JP5352259B2 - Nickel hydroxide-coated nickel particles and method for producing the same - Google Patents

Description

  The present invention relates to nickel particles whose surfaces are coated with nickel hydroxide and a method for producing the same.

  A technique for increasing the dispersibility of nickel particles by covering the surfaces of nickel particles with nickel hydroxide is known. For example, in Patent Document 1, the nickel powder is heated in a hydrogen stream, the oxide or hydroxide on the surface of the nickel particles is reduced, and then the nickel powder is immersed in water and air is bubbled. It is described that nickel oxide or nickel hydroxide is generated on the surface.

Patent Document 2 contains Ni (OH) ₂ and NiO, and the component composition of the surface is 5% to 20% in terms of mol%, Ni (OH) ₂ : 25 to 75%, NiO: 15 to 65%. % Nickel powder is described. This nickel powder is obtained by using a liquid phase reduction method and dropping a nickel salt aqueous solution into a reducing agent aqueous solution to reduce nickel ions.

JP 2003-129103 A JP 2004-330247 A

  Since the nickel powder described in each of the above patent documents is used in a state where the surface is coated with nickel oxide or hydroxide, the electrode film formed from the nickel powder has a high resistance value, Moreover, there is an inconvenience that firing is difficult to occur in the firing temperature range of the metallic nickel powder.

  Accordingly, the present invention provides nickel hydroxide-coated nickel particles and a method for producing the same that can eliminate the various disadvantages of the prior art described above.

The present invention is made in the surface of nickel hydroxide bound in binding strength enough to be removed by an external force being coated, an average particle diameter of Ru 5~500nm der water nickel oxide-coated nickel particles of primary particles,
The bonding force is φ0.1 mm zirconia beads, 4.2 weight times zirconia beads are added to 20% by weight slurry of the particles, and treated with a bead mill for 15 minutes. The nickel hydroxide-coated nickel particles are provided to such an extent that all are removed .

  The present invention also provides a method for producing the nickel hydroxide-coated nickel particles, wherein the nickel hydroxide particles are heated in a state of being suspended in polyols and reduced to nickel. The particles are not completely reduced, but the reaction is terminated in the course of the reduction to generate a large number of fine nickel particles in the nickel hydroxide particles, and then the nickel hydroxide particles are crushed to form water on the surface. The present invention provides a method for producing nickel hydroxide-coated nickel particles characterized by obtaining a large number of nickel particles having a thin layer of nickel oxide.

  According to the present invention, during storage, nickel hydroxide covering the surface of nickel acts as a protective agent, preventing aggregation and improving the dispersibility of the particles. And by removing nickel hydroxide in use, metallic nickel can be easily exposed, so that an increase in resistance of the electrode film formed therefrom can be suppressed. In the case of reducing firing without removing nickel hydroxide, the nickel hydroxide acts as a sintering aid and the low-temperature sinterability is improved.

FIG. 1A is a schematic diagram showing a state in which a large number of nickel core particles are generated in nickel hydroxide particles, and FIG. 1B is a diagram of nickel hydroxide particles in the state shown in FIG. It is a schematic diagram which shows the obtained nickel hydroxide covering nickel particle, FIG.1 (c) shows the state which removed the thin layer of nickel hydroxide from the nickel hydroxide covering nickel particle of the state shown in FIG.1 (b). It is a schematic diagram. FIG. 2 is an electron microscopic image (corresponding to FIG. 1A) showing the nickel hydroxide particles obtained in Example 1 and having a large number of nickel core particles. 3 is a transmission electron microscope image (corresponding to FIG. 1B) showing nickel hydroxide-coated nickel particles obtained by crushing the nickel hydroxide particles in the state shown in FIG. FIG. 4A is an electron microscopic image showing nickel fine particles obtained by removing nickel hydroxide from nickel hydroxide-coated nickel particles in the state shown in FIG. 3, and FIG. It is an electron microscope image which expands and shows the part enclosed by the circle in a). FIG. 5A is an electron microscope image showing the nickel fine particles obtained in Comparative Example 1, and FIG. 5B is an electron microscope image showing an enlarged portion surrounded by a circle in FIG. 5A. It is.

