WO2022137691A1 - ニッケル粉末、その製造方法、導電性組成物及び導電膜 - Google Patents

ニッケル粉末、その製造方法、導電性組成物及び導電膜 Download PDF

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WO2022137691A1
WO2022137691A1 PCT/JP2021/035400 JP2021035400W WO2022137691A1 WO 2022137691 A1 WO2022137691 A1 WO 2022137691A1 JP 2021035400 W JP2021035400 W JP 2021035400W WO 2022137691 A1 WO2022137691 A1 WO 2022137691A1
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nickel
powder
boron
less
ratio
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PCT/JP2021/035400
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English (en)
French (fr)
Japanese (ja)
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秀雄 上杉
安俊 遠藤
卓也 浅野
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三井金属鉱業株式会社
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Priority to KR1020237018356A priority Critical patent/KR20230122581A/ko
Priority to JP2022571058A priority patent/JPWO2022137691A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • 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
    • C25B11/04—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic 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
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to nickel powder, a method for producing the same, a conductive composition and a conductive film.
  • MLCCs monolithic ceramic capacitors
  • the density of wiring is increased in the wiring formation in electronic devices, and the dimensional stability of wiring is improved. Improvement is required. In order to realize these requirements, for example, it is considered to use metal particles having a small particle size as a constituent material of a wiring structure.
  • Patent Document 1 describes a core material made of a composite compound such as a nickel element, a noble metal element, and boron, and a metal on the surface of the core material, for the purpose of solving the problems of shrinkage during sintering and oxidation of metal. Composite fine particles coated with an oxide are disclosed.
  • Patent Document 2 discloses a conductive powder in which a Ni—B alloy powder is precipitated on the surface of the Ni powder for the purpose of imparting oxidation resistance.
  • Patent Documents 1 and 2 When the metal particles described in Patent Documents 1 and 2 are used as a raw material for manufacturing a wiring structure, they may not be able to form a wiring structure having low electrical resistance.
  • the present invention relates to nickel powder having low electrical resistance.
  • the present invention is a nickel powder composed of an aggregate of nickel particles containing an element of boron.
  • the content of the boron element is 0.1% by mass or more and 2.0% by mass or less.
  • the 50% particle size D50 in the number distribution measured by scanning electron microscope observation is 100 nm or less. In the measurement in the depth direction of the powder by the flight time type secondary ion mass spectrometry, when the range from the outermost surface of the powder to the sputter depth of 10 nm in terms of SiO 2 of the powder is measured, the powder is at the maximum.
  • the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion on the surface is A 1
  • the maximum value of the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion in the powder is A max .
  • the present invention is a nickel powder composed of an aggregate of nickel particles containing a boron element.
  • the content of the boron element is 0.1% by mass or more and 2.0% by mass or less.
  • the 50% particle size D50 in the number distribution measured by scanning electron microscope observation is 100 nm or less.
  • NiB and Ni 2 are measured when the range from the outermost surface of the powder to the sputter depth of 10 nm in terms of SiO 2 of the powder is measured.
  • a nickel powder in which the abundance ratio of NiB to the total value of B and Ni 3B is 81% or less.
  • the present invention is a nickel powder composed of an aggregate of nickel particles containing a boron element.
  • the content of the boron element is 0.1% by mass or more and 2.0% by mass or less.
  • the 50% particle size D50 in the number distribution measured by scanning electron microscope observation is 100 nm or less.
  • CV value (%) (standard deviation of particle size by scanning electron microscope observation (nm)) / (arithmetic mean particle size (nm)) ⁇ 100 ... (1)
  • the present invention also comprises a step of mixing a water-soluble nickel source and hydrazine to form a nickel-hydrazine complex, and then further adding a reducing compound containing a boron element to reduce nickel ions. It provides a method for producing nickel powder.
  • FIG. 1A is a scanning electron microscope image of the nickel powder of Example 1
  • FIG. 1B is a scanning electron microscope image of the nickel powder of Comparative Example 1.
  • FIG. 2A shows nickel at each spatter depth in terms of SiO 2 when the nickel powders of Examples 1 to 3 and Comparative Example 1 were measured in the depth direction by time-of-flight secondary ion mass spectrometry. It is a graph showing the ratio of the number of detected ions of boron ion to the number of detected ions of ion
  • FIG. 2 (b) is the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion in the graph of FIG. 2 (a). It is a graph when is first-order differentiated by the spatter depth.
  • FIG. 3 is a 1 H-NMR spectrum of the nickel-hydrazine complex produced in Examples 3, 4, 6 and 7.
  • the present invention relates to a nickel powder composed of an aggregate of nickel particles mainly containing a nickel element and a method for producing the same. Prior to the description of the nickel powder, a suitable method for producing the nickel powder will be described.
  • a water-soluble nickel source and hydrazine are mixed to form a complex of nickel ions and hydrazine (hereinafter, also referred to as a nickel-hydrazine complex).
  • a step of further adding a reducing compound containing an element of boron to reduce nickel ions is provided.
  • a reaction system mainly composed of water will be described as an example.
