WO2019187688A1 - Nickel powder and production method therefor - Google Patents

Nickel powder and production method therefor Download PDF

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Publication number
WO2019187688A1
WO2019187688A1 PCT/JP2019/004468 JP2019004468W WO2019187688A1 WO 2019187688 A1 WO2019187688 A1 WO 2019187688A1 JP 2019004468 W JP2019004468 W JP 2019004468W WO 2019187688 A1 WO2019187688 A1 WO 2019187688A1
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Prior art keywords
nickel powder
nickel
bonds
nitrogen
containing compound
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PCT/JP2019/004468
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French (fr)
Japanese (ja)
Inventor
一元 西島
雅人 大栗
浅井　剛
貢 吉田
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東邦チタニウム株式会社
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Priority to CN201980023766.2A priority Critical patent/CN111936254B/en
Priority to JP2019529663A priority patent/JP6647458B1/en
Priority to KR1020207024904A priority patent/KR102352835B1/en
Publication of WO2019187688A1 publication Critical patent/WO2019187688A1/en

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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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • 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
    • 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
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • One embodiment of the present invention relates to nickel powder and a method for manufacturing the same.
  • Niobium powder is used as a raw material for an internal electrode of a multilayer ceramic capacitor (MLCC).
  • the nickel powder can be produced by reducing nickel chloride gas with a reducing gas such as hydrogen.
  • nickel powder such as nickel oxide can be dispersed in a solvent and reduced using a reducing agent such as hydrazine to produce nickel powder.
  • the former is called a gas phase method, and the latter is called a liquid phase method.
  • One of the embodiments of the present invention is to provide a nickel powder exhibiting a high compression density and having a small volume shrinkage during high-temperature processing, and a method for producing the same.
  • Ni—Ni bond ratio 50% or more of Ni—Ni bonds, Ni—OH bonds, and Ni—O bonds derived from nickel oxide on the surface, and a heat shrinkage rate of 1200 ° C. Is 15% or less.
  • the proportion of Ni—Ni bond and the thermal shrinkage rate are estimated by X-ray photoelectron spectroscopy and thermomechanical analysis, respectively.
  • One embodiment according to the present invention is a method for producing nickel powder.
  • the method includes treating raw nickel powder with a solution of a nitrogen-containing compound.
  • the XPS measurement result of the nickel powder which concerns on one of embodiment of this invention The XPS measurement result of the nickel powder which concerns on one of embodiment of this invention.
  • the XPS measurement result of the nickel powder which concerns on one of embodiment of this invention The XPS measurement result of the nickel powder which concerns on one of embodiment of this invention.
  • the nickel powder 100 according to one embodiment of the present invention and a manufacturing method thereof will be described.
  • Nickel powder Nickel powder 100 is an aggregate of nickel particles, and the number average particle diameter of nickel powder 100 can be 50 nm to 500 nm, 50 nm to 300 nm, or 100 nm to 250 nm. Accordingly, the nickel powder 100 contains at least one nickel particle having a particle diameter in the above range. As the number average particle diameter, for example, the nickel powder 100 is observed with a scanning electron microscope, the particle diameters of a plurality of particles (for example, 1000 particles) are measured, and the average value can be adopted. The particle diameter is the diameter of the smallest circle inscribed in the particle, or the length of the long side of the square having the smallest area inscribed in the particle. Note that the nickel powder 100 may include an organic compound containing an amide group as represented by the following formula, for example, together with nickel particles.
  • Nickel atoms contained in the nickel particles exist in various bonded states.
  • the nickel atoms on the particle surface are not only Ni—Ni bonds but also Ni—OH bonds derived from surface hydroxyl groups, Ni—C bonds derived from carbonate (NiCO 3 ), or Ni derived from nickel oxide (NiOx).
  • a bonding state such as —O bonding can be taken.
  • the ratio of Ni—Ni bonds among Ni—Ni bonds, Ni—OH bonds, and Ni—O bonds is 50% or more.
  • the proportion of Ni—Ni bonds may be 50% or more and 95% or less, 65% or more and 93% or less, 76% or more and 93% or less, or 85% or more and 93% or less.
  • nickel exists as a zero-valent metal (metallic nickel) in the above-described range.
  • the nickel particle surface is a region from the surface of the nickel particle to 5 nm or from the surface to 10 nm.
  • the nickel particles constituting the nickel powder 100 are thin and have Ni—OH bonds and Ni—O bonds on the outermost surface side. It is considered that there is a large amount of Ni having Ni—Ni bonds on the inner side from the outermost surface.
  • the bonding state of nickel atoms can be estimated as follows by XPS (X-ray photoelectron spectroscopy) using a light source such as AlK ⁇ rays.
  • the measurement energy range of Ni2p is 884 to 844 (eV)
  • the measurement energy range of C1s is 298 to 279 (eV).
  • the area of the peak attributed to metallic nickel, that is, the peak derived from the Ni—Ni bond, is the sum of the peak areas of 852.4 (eV) and 858.5 (eV).
  • the peak areas attributed to the Ni—O bond are 853.4 (eV), 854.2 (eV), 855.3 (eV), 858.2 (eV), 860.6 (eV), 863.2 ( eV), and 865.4 (eV) peak area.
  • the peak area attributed to the Ni—OH bond is determined as follows. First, the sum of peak areas of 854.5 (eV), 855.7 (eV), 857.4 (eV), 861.1 (eV), 862.4 (eV), and 865.4 (eV) is obtained. . From this summation, the peak area of 288.5 (eV) attributed to the Ni—C bond is subtracted to obtain the peak area derived from the Ni—OH bond.
  • the peak position of the peak attributed to metallic nickel can be specified if Ni is used as a standard product.
  • the peak position of the peak attributed to the Ni—O bond can be specified by using NiO as a standard product.
  • the peak position of the peak attributed to the Ni—OH bond can be specified by using Ni (OH) 2 .
  • the peak position attributed to the Ni—C bond can be specified by using NiCO 3 .
  • the area ratio is the ratio of metallic nickel determined by XPS measurement.
  • the nickel particles contain metallic nickel on the surface at a high rate, the nickel powder 100 exhibits excellent characteristics.
  • the thermal shrinkage estimated by the thermomechanical analysis method is as low as 15% or less at 1200 ° C.
  • the thermal contraction rate may be 5% or more and 14% or less, or 7% or more and 13% or less.
  • the compression density of the nickel powder 100 is a high value of 4.8 g / cm 3 or more and 6.0 g / cm 3 or less, or 5.0 g / cm 3 or more and 6.0 or less g / cm 3 .
  • the measured value of the thermomechanical analysis method is determined by the following measurement.
  • the nickel powder 100 is formed into a pellet having a diameter of 5 mm and a height of 10 mm.
  • the measurement conditions for the thermomechanical analysis method are as follows: temperature range: room temperature to 1200 ° C., heating rate: 5 ° C./min, atmosphere: 2% H 2 , 98% N 2 mixed gas, 300 mL / min.
  • the thermal shrinkage rate is obtained by using the shrinkage obtained from the height (length) of the pellet at 1200 ° C. when the shrinkage is completed as a ratio to the original height.
  • the said compression density is calculated
  • the obtained nickel powder is molded under a pressure of 0.5 t.
  • the diameter, thickness, and weight of the molded body are measured, and the value obtained thereby is the compression density.
  • a nickel powder 100 according to an embodiment of the present invention can be manufactured by using nickel powder as a raw material, treating it with a nitrogen-containing compound, and drying it.
  • nickel powder produced by a vapor phase method or a liquid phase method can be used as a raw material.
  • raw material nickel powder an example using nickel powder produced by a vapor phase method (hereinafter referred to as raw material nickel powder) as a raw material will be described.
  • the production conditions of the raw material nickel powder can be selected as appropriate.
  • nickel chloride is obtained by spraying chlorine gas on raw materials such as nickel pellets, nickel powder, and nickel ingot.
  • Raw nickel powder can be obtained by vaporizing the nickel chloride and bringing the chlorinated nickel gas into contact with a reducing gas such as hydrogen gas or hydrazine.
  • the raw nickel powder may be further treated with a sulfur-containing compound to form a nickel sulfide coating on the surface.
  • the particle diameter of the raw material nickel powder is not particularly limited, and for example, a raw material nickel powder having a number average particle diameter of 50 nm to 500 nm, 50 nm to 300 nm, or 100 nm to 250 nm can be used.
