.
[3] 알칼리수전해법에사용되는전극은주로니켈도금된탄소강이다.니켈은 비교적가격이싸고알칼라인환경과포지티브한전압에서부식에저항성이커 수전해의전극물질로주목받아왔다.그러나，우수한활성을갖는니켈의 비표면적을높이기위해주로사용되는공정이합금막을형성한후선택적으로 합금증 Ni이아닌다른금속을디알로잉 (dealloying)하는공정으로，비표면적 향상에그한계가있을뿐만아니라공정자체가에너지소모적인한계가있다.
[4] 또한대한민국공개특허제 2013-0084472호와같이,코발트계복합산화물에 대한연구도진행되었으며활성에서좋은결과를보여준바있다.그러나， 전극의제작이전기화학적으로집전체상전구체층을형성한이를열처리하여 산화막을코팅함에따라,층분한코팅층을얻기위해반복적으로코팅을 진행하여야하고，코팅막의안정성이약한문제가있다.
[5] 또한대한민국공개특허제 2001-0071921호와같이,페로브스카이트구조의 복합금속산화물을촉매로활용하는경우도있으나이들페로브스카이트계 촉매는합성이용이하지않으며,일부물질은알칼라인환경에서녹는특성이 있는것으로보고된바있다.또한이러한페로브스카이트계촉매는우수한 결착력을갖는촉매층형성이용이하지않은데，용사방법으로전극에코팅하는 방법을적용할수있으나,고은의 열로인해산화물의형태가변화하는문제를 안고있다.
[6] 한편， LDH(layered double hydroxide)를포함하는니켈계수산화물은수전해시 과전압이작고내식성이우수하여，전해조의전극,축전식탈염장치의전극, 이온수기의전극등다양한산소발생장치나수처리장치의효과적인전극 물질로대두되고있다.그러나,수산화물입자들을전도성기재에코팅하여 전극을제조하는경우,수산화물입자와기재간의결착력이매우떨어지는 문제점과함께，수산화물의낮은전기전도도에의해전극의전기적특성이 떨어지는문제점이 있다.
발명의상세한설명
기술적과제
[7] 본발명의목적은우수한전기화학적활성을갖는전극물질이모재에견고하게 결합되고,높은비표면적을가지며,우수한전기전도도를갖는기능성전극및 이의제조방법을제공하는것이다.
[8] 본발명의다른목적은극히간단하고저가이며신속한공정을통해우수한 전기화학적활성을갖는기능성전극의제조방법올제공하는것이며,나아가, 상은및상압의에너지효율적방법을통해기능성전극을대량생산할수있는 제조방법을제공하는것이다.
과제해결수단
[9] 본발명에따른기능성전극의제조방법은니켈 -금속수산화물판상입자를 함유하는도금액에전도성모재를장입하여전해도금하는단계를포함한다.
[1이 본발명의일실시예에따른제조방법에있어,상기도금시,도금액의교반이 수행될수있다.
[11] 본발명의일실시예에따른제조방법에있어,상기도금액은니켈계도금액일 수있다.
[12] 본발명의일실시예에따른제조방법에있어 ,상기도금액은 0.1내지 20g/L의 니켈 -금속수산화물판상입자를함유할수있다.
[13] 본발명의일실시예에따른제조방법에있어,상기전해도금은 1내지
200mA/cm2의전류밀도로수행될수있다.
[14] 본발명의일실시예에따른제조방법에있어，상기니켈 -금속수산화물판상 입자의금속은 Fe, Al, Mn, Co및 Cr증선택되는하나또는들이상의금속일수 있다.
[15] 본발명의일실시예에따른제조방법에있어,상기니켈 -금속수산화물판상 입자의니켈：금속의몰비는 1： 0.2내지 0.8일수있다.
[16] 본발명의일실시예에따른제조방법에있어 ,상기니켈 -금속수산화물판상 입자의평균직경은 0.5내지 ΙΟμηι일수있다.
[17] 본발명의일실시예에따른제조방법은상기전해도금전，니켈이은공급원， 철이온공급원및수산화기공급원을포함하는화학적욕 (chemical bath)을 이용한화학적용액성장 (CBD; Chemical Bath Deposition),수열합성에의해, 니켈 -금속수산화물판상입자를제조하는단계를더포함할수있다.
[18] 본발명의일실시예에따른제조방법에있어,상기니켈 -금속수산화물판상 입자제조단계는, a)니켈이온공급원및철이은공급원을함유하는금속이은 욕을제공하는단계;및 b)상기금속이온욕에수산화기공급원을투입및 교반하여니켈-철복합금속수산화물을제조하는단계 ;를포함할수있다.
[19] 본발명의일실시예에따른제조방법에있어,상기 b)단계에서,수산화기 공급원은상기금속이온욕의 pH가 6.0내지 12.0이되도록투입될수있다.
[20] 본발명의일실시예에따른제조방법에있어，상기전극은전기분해용전극 또는수처리용전극일수있다.
[21] 본발명은상술한제조방법으로제조된기능성전극을포함한다.
[22] 본발명의일실시예에따른기능성전극은상술한제조방법으로제조되어, 전해도금에의해전도성모재상,니켈 -금속수산화물판상입자에의해 불규칙적인돌출구조를가지며니켈 -금속수산화물판상입자간및니켈 -금속 수산화물판상입자와모재간을결착시키는금속을포함하는도금층이 형성된이형성된것일수있다.
[23] 본발명의일실시예에따른기능성전극에 있어 ,상기도금층의금속은
니켈이거나, Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu및 V중하나또는둘이상 선택되는금속과니켈일수있다.
발명의효과
[24] 본발명에따른기능성전극은,니켈 -금속수산화물판상입자가랜덤한표면 요철을형성함과동시에,금속에의해전도성모재에결착된구조를가짐에 따라,넓은반웅면적을가지면서도현저하게우수한내구성을갖는장점이 있으며,향상된비표면적및니켈—금속수산화물판상입자에의해뛰어난 전기화학적활성을가져，전기분해또는수처리용전극으로매우효과적인 장점이있다.
[25] 본발명에따른기능성전극의제조방법은우수한전기화학적활성을
가지면서도견고한내구성을갖는전극을제조할수있는장점이있으며，단지 도금액에니켈 -금속수산화물판상입자를첨가하여도금하는매우간단한 공정을통해대면적의기능성전극을대량생산할수있는장점이 있다.