  • a water-soluble nickel source and hydrazine are mixed to prepare a first reaction solution.
  • the first reaction solution is preferably prepared under the condition that a nickel-hydrazine complex is formed in the reaction solution. That is, hydrazine in this production method is used as a nickel ion complexing agent. By reducing nickel ions under such conditions, it is possible to efficiently obtain nickel powder having a large amount of nickel having a small electric resistance on the particle surface and having a sharp particle size distribution. Embodiments relating to the conditions under which the nickel-hydrazine complex is formed will be described later. Whether or not a nickel-hydrazine complex is formed in the first reaction solution can be determined by, for example, 1 H-NMR. 1 The measurement conditions by 1 H-NMR will be described in detail in Examples described later.
  • each raw material may be added to a solvent such as pure water at the same time, or each raw material may be added to the solvent in any order.
  • a nickel raw material solution in which a water-soluble nickel source is mixed with a solvent such as pure water is prepared in advance, and then the nickel raw material solution is mixed with a solid hydrazine or a hydrazine aqueous solution.
  • the nickel raw material solution is prepared without containing hydrazine.
  • nickel organic acid salts such as nickel formate, nickel acetate, nickel malonate and nickel succinate
  • nickel inorganic acid salts such as nickel nitrate and nickel sulfate
  • nickel chloride examples include various nickel compounds such as halides and hydroxides such as nickel hydroxide. These nickel compounds may be anhydrous or hydrated. These nickel compounds may be used alone or in combination of two or more.
  • the content of the water-soluble nickel source in the nickel raw material solution is preferably 0.01 mol / L or more and 2.0 mol / L or less, and 0.05 mol / L or more and 1.5 mol / L or less in terms of the molar concentration of the nickel element. More preferred.
  • hydrazine an anhydride may be used, a hydrate such as monohydrate may be used, or a liquid hydrazine compound such as hydrazine carbonate or hydrazine bromate may be used, and hydrazine hydrochloride, hydrazine nitrate, etc. may be used.
  • a solid hydrazine compound such as hydrazine sulfate may be used.
  • these hydrazines or compounds derived from hydrazine are collectively referred to simply as "hydrazine".
  • the amount of hydrazine added is preferably 2 mol or more and 12 mol or less, more preferably 4 per 1 mol of nickel element, from the viewpoint of efficiently advancing complex formation with nickel ions. Add to 10 mol or more and 10 mol or less.
  • Examples of the solvent used for preparing the first reaction solution include at least one of water and an organic solvent.
  • Examples of the organic solvent include alcohols such as monohydric alcohols and polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, esters, ketones, nitrogen-containing heterocyclic compounds, amides, amines and saturated substances. Examples include hydrocarbons.
  • At least one of water and a hydrophilic organic solvent is used as the solvent used for preparing the first reaction solution from the viewpoint of improving the production efficiency due to the reduction of the production cost and the ease of handling at the time of production. It is preferable to use it, and it is more preferable to use only water. By using only water, there is an advantage that it is possible to reduce unintentional mixing of impurities such as carbon elements in the generated nickel particles.
  • the hydrophilic organic solvent monohydric alcohols such as methanol, ethanol, 1-propanol and 2-propanol, and dihydric alcohols such as ethylene glycol, propylene glycol and diethylene glycol are preferably used.
  • the first reaction solution is preferably prepared by further adding a ligand compound other than hydrazine in addition to the water-soluble nickel source and hydrazine.
  • a ligand compound other than hydrazine in addition to the water-soluble nickel source and hydrazine.
  • the ligand compound added to the first reaction solution has a functional group having a lone electron pair in its chemical structure. Therefore, the ligand compound has a function as a complexing promoter that facilitates the formation of a nickel complex in the reaction solution by coordinating with nickel ions in the process of forming particles.
  • the ligand compound has the functional groups of the compound coordinated with the atoms on the surface of the particles to form a steric obstacle, so that the dispersibility between the particles is improved. It is advantageous in that it also has a function as an enhancing dispersant.
  • Examples of the above-mentioned ligand compound include high molecular weight organic compounds and low molecular weight organic compounds. These compounds can be used alone or in combination. In addition, each of these compounds may be anhydrous or hydrated independently.
  • the polymer organic compound referred to in the present invention refers to a compound having a weight average molecular weight of 10,000 or more. Examples of such high molecular weight organic compounds include polyvinylpyrrolidone, sodium carboxymethyl cellulose, and polyoxyalkylene compounds.
  • Low molecular weight organic compounds include linear or branched and aliphatic or aromatic organic acids such as monovalent, divalent or trivalent carboxylic acids, hydroxy acids; primary amines and secondary amines. Examples thereof include aliphatic or aromatic organic amines such as tertiary amines and aromatic amines.
  • a low molecular weight organic compound as the ligand compound from the viewpoint of reducing the content of impurities such as carbon element and nitrogen element in the nickel powder while reducing the production cost, and it is saturated.
  • an unsaturated aliphatic organic acid include aliphatic monovalent carboxylic acids having 1 to 12 carbon atoms such as lauric acid, undecanoic acid, caproic acid, acetic acid, formic acid and crotonic acid, lactic acid, malic acid and citric acid.