  • the nickel powder 100 can be manufactured by treating the raw nickel powder with a mixed solution containing a nitrogen-containing compound or a solution (hereinafter, this mixed solution or solution is also referred to as a dispersant).
  • a mixed solution containing a nitrogen-containing compound or a solution hereinafter, this mixed solution or solution is also referred to as a dispersant.
  • the solvent include water, lower alcohols having 1 to 4 carbon atoms such as ethanol and propanol, glycol solvents such as ethylene glycol and propylene glycol, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide.
  • Nitrile solvents such as acetonitrile, cyclic carbonate solvents such as ethylene carbonate, and the like can be used.
  • water that is a nonflammable solvent and has low toxicity is preferable.
  • the nitrogen-containing compound is preferably a water-soluble nitrogen-containing compound.
  • a nitrogen-containing compound having high solubility in water is used.
  • the nitrogen-containing compound may be composed of a single component, or a mixture containing a plurality of components may be used as the nitrogen-containing compound.
  • the nitrogen-containing compound can be selected from primary alkylamines and aliphatic amides. There is no restriction
  • the alkyl group may be linear or cyclic, and may be branched.
  • tetradecylamine C 14 H 29 NH 2
  • the nitrogen-containing compound may include a primary alkylamine and a carboxylic acid salt.
  • a carboxylic acid for example, a carboxylic acid having 1 to 4 carbon atoms such as formic acid and acetic acid can be used.
  • An example is a salt of tetradecylamine and acetic acid.
  • the above-described aliphatic amide may have a carboxyl group in the molecule.
  • the nitrogen-containing compound may further contain a tertiary amine having an alkyl group containing a hydroxyl group.
  • a compound represented by the following chemical formula can be used as the aliphatic amide.
  • R 1 is selected from an alkyl group having 6 to 18 carbon atoms
  • R 2 is selected from an alkyl group or alkenyl group having 1 to 4 carbon atoms
  • X is selected from an alkylene group having 1 to 5 carbon atoms.
  • undecyl group (C 11 H 23 ), methyl group, and ethylene group can be selected as R 1 , R 2 , and X, respectively.
  • Examples of the tertiary amine having an alkyl group containing a hydroxyl group include triethanolamine.
  • the treatment of the nickel powder 100 with the dispersant can be performed, for example, as follows. First, a slurry of raw material nickel powder, that is, a mixture containing a solvent such as water and raw material nickel, is mixed with a dispersant.
  • the raw material nickel powder in the slurry is such that the concentration of the raw material nickel powder is 90 wt% or more and 99.5 wt% or less and the concentration of the nitrogen-containing compound is 0.5 wt% or more and 10 wt% or less. And the concentration and amount of the dispersant are appropriately controlled.
  • the resulting mixture is stirred under an inert gas atmosphere such as nitrogen or argon.
  • the stirring time can be 1 minute or more and 1 hour or less, 1 minute or more and 30 minutes or less, or 1 minute or more and 10 minutes or less, and is typically 5 minutes.
  • stirring temperature for example, room temperature (15 to 30 degreeC or 15 to 25 degreeC) may be sufficient, and you may stir, heating.
  • the temperature is 40 degreeC or more, and stirring temperature can be selected in the range below the boiling point of a liquid mixture.
  • the ratio of nickel atoms present as metallic nickel on the surface can be effectively increased by performing the treatment particularly at room temperature. Then, it heats up and dries under nitrogen stream. Drying can be 20 ° C. or higher and 200 ° C. or lower, or 110 ° C. or higher and 150 ° C. or lower, and is typically 120 ° C. After drying, the nickel powder 100 may be classified.
  • the nickel powder 100 having a high ratio of nickel atoms present as metallic nickel on the surface and exhibiting a high compression density and a small heat shrinkage rate can be produced.
  • the heat shrinkage ratio of nickel powder When nickel powder is baked and used for electronic parts such as electrodes, if the heat shrinkage ratio of nickel powder is large, it causes a large volume change due to heating, so cracks occur or peels off from adjacent structures It is known that defects are likely to occur.
  • the proportion of nickel atoms present on the surface as a zero-valent metal is higher than when not treated with a dispersant.
  • the inventors have found that the nickel powder 100 exhibits a small shrinkage and has a large compression density. When the compression density is improved, the particle filling rate per unit volume is increased.
  • the voids per unit volume are sufficiently reduced during the formation of the member before the high heat treatment, and even if the nickel particles contract during the firing, the influence is mitigated, and as a result, the occurrence of cracks can be suppressed / reduced. Furthermore, if the thermal contraction rate at high temperature is reduced, the generation of cracks can be further suppressed. For this reason, defects such as generation of cracks during heating and firing and separation from adjacent structures can be greatly suppressed. Therefore, the nickel powder 100 can be used as a material for providing highly reliable electronic components with high yield.
  • Example 1 In this example, the results of evaluating the characteristics of the nickel powder 100 manufactured according to the above manufacturing method will be described.
  • Nickel Powder 15 g of raw material nickel powder having a number average particle diameter of 170 nm produced by a gas phase method was dispersed in 100 mL of water to obtain a nickel slurry. Next, the nitrogen-containing compound was dissolved in water to prepare an aqueous solution of the nitrogen-containing compound. Three types of nitrogen-containing compounds were used: NOF Corporation Cationic MA, Softilt AL-T, and Eslim 221P triethanolamine neutralized product. In addition, as for the Eslime 221P triethanolamine neutralized product, the active ingredient of the nitrogen-containing compound was used in 10% and 20%. The concentration of the nitrogen-containing compound in the total of the raw material nickel powder and the nitrogen-containing compound was 1.0% by weight and 2.0% by weight.
  • An aqueous solution of a nitrogen-containing compound was added to the nickel slurry under a nitrogen atmosphere at room temperature, and two different types of mixed liquids were prepared so that the concentration of each nitrogen-containing compound was the above concentration. After stirring the mixed solution for 5 minutes, the supernatant was removed, washed three times with water, and further heated to 120 ° C. in a nitrogen atmosphere and dried to obtain a nickel powder 100. As a comparative example, a sample not using a nitrogen-containing compound was also prepared, and the influence of the nitrogen-containing compound was examined.
  • XPS Measurement According to the measurement method described in the above embodiment, the proportion of metallic nickel in each nickel powder 100 was determined. For XPS measurement, k-alpha + manufactured by Thermo Fisher Scientific Co., Ltd. was used. The peak area was determined by the following method.
  • the background obtained from the spectrum obtained by the XPS measurement was removed by the Shirley method, and then the waveform was separated by a function combining the Lorentz function and the Gaussian function. Waveform-separated peaks were assigned to each bond as shown in Table 1.
  • the peak area of Ni—Ni bond is the sum of the peak areas of Ni2p3 metal1 and metal2
  • the peak area of Ni—O bond is the sum of the peak areas of Ni2p3 and NiO1 to NiO7
  • the peak area of the Ni—C bond is C1s scan A
  • the peak area of Ni—OH bond was a value obtained by subtracting the peak area of Ni—C bond from the total peak area of scan N from Ni2p3 scan I.
  • the peak area ratio thus obtained was defined as the ratio of each bond.
  • FIGS. 1 to 4 show cation MA (FIG. 1), softilt AL-T (FIG. 2), esliem 221P triethanolamine neutralized product (active ingredient 10%) (FIG. 3), eslime 221P trie as nitrogen-containing compounds, respectively.
  • the ratios of Ni—Ni bond, Ni—OH bond, and Ni—O bond are shown in percentage. As shown in these figures, it was found that the ratio of Ni—Ni bonds was increased when any nitrogen-containing compound was used as compared with the case where no nitrogen-containing compound was used. Further, as a general tendency, it was confirmed that the proportion of Ni—Ni bonds increases as the concentration of the nitrogen-containing compound increases.
  • the raw material nickel powder 100 gave a peak at 398 eV
  • the nickel powder 100 showed a peak at 400 eV (FIG. 7).
  • the peak at 398 eV is a peak attributed to metal nitride, and is considered to be derived from the Ni—N bond.
  • the peak at 400 eV is considered to be derived from the amide bond contained in the nitrogen-containing compound, which is also suggested from the fact that the peak intensity increases with increasing concentration of the nitrogen-containing compound.