도면의간단한설명
[26] 도 1은실시예 1에서제조된니켈 -금속수산화물분말의 X-선회절분석결과를 도시한도면이며,
[27] 도 2는실시예 1에서제조된니켈 -금속수산화물분말의주사전자현미경
관찰사진을도시한도면이며,
[28] 도 3은실시예 1에서제조된니켈 -금속수산화물분말의고배율
주사전자현미경관찰사진을도시한도면이며, [29] 도 4는실시예 1에서제조된기능성전극의주사전자현미경관찰사진이며, [3이 도 5는실시예 1에서제조된기능성전극의고배율주사전자현미경관찰
사진이며,
[31] 도 6은실시예 1에서제조된기능성전극의표면영역올 EDX로원소맵핑한 결과를도시한도면이며,
[32] 도 7은표 1의도금액에서,니켈 -금속수산화물분말을함유하지않는것을 제외하고표 1과동일한도금액을이용하여실시예 1의조건으로도금된 도금층의표면을관찰한주사전자현미경사진이며，
[33] 도 8은실시예 1, 2및 3에서제조된기능성전극의 LVS측정결과를도시한 도면이며，
[34] 도 9는실시예 4에서제조된기능성전극의 LVS측정결과를도시한도면이며, [35] 도 10은실시예 3에서제조된기능성전극의 CV측정결과를도시한도면이다.
[36]
발명의실시를위한형태
[37] 이하첨부한도면들을참조하여본발명의기능성전극및이의제조방법을 상세히설명한다.다음에소개되는도면들은당업자에게본발명의사상이 층분히전달될수있도록하기위해 예로서제공되는것이다.따라서，본발명은 이하제시되는도면들에한정되지않고다른형태로구체화될수도있으며,이하 제시되는도면들은본발명의사상을명확히하기위해과장되어도시될수 있다.이때,사용되는기술용어및과학용어에있어서다른정의가없다면,이 발명이속하는기술분야에서통상의지식을가진자가통상적으로이해하고 있는의미를가지며,하기의설명및첨부도면에서본발명의요지를
불필요하게흐릴수있는공지기능및구성에대한설명은생략한다.
[38] 니켈 -금속수산화물은매우낮은 OER전위를가지며알칼리전해질에대한 부식저항성이높아，전기분해나수처리전극의전극물질 (촉매물질)로주목받고 있는물질이다.그러나,니켈 -금속수산화물을전극물질로사용하고자하는 경우,수열합성둥을이용하여입자를합성한후전도성기재에코팅하는방법이 주로사용되었다.그러나,이러한방법은수산화물을전도성기재에강하게 고착시키기어려워，전극의내구성및수명이떨어지는문제점이있다.나아가, 전도성기재에직접적으로수산화물을합성하여코팅시킨다하더라도， 수산화물의전기전도도가 Ni과같은금속보다떨어져전극의특성을
저하시키는문제점이 있다.
[39] 본출원인은이러한니켈—금속수산화물의우수한전기화학적활성을가짐과 동시에,니켈 -금속수산화물이기재에매우견고하게결착되고，전기전도도및 비표면적의향상이가능한기능성전극을제조하고자장기간연구를
수행하였다.
[4이 연구결과，놀랍게도전해도금시도금액에니켈-금속수산화물입자를 투입하는경우,도금되는금속과함께니켈 -금속수산화물또한기재에 ᅵ퇴적 (deposition)됨을발견하였다.이를심화한결과,도금되는금속이니켈 -금속 수산화물입자간및니켈 -금속수산화물입자와기재간을결착시키는바인더의 역할을하여 ,니켈 -금속수산화물입자가기재에매우강하게고착될수있으며, 또한，도금되는금속이안정적인전기전도경로를제공하는도전재의역할올 하여니켈—금속수산화물입자의낮은전기전도도를보상할수있음을 발견하였으며 ,나아가,니켈 -금속수산화물자체의우수한전기화학적활성과 함께 ,니켈 -금속수산화물입자에의해불규칙한돌출구조가형성되어 전기화학적반웅면적또한증진됨을발견하여,본발명을출원하기에이르렀다.
[41] 상술한발견에기반한본발명에따른기능성전극의제조방법은니켈 -금속 수산화물판상입자를함유하는도금액에전도성모재를장입하여전해 도금하는단계를포함한다.
[42] 본발명에 있어,기능성전극은전기분해용전극또는수처리용전극을의미할 수있다.전기분해용전극은 HER(hydrogen-evolution reaction)전극또는
OER(oxygen-evolution reaction)전극올의미할수있다.또한,수처리용전극은 축전식탈염장치또는이은수기등의전극을의미할수있다.보다구체적으로, 본발명의기능성전극은알칼리수전해용전극일수있으며，보다더
구체적으로기능성전극은알칼리수전해용 HER전극또는알칼리수전해용 OER전극일수있다.
[43] 상술한바와같이 ,본발명은전기화학적활성이뛰어난,니켈 -금속수산화물 판상입자자체를도금액에첨가하여전도성모재를도금하는극히간단하고 용이한방법을통해 ,니켈 -금속수산화물판상입자자체가도금금속 (이하， 전해도금에의해모재에도금되는금속을도금금속이라함)과함께전도성 모재에퇴적 (deposition)되어,랜덤하게퇴적되는니켈 -금속수산화물판상 입자에의해블규칙적인돌출구조를가지며니켈 -금속수산화물판상입자간 및니켈 -금속수산화물판상입자와모재간올결착시키는금속을포함하는 도금층이형성될수있다.
[44] 제조되는전극은니켈 -금속수산화물판상입자에의해,우수한전기화학적 활성을가질뿐만아니라，니켈 -금속수산화물판상입자들이도금금속에의해 전도성모재에매우강하게결착됨에따라，매우우수한내구성을가질수 있으며,도금금속에의해우수한전기전도도를가질수있다.또한，니켈 -금속 수산화물판상입자가도금금속에의해전도성모재의임의의위치에서로 상이한임의의각도로돌출되며결착됨에따라，블규칙한형태의표면요철을 발생시켜，제조되는전극의전기화학적활성면적을향상시킬수있다.나아가, 이러한블규칙한형태의조대한표면요철들은표면거칠기의증가에의한활성 영역의증진과함께,발생하는산소기포의부착방지및탈착유도에도 효과적이다.