  • the aliphatic hydroxy acid of the above is preferably mentioned.
  • the content of the ligand compound in the first reaction solution is preferably 0.1 mol or more and 0.8 mol or less with respect to 1 mol of the nickel element. It is more preferably 2 mol or more and 0.6 mol or less.
  • the desired nickel conductivity can be obtained even when the obtained nickel powder is used for an electrode application of an electronic component or an electrode catalyst application of a fuel cell, for example. It is possible to improve the catalytic activity and suppress the generation of voids and cracks caused by the gas derived from impurities. From the viewpoint of making these effects more remarkable, the smaller the content of the ligand compound, the more preferable.
  • One embodiment of the condition for forming a complex of nickel ion and hydrazine is a method of mixing a water-soluble nickel source and hydrazine under acidic conditions.
  • Specific examples thereof include a method in which the pH is adjusted in advance so that the nickel raw material solution becomes acidic, and then various hydrazines are mixed with the nickel raw material solution.
  • the precipitation of nickel hydroxide due to the hydroxylation of the nickel salt or nickel salt as a raw material is suppressed before mixing with hydrazine, and a nickel-hydrazine complex is efficiently formed. Can be made to.
  • the acidic condition means that the pH is less than 7.0, preferably 2.0 or more and 6.5 or less, and more preferably 3.0 or more and 6.0 or less.
  • Various acids and basic substances can be used to adjust the pH, and in order to make acidic conditions, for example, organic acids such as citric acid, acetic acid, formic acid, and lauric acid or salts thereof are used as the above-mentioned ligand compounds. Or at least one of inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid can be further added to the nickel raw material solution.
  • the basic substance for example, sodium hydroxide, potassium hydroxide, or aqueous ammonia can be used as the basic substance.
  • the first reaction solution under non-heating conditions.
  • Specific examples thereof include a method in which a nickel raw material solution and, if necessary, a ligand compound are mixed in advance under non-heating conditions, and then various hydrazines are mixed with the nickel raw material solution.
  • the non-heating condition is, for example, a temperature range of 5 ° C. or higher and lower than 40 ° C. Even by preparing the first reaction solution under such conditions, the reduction of nickel ions by hydrazine does not proceed, or the reaction rate of complex formation can be maintained at a condition sufficiently faster than the reduction reaction rate. While maintaining the conditions under which a complex of hydrazine and hydrazine is formed, the reduction of nickel ions, which will be described later, can be efficiently performed. This condition may be adopted alone or in combination with the acidic condition described above.
  • the first reaction solution in which the nickel-hydrazine complex is formed is mixed with the reducing compound containing a boron element to obtain a second reaction solution.
  • nickel ions are reduced to obtain an aggregate of nickel particles.
  • the first reaction solution in which the nickel-hydrazine complex is formed is in a neutral or basic condition having a pH of 7.0 or more due to the addition of hydrazine. Further, as described later, it is also preferable to heat the second reaction solution to carry out the reduction reaction from the viewpoint of improving the production efficiency.
  • a reducing solution containing a reducing compound containing a boron element separately from the first reaction solution prior to the preparation of the second reaction solution.
  • the reducing compound containing a boron element in this production method is used as a reducing agent for nickel ions.
  • the preparation of the reducing solution should be carried out under non-heating conditions in the same manner as the preparation of the first reaction solution, thereby suppressing the hydrolysis reaction of the reducing compound containing the boron element in the solution and sufficiently advancing the reducing reaction. Therefore, it is advantageous in that particles having a small diameter and a small variation in particle size can be obtained.
  • the same solvent as the above-mentioned solvent used in the preparation of the first reaction solution can be used.
  • at least one of water and a hydrophilic organic solvent may be used as the solvent for preparing the reducing solution. It is preferable to use only water, more preferably.
  • the reducing compound containing a boron element is added under basic conditions of pH 9.0 or higher. It is preferable to do so.
  • Basic substances such as sodium hydroxide, potassium hydroxide, and aqueous ammonia can be used to adjust the pH.
  • the reducing compound containing an element of boron examples include at least one of hydrogenated boride and aminoborane. Further, the reducing compound containing a boron element may be in a solid state or in a liquid state. Of these, from the viewpoint of efficiently advancing the reduction reaction of nickel ions, it is more preferable to use hydrogenated boride as the reducing compound containing an element of boron.
  • borohydride examples include sodium borohydride, ammonium borohydride, potassium borohydride, lithium borohydride, aluminum borohydride, zinc borohydride and other water-soluble borohydrides or water-soluble borohydrides thereof. It is preferable to use salt.
  • aminoborane it is preferable to use secondary aminoborane such as diethylaminoborane and dimethylaminoborane, and tertiary aminoborane such as triethylaminoborane and trimethylaminoborane.
  • the above-mentioned hydrogenated boride and aminoborane can be used alone or in combination of two or more.