  Hereinafter, the present invention will be described based on preferred embodiments thereof. The nickel hydroxide-coated nickel particles of the present invention are obtained by coating the surface of core particles made of metallic nickel with a thin layer of nickel hydroxide. The thin layer of nickel hydroxide may completely cover the entire surface of the nickel core particles, or may be partially coated so that the surface of the nickel core particles is partially exposed.

  The thin layer of nickel hydroxide is composed of hydroxide, its hydrate or both. By the presence of a thin layer of nickel hydroxide on the surface of the nickel core particles, this thin layer acts as a protective agent, and the aggregation of the particles is effectively prevented. This advantageous effect is particularly remarkable when the particle size of the nickel hydroxide-coated nickel particles is extremely small, for example, when the average particle size of the primary particles is preferably 5 to 500 nm, more preferably 5 to 300 nm. . In addition, the thin layer of nickel hydroxide acts as a sintering aid when, for example, nickel hydroxide-coated nickel particles are reduced and fired to form an electrode film, so that the low temperature sinterability is improved. There is also. The average particle diameter of the primary particles of the nickel hydroxide-coated nickel particles can be measured by observing the nickel hydroxide-coated nickel particles with a TEM.

  It is preferable that the thin layer of nickel hydroxide has a thickness sufficient to sufficiently exhibit the above-described advantages. Specifically, although depending on the particle diameter of the nickel core particles, the thickness of the nickel hydroxide thin layer is preferably 1 to 50 nm, particularly 1 to 10 nm. The thickness of the nickel hydroxide thin layer can be measured, for example, by observation with a transmission electron microscope (TEM) of nickel hydroxide-coated nickel particles.

  One feature of nickel hydroxide-coated nickel particles is that a thin layer of nickel hydroxide coats the surface of the nickel core particles with a bonding force that is low enough to be removed from the surface of the nickel core particles by external force. Have. On the other hand, in the nickel powder described in Patent Documents 1 and 2 described above, nickel hydroxide and nickel oxide are chemically bonded to the surface of metallic nickel due to the manufacturing method. Therefore, it is not easy to remove from the surface of metallic nickel by external force. The external force refers to a mechanical force applied when the agglomerated particles are crushed or pulverized using a media mill such as a bead mill or a ball mill.

  The fact that the nickel hydroxide thin layer covers the surface of the nickel core particles with a low bonding force has the following advantages. That is, during storage of the nickel hydroxide-coated nickel particles, the action of the nickel hydroxide thin layer prevents aggregation of the nickel hydroxide-coated nickel particles as described above, and maintains high dispersibility. Therefore, it is economical because it is not necessary to perform a surface modification treatment using a polymer dispersant or the like separately.

  Another advantage is as follows. That is, when nickel hydroxide-coated nickel particles are used, the nickel hydroxide-coated nickel particles can be easily formed by applying an external force to the nickel hydroxide-coated nickel particles using a media mill such as a bead mill or a ball mill. It can be removed and the nickel metal surface of the nickel core particles can be exposed. When, for example, an electrode film is formed using an ink or paste made of nickel core particles obtained in this way, the film becomes uniform due to high dispersibility, and contact between metallic nickel is reliably ensured, and the electrode An increase in the electrical resistance of the film can be suppressed. It is also possible to suppress an increase in sintering temperature when the electrode film is formed by firing in a reducing atmosphere. However, as described above, the thin layer of nickel hydroxide itself acts as a sintering aid, so that it is not removed and the electrode film is formed by reducing and firing the nickel hydroxide-coated nickel particles. Even if it forms, the raise of sintering temperature and the increase in electrical resistance can be suppressed.