[45] 본발명의일실시예에따른제조방법에있어，전해도금시도금액의교반이 수행되는것이유리하다.통상의전해도금시교반이수행되는경우보다치밀한 도금이수행되는것으로알려져 있다.도금액의교반은도금액에함유된 니켈 -금속수산화물판상입자를균일하게분산시키고，도금액에함유된 니켈 -금속수산화물판상입자를균일하고효과적으로모재에퇴적시키기위해 수행되는것이다.도금액의교반속도가너무느린경우，도금액내니켈 -금속 수산화물판상입자의균일한분산이담보되지않을위험이 있으며，모재에 퇴적되는니켈 -금속수산화물판상입자의균일성이떨어질위험이 있다.반면, 교반속도가너무빠른경우니켈 -금속수산화물판상입자가모재에안정적으로 결착되기전교반에의해야기되는물리적충격에의해니켈 -금속수산화물판상 입자가다시도금액으로떨어져나갈위험이있다.이에따라,대면적의 모재에도안정적으로균일하게니켈 -금속수산화물판상입자가퇴적되기 위해서，도금액은 100내지 500rpm,구체적으로는 200내지 400 rpm으로 교반되는것이유리하며，이러한교반상태가유지되며전해도금이수행되는 것이좋다.
[46] 다량의니켈 -금속수산화물판상입자를전도성모재에퇴적시킴과동시에 도금금속이바인더로작용하는적정량으로퇴적되기위해서는,통상의도금 조건대비매우낮은전류조건으로장시간동안도금이수행되는것이좋다.즉, 니켈 -금속수산화물판상입자가전도성모재에균일하고보다고밀도로 퇴적되며도금금속이니켈-금속수산화물판상입자간,니켈-금속수산화물 판상입자와모재간을결착시키는바인더의형태로도금이이루어지기 위해서는,통상의도금조건대비매우낮은전류조건으로장시간동안도금이 수행되는것이좋다.구체적인예로,전해도금은 1내지 200mA/cm2의낮은전류 밀도로수행되는것이좋으며,보다좋게는 5내지 50mA/cm2의전류밀도,보다 더좋게는 5내지 25mA/cm2으로수행되는것이좋다.이러한전류밀도는 니켈 -금속수산화물판상입자의 랜덤한퇴적에의해야기되는표면요철을 훼손시키기않으면서도모재에퇴적되는니켈 -금속수산화물판상입자가도금 금속에의해견고하고강하게모재및 /또는이웃하는니켈 _금속수산화물판상 입자에결착될수있는조건이다.또한,이러한전류밀도는니켈 -금속수산화물 판상입자와함께모재에퇴적되는도금금속들이섬 (island)형태가아닌,서로 연결된연속체 (continuum)로도금이수행되며，니켈 -금속수산화물판상입자와 무관하게안정적인저저항전류이동경로를제공할수있는조건이다.전해도금 시간은，니켈 -금속수산화물판상입자및도금금속을함유하는도금층이 모재를안정적으로덮을수있는정도로형성될수있는시간이면족하다. 구체적이며비한정적인일예로, 1내지 3시간동안전해도금이수행될수있다.
[47] 도금액에함유되는니켈 -금속수산화물판상입자의농도 (g/L)는도금액의 액내전기저항을과도하게증가시키기않고금속의도금에부영향 (negative effect)을야기하지않으면서도전해도금시모재에층분한양의니켈 -금속 수산화물판상입자가공급될수있는농도인것이유리하다.구체적인일예로, 도금액은 1내지 20g/L의니켈 -금속수산화물관상입자를함유할수있으며, 보다구체적으로 1내지 I5g/L의니켈 -금속수산화물판상입자를함유할수 있다.이러한농도는상술한교반이수행되는경우에도액내저항의불균일한 변화등을야기하지않으며,전류밀도등의제어에의해설계된바에따라 니켈 -금속수산화물판상입자와함께도금금속이안정적이고재현성있게 퇴적될수있도록하는농도이며,모재의표면을균일하게덮을수있는정도의 니켈 -금속수산화물판상입자가공급될수있는농도이다.
본발명의일실시예에따른제조방법에있어,도금액은종래금속을전해 도금하기위해사용되는도금액 (산성，중성또는알칼리성도금액을포함함)이면 사용가능하다.다만,본발명에따른기능성전극이전기분해또는수처리용 기능성전극임에따리-,도금액은수처리나전기분해등에활성을갖는금속의 도금액인것이좋다.일예로,도금액은니켈계도금액일수있으며,니켈계 도금액은니켈도금액또는 Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu및 V중하나또는 둘이상선택되는금속과니켈의도금액일수있다.니켈계도금액은산성 도금액,중성도금액또는염기성도금액일수있으며，도금액의 pH와무관하게 도금금속과판상입자가동시도금될수있다.구체적인일예로,니켈계 도금액은니켈을포함한도금하고자하는금속의이온을함유하는액일수있다. 도금하고자하는금속의이은을공급하는도금금속이온공급원은특별히 한정되지않으나,도금하고자하는금속의황산염，사안화염,붕불화염，염화물， 탄산염，피로인산염，술파민산염 ,염화물,산화물，알칸술포네이트 (일예로 메탄술포네이트,프로판술포네이트등),알카놀슬포네이트 (일예로,
프로판올슬포네이트등),유기산염 (일예로,아세테이트염,시트레이트염 , 타르타레이트염등)등을포함할수있으며，단독또는두종이상의금속이온 공급원을함유할수있다ᅳ도금액내도금금속이온공급원의농도는특별히 한정되지않으나 100내지 200g/L의농도일수있다.또한， pH가 8내지 11인 알칼라인도금액인경우,암모니아,수산화나트륨ᅳ수산화칼륨등과같은염기성 물질에의해그 pH가조절될수있으며 , ρΗ가 2내지 6인산성도금액인경우， 황산,질산또는염산등과같은산성물질에의해그 pH가조절될수있다.또한, 니켈계도금액은염소이온이 액증에존재할수있으며,염소이온공급원으로 염화물을포함할수있다.염화물은염화나트륨을포함하는금속염화물또는 염화암모늄등을들수있으며,도금액은 5내지 15g/L의 염화물을함유할수 있으나이에한정되는것은아니디-.또한,도금액은산성도금액，증성도금액 또는염기성도금액에통상적으로사용되는완층제를더포함할수있으며, 완층제는구연산염둥과같은유기산염，붕산과같은무기산또는