  • an organic compound having an amide group is adsorbed on the surface of the nickel particles of the nickel powder 100 according to the embodiment of the present invention.
  • the nickel powder 100 contains an organic compound having an amide group.
  • thermal shrinkage rate was determined by the above method using nickel powder 100 manufactured using Eslime 221P triethanolamine neutralized product (active ingredient 20%) as a nitrogen-containing compound.
  • the equipment used was TMA8310 manufactured by Rigaku Corporation.
  • the shrinkage rate was 18%, and the volume was greatly reduced by heating.
  • the shrinkage rate decreases as the concentration of the nitrogen-containing compound increases, and when the concentration of the nitrogen-containing compound is 2.0%, the heat of 10% Shrinkage rate. From these results, it was confirmed that the nickel powder 100 exhibits a lower heat shrinkage rate as the proportion of nickel atoms present as metallic nickel on the surface is higher.
  • the compression density was measured by the above method using nickel powder 100 produced using a neutralized product of Esliem 221P triethanolamine (active ingredient 20%) as a nitrogen-containing compound.
  • the equipment is ENERPAC S.M. manufactured by Toyo Hydraulic Machinery Co., Ltd. Using E, the load was changed to 0.5 t, 1.0 t, and 3 t.
  • the compression density of the nickel powder 100 tends to increase as the concentration of the nitrogen-containing compound increases, that is, as the proportion of nickel atoms present as metallic nickel on the surface increases. I found out. For example, it was confirmed that when the concentration of the nitrogen-containing compound in the total of the raw material nickel powder and the nitrogen-containing compound is 2.0% by weight, the compression density increases by 15% compared to the nickel powder of the comparative example.

Abstract

One of the problems addressed by the present invention is to provide: a nickel powder which has a high compacted density, and a small volume reduction under high temperature treatment; and a production method therefor. The nickel powder contains nickel particles, and among the Ni-Ni bonds, Ni-OH bonds, and Ni-O bonds derived from nickel oxide on the surface of the nickel particles, the proportion of Ni-Ni bonds is at least 50%, and the thermal shrinkage rate is at most 15% at 1200°C. The proportion of Ni-Ni bonds and the thermal shrinkage rate are estimated by X-ray photoelectron spectroscopy and thermomechanical analysis, respectively.

Description

ニッケル粉体、およびその製造方法Nickel powder and method for producing the same
　本発明の実施形態の一つは、ニッケル粉体、およびその製造方法に関する。 One embodiment of the present invention relates to nickel powder and a method for manufacturing the same.
　微細な金属粒子（金属粉体）は種々の分野で利用されており、例えばニッケル粉体は、積層セラミックコンデンサ（ＭＬＣＣ）の内部電極用の原材料として利用されている。ニッケル粉体は、ニッケルの塩化物のガスを水素などの還元性ガスで還元することで製造することができる。あるいは酸化ニッケルなどのニッケル塩を溶媒中に分散させ、ヒドラジンなどの還元剤を用いて還元することでニッケル粉体を製造することも可能である。前者は気相法と呼ばれ、後者は液相法と呼ばれる。このような方法で得られるニッケル粉体の表面を適宜処理することで、その特性や焼結時の挙動を制御することができる（特許文献１、２参照）。 Fine metal particles (metal powder) are used in various fields. For example, nickel powder is used as a raw material for an internal electrode of a multilayer ceramic capacitor (MLCC). The nickel powder can be produced by reducing nickel chloride gas with a reducing gas such as hydrogen. Alternatively, nickel powder such as nickel oxide can be dispersed in a solvent and reduced using a reducing agent such as hydrazine to produce nickel powder. The former is called a gas phase method, and the latter is called a liquid phase method. By appropriately treating the surface of the nickel powder obtained by such a method, the characteristics and behavior during sintering can be controlled (see Patent Documents 1 and 2).
特開２０１４－２９０１３号公報JP 2014-29013 A 特開２００６－１５２４３９号公報JP 2006-152439 A
　本発明の実施形態の一つは、高い圧縮密度を示し、高温処理において体積収縮が小さいニッケル粉体、およびその製造方法を提供することを目的の一つとする。 One of the embodiments of the present invention is to provide a nickel powder exhibiting a high compression density and having a small volume shrinkage during high-temperature processing, and a method for producing the same.
　本発明に係る実施形態の一つはニッケル粉体である。このニッケル粉体は、表面におけるＮｉ－Ｎｉ結合、Ｎｉ－ＯＨ結合、および酸化ニッケルに由来するＮｉ－Ｏ結合のうち、Ｎｉ－Ｎｉ結合の割合が５０％以上であり、熱収縮率が１２００℃において１５％以下である。Ｎｉ－Ｎｉ結合の割合と熱収縮率は、それぞれＸ線光電子分光法と熱機械分析法によって見積もられる。 One of the embodiments according to the present invention is nickel powder. This nickel powder has a Ni—Ni bond ratio of 50% or more of Ni—Ni bonds, Ni—OH bonds, and Ni—O bonds derived from nickel oxide on the surface, and a heat shrinkage rate of 1200 ° C. Is 15% or less. The proportion of Ni—Ni bond and the thermal shrinkage rate are estimated by X-ray photoelectron spectroscopy and thermomechanical analysis, respectively.
　本発明に係る実施形態の一つは、ニッケル粉体を製造する方法である。この方法は、原料ニッケル粉体を窒素含有化合物の溶液で処理することを含む。 One embodiment according to the present invention is a method for producing nickel powder. The method includes treating raw nickel powder with a solution of a nitrogen-containing compound.
本発明の実施形態の一つに係るニッケル粉体のＸＰＳ測定結果。The XPS measurement result of the nickel powder which concerns on one of embodiment of this invention. 本発明の実施形態の一つに係るニッケル粉体のＸＰＳ測定結果。The XPS measurement result of the nickel powder which concerns on one of embodiment of this invention. 本発明の実施形態の一つに係るニッケル粉体のＸＰＳ測定結果。The XPS measurement result of the nickel powder which concerns on one of embodiment of this invention. 本発明の実施形態の一つに係るニッケル粉体のＸＰＳ測定結果。The XPS measurement result of the nickel powder which concerns on one of embodiment of this invention. 本発明の実施形態の一つに係るニッケル粉体の熱機械分析（ＴＭＡ）結果。The thermomechanical analysis (TMA) result of the nickel powder which concerns on one of embodiment of this invention. 本発明の実施形態の一つに係るニッケル粉体の圧縮密度測定結果。The compression density measurement result of nickel powder concerning one of the embodiments of the present invention. 本発明の実施形態の一つに係るニッケル粉体、および原料ニッケル粉体のＸＰＳ測定結果。The XPS measurement result of the nickel powder which concerns on one of embodiment of this invention, and raw material nickel powder. 本発明の実施形態の一つに係るニッケル粉体の製造フローManufacturing flow of nickel powder according to one embodiment of the present invention
　以下、本発明の各実施形態について、図面等を参照しつつ説明する。但し、本発明は、その要旨を逸脱しない範囲において様々な態様で実施することができ、以下に例示する実施形態の記載内容に限定して解釈されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention can be implemented in various modes without departing from the gist thereof, and is not construed as being limited to the description of the embodiments exemplified below.
　以下、本発明の実施形態の一つに係るニッケル粉体１００とその製造方法について説明を行う。 Hereinafter, the nickel powder 100 according to one embodiment of the present invention and a manufacturing method thereof will be described.
１．ニッケル粉体
　ニッケル粉体１００はニッケルの粒子の集合体であり、ニッケル粉体１００の個数平均粒子径は５０ｎｍ以上５００ｎｍ以下、５０ｎｍ以上３００ｎｍ以下、あるいは１００ｎｍ以上２５０ｎｍとすることができる。したがって、ニッケル粉体１００は上記範囲の粒子径を有するニッケルの粒子を少なくとも一つ含有する。個数平均粒子径としては、例えば走査電子顕微鏡によりニッケル粉体１００を観察し、複数の粒子（例えば１０００個）の粒径を測定し、その平均値を採用することができる。粒子径は粒子を内接する最小円の直径、あるいは粒子を内接する最小面積の四角形の長辺の長さである。なお、ニッケル粉体１００は、ニッケルの粒子とともに例えば後述の式で表されるようなアミド基を含む有機化合物を含んでもよい。 1. Nickel powder Nickel powder 100 is an aggregate of nickel particles, and the number average particle diameter of nickel powder 100 can be 50 nm to 500 nm, 50 nm to 300 nm, or 100 nm to 250 nm. Accordingly, the nickel powder 100 contains at least one nickel particle having a particle diameter in the above range. As the number average particle diameter, for example, the nickel powder 100 is observed with a scanning electron microscope, the particle diameters of a plurality of particles (for example, 1000 particles) are measured, and the average value can be adopted. The particle diameter is the diameter of the smallest circle inscribed in the particle, or the length of the long side of the square having the smallest area inscribed in the particle. Note that the nickel powder 100 may include an organic compound containing an amide group as represented by the following formula, for example, together with nickel particles.