  By using φ0.1 mm zirconia beads as an example of the bonding strength of a thin layer of nickel hydroxide, by adopting a condition of adding 4.2 times by weight zirconia beads to a 20 wt% slurry and treating for 15 minutes, When substantially all of the nickel hydroxide thin layer is removed, it can be said that the nickel hydroxide thin layer covers the surface of the nickel core particles with low bonding strength.

  The particle size of the nickel core particles after the thin layer of nickel hydroxide is removed from the nickel hydroxide-coated nickel particles is very small. There is no big difference. In other words, the particle diameter of the nickel core particles is approximately the same as the above-described range with respect to the particle diameter of the nickel hydroxide-coated nickel particles, on condition that the particle diameter of the nickel hydroxide-coated nickel particles is smaller.

  The shape of the nickel hydroxide-coated nickel particles is not particularly critical in the present invention, and can take various shapes depending on the production method. The shape of the nickel hydroxide-coated nickel particles is generally approximately spherical. As described above, since the nickel hydroxide thin layer is very thin, the shape of the nickel hydroxide-coated nickel particles reflects the shape of the core nickel core particles. Therefore, the shape of the nickel core particles is also generally spherical.

  The nickel hydroxide-coated nickel particles are preferably stored in the state of a slurry dispersed in water from the viewpoint of preventing aggregation of the particles. The concentration of nickel hydroxide-coated nickel particles in the slurry is preferably about 1 to 80% by weight from the viewpoints of handleability and prevention of aggregation. Aggregation of the nickel hydroxide-coated nickel particles in the slurry state is difficult to occur. However, if necessary, a dispersing agent or the like may be added to the slurry to further suppress the aggregation.

  Next, the suitable manufacturing method of the nickel hydroxide coating nickel particle of this invention is demonstrated. This production method is roughly divided into (a) a step of preparing nickel hydroxide particles, and (b) a step of reducing the prepared nickel hydroxide particles. Hereinafter, each process will be described.

  In the step (i) of preparing nickel hydroxide particles, nickel hydroxide particles prepared using a nickel source may be used, or commercially available nickel hydroxide particles may be used as they are. In any case, the nickel hydroxide particles preferably have a particle size of 1 to 30 μm, particularly 1 to 20 μm, from the viewpoint of obtaining uniform and fine nickel hydroxide-coated nickel particles.

  In preparing nickel hydroxide using a nickel source, for example, the following method can be employed. As the nickel source, a water-soluble compound of nickel, for example, nickel acetate, nickel sulfate, nickel chloride, nickel bromide, nickel nitrate or the like is used. These compounds are dissolved in water to prepare an aqueous solution.

  There is no restriction | limiting in particular in the density | concentration of the nickel ion in aqueous solution, The solubility of the said water-soluble nickel compound becomes an upper limit of the density | concentration of nickel ion. In order to improve the dispersibility of nickel hydroxide, a dispersant such as polyvinyl pyrrolidone or polyvinyl alcohol may be added to the aqueous solution as necessary. The aqueous solution thus prepared is added with a strong alkali such as potassium hydroxide or sodium hydroxide to produce nickel hydroxide. When nickel hydroxide is produced at a low temperature (for example, more than 0 ° C. and 60 ° C. or less), uniform nickel hydroxide tends to be produced. On the other hand, when nickel hydroxide is produced at a high temperature (for example, more than 60 ° C. and 100 ° C. or less), nickel hydroxide having high crystallinity tends to be produced.

  In the step (b) of reducing nickel hydroxide particles, nickel hydroxide thus produced or commercially available nickel hydroxide is dispersed in polyols to form a slurry, which is used well in the technical field. Nickel hydroxide is reduced using a polyol method, which is a known reduction method. The concentration of nickel hydroxide in the slurry is preferably 10 to 200 g / l, more preferably 20 to 100 g / l from the viewpoint that nickel hydroxide can be successfully reduced.