탄산나트륨등과같은탄산염등을들수있으나,이에한정되는것은아니다. 이러한완충제는금속도금분야에서공지의양으로도금액에사용될수있다. 이와함께,도금액은,필요시선택적으로,욕의안정성,금속의석출 (deposition) 거동,석출된금속의품질및전류이동둥을향상하기위해,도금금속의 도금액에통상적으로사용되는가속제 ,광택제 ,평탄제，습윤제 ,도전성염， 및 /또는웅력완화제등을더포함할수있다.일예로，가속제는황함유
유기화합물을들수있으며 ,구체적인일예로,
Ν,Ν-디메틸—디티오카르밤산— (3-설포프로필)에스테르, 3-메르캅토 -1-프로판 설폰산，피리디늄프로필설포베타인,비스-설포에틸디설파이드，또는
3- (2-벤즈티아졸릴티오) -1-프로판설폰산소듐염등을들수있다.일예로， 억제제는산소함유사슬형고분자를들수있으며，구체적인일예로,
카르복시메틸셀를로즈,옥탄을폴리알킬렌글리콜에테르,
폴리에틸렌글리콜에테르,올레산폴리글리콜에스테르，폴리에틸렌프로필렌 글리콜,폴리에틸렌글리콜，폴리에틸렌글리콜디메틸에테르,
폴리옥시프로필렌글리콜,폴리프로필렌글리콜,폴리비닐알콜,스테아르산 폴리글리콜에스테르，스테아릴알콜폴리글리콜에테르，
β_나프를ᅳ폴리에틸렌글리콜에테르,에틸렌옥사이드―프로필렌옥사이드 코폴리머또는부틸알코올-에틸렌옥사이드 -프로필렌옥사이드코폴리머등을 들수있다.일예로，평탄제는함질소유기물올들수있으며，구체적인일예로，
4-메르캅토피리딘, 2-메르캅토피리딘, 2-메르캅토티아졸린，벤조트리아졸, 벤조티아졸,벤즈이미다졸, 0-아미노페놀， 2,1,3-벤조티아지아졸,페닐렌디아민,
2-메르캅토벤조티아졸,에틸렌티오우레아，티오우레아，티아디아졸,이미다졸, 모노에탄을아민，디에탄을아민,트리에탄올아민,디메틸아민,에틸렌디아민， 디에틸렌트리아민，아세트아미드,프로필아미드，벤즈아미드，아크¾아미드， 메타크릴아미드， Ν,Ν-디메틸아크릴아미드，라우릴디메틸베타인,
라우라미도프로필베타인, 1-(3—술포프로필)피리디늄베타인 (PPS)또는
3-포르밀 -1-(3-술포프로필)피리디늄베타인 (FPPS)등을들수있다.일예로, 옹력완화제는나프탈렌，사카린，슬폰산소다，슬폰아미드,젤라틴,부텐디올， 쿠마린,포르말린둥을들수있다.이러한첨가제는금속도금분야에서공지의 양으로도금액에사용될수있다,
[49] 니켈 -금속수산화물판상입자를함유하는도금액을이용한도금시，도금은 상온내지 70°C의온도에서수행될수있다.이때,상은이라함은외부에서 도금액에인위적인열에너지를인가하지않는상태의온도를의미할수있으며， 구체적인일예로， 15내지 30°C,보다구체적으로 20내지 25°C를의미할수있다. 보다구체적으로,알칼라인도금액을이용하는경우전해도금은상온에서 수행될수있으며,산성도금액을이용하는경우전해도금은 30내지 70°C의 은도에서수행될수있다.
[50] 니켈-금속수산화물은종래수전해또는수처리전극의전극 (또는촉매)물질로 사용되는어떠한니켈계수산화물도사용가능하며 ,니켈 -금속수산화물은 LDH(layered double hydroxide)구조를포함할수있다.비한정적인일예로, 니켈 -금속수산화물의금속은 Fe, Al, Mn, Co및 Cr에서하나또는둘이상 선택되는금속일수있으며,구체적인일예로니켈-금속수산화물의금속은 Fe를포함할수있으나,이에한정되는것은아니다.
[51] 도금액에함유되는니켈 -금속수산화물판상입자는니켈:금속의몰비가 1： 0.2내지 0.8일수있다.산소발생반응시작은과전압발생측면에서，니켈-철 복합금속수산화물에함유된니켈:금속의몰비는 1： 0.2내지 0.8，좋게는 1: 0.2 내지 0.5일수있다.
[52] 도금액에함유되는니켈 -금속수산화물판상입자는평균직경이 0.5내지
ΙΟμπι,구체적으로는 1내지 5μιη일수있다.이러한크기의니켈 -금속수산화물 판상입자는도금금속과함께모재에퇴적및결착되어도,니켈 -금속수산화물 판상입자자체에의한불규칙한형태의돌출구조가효과적으로형성되면서도 모재표면전반적으로균일한돌출구조가형성될수있어,비표면적향상에 유리하다.
[53] 니켈 -금속수산화물판상입자는종래의공침법이나수열합성등을이용하여 제조된것일수있으나，이에한정되지않는다.
[54] 그러나，후슬하는바와같이 ,화학적용액성장을이용하여제조된니켈-철 수산화물판상입자의경우，간단하고저가이며신속한공정을통해수산화물 판상입자를대량생산할수있고,상온및상압반웅임에따라,에너지 효율적으로수산화물판상입자를생산할수있어유리하다.또한,화학적 욕에서자발적인핵생성및성장에의해판형의수산화물이제조됨에따라,매우 조대하며비표면적또한향상된판상입자의제조가가능하다.
[55] 상세하게 ,본발명의일실시예에따른제조방법은,전해도금전,니켈이온 공급원，철이온공급원및수산화기공급원을포함하는화학적욕 (chemical bath)을이용한화학적용액성장 (CBD; Chemical Bath Deposition)에의해, 니켈-철수산화물판상입자를제조하는단계를더포함할수있다.이때,화학적 욕에함유되는철이온공급원및니켈이온공급원은,황산니켈 -염화철 (Π)또는 염화니켈 (Π) -황산철 (II)인것이유리하다.
[56] 수산화기공급원은염기성물질일수있다.즉,니켈-철금속수산화물을
이루는물질공급원인수산화기공급원으로염기성물질이사용될수있다. 수산화기공급원으로써의염기성물질은암모니아일수있다.이때,수산화기 공급원이암모니아라함은,화학적욕의용매가물인경우,암모니아수를 포함하는것으로해석되어야한다.
[57] 구체적으로,니켈 -금속수산화물판상입자의제조단계는， a)니켈이온공급원 및철이온공급원을함유하는금속이온욕을제공하는단계 ;및 b)금속이온 욕에수산화기공급원을투입및교반하여니켈-철수산화물판상입자를 제조하는단계 ;를포함할수있다.