　ニッケル粒子に含まれるニッケル原子は、種々の結合状態で存在する。例えば粒子表面のニッケル原子は、Ｎｉ－Ｎｉ結合のみならず、表面水酸基に由来するＮｉ－ＯＨ結合、炭酸塩（ＮｉＣＯ3）に由来するＮｉ－Ｃ結合、あるいは酸化ニッケル（ＮｉＯｘ）に由来するＮｉ－Ｏ結合などの結合状態を取ることができる。ニッケル粉体１００のニッケル粒子表面では、Ｎｉ－Ｎｉ結合、Ｎｉ－ＯＨ結合、およびＮｉ－Ｏ結合のうち、Ｎｉ－Ｎｉ結合の割合が５０％以上である。Ｎｉ－Ｎｉ結合の割合は、５０％以上９５％以下、６５％以上９３％以下、７６％以上９３％以下、あるいは８５％以上９３％以下としてよい。すなわち、ニッケル粉体１００のニッケル粒子表面において、上述した範囲の割合でニッケルは０価の金属（金属ニッケル）として存在する。なお、ここでニッケル粒子表面とは、ニッケル粒子の表面から５ｎｍまで、あるいは表面から１０ｎｍまでの領域である。発明者らの推定であるが、窒素含有化合物やアミド基を含む有機化合物を除いて考えると、ニッケル粉体１００を構成するニッケル粒子は最表面側に薄くＮｉ－ＯＨ結合およびＮｉ－Ｏ結合を有するＮｉが存在し、該最表面から内側においてＮｉ－Ｎｉ結合を有するＮｉが多く存在すると考えられる。 Nickel atoms contained in the nickel particles exist in various bonded states. For example, the nickel atoms on the particle surface are not only Ni—Ni bonds but also Ni—OH bonds derived from surface hydroxyl groups, Ni—C bonds derived from carbonate (NiCO 3 ), or Ni derived from nickel oxide (NiOx). A bonding state such as —O bonding can be taken. On the nickel particle surface of the nickel powder 100, the ratio of Ni—Ni bonds among Ni—Ni bonds, Ni—OH bonds, and Ni—O bonds is 50% or more. The proportion of Ni—Ni bonds may be 50% or more and 95% or less, 65% or more and 93% or less, 76% or more and 93% or less, or 85% or more and 93% or less. That is, on the surface of the nickel particles of the nickel powder 100, nickel exists as a zero-valent metal (metallic nickel) in the above-described range. Here, the nickel particle surface is a region from the surface of the nickel particle to 5 nm or from the surface to 10 nm. As estimated by the inventors, when excluding nitrogen-containing compounds and organic compounds containing amide groups, the nickel particles constituting the nickel powder 100 are thin and have Ni—OH bonds and Ni—O bonds on the outermost surface side. It is considered that there is a large amount of Ni having Ni—Ni bonds on the inner side from the outermost surface.
　ニッケル原子の結合状態は、例えばＡｌＫα線などの光源を用いるＸＰＳ（Ｘ線光電子分光）により、以下のように見積もることができる。Ｎｉ２ｐの測定エネルギー範囲は８８４～８４４（ｅＶ）とし、Ｃ１ｓの測定エネルギー範囲は２９８～２７９（ｅＶ）とする。金属ニッケルに帰属するピーク、すなわちＮｉ－Ｎｉ結合に由来するピークの面積は、８５２．４（ｅＶ）および８５８．５（ｅＶ）のピーク面積の合算とする。Ｎｉ－Ｏ結合に帰属するピーク面積は、８５３．４（ｅＶ）、８５４．２（ｅＶ）、８５５．３（ｅＶ）、８５８．２（ｅＶ）、８６０．６（ｅＶ）、８６３．２（ｅＶ）、および８６５．４（ｅＶ）のピーク面積の合算とする。Ｎｉ－ＯＨ結合に帰属するピーク面積は以下により求める。まず、８５４．５（ｅＶ）、８５５．７（ｅＶ）、８５７．４（ｅＶ）、８６１．１（ｅＶ）、８６２．４（ｅＶ）および８６５．４（ｅＶ）のピーク面積の合算を求める。この合算からＮｉ－Ｃ結合に帰属される２８８．５（ｅＶ）のピーク面積を引いてＮｉ－ＯＨ結合に由来するピーク面積とする。なお、金属ニッケルに帰属するピークのピーク位置は標準品としてＮｉを使用すれば特定可能である。Ｎｉ－Ｏ結合に帰属するピークのピーク位置は標準品としてＮｉＯを使用すれば特定可能である。Ｎｉ－ＯＨ結合に帰属するピークのピーク位置はＮｉ（ＯＨ）2を使用すれば特定可能である。Ｎｉ－Ｃ結合に帰属するピーク位置はＮｉＣＯ3を使用すれば特定可能である。本明細書と請求項では、Ｎｉ－Ｎｉ結合に帰属するピーク面積、Ｎｉ－Ｏ結合に帰属するピーク面積、およびＮｉ－ＯＨ結合に帰属するピーク面積の合計に占めるＮｉ－Ｎｉ結合に帰属するピーク面積の割合が、ＸＰＳ測定により求めた金属ニッケルの割合である。 The bonding state of nickel atoms can be estimated as follows by XPS (X-ray photoelectron spectroscopy) using a light source such as AlKα rays. The measurement energy range of Ni2p is 884 to 844 (eV), and the measurement energy range of C1s is 298 to 279 (eV). The area of the peak attributed to metallic nickel, that is, the peak derived from the Ni—Ni bond, is the sum of the peak areas of 852.4 (eV) and 858.5 (eV). The peak areas attributed to the Ni—O bond are 853.4 (eV), 854.2 (eV), 855.3 (eV), 858.2 (eV), 860.6 (eV), 863.2 ( eV), and 865.4 (eV) peak area. The peak area attributed to the Ni—OH bond is determined as follows. First, the sum of peak areas of 854.5 (eV), 855.7 (eV), 857.4 (eV), 861.1 (eV), 862.4 (eV), and 865.4 (eV) is obtained. . From this summation, the peak area of 288.5 (eV) attributed to the Ni—C bond is subtracted to obtain the peak area derived from the Ni—OH bond. In addition, the peak position of the peak attributed to metallic nickel can be specified if Ni is used as a standard product. The peak position of the peak attributed to the Ni—O bond can be specified by using NiO as a standard product. The peak position of the peak attributed to the Ni—OH bond can be specified by using Ni (OH) 2 . The peak position attributed to the Ni—C bond can be specified by using NiCO 3 . In the present specification and claims, the peak attributed to the Ni—Ni bond in the total of the peak area attributed to the Ni—Ni bond, the peak area attributed to the Ni—O bond, and the peak area attributed to the Ni—OH bond. The area ratio is the ratio of metallic nickel determined by XPS measurement.
　上述したようにニッケル粒子は高い割合で表面に金属ニッケルを含むため、ニッケル粉体１００は優れた特性を示す。例えば熱機械分析法によって見積もられる熱収縮率は、１２００℃において１５％以下と低い。熱収縮率は５％以上１４％以下、あるいは７％以上１３％以下であってよい。また、ニッケル粉体１００の圧縮密度も、４．８ｇ／ｃｍ3以上６．０ｇ／ｃｍ3以下、あるいは５．０ｇ／ｃｍ3以上６．０以下ｇ／ｃｍ3と高い値となる。 As described above, since the nickel particles contain metallic nickel on the surface at a high rate, the nickel powder 100 exhibits excellent characteristics. For example, the thermal shrinkage estimated by the thermomechanical analysis method is as low as 15% or less at 1200 ° C. The thermal contraction rate may be 5% or more and 14% or less, or 7% or more and 13% or less. Also, the compression density of the nickel powder 100 is a high value of 4.8 g / cm 3 or more and 6.0 g / cm 3 or less, or 5.0 g / cm 3 or more and 6.0 or less g / cm 3 .