  Examples of polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. 2,3-butanediol 1,5-pentanediol, polyethylene glycol, and the like can be used. These polyols can be used alone or in combination of two or more. Among these polyols, ethylene glycol is preferable because it has a low boiling point, is liquid at room temperature, and has excellent handleability. The polyols function as a reducing agent for the nickel salt and also function as a solvent.

  Considering this from the viewpoint of a reducing agent, the amount of polyol used may be appropriately adjusted according to the amount of nickel in the reaction solution, so that there is no need to provide any particular limitation. On the other hand, when trying to function as a solvent, the properties of the reaction solution change according to the concentration of the polyols in the reaction solution, so there is a certain appropriate concentration range. From this viewpoint, the concentration of the polyols in the reaction solution is preferably set in the range of 50 to 99.8% by weight.

  It is preferable to contain a dispersant in the nickel hydroxide slurry. As the dispersant, for example, a water-soluble polymer can be used. Examples of the water-soluble polymer compound include nitrogen-containing organic compounds such as polyvinyl pyrrolidone, polyacrylamide, poly (2-methyl-2-oxazoline), and polyvinyl alcohol. These dispersants can be used alone or in combination of two or more. Among these, polyvinylpyrrolidone is particularly preferable because it has a remarkable effect as a dispersant and can sharpen the particle size distribution of the nickel core particles produced by reduction. The molecular weight of these polymers may be appropriately adjusted according to the degree of water solubility and dispersibility. The amount of the dispersant in the nickel hydroxide slurry is preferably such that the dispersant is 0.01 to 30 parts by weight with respect to 100 parts by weight of nickel. By setting to this range, the dispersion effect can be sufficiently exhibited without excessively increasing the viscosity of the nickel hydroxide slurry.

  The nickel hydroxide slurry may contain a noble metal catalyst. As a result, fine noble metal core particles are generated in the initial stage of reduction, and nickel is smoothly reduced starting from the core particles. As the noble metal catalyst, for example, a noble metal compound such as a water-soluble salt of a noble metal can be used. Examples of water-soluble salts of noble metals include water-soluble salts such as palladium, silver, platinum, and gold. In the case of using palladium as the noble metal, for example, palladium chloride, palladium nitrate, palladium acetate, ammonium palladium chloride and the like can be used. When silver is used, for example, silver nitrate, silver lactate, silver oxide, silver sulfate, silver cyclohexane acid, silver acetate, or the like can be used. When platinum is used, for example, chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate and the like can be used. When gold is used, for example, chloroauric acid, sodium chloroaurate, etc. can be used. Of these, palladium nitrate, palladium acetate, silver nitrate and silver acetate are preferably used because they are inexpensive and economical. The noble metal catalyst can be used by adding in the form of the above compound or in the form of an aqueous solution in which the compound is dissolved in water. The amount of the noble metal catalyst contained in the nickel hydroxide slurry is preferably 0.1 to 5 parts by weight, particularly 0.5 to 1 part by weight of the noble metal with respect to 100 parts by weight of nickel.

  The nickel hydroxide slurry may contain amino acids. By containing an amino acid, the nickel core particles produced can be made even finer. Examples of amino acids that can be used include alanine, asparagine, aspartic acid, glutamine, glutamic acid, histidine, arginine, leucine, isoleucine, lysine, cystine, methionine, phenylalanine, serine, and verine. These amino acids can be used alone or in combination of two or more. The amount of amino acids in the nickel hydroxide slurry is preferably 1 to 50 parts by weight, particularly 20 to 40 parts by weight, based on 100 parts by weight of nickel. The amino acid may be either D-form or L-form.

  The nickel hydroxide slurry may contain an amine organic compound. Amine-based organic compounds act as a reduction reaction control agent, and in addition to the effect of increasing the reduction rate, they have the effect of dispersing the precious metal ultrafine particles generated in the early stage of the reaction. Contributes to uniform diameter. As the amine organic compound, a water-soluble polymer having an amino group or an imino group in the main chain or side chain is preferably used. Examples of such water-soluble polymers include polyvinylamine, polyallylamine, polydiallylamine, and polyethyleneimine. Of these, polyethyleneimine and polyallylamine are preferable. The amount of the amine organic compound in the nickel hydroxide slurry is preferably 20 g / l or less.