[58] 금속이온욕은,니켈이온공급원이물에용해된니켈이온수용액과철이온 공급원이물에용해된철이은수용액을혼합하여금속이온욕을제조할수 있다.이후, b)단계에서수산화기공급원이물에용해된염기성수용액을 금속이온욕에흔합함으로써，화학적욕을제조하여,제조된화학적욕으로부터 자발적으로핵생성및성장된니켈-철수산화물판상입자를제조할수있다.
[59] 이띠ᅵ，화학적욕에함유된니켈이온과철이온의몰비를제어함으로써，
니켈-철복합금속수산화물에함유된니켈이은과철이은의몰비가조절될수 있다.즉,화학적욕에함유된니켈이온과철이온의몰비를조절함으로써， 화학적용액성장으로제조되는니켈-철수산화물판상입자의니켈이온과철 이온의함량을직접적으로조절할수있다.
[60] 화학적욕에서，니켈이온공급원에의한니켈이온：철이온공급원에의한철 이은의몰비는 1： 0.2내지 0.8일수있다.즉,화학적욕은니켈이은：철이온의 몰비가 1： 0.2내지으8이되도록니켈이온공급원과철이온공급원을함유할수 있다.
[61] b)단계에서，수산화기공급원은금속이온욕의 pH가 6.0내지 12.0이되도록 투입될수있으나，이에한정되는것은아니다.
[62] 상술한화학적용액성장으로제조되는니켈-철수산화물판상입자는평균 직경이 1내지 5μπι인판상형조립입자와평균직경이 50내지 200nm인판상형 미립입자의웅집체가복합화된복합입자일수있으며 ,판상형미립입자의 웅집체가조립입자로부터연장된구조를가질수있다.즉,상술한화학적용액 성장법을통해합성되는니켈-철수산화물판상입자는조립입자와미립입자의 웅집체가물리적으로서로독립되어존재하는것이아니며,판상형미립입자의 웅집체가조립입자로부터연장되어 일체를이루는구조일수있다.평균직경이 1내지 5μηι인판상형조립입자와평균직경이 50내지 200nm인판상형미립 입지 -들이웅집된웅집체를포함하되，미립입자의웅집체가조립입자로부터 연장된구조는,산소발생전극,수분해전극또는수처리전극등의활물질로, 니켈 -금속수산화물판상입자의집합체가매우효과적임올의미한다.상세하게， 상술한화학적용액성장법으로제조되는니켈 -금속수산화물판상입자는,조립 입자들에의해매우큰표면요철을유발함과동시에,조립입자자체에 존재하는미립자들의웅집체에의해높은비표면적을가질수있다.웅집체는 평균직경이 50내지 200nm인판상형미립입자들이웅집된것일수있다.
상세하게，웅집체는다수개의판상형미립입자가서로다른각도로결합되며 블규칙한형태의다각형공극들이형성된것일수있다.응집체의다각형 공극들은판상형미립입자들이조립입자로부터연장되되,미립입자들의 판들이조립입자의판과평행이아닌임의 (random)의각도를형성하며
블규칙하게연장되며,연장된미립입자들의판들이서로맞닿아형성된것일수 있다.웅집체의다각형공극들은비표면적의증가에의한활성영역의증진과 함께 ,발생하는산소기포의부착방지및탈착유도에도매우효과적이다.
상술한화학적용액성장법으로제조되는니켈-철수산화물판상입자는미립 입자들의웅집체에의해,매우높은비표면적을가질수있다.상세하게, 집합체의 BET비표면적은 20mVg이상일수있으며,구체적으로 20내지 100m2 /g일수있다. [63] 본발명의일실시예에따른제조방법에있어,전도성모재는집전체및 물리적인지지체의 역할을수행할수있는물질이면사용가능하다.상세하게， 전도성모재는통상의수처리장치또는수전해장치에서,전극물질 (활물질, 촉매물질)을지지하며전류의안정적인이동을담보하는데사용되는물질이면 무방하다.산소발생수전해전극의일예로，집전체는니켈판재일수있으나,본 발명이집전체의물질에의해한정되는것은아니디-.
[64] 본발명은상술한제조방법으로제조된기능성전극을포함한다.이때，기능성 전극은전기분해용전극또는수처리용전극일수있다.전기분해용전극은 HER(hydrogen-evolution reaction)전극또는 OER(oxygen-evolution reaction) 전극일수있으며，수처리용전극은축전식탈염장치또는이은수기용전극일 수있다.보다구체적으로，본발명의기능성전극은알칼리수전해용 OER 전극일수있다.
[65] 상세하게，기능성전극은，전해도금시,도금액자체에함유된니켈 -금속
수산화물판상입자가도금금속과함께모재에랜덤하게퇴적되어,도금금속에 의해서로간및모재에결착되어형성된도금층을포함한디-.이에따라,기능성 전극은모재,및전해도금에의한금속과니켈 -금속수산화물판상입자의동시 퇴적에의해,모재상,니켈—금속수산화물판상입자에의해불규칙적인돌출 구조를가지며니켈 -금속수산화물판상입자간및니켈 -금속수산화물판상 입자와모재간을결착시키는금속을포함하는도금층을포함할수있다.이때 , 도금층의금속은니켈계금속일수있으며，니켈계금속은니켈이거나,니켈과 Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu및 V에서하나또는둘이상선택되는금속의 고용체，함금또는흔함물일수있다.도금층의금속이니켈과이종금속 (Mo, Co, Fe, Zn, Cr, Mn, W, Cd, Cu및 V에서하나또는둘이상선택되는금속)을 포함하는경우,도금층의금속은 50증량 %이상,구체적으로는 60내지
95중량 %의니켈을함유할수있으나,본발명이도금층의금속에함유되는니켈 함량에의해한정되는것은아니다.
[66] (실시예 1)
[67] 니켈 -금속수산화물판상입자의제조
[68] 1M황산니켈 (NiS04)수용액 40ml와 0.5M염화철 (n)(FeCl2)수용액 40ml를흔합 및교반 (300rpm)하며， 25중량 %암모니아수 10ml를투입하고,상온 (25°C)및 상압 (lata)에서 30분간반웅시켰다.이후수득된입자상을필터링하여회수한후 탈이온수로세척하고 70oC오본에서 24시간동안건조하여 NiFe0.5수산화물판상 입자를제조하였다.