  • the mixing of the first reaction solution and the reducing solution one may be added to the other and mixed, or these solutions may be mixed at the same time. Further, the mixing of these solutions may be batch addition or sequential addition by dropping or the like. In any form, performing the mixing of the first reaction solution and the reducing solution under non-heating conditions from the start to the end causes the reduction reaction to proceed slowly, has a small particle size, and is obtained. It is preferable in that the variation in the particle size of the particles can be reduced.
  • the second reaction solution by sequentially adding the reducing solution to the first reaction solution.
  • the progress of the reduction reaction of nickel ions from the nickel-hydrazine complex can be appropriately controlled, and nickel and nickel boride produced by the reduction can be slowly precipitated.
  • particles having a large amount of nickel elements on the surface and a small particle size can be efficiently generated, and the resulting aggregate of particles has a sharp particle size distribution.
  • the pH of the second reaction solution it is necessary to adjust the pH of the second reaction solution so as to have a neutral or basic condition of 7.0 or more, that is, a reducing compound containing hydrazine and an element of boron. It is preferable in that the decomposition of the nickel ion can be suppressed and the reduction of the nickel ion can be efficiently performed.
  • the second reaction solution have the above-mentioned pH conditions, for example, the first reaction solution prepared by the above-mentioned method and the reducing solution may be mixed. When the second reaction solution is heated as described later, it is preferable to adjust the pH of the second reaction solution before heating (non-heating).
  • the addition rate is preferably 0.005 L / min or more and 10 L / min or less, and more preferably 0.05 L / min or more and 1 L / min or less.
  • the total content of the reducing compound containing the boron element in the second reaction solution is preferably 0.05 mol or more and 1.5 mol or less, and further, with respect to 1 mol of the nickel element.
  • the reducing solution is mixed so as to be preferably 0.1 mol or more and 1.0 mol or less.
  • the nickel ions are reduced by a reducing compound containing hydrazine and an element of boron with the fine particles of the nickel borohydride generated in the second reaction solution as nuclei, and gradually precipitated as metallic nickel or nickel borohydride on the surface of the particles. And the grain grows. Since such grain growth occurs simultaneously in each of the fine particles in the second reaction solution, the grain growth of each particle is controlled to be uniform. As a result, it is considered that the abundance of the nickel element increases toward the particle surface, the particle size becomes small, and an aggregate of particles having a sharp particle size distribution can be efficiently obtained. Further, the constituent particles of the powder thus obtained are typically spherical in shape.
  • the heating conditions of the second reaction solution are preferably 40 ° C. or higher and 90 ° C. or lower, more preferably 60 ° C. or higher and 80 ° C. or lower, and heating is performed so as to maintain until the completion of aging.
  • the aging time is preferably 10 minutes or more and 120 minutes or less. Further, from the viewpoint of uniformly causing a reduction reaction to obtain nickel powder having little variation in particle size, it is also preferable to continue stirring the second reaction solution from the start to the end of aging.
  • the nickel particles thus obtained are washed by a decantation method or the like, and then the particles are dispersed in an organic solvent such as water or alcohol to have a conductive composition having the form of a slurry, ink, paste or the like described later. It may be a thing. Further, the washed nickel particles may be dried to form a dry powder which is an aggregate of the particles.
  • Nickel particles constituting nickel powder contain boron element in addition to containing nickel element as a main component.
  • the elemental boron contained in the nickel particles is derived from the reducing compound containing the elemental boron in the above-mentioned production method. By containing the boron element, the coercive force of the metallic nickel is appropriately reduced, so that magnetic aggregation can be suppressed, and the handleability of the powder becomes high.
  • the nickel particles inevitably contain elements other than the nickel element and the boron element, for example, oxygen element, carbon element, nitrogen element, sulfur element and the like. It's not a thing. These other elements that can be inevitably mixed can be derived from oxygen and carbon dioxide in the atmosphere, or raw materials for production such as hydrazine and nickel sources.
  • the content of the boron element in the nickel particles is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more because it exhibits oxidation resistance and sintering resistance. Is. Further, in order to sufficiently develop the conductivity of nickel, it is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and further preferably 1.0% by mass or less. In addition to this, the coercive force of metallic nickel is appropriately reduced to improve the handleability of the powder.
  • the presence or absence of the boron element and its content in the nickel particles can be measured by, for example, time-of-flight secondary ion mass spectrometry (TOF-SIMS) or inductively coupled plasma emission spectroscopy (ICP-AES).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • ICP-AES inductively coupled plasma emission spectroscopy
  • the content of the nickel element in the nickel particles is more than 50% by mass, preferably 80% by mass or more and 99% by mass or less, and more preferably 85% by mass or more and 97% by mass or less.
  • the content of the nickel element is in such a range, the conductivity of nickel is sufficiently exhibited and the electric resistance is reduced.
  • the presence or absence of the nickel element and its content in the nickel particles can be measured by the same method as the measurement of the boron element.
  • the nickel powder has a 50% particle diameter D50 in the number distribution measured by scanning electron microscope observation, preferably 100 nm or less, more preferably 90 nm or less, still more preferably 80 nm or less. Further, D50 is realistically more than 20 nm, preferably 30 nm or more. By having such a D50, it is possible to reduce problems such as interruption of the conductive film such as the obtained electrode. Further, when the powder is contained in a conductive paste or the like and used, good filling property can be exhibited. The result is a powder or conductive film with reduced electrical resistance.