　上記熱機械分析法の測定値は以下の測定により求められる。まず、ニッケル粉体１００をφ５ｍｍ、高さ１０ｍｍのペレットに成形する。熱機械分析法測定の測定条件は温度範囲：室温から１２００℃、昇温速度：５℃／分、雰囲気：２％Ｈ2、９８％Ｎ2の混合ガス、３００ｍＬ／分とする。収縮が終了した１２００℃のときのペレットの高さ（長さ）から求めた収縮分をもとの高さに対する割合として熱収縮率が求まる。また、上記圧縮密度は以下の測定により求められる。ニッケル粉体１ｇに樟脳３ｗｔ％とアセトンを加え、混合物が乾燥するまで攪拌する。得られたニッケル粉体を圧力０．５ｔの条件で成形する。成形体の直径、厚み、および重量を測定し、これにより得られる値が圧縮密度である。 The measured value of the thermomechanical analysis method is determined by the following measurement. First, the nickel powder 100 is formed into a pellet having a diameter of 5 mm and a height of 10 mm. The measurement conditions for the thermomechanical analysis method are as follows: temperature range: room temperature to 1200 ° C., heating rate: 5 ° C./min, atmosphere: 2% H 2 , 98% N 2 mixed gas, 300 mL / min. The thermal shrinkage rate is obtained by using the shrinkage obtained from the height (length) of the pellet at 1200 ° C. when the shrinkage is completed as a ratio to the original height. Moreover, the said compression density is calculated | required by the following measurements. Add 3 wt% camphor and acetone to 1 g of nickel powder and stir until the mixture is dry. The obtained nickel powder is molded under a pressure of 0.5 t. The diameter, thickness, and weight of the molded body are measured, and the value obtained thereby is the compression density.
２．製造方法
　図８に示すように、本発明の実施形態に係るニッケル粉体１００は、ニッケル粉体を原料として用い、これを窒素含有化合物と処理し、乾燥することで製造することができる。この製造方法では、気相法、あるいは液相法で製造されたニッケル粉体を原料として用いることができる。以下、気相法で製造されたニッケル粉末（以下、原料ニッケル粉体と記す）を原料として用いる例により説明を行う。 2. Manufacturing Method As shown in FIG. 8, a nickel powder 100 according to an embodiment of the present invention can be manufactured by using nickel powder as a raw material, treating it with a nitrogen-containing compound, and drying it. In this production method, nickel powder produced by a vapor phase method or a liquid phase method can be used as a raw material. Hereinafter, an example using nickel powder produced by a vapor phase method (hereinafter referred to as raw material nickel powder) as a raw material will be described.
　原料ニッケル粉体の製造条件は適宜選択することができる。通常、ニッケルペレット、ニッケル粉末、ニッケルインゴットなどの原料に塩素ガスを吹き付けて塩化ニッケルを得る。この塩化ニッケルを気化し、塩化したニッケルガスを水素ガスやヒドラジンなどの還元性ガスと接触させることで原料ニッケル粉体を得ることができる。この原料ニッケル粉体をさらに硫黄含有化合物で処理し、表面に硫化ニッケルの被膜を形成してもよい。原料ニッケル粉体の粒径に特に制約は無く、例えば個数平均粒子径が５０ｎｍ以上５００ｎｍ以下、５０ｎｍ以上３００ｎｍ以下、あるいは１００ｎｍ以上２５０ｎｍの原料ニッケル粉体を用いることができる。 The production conditions of the raw material nickel powder can be selected as appropriate. Usually, nickel chloride is obtained by spraying chlorine gas on raw materials such as nickel pellets, nickel powder, and nickel ingot. Raw nickel powder can be obtained by vaporizing the nickel chloride and bringing the chlorinated nickel gas into contact with a reducing gas such as hydrogen gas or hydrazine. The raw nickel powder may be further treated with a sulfur-containing compound to form a nickel sulfide coating on the surface. The particle diameter of the raw material nickel powder is not particularly limited, and for example, a raw material nickel powder having a number average particle diameter of 50 nm to 500 nm, 50 nm to 300 nm, or 100 nm to 250 nm can be used.
　ニッケル粉体１００は、原料ニッケル粉体を窒素含有化合物を含む混合液、あるいは溶液（以下、この混合液や溶液を分散剤とも言う）と処理することで製造することができる。溶媒としては、水、エタノールやプロパノールなどの炭素数１以上４以下の低級アルコール、エチレングリコール、プロピレングリコールなどのグルコール系溶媒、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミドなどのアミド系溶媒、アセトニトリルなどのニトリル系溶媒、エチレンカルボナートなどの環状カルボナート系溶媒などを用いることができる。中でも不燃性溶媒であり、かつ、毒性の低い水が好適である。 The nickel powder 100 can be manufactured by treating the raw nickel powder with a mixed solution containing a nitrogen-containing compound or a solution (hereinafter, this mixed solution or solution is also referred to as a dispersant). Examples of the solvent include water, lower alcohols having 1 to 4 carbon atoms such as ethanol and propanol, glycol solvents such as ethylene glycol and propylene glycol, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. Nitrile solvents such as acetonitrile, cyclic carbonate solvents such as ethylene carbonate, and the like can be used. Among them, water that is a nonflammable solvent and has low toxicity is preferable.
　窒素含有化合物としては水溶性の窒素含有化合物が好ましい。水を溶媒として用いる場合には、水に対する溶解度が高い窒素含有化合物が用いられる。窒素含有化合物は単独成分で構成されても良く、複数成分を含む混合物を窒素含有化合物として使用してもよい。 The nitrogen-containing compound is preferably a water-soluble nitrogen-containing compound. When water is used as a solvent, a nitrogen-containing compound having high solubility in water is used. The nitrogen-containing compound may be composed of a single component, or a mixture containing a plurality of components may be used as the nitrogen-containing compound.
　窒素含有化合物としては、一級アルキルアミンや脂肪族アミドから選択することができる。一級アルキルアミンの炭素数、および脂肪族アミド基の炭素や窒素に結合されるアルキル基の炭素数に制約は無く、１以上１８以下から選択することができる。また、アルキル基は直鎖状でも環状でもよく、分岐していてもよい。一級アルキルアミンとしては、テトラデシルアミン（Ｃ14Ｈ29ＮＨ2）が例示される。 The nitrogen-containing compound can be selected from primary alkylamines and aliphatic amides. There is no restriction | limiting in carbon number of primary alkylamine, and carbon number of the alkyl group couple | bonded with carbon of an aliphatic amide group, or nitrogen, It can select from 1-18. The alkyl group may be linear or cyclic, and may be branched. As the primary alkylamine, tetradecylamine (C 14 H 29 NH 2 ) is exemplified.
　あるいは窒素含有化合物は、一級アルキルアミンとカルボン酸の塩を含んでもよい。カルボン酸としては、例えばギ酸、酢酸など、炭素数が１以上４以下のカルボン酸を用いることができる。一例として、テトラデシルアミンと酢酸の塩が挙げられる。 Alternatively, the nitrogen-containing compound may include a primary alkylamine and a carboxylic acid salt. As the carboxylic acid, for example, a carboxylic acid having 1 to 4 carbon atoms such as formic acid and acetic acid can be used. An example is a salt of tetradecylamine and acetic acid.
　上述した脂肪族アミドは、分子内にカルボキシル基を有していてもよい。この場合、窒素含有化合物はさらに水酸基を含むアルキル基を有する三級アミンを含んでもよい。脂肪族アミドとしては、例えば以下の化学式で表される化合物を用いることができる。 The above-described aliphatic amide may have a carboxyl group in the molecule. In this case, the nitrogen-containing compound may further contain a tertiary amine having an alkyl group containing a hydroxyl group. As the aliphatic amide, for example, a compound represented by the following chemical formula can be used.