[69] 기능성전극의제조
[70] 제조된 NiFe0.5수산화물판상입자를이용하고물을용매로하여 ,표 1에따른 Ni도금액을제조한후, Ni을 +극으로，전도성모재인니켈판재를 -극으로 전해도금을수행하여,기능성전극을제조하였다.전해도금은도금액을
200rpm으로교반하여 ,상온에서 10mA/cm2의전류밀도로 90분동안수행되었다. [71] (표 1)
Figure imgf000013_0001
[73] (실시예 2)
[74] 니켈 -금속수산화물판상입자의제조
[75] 1M황산니켈 (NiS04)수용액 160ml와 0.25M염화철 (n)(FeCl2)수용액 160ml를 혼합및교반 (300rpm)하며， 28증량 %암모니아수 35ml를투입하고，상온 (25°C)및 상압 (latm)에서 60분간반웅시켰다.이후수득된입자상올필터링하여회수한후 탈이온수로세척하고 70oC오본에서 24시간동안건조하여 NiFe0.25수산화물 판상입자를제조하였다.
[76] 표 1에따른도금액과동일하되 , NiFe0.5수산화물판상입자대신제조된 NiFe^ 수산화물판상입자를 5g/L의농도로하여도금을수행하였다.도금조건은 실시예 1과동일하였다.
[77] (실시예 3)
[78] 실시예 2와동일하게 NiFe0.25수산화물판상입자를제조한후,물을용매로표 2에따라 Ni-Mo도금액을제조하였다.이후, Ni-Mo합금 (Mo 25\ %)을 +극으로, 전도성모재인니켈판재를 -극으로하여전해도금을수행하였다.전해도금은 도금액을 200rpm으로교반하여 , 50°C에서 lOmA/cm1의전류밀도로 90분동안 수행되었다.
[79] (표 2)
Figure imgf000013_0002
[81] (실시예 4)
[82] 실시예 2에서제조된 NiFe0.25수산화물판상입자를사용하되，물을용매로표
3에따라니켈도금액을제조하였다.
[83] (표 3)
Figure imgf000014_0001
[85] 이후, Ni을 +극으로,전도성모재인니켈판재를 -극으로하여전해도금을
수행하였다.전해도금은도금액을 200rpm으로교반하여，상온에서 5mA/cm2의 전류밀도로 50분동안수행되었다.
[86] 에너지분산형광 X-선분석 (EDX; Energy Dispersive X-ray Spectrometer)결과, 실시예 1에서제조된분말은 21.6 atomic Ni및 16.5 atomic% Fe를함유하였다. 원소별맵핑결과, Ni및 Fe가균질하게분포함올확인하였으며,균질한조성의 분말상이제조됨을확인하였다.또한,실시예 3에서제조된분말을 X-선희절 분석시험한결과,도 1과같이니켈 -금속수산화물이제조됨을확인하였다.
[87] 도 2는실시예 1에서제조된분말의주사전자현미경으로관찰한사진이다.도 2에서알수있듯이,판상의조립입자및판상의조립입자에결착된판상의 미세입자들이응집된응집체들이제조됨을확인하였디-.주사전자현미경관찰 결과， 1내지 5 μπι의크기를갖는판상의조립입자와함께， 50nm내지 150nm의 크기를갖는판상의미립입자들이응집되어 200내지 800nm의크기를갖는 웅집체가제조됨을확인하였다.
[88] 도 3은판상의미립입자들의웅집체를관찰한고배율주사전자현미경
사진이다.웅집체들올관찰한결과,조립입자에결착된판상형미립입자들이 서로다른각도로결합되며불규칙한형태의다각형공극들을갖는웅집체가 형성됨을확인하였다.실시예 1에서제조된분말의 BET비표면적을측정한 결과， 25mVg의비표면적을갖는 Ni-Fe수산화물의분말이제조됨을확인하였다.
[89] 도 4는실시예 1에서제조된기능성전극의주사전자현미경관찰사진이다.도 4에서알수있듯이,전도성모재 (Ni판재)에 Ni-Fe수산화물관상입자들과 Ni가 동시도금되어,전도성모재표면이 Ni-Fe수산화물판상입자들에의해 균일하게뒤덮이며거대표면요철들이형성된도금층이제조됨을알수있다. 또한，도 5로도시한동일전극의고배율주사전자현미경사진에서알수있듯이, 도금액에투입된 Ni-Fe수산화물판상입자들이 랜덤하게전도성모재표면에 위치하며，도금금속인니켈에의해강하게결착되어 있는것을알수있다.
[9이 실시예 1에서제조된기능성전극의표면을， 25μπιχ20μπι영역에대해,에너지 분산형광 X-선분석 (EDX)한결과，제조된전극은 43.24 atomic% Ni및 2.89 atomic% Fe를함유함을확인하였다.도 4내지도 5의주사전자현미경및 EDX 분석결과를통해,도금액에투입된 Ni-Fe수산화물판상입자가도금금속인 Ni과함께동시도금됨을확인할수있다.또한， Ni-Fe수산화물판상입자들과 함께 Ni이도금됨에따라,표면에니켈이도금되며 Fe의함량이판상입자 자체보다낮게검출됨을알수있다.
[91] 도 6은실시예 1에서제조된기능성전극의표면영역을 EDX로원소맵핑한 결과로，도 6(a)는맵핑대상표면의주사전자현미경시-진이며,도 6(b)는 Fe Kal (검은색)과 Ni Kal(회색)의맵핑결과이디.도 6에서알수있듯이,영역별 원소맵핑결과,니켈성분이고르게분포하고철성분이판상의돌출구조 부분에집증되어검출됨을알수있다.이에따라,수산화물판상입자의구조적 특성이나타나면서도수산화물판상입자가도금금속에의해전도성모재에 강하게결착된기능성전극이제조됨을알수있다.
[92] 반면도 7은표 1의도금액에서 , Ni-Fe수산화물판상입자를함유하지않는 것을제외하고표 1과동일한도금액올이용하여실시예 1의조건으로도금올 수행한후,도금층의표면을관찰한주사전자현미경사진이다.도 7과같이 알칼라인도금욕에서매우낮은저전류상태로도금을수행한경우,표면균열이 발생함을알수있으며，이는도금증발생한수소에의한인장력 (tensile stress)에 기인한것으로해석된다.이때도 7과도 4가동일한배율의관찰사진임을 주목해야한다.도 4와같이실시예를통해제조된기능성전극의경우 Ni막 도금시발생하는거대크랙 (crack)들이존재하지않음을알수있다.이는,기능성 전극의도금층이, Ni-Fe수산화물판상입자가니켈도금막에랜덤하게박혀 있는형태가아닌， Ni-Fe수산화물판상입자들이 Ni금속에의해전도성모재에 결착되는형태임을의미하는것이다.