  The slurry containing the above components is heated with stirring to reduce nickel hydroxide. The heating temperature can be appropriately set according to the degree of reduction of nickel hydroxide. Although depending on the type of polyol used, nickel hydroxide can be successfully reduced by heating at 150 to 210 ° C. under atmospheric pressure.

  This production method is characterized in that the reduction of nickel hydroxide is not performed completely, and the reaction is terminated during the reduction. Since nickel hydroxide has a layer structure, when nickel hydroxide is reduced in the form of particles, polyols enter between the layer structures of nickel hydroxide, and reduction occurs throughout the particles. That is, reduction does not occur from the surface of the nickel hydroxide particles toward the center, but a large number of nickel nuclei are generated in the particles, and nickel core particles are generated starting from the nuclei. And it is important in this manufacturing method that a reduction reaction is complete | finished when many nickel core particle | grains which have the target particle diameter are produced | generated. In general, the heating time is preferably 1 to 20 hours, particularly 3 to 16 hours, provided that the heating temperature is within the range described above. FIG. 1 (a) schematically shows a state in which the reduction reaction has been terminated halfway. As shown in the figure, in one nickel hydroxide particle 10, a large number of nickel core particles 12 are dispersed in a matrix 11 of unreduced nickel hydroxide.

  When nickel hydroxide particles in the state shown in FIG. 1 (a) are obtained, the slurry is cooled to room temperature, and then the particles are solid-liquid separated from the slurry. Since the nickel core particles 12 are not firmly bonded to the nickel hydroxide matrix 11, the nickel hydroxide particles are crushed by an external force applied during repeated washing and solid-liquid separation operations. The nickel core particles 12 are separated from the nickel hydroxide matrix 11 shown in FIG. As a result, as shown in FIG. 1B, nickel hydroxide-coated nickel particles 20 in which the surfaces of the nickel core particles 21 are coated with a thin layer 22 of nickel hydroxide are obtained. FIG. 1B shows a state where the entire area of the nickel core particles 22 is uniformly covered with a thin layer 22 of nickel hydroxide. This state is shown for the understanding of the present invention. The actual state is shown in a simplified manner. Actually, there are particles in which a part of the nickel core particle 22 is exposed, or even if the entire region of the nickel core particle 22 is covered with the thin layer 22. There are also particles whose thickness is not uniform. The nickel hydroxide-coated nickel particles 20 thus obtained are prevented from agglomerating between the particles 20 by the action of the nickel hydroxide thin layer 21 and are in a highly dispersed state in a medium such as water.

  The above production method has the advantage that the nickel hydroxide-coated nickel particles 20 that are fine and highly dispersible can be obtained by a simple operation that only controls the reaction time of the reduction. In addition, the above manufacturing method does not require a large number of post-processing steps performed by conventional methods and surface modification by controlling the atmosphere.

  The nickel hydroxide-coated nickel particles thus obtained are used, for example, in the form of ink or paste. In this case, in the storage state until the ink or paste is prepared, the nickel hydroxide-coated nickel particles are maintained in a highly dispersed state as described above in a medium such as water. As described above, the nickel hydroxide thin layer 21 is removed immediately before preparing the ink or paste to form the nickel particles 30, and the nickel particles are used as a raw material to maintain high dispersibility. A paste can be obtained. As described above, the nickel hydroxide thin layer 21 covers the surface of the nickel core particle 22 with a bonding force that is low enough to be removed from the surface of the nickel core particle 22 by an external force. Removal of 21 is easy. When an electrode film is formed, for example, by reduction firing using such nickel ink or nickel paste, the electrode film becomes uniform and has low resistance.

  Ink and paste can also be prepared using nickel hydroxide-coated nickel particles themselves without removing the thin layer of nickel hydroxide. When such an ink or paste is used to form an electrode film, for example, by reduction firing, the low temperature sinterability is improved by the action of a firing aid of a thin layer of nickel hydroxide.