  • D50 can be measured by the following method. First, from a scanning electron microscope image of nickel powder at a magnification of 150,000 times, 200 or more particles in which the particles do not overlap are randomly selected and the particle size (Haywood diameter) is measured. Then, from the obtained particle size of each particle, a particle size distribution based on the number standard is obtained. Then, the median particle size of the particle size distribution based on the number standard is defined as D50 in the present invention.
  • the nickel particles contain a boron element, it is preferable that the abundance ratios of the nickel element and the boron element are different between the particle surface and the particle center.
  • the surface of the powder is converted into SiO 2 of the powder.
  • the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion on the outermost surface of the nickel powder is defined as A1.
  • the maximum value of the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion in the range from the outermost surface of the nickel powder to the sputter depth of 10 nm in terms of SiO 2 is defined as A max .
  • the ratio of A max to A 1 is preferably 12 or more, more preferably 12 or more and 5000 or less, still more preferably 20 or more and 5000 or less, still more preferably 20 or more and 3000 or less, and even more. It is preferably 20 or more and 1000 or less.
  • the A max / A 1 ratio described above indicates that the relative abundance ratio of the boron element increases continuously or stepwise when observed from the surface of the powder sample toward the inside. These are consistent with the trend of change in the relative abundance of boron elements in each particle. That is, it is shown that the relative abundance ratio of the boron element in the particles increases continuously or stepwise when observed from the particle surface toward the particle center in each particle. On the other hand, the more uniformly the element boron and the element nickel are present in the particles, the closer the A max / A 1 ratio becomes to 1. Further, in the case of nickel powder composed of particles containing a boron element or particles having a layer on the surface as in the prior art, the A max / A 1 ratio tends to be small.
  • the fact that the A max / A 1 ratio is in the above-mentioned range indicates that a large amount of nickel element is present on the particle surface, and therefore, due to this, the conductivity of nickel is sufficiently sufficient. It becomes a powder that can be expressed in the above and has low electrical resistance.
  • a 2 be the ratio of.
  • the ratio of A 2 to A max (A max / A 2 ) is preferably 1.35 or more and 3.00 or less, more preferably 1.40 or more and 2.80 or less, and further preferably 1.50 or more and 2 It is .60 or less.
  • a 2 described above is synonymous with the average number of detected ions of boron ions with respect to the number of detected ions of nickel ions in a plurality of particles
  • the above-mentioned A max divided by A 2 is the A max / A 2 ratio.
  • a max , A 1 and A 2 can be measured by the following method using TOF-SIMS.
  • the measurement sample for TOF-SIMS nickel powder molded into pellets using a press machine is used. Specifically, about 10 mg of the powder sample is weighed in an aluminum container having a size of ⁇ 5.2 mm and a height of 2.5 mm, and a press machine (manufactured by AS ONE, product number: 1-312-01) and an adapter (product number: 1-). Using 312-03), pressurize with the aluminum container with a predetermined stroke (25 mm) to take out the pellet molded product of nickel powder supported by the aluminum container.
  • the pellet molded product obtained by the above method is subjected to mass spectrometry of scattered ions while sputtering from the sample surface toward the inside using TOF-SIMS, and the depth from the outermost surface is performed. Is sputtered depth [nm] (SiO 2 conversion) to obtain a mass spectrum in the depth direction. From the number of detected ions of nickel ion and boron ion measured at each sputter depth, the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion at each sputter depth is calculated.
  • the analytical conditions shown below are common to the TOF-SIMS measurements herein.
  • TOF-SIMS device TRIFT IV manufactured by ULVAC FI Co., Ltd.
  • Spatter mode Phased Profile
  • the total of the peak intensities (counts) existing in a specific mass number m / z range is calculated as the number of detected ions (count) of each fragment.
  • the mass conversion (calibration) of the flight time is performed using the peaks of CH 3 , C 2 H 3 , C 3 H 5 , and Ni.
  • the range of the mass number m / z of each fragment is preferably the following range.
  • B: m / z 126.800 to 127.000 Ni 3
  • B: m / z 184.700 to 184.950
  • Nickel powder has the presence of nickel boride (hereinafter, also referred to as Ni x B; where X is an integer of 1 to 3) in the range from the outermost surface of the powder to a sputter depth of 10 nm in terms of SiO 2 . It is preferable that the ratio is in a predetermined range. Specifically, when measured in the depth direction of the powder by TOF-SIMS in the above-mentioned depth range, nickel in each spatter depth is in the range from the outermost surface of the powder to the spatter depth of 10 nm in terms of SiO 2 .
  • W1 be the total ratio of the number of detected ions of NiB ion to the number of detected ions of ion.
  • the total ratio of the number of detected ions of Ni 2B ions to the number of detected ions of nickel ions at each spatter depth is W2.
  • the total ratio of the number of detected ions of Ni 3B ions to the number of detected ions of nickel ions at each spatter depth is W3.
