KR101324527B1 - Apparatus for manufacturing fine nickel powders and method of manufacturing fine nickel powders using the same - Google Patents
Apparatus for manufacturing fine nickel powders and method of manufacturing fine nickel powders using the same Download PDFInfo
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- KR101324527B1 KR101324527B1 KR20100127146A KR20100127146A KR101324527B1 KR 101324527 B1 KR101324527 B1 KR 101324527B1 KR 20100127146 A KR20100127146 A KR 20100127146A KR 20100127146 A KR20100127146 A KR 20100127146A KR 101324527 B1 KR101324527 B1 KR 101324527B1
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Abstract
The present invention relates to a device capable of producing nickel powder directly using a slurry reduction method and a method for preparing nickel powder which can improve dispersibility and reducing property using the same, and may contain a solution in which a nickel compound is dissolved, and a slurry Induces uniform mixing and uniform particle size distribution of a reactor having a reducing agent inlet for using a reducing method, a drop-wiser for supplying a reducing agent to the reactor, and a reducing agent for forming a nickel powder precursor In order to maintain the precursor reduction reaction in the reactor (Stirrer) that can mix the contents inside the reactor and the heating mantle (Heating mantle) for 90 to 120 minutes at a temperature of 60 ~ 80 ℃ It provides a nickel powder manufacturing apparatus comprising, the concentration of NiCl 2 in the precursor is 1.5M or more, and the precursor The present invention relates to a method for reducing a concentration of NaOH, which is a reducing agent, to 4.5-6M, so that a uniform fine nickel powder having a particle size of 0.1-0.2 μm may be produced.
Description
The present invention relates to a technique for manufacturing fine nickel powder used in a multi-layer ceramic capacitor (MLCC) and the like, and more particularly, an apparatus capable of directly producing fine nickel powder using a slurry reduction method and the same. It relates to a method for producing fine nickel powder for MLCC used.
Nickel powder for electronic materials is mainly used for electrode materials of MLCC.
1 schematically shows a cross section of a typical MLCC.
As shown in FIG. 1, in the MLCC, a dielectric 110 and an
The dielectric 110 is formed to a thickness of about 6㎛, the
At this time, nickel powder is mainly used as a material of the
Conventionally, nickel powder for forming an electrode of such MLCC is produced from an aqueous solution of nickel salt by a liquid phase reduction method.
However, the nickel powder prepared by the liquid reduction method has a problem in that it is difficult to apply for electronic materials such as MLCC electrodes because the aggregation and the shape and size are difficult to control.
It is an object of the present invention to provide a production apparatus capable of producing nickel powder using a slurry reduction method.
Another object of the present invention is to provide a method for producing nickel powder having excellent dispersibility and yield using a slurry reduction method.
The apparatus for preparing fine nickel powder using the slurry reduction method according to the embodiment of the present invention for achieving the above object includes a reactor in which a nickel compound is dissolved and a reducing agent inlet for using the slurry reduction method is provided. A drop wiser for supplying a reducing agent to the reactor and a stirrer capable of mixing the contents of the reactor to induce uniform mixing and uniform particle size distribution of the reducing agent for forming a nickel powder precursor. (Stirrer) and a heating mantle (Heating mantle) for maintaining for 90 to 120 minutes at a temperature of 60 ~ 80 ℃ while maintaining the precursor reduction reaction in the reactor;
In addition, the fine nickel powder production method using the slurry reduction method according to an embodiment of the present invention for achieving the above another object is a method for producing nickel powder with the above-described nickel powder production apparatus, (a) a nickel compound in the reactor Injecting the dissolved solution, (b) injecting a primary reducing agent into the solution to form a nickel powder precursor, and (c) injecting a secondary reducing agent into the reactor to convert the precursor into nickel powder. Reducing, and (d) washing the nickel powder obtained through the step (c) and (e) drying the washed nickel powder.
The fine nickel powder production method using the slurry reduction method according to the present invention is easy to control the shape and particle size of 0.1 ~ 0.2㎛ using the slurry reduction method, and also has the advantage of improving the dispersibility and yield of the nickel powder.
Therefore, the manufactured nickel powder is suitable for use as an electrode material such as MLCC (Multi Layer Ceramic Capacitor).
1 schematically shows a cross section of a typical MLCC.