  The nickel hydroxide-coated nickel particles produced by the above method are particularly suitably used for forming internal electrodes of a multilayer ceramic capacitor.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” means “% by weight”.

[Example 1]
In a 500 ml beaker, 445 g ethylene glycol, 32.3 g nickel hydroxide particles (average particle size 5 μm), 4.3 g polyvinylpyrrolidone, 10 g polyethyleneimine, 4 g L-arginine, 0.69 ml aqueous palladium nitrate solution (Concentration: 100 g / l) was added to prepare a slurry. The slurry was heated with stirring and subjected to a reduction reaction at 190 ° C. for 13 hours. Thereafter, heating was stopped to complete the reduction, and the mixture was naturally cooled to room temperature. In this way, a large number of nickel fine particles were generated in the nickel hydroxide particles. This state corresponds to FIG.

  Next, the slurry was filtered, and the particles were solid-liquid separated by decantation with water, whereby the nickel hydroxide particles were crushed and the nickel hydroxide-coated nickel particles present therein were separated. . This state corresponds to FIG. The primary particle average particle diameter of the particles by TEM observation was 20 nm, and the thickness of the nickel hydroxide thin layer was 2 nm on average. The shape of the particles was approximately spherical.

  The thus obtained 20% slurry of nickel hydroxide-coated nickel particles was treated with a bead mill. Specifically, a 0.1% zirconia bead (0.1 mmφ manufactured by Nikkato Co., Ltd.) was mixed 4.2 times by weight with a 20% nickel slurry, and then treated for 30 minutes. By this treatment, a thin layer of nickel hydroxide in the nickel hydroxide-coated nickel particles was removed, and spherical nickel fine particles (average particle diameter of primary particles 20 nm) with nickel exposed on the surface were obtained. This state corresponds to FIGS. 4 (a) and 4 (b). As is clear from the figure, it can be seen that the nickel fine particles obtained in this example are uniformly arranged and have a very good dispersion state.

[Comparative Example 1]
In Example 1, the same operation as in Example 1 was performed except that the reduction reaction was carried out for 22 hours to completely reduce nickel hydroxide. The state of the nickel fine particles thus obtained is shown in FIGS. 5 (a) and 5 (b). As is clear from the figure, the nickel fine particles obtained in this comparative example had a remarkable aggregation of particles.

10 Nickel hydroxide particles 11 Nickel hydroxide matrix 12 Nickel core particles 20 Nickel hydroxide coated nickel particles 21 Nickel core particles 22 Thin layer of nickel hydroxide 30 Nickel particles

Claims (4)

Will be the surface with nickel hydroxide bound in binding strength enough to be removed by an external force being coated, an average particle diameter of Ru 5~500nm der water nickel oxide-coated nickel particles of primary particles,
The bonding force is φ0.1 mm zirconia beads, 4.2 weight times zirconia beads are added to 20% by weight slurry of the particles, and treated with a bead mill for 15 minutes. Nickel hydroxide-coated nickel particles that are sufficient to remove all The nickel hydroxide-coated nickel particles according to claim 1 , wherein the thin layer of nickel hydroxide has a thickness of 1 to 50 nm . A method for producing nickel hydroxide-coated nickel particles according to claim 1,
When nickel hydroxide particles are heated in a state of being suspended in polyols and reduced to nickel, the nickel hydroxide particles are not completely reduced, and the reaction is terminated in the middle of the reduction. Many nickel particles are generated in the nickel oxide particles,
Next, the nickel hydroxide particles are crushed to obtain a large number of nickel particles having a thin layer of nickel hydroxide on the surface. Producing nickel hydroxide-coated nickel particles according to the method of claim 3,
Next, an external force is applied to the nickel hydroxide-coated nickel fine particles to remove the nickel hydroxide coating, and a method for producing nickel fine particles.