  • the percentages P1, P2, and P3 of W1, W2, and W3 with respect to the total value (W1 + W2 + W3) of the above-mentioned NiB, Ni2B, and Ni3B are set to the abundance ratios of NiB, Ni2B, and Ni3B , respectively. %).
  • the abundance ratio P1 of NiB with respect to the total value of NiB, Ni 2 B and Ni 3 B is preferably 81% or less, more preferably 50% or more and 80% or less, and further preferably 55% or more and 78%. It is as follows. Within the above-mentioned ratio range, the powder can effectively exhibit sintering resistance and oxidation resistance and has low electrical resistance.
  • the abundance ratio P2 of Ni 2 B with respect to the total value of Ni B, Ni 2 B and Ni 3 B is preferably 14% or more and 45% or less, more preferably 20% or more and 40% or less, and further preferably 25% or more. It is 35% or less. Since Ni 2 B has a lower electric resistance than Ni B, it becomes a powder having an even lower electric resistance by being in the above-mentioned ratio range.
  • the abundance ratio P3 of Ni 3 B with respect to the total value of Ni B, Ni 2 B and Ni 3 B is preferably 5% or more and 25% or less, more preferably 8% or more and 20% or less, and further preferably 10 % Or more and 15% or less. Since Ni 3 B has a lower electric resistance than Ni B, it becomes a powder having a lower electric resistance by being in the above-mentioned ratio range.
  • the nickel powder has a predetermined peak when plotting the relationship between the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion by TOF-SIMS and the sputter depth (nm) in terms of SiO 2 . It is preferable to have. Specifically, the ratio of the number of detected ions of boron ion to the number of detected ions of nickel ion is measured in the depth direction of the powder by TOF-SIMS, and the spatter depth (nm) in terms of SiO 2 is defined as x.
  • Both the intersections and peaks in the above-mentioned first derivative are included in the range of 0 ⁇ x ⁇ 10 corresponding to the range from the outermost surface of the nickel powder to the sputter depth of 10 nm in terms of SiO 2 of the powder. Is also preferable. Further, it is also preferable that the position of the x-axis where the peak is observed is larger than the position of the x-axis where the intersection is observed, provided that the range is 0 ⁇ x ⁇ 10. That is, it is preferable that the peak is observed in a range where x is larger than the intersection. The position of the peak on the x-axis is determined based on the position of the negative peak top in the first derivative.
  • the observation of the above-mentioned desired peak within a predetermined range of the spatter depth indicates that the abundance ratio of the elemental boron in the nickel particles is relatively large from the particle surface toward the particle center. It also shows that the abundance ratio of the nickel element in the particles is relatively large from the center of the particles toward the surface of the particles. Therefore, by observing such a peak, the electric resistance can be reduced by the nickel element abundantly present on the surface, and the coercive force of the metallic nickel can be reduced by appropriately containing the boron element in the particles. At the same time, it is possible to sufficiently develop the sintering resistance and oxidation resistance of the particles.
  • the relative abundance ratio of the boron element is continuously reduced from the center of the particle to the surface of the particle, and the relative abundance ratio of the nickel element is continuous. It shows that the concentration gradient becomes large enough, and it is possible to obtain a powder having a sufficiently low electric resistance as a material for forming an electrode.
  • Nickel powder preferably has a coefficient of variation CV value within a predetermined range, which is one of the indicators that the variation in particle size is small.
  • the coefficient of variation CV value represented by the following formula (1) is preferably 20% or less, more preferably 18% or less, still more preferably 16% or less.
  • the CV value is in such a range, the size of the nickel particles is uniform and the dispersibility of the particles is high.
  • the conductive composition containing nickel particles is applied to other members, a smooth thin layer can be obtained. Further, it is possible to reduce the variation in the thickness of the conductive film obtained by sintering the thin layer of the conductive composition and reduce the interruption of the electrodes.
  • CV value (%) (standard deviation of particle size by scanning electron microscope observation (nm)) / (arithmetic mean particle size (nm)) x 100 ... (1)
  • the standard deviation of the particle size in the above formula (1) can be calculated from the particle size distribution based on the number standard created at the time of measurement and calculation of D50.
  • the arithmetic mean particle size of the nickel powder is the particle size in the arithmetic mean value of the particle size distribution based on the number standard created at the time of measurement and calculation of D50.
  • the shape of the nickel particles is one or more of various shapes such as spherical, flake-shaped, and polyhedral-shaped.
  • the shape of the nickel particles is preferably spherical. Since the particle shape is spherical, the density of the sintered body obtained after sintering the powder containing the particles can be increased. When the powder is used as a wiring material, the density of the wiring can be increased and the dimensional stability of the wiring can be improved.
  • the spherical shape of the particles means that the circularity coefficient measured by the following method is 0.65 or more, and more preferably 0.70 or more.
  • the circularity coefficient 200 particles in which the particles do not overlap are randomly selected from the scanning electron microscope images of the particles to be measured, the area of the two-dimensional projection image of the particles is S, and the peripheral length is L.