Figure JPOXMLDOC01-appb-C000002
 　ここで、Ｒ1は炭素数６以上１８以下のアルキル基から、Ｒ2は炭素数１以上４以下のアルキル基あるいはアルケニル基から、Ｘは炭素数１から５のアルキレン基から選択される。一例として、Ｒ1、Ｒ2、Ｘとしてそれぞれウンデシル基（Ｃ11Ｈ23）、メチル基、エチレン基を選択することができる。水酸基を含むアルキル基を有する三級アミンとしては、例えばトリエタノールアミンが挙げられる。
Figure JPOXMLDOC01-appb-C000002
 Here, R 1 is selected from an alkyl group having 6 to 18 carbon atoms, R 2 is selected from an alkyl group or alkenyl group having 1 to 4 carbon atoms, and X is selected from an alkylene group having 1 to 5 carbon atoms. As an example, undecyl group (C 11 H 23 ), methyl group, and ethylene group can be selected as R 1 , R 2 , and X, respectively. Examples of the tertiary amine having an alkyl group containing a hydroxyl group include triethanolamine.
　ニッケル粉体１００の分散剤による処理は、例えば以下のように行うことができる。まず、原料ニッケル粉体のスラリー、すなわち水などの溶媒と原料ニッケルを含む混合物を作製し、これと分散剤とを混合する。この混合液において原料ニッケル粉体の濃度が９０重量％以上９９．５重量％以下、窒素含有化合物の濃度が０．５重量％以上１０重量％以下となるように、スラリー中の原料ニッケル粉体の量や分散剤の濃度、量が適宜制御される。得られる混合液を窒素やアルゴンなどの不活性ガスの雰囲気下で攪拌する。攪拌時間は１分以上１時間以下、１分以上３０分以下、あるいは１分以上１０分以下とすることができ、典型的には５分である。攪拌温度にも制約は無く、例えば室温（１５℃以上３０℃以下、あるいは１５℃以上２５℃以下）でも良く、加熱しながら攪拌を行ってもよい。加熱する場合、その温度は４０℃以上であり混合液の沸点以下の範囲で攪拌温度を選択することができる。実施例で示すように、特に室温で処理を行うことで、表面において金属ニッケルとして存在するニッケル原子の割合を効果的に増大させることができる。その後、昇温を行い、窒素気流下で乾燥する。乾燥は、２０℃以上２００℃以下、あるいは１１０℃以上１５０℃以下とすることができ、典型的には１２０℃である。乾燥後、ニッケル粉体１００に対して分級を行ってもよい。 The treatment of the nickel powder 100 with the dispersant can be performed, for example, as follows. First, a slurry of raw material nickel powder, that is, a mixture containing a solvent such as water and raw material nickel, is mixed with a dispersant. The raw material nickel powder in the slurry is such that the concentration of the raw material nickel powder is 90 wt% or more and 99.5 wt% or less and the concentration of the nitrogen-containing compound is 0.5 wt% or more and 10 wt% or less. And the concentration and amount of the dispersant are appropriately controlled. The resulting mixture is stirred under an inert gas atmosphere such as nitrogen or argon. The stirring time can be 1 minute or more and 1 hour or less, 1 minute or more and 30 minutes or less, or 1 minute or more and 10 minutes or less, and is typically 5 minutes. There is no restriction | limiting also in stirring temperature, for example, room temperature (15 to 30 degreeC or 15 to 25 degreeC) may be sufficient, and you may stir, heating. When heating, the temperature is 40 degreeC or more, and stirring temperature can be selected in the range below the boiling point of a liquid mixture. As shown in the examples, the ratio of nickel atoms present as metallic nickel on the surface can be effectively increased by performing the treatment particularly at room temperature. Then, it heats up and dries under nitrogen stream. Drying can be 20 ° C. or higher and 200 ° C. or lower, or 110 ° C. or higher and 150 ° C. or lower, and is typically 120 ° C. After drying, the nickel powder 100 may be classified.
　上記製造方法により、表面において金属ニッケルとして存在するニッケル原子の割合が高く、これに起因して高い圧縮密度と小さな熱収縮率を示すニッケル粉体１００を製造することができる。 According to the above production method, the nickel powder 100 having a high ratio of nickel atoms present as metallic nickel on the surface and exhibiting a high compression density and a small heat shrinkage rate can be produced.
　ニッケル粉体を焼成して電極などの電子部品に利用する場合、ニッケル粉体の熱収縮率が大きいと加熱によって大きな体積変化を伴うため、クラックが発生する、あるいは隣接する構造体から剥離するなどの不良が発生しやすいことが知られている。これに対し、本実施形態に係るニッケル粉体１００では、分散剤で処理していな場合と比較し、ニッケル原子は表面において０価の金属として存在する割合が高い。その結果、実施例で示すように、ニッケル粉体１００は小さい収縮率を示し、かつ、大きな圧縮密度を有することが発明者らによって見出された。圧縮密度が向上すると単位体積あたりの粒子充填割合が高まる。よって、高熱処理前の部材形成時に単位体積当たりの空隙が十分に減少し、仮に焼成時にニッケル粒子が収縮してもその影響が緩和され、結果としてクラックの発生を抑制・低下できると考えられる。さらに、高温での熱収縮率が小さくなれば、クラック発生をより抑制できる。このため、加熱焼成時のクラックの発生や隣接する構造体からの剥離といった不良を大幅に抑制することができる。したがって、ニッケル粉体１００は、信頼性の高い電子部品を歩留まり良く提供するための材料として利用することが可能である。 When nickel powder is baked and used for electronic parts such as electrodes, if the heat shrinkage ratio of nickel powder is large, it causes a large volume change due to heating, so cracks occur or peels off from adjacent structures It is known that defects are likely to occur. On the other hand, in the nickel powder 100 according to the present embodiment, the proportion of nickel atoms present on the surface as a zero-valent metal is higher than when not treated with a dispersant. As a result, as shown in Examples, the inventors have found that the nickel powder 100 exhibits a small shrinkage and has a large compression density. When the compression density is improved, the particle filling rate per unit volume is increased. Therefore, it is considered that the voids per unit volume are sufficiently reduced during the formation of the member before the high heat treatment, and even if the nickel particles contract during the firing, the influence is mitigated, and as a result, the occurrence of cracks can be suppressed / reduced. Furthermore, if the thermal contraction rate at high temperature is reduced, the generation of cracks can be further suppressed. For this reason, defects such as generation of cracks during heating and firing and separation from adjacent structures can be greatly suppressed. Therefore, the nickel powder 100 can be used as a material for providing highly reliable electronic components with high yield.
１．実施例１
　本実施例では、上記製造方法に従って製造したニッケル粉体１００の特性を評価した結果について説明する。 1. Example 1
In this example, the results of evaluating the characteristics of the nickel powder 100 manufactured according to the above manufacturing method will be described.
１－１．ニッケル粉体の製造
　気相法により製造した、個数平均粒子径１７０ｎｍの原料ニッケル粉体１５ｇを１００ｍＬの水に分散させてニッケルスラリーを得た。次に、窒素含有化合物を水に溶解して窒素含有化合物の水溶液を調製した。窒素含有化合物としては、日油株式会社製のカチオンＭＡ、ソフティルトＡＬ－Ｔ、エスリーム２２１Ｐトリエタノールアミン中和品の三種類を用いた。なお、エスリーム２２１Ｐトリエタノールアミン中和品は、窒素含有化合物の有効成分が１０％、２０％の二種類を用いた。原料ニッケル粉体および窒素含有化合物の合計における窒素含有化合物の濃度は、１．０重量％、２．０重量％とした。 1-1. Production of Nickel Powder 15 g of raw material nickel powder having a number average particle diameter of 170 nm produced by a gas phase method was dispersed in 100 mL of water to obtain a nickel slurry. Next, the nitrogen-containing compound was dissolved in water to prepare an aqueous solution of the nitrogen-containing compound. Three types of nitrogen-containing compounds were used: NOF Corporation Cationic MA, Softilt AL-T, and Eslim 221P triethanolamine neutralized product. In addition, as for the Eslime 221P triethanolamine neutralized product, the active ingredient of the nitrogen-containing compound was used in 10% and 20%. The concentration of the nitrogen-containing compound in the total of the raw material nickel powder and the nitrogen-containing compound was 1.0% by weight and 2.0% by weight.