[93] 실시예 3에서제조된기능성전극의표면을， 120μπιχ60μιη영역에대해,에너지 분산형광 X-선분석 (EDX)한결과，제조된전극은 17.13 atomic% Mo, 51.64 atomic Ni및 0.18 atomic Fe를함유함을확인하였다.이를통해 Mo-Ni의복합 도금액을이용한경우에도 Mo및 Ni의도금금속과함께 Ni-Fe수산화물판상 입자가동시도금됨을알수있다.
[94] 제조된전극의전기화학적특성올평가하기위해,상온에서 1M KOH수용액을 전해질로, 5mV/min의스캔속도조건으로선형스캔전압전류법 (LVS)을 실시하여,제조된산소발생반웅 (OER)의활성을측정하였다.이때，카운터 전극은 Ni이었으며，기준전극은 Hg/HgO이었다.
[95] 도 8은실시예 1에서제조된기능성전극 (도 8의 NiFe0.5+Ni),실시예 2에서 제조된기능성전극 (도 8의 NiFe0.25+Ni),실시예 3에서제조된기능성전극 (도 8의 NiFe0.25+NiMo),표 1의도금액에서, Ni-Fe수산화물판상입자를함유하지 않는것을제외하고표 1과동일한도금액을이용하여실시예 1의조건으로 도금을수행하여제조된비교예 1의 Ni전극 (도 8의 Ni)및레이니니켈을 전극으로사용한비교예 2의전극 (도 8의 Raney Ni)의 LVS결과를측정도시한 도면이다.이때,레이니니켈은 APS(atmospheric plasma spraying)을이용하여 제조된레이니니켈이었다.
[96] 도 8에서알수있듯이，실시예 1내지 3을통해제조된기능성전극의경우, OER반옹특성이현저하게향상됨을알수있으며，특히,실시예 1에서제조된 기능성전극의경우, 100mA/cm2의전류밀도에서 595mV의산소발생반웅 전압 (vs. Hg/HgO)을가져,레이니니켈 (749.3mV)대비 80%이하의산소 발생반웅전압을가짐을알수있다.
[97] 또한,표 2의도금액에서 , Ni-Fe수산화물판상입자를함유하지않는것을 제외하고표 2와동일한도금액을이용하여실시예 3의조건으로도금올 수행하여제조된 Ni-Mo전극 (비교예 3의전극)과실시예 3에서제조된전극의 OER특성을살피면, Ni-Mo전극 (비교예 3의전극)의경우 1085.3mV의산소 발생반웅전압을가지나，실시예 3에서제조된전극의경우 681.8mV의산소 발생반웅전압을가져， Ni-Mo전극 (비교예 3의전극)대비약 62%수준으로 현저하게향상된반웅특성을가짐을알수있다.
[98] 도 9는실시예 4에서제조된기능성전극 (도 9의 NiFe0.25+Ni)및 Ni-Fe
수산화물판상입자를함유하지않는것을제외하고표 3과동일한도금액을 이용하여실시예 3의조건으로도금을수행하여제조된 Ni전극 (도 9의 Ni)의 LVS결과를측정도시한도면이다.도 9에서알수있듯이,실시예 4를통해 제조된기능성전극또한, OER반옹특성이현저하게향상됨올알수있으며 , 상세하게,실시예 4에서제조된기능성전극의경우， lOOmA/cm2의전류밀도에서 650mV의산소발생반응전압 (vs. Hg HgO)을가짐올알수있다.
[99] 도 10상온에서 1M KOH수용액을전해질로， 50mV/min의스캔속도조건으로 순환전압전류법 (Cyclic Voltammetry)을실시한결과를도시한도면이다. HER 테스트시 ,카운터전극은 N 었으며，기준전극은 Hg/HgO이었다.상세하게，도 10(a)는표 2의도금액에서, Ni-Fe수산화물판상입자를함유하지않는것을 제외하고표 2와동일한도금액을이용하여실시예 3의조건으로도금을 수행하여제조된 Ni-Mo전극의 CV측정결과를도시한도면이며，도 10(b)는 실시예 3에서제조된기능성전극의 CV측정결과를도시한도면이다. LVS실험 결과, HER테스트에서도， Ni-Fe수산화물판상입자를복합도금한전극의 활성이보다우수함을알수있었으며,도 10에서알수있듯이산화면적이 실시예 3에서제조된전극이현저하게넓으며,산화반응에서흐르는전류의양 또한비교예 3의전극대비 10배가량증가함을알수있었다.또한, 1M KOH 수용액을전해질로, 0.1mV/min의스캔속도조건으로 LVS테스트결과, 100mA/cm2의전류밀도에서비교예 3의전극 (Ni-Mo전극)의경우 -1.190V의 수소발생반웅전압 (vs. Hg/HgO)을가지며,비교예 1의 Ni전극의경우 -1.490V의 수소발생반웅전압을가짐을확인하였으며,반면，실시예 3에서제조된전극의 경우 -1.168V의수소발생반응전압을가지며,실시예 2에서제조된전극의경우 -1.396V의수소발생반웅전압을가져， Ni-Fe수산화물판상입자와도금금속이 동시도금된경우， HER반웅의활성이보다우수함을알수있다.
[100] OER테스트및 HER테스트결과에서알수있듯이,니켈 -금속수산화물판상 입자와도금금속이동시도금된경우,비표면적의확대와니켈-금속수산화물 판상입자자체의상호작용에의해,제조된전극의전기화학적활성이현저하게 증가함을알수있다.
[101] 이상과같이본발명에서는특정된사항들과한정된실시예및도면에의해 설명되었으나이는본발명의보다전반적인이해를돕기위해서제공된것일 뿐,본발명은상기의실시예에한정되는것은아니며,본발명이속하는 분야에서통상의지식을가진자라면이러한기재로부터다양한수정및변형이 가능하다.
[102] 따라서，본발명의사상은설명된실시예에국한되어정해져서는아니되며， 후술하는특허청구범위뿐아니라이특허청구범위와균등하거나등가적변형。 있는모든것들은본발명사상의범주에속한다고할것이다.

Claims

청구범위
[청구항 1] 니켈 -금속수산화물판상입자를함유하는도금액에전도성모재를
장입하여전해도금하는단계를포함하는기능성전극의제조방법 .