  • the circularity coefficient of the particles is calculated from the equation of 4 ⁇ S / L 2 , and the arithmetic average value of the circularity coefficient of each particle is taken as the above-mentioned circularity coefficient.
  • the circularity coefficient of the particle is 1, so it can be said that the higher the numerical value of the circularity coefficient, the closer the particle is to a true sphere.
  • the upper limit of the circularity coefficient of the nickel particles is preferably as close to 1 as possible, but 0.95 or less is realistic.
  • the content of the carbon element in the nickel powder is preferably 1.5% by mass or less, more preferably 1.0% by mass, from the viewpoint of keeping the electric resistance low when the nickel powder is used for, for example, an electrode or a conductive paste. % Or less, more preferably 0.5% by mass or less, and 0.1% by mass or more is realistic.
  • the content of the carbon element can be measured, for example, by using a carbon analyzer EMIA-Expert manufactured by HORIBA, Ltd.
  • the particles constituting the nickel powder may be coated or surface-treated with an organic substance or an inorganic substance.
  • an inorganic substance for example, by coating with an inorganic oxide stable to heat and oxygen such as SiO 2 and ZrO 2 , oxidation resistance and sintering resistance can be improved.
  • the surface treatment with an organic substance for example, by adhering an organic dispersant such as an amine or a carboxylic acid to the surface of the particles, it is possible to suppress the aggregation of the particles and improve the dispersibility of the particles.
  • the volume resistivity ( ⁇ ⁇ cm) of the nickel powder of the present invention is preferably 1 ⁇ 10 3 ⁇ ⁇ cm or less from the viewpoint of being suitably used as a conductive composition or the like as described later.
  • the volume resistivity ( ⁇ ⁇ cm) is more preferably 1 ⁇ 10 2 ⁇ ⁇ cm or less.
  • the volume resistivity ( ⁇ ⁇ cm) is measured by the method described in Examples described later.
  • Nickel powder is suitably used as a metal filler to be blended in a conductive composition.
  • the conductive composition contains nickel powder as a metal filler and a solvent, and preferably contains a binder resin.
  • Examples of the form of the conductive composition include a conductive slurry, a conductive ink, and a conductive paste.
  • Examples of the solvent used in the conductive composition include water, alcohol, ketone, ester, ether and hydrocarbon. Among them, at least one of alcohols such as tarpineol and dihydrotarpineol, and ethers such as ethyl carbitol and butyl carbitol are preferable.
  • examples of the binder resin used in the conductive composition include at least one of acrylic resin, epoxy resin, polyester resin, polycarbonate resin, cellulose resin and the like.
  • the conductive composition can form a conductive film having a desired pattern by, for example, applying the conductive composition to the surface of the surface to be applied by a predetermined means to form a coating film. If necessary, the coating film may be heated to form a conductive film. Since the nickel powder contained in the conductive composition has a small particle size and a sharp particle size distribution, it is possible to form a conductive film having a high density. As a result, the obtained conductive film is less likely to cause an unintended break and has a small electric resistance.
  • the above-mentioned conductive film can form, for example, a wiring circuit of a printed wiring board or an electrode of a chip component. It can also be used as a via filling material in a printed wiring board or as an adhesive when surface-mounting an electronic device on a printed wiring board. In addition, it can be used as a bonding material for bonding a substrate and a chip, such as a material for die bonding.
  • the above-mentioned conductive composition or conductive film can be used as an electrode catalyst of a battery or an electrode catalyst in a water electrolysis cell, and can be particularly preferably used as a catalyst in a hydrogen electrode.
  • a battery or a water electrolysis cell include a solid oxide fuel cell (SOFC), a proton conduction fuel cell (PCFC), a solid oxide water electrolysis cell (SOEC), or a proton conduction water electrolysis cell. (PCEC) and the like can be mentioned, but the present invention is not limited to these.
  • Example 1 (1) Preparation of nickel raw material solution
  • Nickel sulfate hexahydrate was used as a water-soluble nickel source.
  • 26.285 g of nickel sulfate hexahydrate and 5.161 g of trisodium citrate as a ligand compound were dissolved in 400.0 g of pure water, and then stirred at room temperature (25 ° C.) for 30 minutes.
  • To obtain a nickel raw material solution The pH of this aqueous solution at 25 ° C. was 5.7.
  • the content of the water-soluble nickel source in the nickel raw material solution was 0.25 mol / L in terms of the molar concentration of the nickel element.
  • the second reaction solution was heated to a temperature of 70 ° C., and the mixture was stirred for 80 minutes while maintaining this temperature for aging.
  • the second reaction solution after the completion of aging was decanted with pure water, and further subjected to solvent substitution with ethanol. After that, it was concentrated by decantation and vacuum dried of the solid content in this order to obtain a dry powder of the target nickel particles.
  • the scanning electron microscope image of the nickel powder obtained in this Example is shown in FIG. 1 (a).
  • Example 2 A dry powder of nickel particles was obtained in the same manner as in Example 1 except that 1.892 g of sodium borohydride was used in the preparation of the reducing solution. The molar ratio of sodium borohydride to the elemental nickel was 0.50.