Figure 2 schematically shows a fine nickel powder production apparatus using a slurry reduction method according to an embodiment of the present invention.
3 is a flow chart schematically showing a method for producing fine nickel powder using the manufacturing apparatus shown in FIG. 2.
4 to 6 are SEM pictures showing the form of nickel powder formed according to the reaction time conditions of the method for producing a fine nickel powder according to the present invention.
Figure 7 is a graph showing the nickel powder XRD pattern formed according to the reaction time conditions of the method for producing a fine nickel powder according to the present invention.
8 to 10 are SEM pictures showing the form of nickel powder formed according to the precursor concentration conditions of the method for producing a fine nickel powder according to the present invention.
11 is a graph showing the nickel powder XRD pattern formed according to the precursor concentration conditions of the fine nickel powder production method according to the present invention.
12 and 13 are SEM pictures showing the form of nickel powder formed according to the precursor reducing agent concentration conditions of the method for producing a fine nickel powder according to the present invention.
14 is a graph showing the nickel powder XRD pattern formed according to the precursor reducing agent concentration conditions of the fine nickel powder production method according to the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent with reference to the embodiments and drawings described in detail below.
However, it is to be understood that the present invention is not limited to the disclosed embodiments, but may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It is intended that the disclosure of the present invention be limited only by the terms of the appended claims.
Hereinafter, a fine nickel powder production apparatus using the slurry reduction method according to the present invention and a fine nickel powder production method for MLCC using the same will be described in detail.
Figure 2 schematically shows a fine nickel powder production apparatus using a slurry reduction method according to an embodiment of the present invention.
Referring to FIG. 2, a three-
Next, a
In the three-necked reactor, a reagent used for preparing nickel powder is added.
At this time, distilled water in which a nickel source is dissolved is used as a main raw material of the reagent. A primary reducing agent for preparing a precursor by reducing nickel in the nickel source is added, and a second reducing agent for reducing a nickel powder precursor is added. Used.
In addition, the manufacturing apparatus for the slurry reduction method according to the present invention may include a timer device for controlling the reaction holding time of the reduction from the precursor to the nickel powder after forming the nickel powder precursor in the nickel source solution between 90 minutes and 120 minutes. have.
When the reaction holding time was less than 90 minutes, a spherical nickel powder having a uniform particle size of 0.1 to 0.2 µm could not be obtained. In addition, since the fine powder is no longer formed when it exceeds 120 minutes, waste unnecessary time, it is preferable to use a timer device that the reaction time is set to 90 to 120 minutes.
Next, when the concentration of the precursor is less than 1.5M can be seen that the precursor is not reduced, in order to prevent this, the nickel powder manufacturing apparatus according to the present invention by monitoring the case where the concentration of the precursor is less than 1.5M, concentration It includes a drop-wiser to hold.
In addition, the drop-wiser allows the concentration of NaOH, the secondary reducing agent, to be adjusted to 4.5 to 6.0 M to minimize the residual ratio of Ni (OH) 2 . .
3 is a flow chart schematically showing a method for producing fine nickel powder using the manufacturing apparatus shown in FIG. 2.
Referring to FIG. 3, nickel compounds such as NiCl 2 · 6H 2 O, Ni (OH) 2, and NiSO 4 · 6H 2 O are used as the
First, the
Next, a step of adding a secondary reducing
Next, the resulting nickel powder is filtered and washed several times with distilled water and alcohol, followed by a washing and drying step (S330) for drying at least 80 hours in an oven of 80 ℃ or more.
Next, the analysis step (S340) of selecting the powder that can be applied to the actual MLCC by observing the shape and size of the finished nickel powder is performed.
As a result of the analysis, according to the slurry reduction method according to the present invention, it was found that the characteristics of the fine nickel powder were changed according to the reaction time for reducing the precursor, the concentration of the nickel powder precursor, and the concentration of NaOH as the secondary reducing agent.
Example
Hereinafter, the fine nickel powder production apparatus using the slurry reduction method and the fine nickel powder production method for MLCC using the same according to a preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.
Details that are not described herein will be omitted since the description can be inferred by those skilled in the art.
First, 1.5M NiCl 2 , 6M N 2 H 4 , 4.5M NaOH was used to examine the effects of the reaction time as experimental conditions, and the reaction time was experimented under the conditions of 30 minutes, 60 minutes and 90 minutes. .