[청구항 2] 제 1항에있어서，
상기도금시,도금액의교반이수행되는기능성전극의제조방법.
[청구항 3] 제 1항에 있어서,
상기도금액은니켈계도금액인기능성전극의제조방법.
[청구항 4] 제 1항에 있어서,
상기도금액은 O.lg/L내지 20g L의니켈 -금속수산화물판상입자를 함유하는기능성전극의제조방법 .
[청구항 5] 제 1항에 있어서,
상기전해도금은 1내지 200mA/cm2의전류밀도로수행되는기능성 전극의제조방법.
[청구항 6] 제 1항에 있어서,
상기니켈 -금속수산화물판상입자의금속은 Fe, Al, Mn, Co및 Cr중 선택되는하나또는둘이상의금속인기능성전극의제조방법 .
[청구항 7] 제 6항에 있어서,
상기니켈 -금속수산화물판상입자의니켈:금속의몰비는 1： 0.2내지
0.8인기능성전극의제조방법 .
[청구항 8] 제 6항에 있어서，
상기니켈 -금속수산화물판상입자의평균직경은 0.5내지 ΙΟμπι인 기능성전극의제조방법.
[청구항 9] 제 1항에 있어서,
상기전해도금전，니켈이은공급원，철이온공급원및수산화기 공급원을포함하는화학적욕 (chemical bath)을이용한화학적용액 성장 (CBD; Chemical Bath Deposition),수열합성에의해，니켈 -금속 수산화물판상입자를제조하는단계를더포함하는기능성전극의 제조방법ᅳ
[청구항 10] 제 9항에 있어서，
상기니켈 -금속수산화물판상입자제조단계는,
a)니켈이은공급원및철이온공급원을함유하는금속이온욕을 제공하는단계 ;및
b)상기금속이온욕에수산화기공급원을투입및교반하여니켈—철복합 금속수산화물을제조하는단계 ;를포함하는기능성전극의제조방법 .
[청구항 11] 제 10항에 있어서，
상기 b)단계에서,수산화기공급원은상기금속이온욕의 pH가 6.0내지 12.0이되도록투입되는기능성전극의제조방법.
[청구항 12] 제 1항에있어서，
상기전극은전기분해용전극또는수처리용전극인기능성전극의 제조방법.
[청구항 13] 제 1항내지제 12항증어느한항에따른제조방법으로제조되어,전해 도금에의해전도성모재상，니켈 -금속수산화물판상입자에의해 불규칙적인돌출구조를가지며니켈 -금속수산화물판상입자간및 니켈 -금속수산화물판상입자와모재간을결착시키는금속을포함하 도금층이형성된기능성전극.
[청구항 14] 제 13항에 있어서,
상기기능성전극은 HER(hydrc)gen-evolution reaction)전극또는 OER(oxygen-evolution reaction)전극인기능성전극.
PCT/KR2017/009091 2016-10-21 2017-08-21 기능성 전극 및 이의 제조방법 Ceased WO2018074723A1 (ko)

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KR102390091B1 (ko) * 2020-05-22 2022-04-25 서울대학교산학협력단 비귀금속 다성분계 합금을 활용한 고성능 수전해 촉매 전극의 제작
KR102738365B1 (ko) * 2020-11-11 2024-12-03 한화솔루션 주식회사 음이온 교환막 수전해용 산화 전극
WO2022191035A1 (ja) * 2021-03-12 2022-09-15 国立研究開発法人物質・材料研究機構 層状複水酸化物を表面に有する金属板及びその製造方法
JP7669028B2 (ja) * 2021-04-09 2025-04-28 国立研究開発法人物質・材料研究機構 層状複水酸化物を表面に有する金属板の製造方法
KR102850866B1 (ko) * 2022-08-31 2025-08-28 울산과학기술원 복합 금속 구조체를 포함하는 전극 및 이의 제조방법
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11229170A (ja) * 1998-02-18 1999-08-24 Permelec Electrode Ltd 活性化陰極
JP2001098397A (ja) * 1999-09-28 2001-04-10 Murata Mfg Co Ltd 電極形成方法
JP2008071533A (ja) * 2006-09-12 2008-03-27 Sumitomo Electric Ind Ltd アルカリ電池用ニッケル電極の製造方法およびアルカリ電池用ニッケル電極
KR20130125235A (ko) * 2012-05-08 2013-11-18 삼성에스디아이 주식회사 복합 금속 전구체, 이로부터 형성된 전극 활물질, 이를 포함하는 리튬 이차 전지용 양극 및 이를 구비한 리튬 이차 전지
KR20150115831A (ko) * 2013-01-30 2015-10-14 스미토모 긴조쿠 고잔 가부시키가이샤 니켈코발트 복합 수산화물 및 그 제조 방법

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6110855A (ja) * 1984-06-26 1986-01-18 Asahi Glass Co Ltd 電池用電極及びその製造方法
JP3158416B2 (ja) * 1990-07-30 2001-04-23 新神戸電機株式会社 ペースト式ニッケルカドミウム蓄電池用陰極板
JP4066472B2 (ja) * 1997-06-10 2008-03-26 堺化学工業株式会社 板状水酸化ニッケル粒子、その製造方法及びこれを原料とするリチウム・ニッケル複合酸化物粒子の製造方法
JP5568849B2 (ja) * 2008-09-09 2014-08-13 住友金属鉱山株式会社 板状ニッケル含有水酸化物とその製造方法及びそれを用いた板状ニッケル含有オキシ水酸化物とその製造方法
DK2862960T3 (da) * 2012-06-18 2020-03-23 Asahi Chemical Ind Bipolær alkalisk vandelektrolyseenhed

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11229170A (ja) * 1998-02-18 1999-08-24 Permelec Electrode Ltd 活性化陰極
JP2001098397A (ja) * 1999-09-28 2001-04-10 Murata Mfg Co Ltd 電極形成方法
JP2008071533A (ja) * 2006-09-12 2008-03-27 Sumitomo Electric Ind Ltd アルカリ電池用ニッケル電極の製造方法およびアルカリ電池用ニッケル電極
KR20130125235A (ko) * 2012-05-08 2013-11-18 삼성에스디아이 주식회사 복합 금속 전구체, 이로부터 형성된 전극 활물질, 이를 포함하는 리튬 이차 전지용 양극 및 이를 구비한 리튬 이차 전지
KR20150115831A (ko) * 2013-01-30 2015-10-14 스미토모 긴조쿠 고잔 가부시키가이샤 니켈코발트 복합 수산화물 및 그 제조 방법

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