  • Example 3 A dry powder of nickel particles was obtained in the same manner as in Example 1 except that 2.648 g of sodium borohydride was used in the preparation of the reducing solution. The molar ratio of sodium borohydride to the elemental nickel was 0.70.
  • Example 4 A dry powder of nickel particles was obtained by the same method as in Example 3 except that trisodium citrate / dihydrate as a ligand compound was not used in the preparation of the nickel raw material solution. The molar ratio of trisodium citrate to elemental nickel was zero.
  • Example 5 In the preparation of the nickel raw material solution, a dry powder of nickel particles was obtained by the same method as in Example 3 except that 10.323 g of trisodium citrate / dihydrate was dissolved in 400.0 g of pure water. The molar ratio of trisodium citrate to elemental nickel was 0.35.
  • Example 6 A dry powder of nickel particles was obtained in the same manner as in Example 3 except that 15.484 g of trisodium citrate dihydrate was dissolved in 400.0 g of pure water in the preparation of the nickel raw material solution. The molar ratio of trisodium citrate to elemental nickel was 0.53.
  • Example 7 A dry powder of nickel particles was obtained in the same manner as in Example 3 except that 20.646 g of trisodium citrate / dihydrate was dissolved in 400.0 g of pure water in the preparation of the nickel raw material solution. The molar ratio of trisodium citrate to elemental nickel was 0.70.
  • Example 8 In the preparation of the nickel raw material solution, in addition to nickel sulfate hexahydrate and trisodium citrate, 0.587 g of a dispersant (Marialim FA-1150AM-08 manufactured by Nichiyu Co., Ltd.) was used to make 400 g of pure water. A dry powder of nickel particles was obtained in the same manner as in Example 2 except that it was dissolved. The molar ratio of sodium borohydride to the elemental nickel was 0.50.
  • a dispersant Malarialim FA-1150AM-08 manufactured by Nichiyu Co., Ltd.
  • the volume resistivity ( ⁇ ⁇ cm) was measured using a sample obtained by pellet-molding about 30 mg of nickel powder in Examples and Comparative Examples with a press machine. Pellet molding was performed by pressurizing 2 tons using a MiNi-Pellet Press (manufactured by Specac) and a 7 mm die. The volume resistivity was measured by a 4-terminal 4-probe method using a Lorester-GP (MCP-T610 manufactured by Mitsubishi Chemical Analytec Co., Ltd.) by pressing a QPP type probe against the pellet surface. The lower the volume resistivity, the higher the conductivity. The results are shown in Table 1 below. In the comparative example, the volume resistivity of the sample exceeded the upper limit of detection and could not be measured.
  • the nickel-hydrazine complex produced in the nickel raw material solution should be [Ni (N 2 H 4 ) 4 ] SO 4 , [Ni (N 2 H 4 ) 3 ] SO 4 , or a mixture thereof.
  • the nickel raw material solution should be [Ni (N 2 H 4 ) 4 ] SO 4 , [Ni (N 2 H 4 ) 3 ] SO 4 , or a mixture thereof.
  • the measurement conditions of 1 H-NMR shown in FIG. 3 are as follows. Magnetic field: 14.1T (1H 600MHz) Spectrometer: AVANCE NEO600 manufactured by Bruker Software for measurement and data processing: Bruker TopSpin NMR probe: 1.3 mm MAS probe Sample rotation speed: 60 kHz Standard sample of chemical shift value and radio frequency intensity: Adamantane Criteria for chemical shift value: The peak of 1 H-NMR of adamantane is 1.91 ppm.
  • Radio wave pulse width 2.5 ⁇ sec
  • Radio wave pulse intensity 100 kHz (when the irradiation center is 1.91 ppm, the peak intensity of the 1 H-NMR spectrum of adamantane is the maximum intensity at the radio wave pulse width of 2.5 ⁇ sec).
  • Radio wave pulse irradiation center 4.7 ppm
  • Observation point interval 2 ⁇ sec
  • Number of observation points 20,000
  • Number of spectral points 65536 Window function: No window function used
  • a nickel powder having a low electrical resistance is provided.
PCT/JP2021/035400 2020-12-23 2021-09-27 ニッケル粉末、その製造方法、導電性組成物及び導電膜 WO2022137691A1 (ja)

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JP2015151590A (ja) * 2014-02-17 2015-08-24 住友金属鉱山株式会社 水素還元ニッケル粉の製造に用いる種結晶の製造方法

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JP2004068090A (ja) 2002-08-07 2004-03-04 Murata Mfg Co Ltd 導電性粉末の製造方法、導電性粉末、導電性ペーストおよび積層セラミック電子部品

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JPS54123582A (en) * 1978-02-28 1979-09-25 Comp Generale Electricite Cathod for electrolysis apparatus and its manufacture
JPH04104470A (ja) * 1990-08-23 1992-04-06 Meidensha Corp 固体電解質型燃料電池用電極の製造方法
JP2007277709A (ja) * 2006-04-11 2007-10-25 Samsung Electro-Mechanics Co Ltd ニッケルナノ粒子の製造方法
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