　室温、窒素雰囲気下でニッケルスラリーに窒素含有化合物の水溶液を加え、それぞれの窒素含有化合物の濃度が上記濃度となるように、異なる二種類の混合液を調整した。混合液を５分攪拌した後、上澄みを除去し、水を用いて三回洗浄し、さらに窒素雰囲気下で１２０℃に加熱して乾燥することでニッケル粉体１００を得た。比較例として窒素含有化合物を用いない試料も調整し、窒素含有化合物の影響を検討した。 An aqueous solution of a nitrogen-containing compound was added to the nickel slurry under a nitrogen atmosphere at room temperature, and two different types of mixed liquids were prepared so that the concentration of each nitrogen-containing compound was the above concentration. After stirring the mixed solution for 5 minutes, the supernatant was removed, washed three times with water, and further heated to 120 ° C. in a nitrogen atmosphere and dried to obtain a nickel powder 100. As a comparative example, a sample not using a nitrogen-containing compound was also prepared, and the influence of the nitrogen-containing compound was examined.
１－２．ＸＰＳ測定
　上記実施形態に記載した測定方法に従い、各ニッケル粉体１００における金属ニッケルの割合を求めた。ＸＰＳ測定にはサーモフィッシャーサイエンティフィク株式会社製ｋ－ａｌｐｈａ＋を使用した。ピーク面積は以下の方法により求めた。 1-2. XPS Measurement According to the measurement method described in the above embodiment, the proportion of metallic nickel in each nickel powder 100 was determined. For XPS measurement, k-alpha + manufactured by Thermo Fisher Scientific Co., Ltd. was used. The peak area was determined by the following method.
　ＸＰＳ測定によって得られたスペクトルに対し、シャーリー法でバックグラウンドを除去した後、ローレンツ関数とガウス関数を組み合わせた関数で波形分離を行った。波形分離されたピークを、表１に示すように各結合に帰属した。Ｎｉ－Ｎｉ結合のピーク面積はＮｉ２ｐ３　ｍｅｔａｌ１とｍｅｔａｌ２のピーク面積の合計とし、Ｎｉ－Ｏ結合のピーク面積はＮｉ２ｐ３、ＮｉＯ１からＮｉＯ７のピーク面積の合計とし、Ｎｉ－Ｃ結合のピーク面積はＣ１ｓ　ｓｃａｎ　Ａのピーク面積とし、Ｎｉ－ＯＨ結合のピーク面積はＮｉ２ｐ３　ｓｃａｎ　Ｉからｓｃａｎ　Ｎのピーク面積の合計からＮｉ－Ｃ結合のピーク面積を差し引いた値とした。こうして得られたピーク面積比を各結合の割合とした。 The background obtained from the spectrum obtained by the XPS measurement was removed by the Shirley method, and then the waveform was separated by a function combining the Lorentz function and the Gaussian function. Waveform-separated peaks were assigned to each bond as shown in Table 1. The peak area of Ni—Ni bond is the sum of the peak areas of Ni2p3 metal1 and metal2, the peak area of Ni—O bond is the sum of the peak areas of Ni2p3 and NiO1 to NiO7, and the peak area of the Ni—C bond is C1s scan A The peak area of Ni—OH bond was a value obtained by subtracting the peak area of Ni—C bond from the total peak area of scan N from Ni2p3 scan I. The peak area ratio thus obtained was defined as the ratio of each bond.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　結果を図１から図４に示す。図１から図４はそれぞれ、窒素含有化合物としてカチオンＭＡ（図１）、ソフティルトＡＬ－Ｔ（図２）、エスリーム２２１Ｐトリエタノールアミン中和品（有効成分１０％）（図３）、エスリーム２２１Ｐトリエタノールアミン中和品（有効成分２０％）（図４）を用いて製造されたニッケル粉体１００の測定結果である。これらの図では、Ｎｉ－Ｎｉ結合、Ｎｉ－ＯＨ結合、Ｎｉ－Ｏ結合の割合が百分率で示されている。これらの図に示すように、いずれの窒素含有化合物を用いても、窒素含有化合物を用いない場合と比較してＮｉ－Ｎｉ結合の割合が増大していることが分かった。また、一般的な傾向として、Ｎｉ－Ｎｉ結合の割合は窒素含有化合物の濃度が増大するにしたがって増大することが確認された。 The results are shown in FIGS. FIGS. 1 to 4 show cation MA (FIG. 1), softilt AL-T (FIG. 2), esliem 221P triethanolamine neutralized product (active ingredient 10%) (FIG. 3), eslime 221P trie as nitrogen-containing compounds, respectively. It is a measurement result of the nickel powder 100 manufactured using the ethanolamine neutralized product (active ingredient 20%) (FIG. 4). In these figures, the ratios of Ni—Ni bond, Ni—OH bond, and Ni—O bond are shown in percentage. As shown in these figures, it was found that the ratio of Ni—Ni bonds was increased when any nitrogen-containing compound was used as compared with the case where no nitrogen-containing compound was used. Further, as a general tendency, it was confirmed that the proportion of Ni—Ni bonds increases as the concentration of the nitrogen-containing compound increases.
　ここで、原料ニッケル粉体と、エスリーム２２１Ｐトリエタノールアミン中和品（有効成分２０％）を窒素含有化合物として用いて製造されたニッケル粉体１００の３９０ｅＶから４１０ｅＶの範囲におけるスペクトルを比較したところ、原料ニッケル粉体は３９８ｅＶにピークを与えるのに対し、ニッケル粉体１００は４００ｅＶにピークを示すことが分かった（図７）。３９８ｅＶのピークは金属窒化物に帰属されるピークであり、Ｎｉ－Ｎ結合に由来するものと考えられる。一方、４００ｅＶのピークは窒素含有化合物に含まれるアミド結合に由来するものと考えられ、これは、窒素含有化合物の濃度の増大とともにこのピーク強度が増大することからも示唆される。このことから、本発明の実施形態に係るニッケル粉体１００のニッケル粒子表面には、アミド基を有する有機化合物が吸着していることが示唆される。換言すると、ニッケル粉体１００はアミド基を有する有機化合物を含むと言える。 Here, when the spectrum in the range of 390 eV to 410 eV of the nickel powder 100 manufactured using the raw material nickel powder and the Eslime 221P triethanolamine neutralized product (active ingredient 20%) as a nitrogen-containing compound was compared, It was found that the raw material nickel powder gave a peak at 398 eV, whereas the nickel powder 100 showed a peak at 400 eV (FIG. 7). The peak at 398 eV is a peak attributed to metal nitride, and is considered to be derived from the Ni—N bond. On the other hand, the peak at 400 eV is considered to be derived from the amide bond contained in the nitrogen-containing compound, which is also suggested from the fact that the peak intensity increases with increasing concentration of the nitrogen-containing compound. This suggests that an organic compound having an amide group is adsorbed on the surface of the nickel particles of the nickel powder 100 according to the embodiment of the present invention. In other words, it can be said that the nickel powder 100 contains an organic compound having an amide group.
１－３．熱収縮率測定
　エスリーム２２１Ｐトリエタノールアミン中和品（有効成分２０％）を窒素含有化合物として用いて製造されたニッケル粉体１００を使用し、上記方法により熱収縮率を求めた。機器はリガク株式会社製ＴＭＡ８３１０を使用した。 1-3. Measurement of thermal shrinkage rate The thermal shrinkage rate was determined by the above method using nickel powder 100 manufactured using Eslime 221P triethanolamine neutralized product (active ingredient 20%) as a nitrogen-containing compound. The equipment used was TMA8310 manufactured by Rigaku Corporation.
　結果を図５に示す。図５に示すように、窒素含有化合物を使用していない場合には収縮率は１８％となり、加熱によって体積が大きく減少することが分かった。これに対し窒素含有化合物を使用して製造されたニッケル粉体１００では、窒素含有化合物の濃度が増大するにつれて収縮率は低下し、窒素含有化合物の濃度が２．０％の時には１０％の熱収縮率であった。これらの結果から、表面において金属ニッケルとして存在するニッケル原子の割合が高いほどニッケル粉体１００は低い熱収縮率を示すことが確認された。 The results are shown in FIG. As shown in FIG. 5, it was found that when no nitrogen-containing compound was used, the shrinkage rate was 18%, and the volume was greatly reduced by heating. On the other hand, in the nickel powder 100 manufactured using the nitrogen-containing compound, the shrinkage rate decreases as the concentration of the nitrogen-containing compound increases, and when the concentration of the nitrogen-containing compound is 2.0%, the heat of 10% Shrinkage rate. From these results, it was confirmed that the nickel powder 100 exhibits a lower heat shrinkage rate as the proportion of nickel atoms present as metallic nickel on the surface is higher.
１－４．圧縮密度測定
エスリーム２２１Ｐトリエタノールアミン中和品（有効成分２０％）を窒素含有化合物として用いて製造されたニッケル粉体１００を用い、上記方法により圧縮密度を測定した。機器は東洋油圧機械株式会社製ＥＮＥＲＰＡＣ Ｓ．Ｅを用い、負荷を０．５ｔ、１．０ｔ、３ｔと変えて測定した。 1-4. Compression Density Measurement The compression density was measured by the above method using nickel powder 100 produced using a neutralized product of Esliem 221P triethanolamine (active ingredient 20%) as a nitrogen-containing compound. The equipment is ENERPAC S.M. manufactured by Toyo Hydraulic Machinery Co., Ltd. Using E, the load was changed to 0.5 t, 1.0 t, and 3 t.
　結果を表２と図６に示す。表２と図６から理解されるように、窒素含有化合物の濃度が増大するほど、すなわち、表面において金属ニッケルとして存在するニッケル原子の割合が高いほどニッケル粉体１００の圧縮密度は増大する傾向があることが分かった。例えば原料ニッケル粉体および窒素含有化合物の合計における窒素含有化合物の濃度が２．０重量％の時には、比較例のニッケル粉体と比較し、１５％圧縮密度が増大することが確認された。 The results are shown in Table 2 and FIG. As understood from Table 2 and FIG. 6, the compression density of the nickel powder 100 tends to increase as the concentration of the nitrogen-containing compound increases, that is, as the proportion of nickel atoms present as metallic nickel on the surface increases. I found out. For example, it was confirmed that when the concentration of the nitrogen-containing compound in the total of the raw material nickel powder and the nitrogen-containing compound is 2.0% by weight, the compression density increases by 15% compared to the nickel powder of the comparative example.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明の実施形態として上述した各実施形態は、相互に矛盾しない限りにおいて、適宜組み合わせて実施することができる。また、各実施形態の表示装置を基にして、当業者が適宜構成要素の追加、削除もしくは設計変更を行ったもの、又は、工程の追加、省略もしくは条件変更を行ったものも、本発明の要旨を備えている限り、本発明の範囲に含まれる。 The embodiments described above as embodiments of the present invention can be implemented in appropriate combination as long as they do not contradict each other. Also, those in which those skilled in the art appropriately added, deleted, or changed the design based on the display device of each embodiment, or those in which the process was added, omitted, or changed in conditions are also included in the present invention. As long as the gist is provided, it is included in the scope of the present invention.
　上述した各実施形態の態様によりもたらされる作用効果とは異なる他の作用効果であっても、本明細書の記載から明らかなもの、又は、当業者において容易に予測し得るものについては、当然に本発明によりもたらされるものと解される。 Of course, other operational effects different from the operational effects brought about by the aspects of the above-described embodiments are obvious from the description of the present specification or can be easily predicted by those skilled in the art. It is understood that this is brought about by the present invention.
　１００：ニッケル粉体 100: Nickel powder

Claims (13)

  1. 　ニッケル粒子を含み、
    　Ｘ線光電子分光法によって見積もられた、前記ニッケル粒子の表面におけるＮｉ－Ｎｉ結合、Ｎｉ－ＯＨ結合、および酸化ニッケルに由来するＮｉ－Ｏ結合のうち、Ｎｉ－Ｎｉ結合の割合が５０％以上であり、
    　熱機械分析法によって見積もられる熱収縮率が１２００℃において１５％以下であるニッケル粉体。     Contains nickel particles,
    Of the Ni—Ni bonds, Ni—OH bonds, and Ni—O bonds derived from nickel oxide on the surface of the nickel particles estimated by X-ray photoelectron spectroscopy, the ratio of Ni—Ni bonds is 50% or more. And
    Nickel powder whose thermal shrinkage estimated by thermomechanical analysis is 15% or less at 1200 ° C.
  2. 　前記ニッケル粉体の個数平均粒子径は、５０ｎｍ以上５００ｎｍ以下である、請求項１に記載のニッケル粉体。 The nickel powder according to claim 1, wherein the nickel powder has a number average particle diameter of 50 nm or more and 500 nm or less.
  3. 　アミド基を含む有機化合物をさらに含む、請求項１に記載のニッケル粉体。 The nickel powder according to claim 1, further comprising an organic compound containing an amide group.
  4. 　原料ニッケル粉体を窒素含有化合物を含む混合液あるいは溶液で処理することを含む、ニッケル粉体を製造する方法。 A method for producing nickel powder, comprising treating raw material nickel powder with a mixed solution or solution containing a nitrogen-containing compound.
  5. 　前記処理は、１５℃以上３０℃以下の範囲から選択される温度で行われる、請求項４に記載の方法。 The method according to claim 4, wherein the treatment is performed at a temperature selected from a range of 15 ° C or higher and 30 ° C or lower.
  6. 　前記窒素含有化合物は、一級アルキルアミン、脂肪族アミドから選択される、請求項４に記載の方法。 The method according to claim 4, wherein the nitrogen-containing compound is selected from primary alkylamines and aliphatic amides.
  7. 　前記窒素含有化合物は、一級アルキルアミンとカルボン酸の塩を含む、請求項４に記載の方法。 The method according to claim 4, wherein the nitrogen-containing compound includes a salt of a primary alkylamine and a carboxylic acid.
  8. 　前記脂肪族アミドは、分子内にカルボキシル基を含む、請求項６に記載の方法。 The method according to claim 6, wherein the aliphatic amide contains a carboxyl group in the molecule.
  9. 　前記脂肪族アミドは、以下の化学式で表され、
    Figure JPOXMLDOC01-appb-C000001
     　Ｒ1は炭素数６以上１８以下のアルキル基であり、Ｒ2は炭素数１以上４以下のアルキル基あるいはアルケニル基であり、Ｘは炭素数１から５のアルキレン基である、請求項８に記載の方法。     The aliphatic amide is represented by the following chemical formula:
    Figure JPOXMLDOC01-appb-C000001
     R 1 is an alkyl group having 6 to 18 carbon atoms, R 2 is an alkyl group or alkenyl group having 1 to 4 carbon atoms, and X is an alkylene group having 1 to 5 carbon atoms. The method described.
  10. 　前記処理は、前記原料ニッケル粉体および前記窒素含有化合物の合計における前記原料ニッケル粉体が９０重量％以上９９．５重量％以下、前記窒素含有化合物が０．５重量％以上１０重量％以下の濃度となるように行われる、請求項４に記載の方法。 In the treatment, the raw nickel powder in the total of the raw nickel powder and the nitrogen-containing compound is 90 wt% or more and 99.5 wt% or less, and the nitrogen-containing compound is 0.5 wt% or more and 10 wt% or less. The method according to claim 4, wherein the method is performed so as to obtain a concentration.
  11. 　前記原料ニッケル粉体は気相法で製造される、請求項４に記載の方法。 The method according to claim 4, wherein the raw nickel powder is produced by a vapor phase method.
  12. 　前記溶液の溶媒が水である、請求項４に記載の方法。 The method according to claim 4, wherein the solvent of the solution is water.
  13. 　前記処理は、前記ニッケル粉体に含まれるニッケル粒子が有するＮｉ－Ｎｉ結合、Ｎｉ－ＯＨ結合、および酸化ニッケルに起因するＮｉ－Ｏ結合のうち、Ｎｉ－Ｎｉ結合の割合が５０％以上であり、かつ前記ニッケル粉体の熱収縮率が１２００℃において１５％以下となるように行われ、
    　前記Ｎｉ－Ｎｉ結合の前記割合と前記熱収縮率は、それぞれＸ線光電子分光法と熱機械分析法によって見積もられる、請求項４に記載の方法。     In the treatment, the proportion of Ni—Ni bonds among Ni—Ni bonds, Ni—OH bonds, and Ni—O bonds attributed to nickel oxide contained in nickel particles contained in the nickel powder is 50% or more. And the thermal contraction rate of the nickel powder is 15% or less at 1200 ° C.,
    The method according to claim 4, wherein the ratio of the Ni-Ni bond and the thermal shrinkage rate are estimated by X-ray photoelectron spectroscopy and thermomechanical analysis, respectively.
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