First, after dissolving NiCl 2 · 6H 2 O, N 2 H 4 was added to form a nickel-hydrazine complex compound (precursor) as in
[Reaction Scheme 1]
NiCl 2 + N 2 H 4 → [Ni (N 2 H 4 ) n] Cl 2 , n = 2, 3
At this time, in the case of n = 2, a blue complex was formed, and in the case of n = 3, a purple complex was formed, which indicates that
Next, NaOH was added to the complex-formed solution by using a drop-wiser to form Ni (OH) 2 .
In this case, it can be seen that NaOH serves to form a nickel-hydrazine complex compound as Ni (OH) 2 according to
[Reaction Scheme 2]
[Ni (N 2 H 4 ) n] Cl 2 + 2 NaOH → Ni (OH) 2 + nN 2 H 4 + 2NaCl
Next, a reduction reaction proceeds as shown in Scheme 3 by N 2 H 4 generated by the reaction of the nickel-hydrazine complex compound with NaOH.
Scheme 3
2 Ni (OH) 2 + N 2 H 4 → 2Ni + N 2 + 4H 2 O
At this time, the color of the solution gradually changed to black as the reduction reaction started, which is a phenomenon generated by reduction of Ni (OH) 2 by hydrazine, and thus the nickel metal powder becomes black.
Hereinafter, comparative analysis of the specific picture is as follows.
4 to 6 are SEM (JEOL JSM 6400) pictures showing the form of nickel powder formed according to the reaction time conditions of the method for producing a fine nickel powder according to the present invention, Figure 7 is a reaction of the method for producing a fine nickel powder according to the present invention It is a graph showing the nickel powder XRD (Philips MPD) pattern formed according to the time conditions.
4 is a precursor form after 30 minutes of reaction time, and it can be seen that ultrafine particles are mixed around particles having a relatively large diameter. In this case, referring to FIG. 7, it can be seen that the nickel powder generated up to 30 minutes of the first XRD analysis result (a) is Ni (OH) 2 .
Next, FIG. 5 shows a precursor form after 60 minutes of reaction time, and it can be seen that nickel spherical particles having a diameter of 0.2 μm appear around large particles having a size of about 1.5 to 3 μm. In this case, referring to FIG. 7, it can be seen that the large particles are Ni (OH) 2 in the second XRD analysis result (b).
Next, FIG. 6 shows that most of the large particles are formed of fine nickel powder as precursor form after 90 minutes of reaction time. At this time, referring to the second XRD analysis result (c) of FIG. 7, it can be seen that most of the powder is nickel, and the particle diameter of each powder is 0.18 μm.
In addition, depending on the concentration of the precursor (nickel-hydrazine complex) in the above-described reaction, the particle size of the fine nickel particles may be different, look at an embodiment thereof as follows.
First, raw materials for basic nickel supply were used as described above 1.5M NiCl 2 , 6M N 2 H 4 , 4.5M NaOH, and the reaction time was tested under the condition of 90 minutes.
Then, the experiment was carried out while changing the concentration of the initial nickel-hydrazine complex in the solution to 0.5, 1.0, 1.5M.
8 to 10 are SEM pictures showing the form of nickel powder formed according to the precursor concentration conditions of the fine nickel powder manufacturing method according to the present invention, Figure 11 is formed according to the precursor concentration conditions of the fine nickel powder manufacturing method according to the present invention It is a graph showing the nickel powder XRD pattern.
8 is a SEM image showing the nickel powder prepared when the concentration of the nickel-hydrazine complex compound is 0.5M. Referring to the XRD result of FIG. 11, the particle size of the powder is 50 μm or more and mixed with Ni (OH) 2. It can be seen that.
Next, FIG. 9 is an SEM image of nickel powder prepared when the concentration of the nickel-hydrazine complex compound is 1.0M. Referring to the XRD result of FIG. 11, the particle size of the powder is 0.1 μm, and a trace amount of Ni (OH) is shown. It can be seen that it is mixed with 2 .
Next, FIG. 10 is an SEM image showing the nickel powder prepared when the concentration of the nickel-hydrazine complex compound is 1.5M. Referring to the XRD result of FIG. 11, the particle size of the powder is 0.18 μm, and Ni (OH) 2 It can be seen that is mostly reduced to nickel powder.
In addition, in addition to the concentration of the precursor (nickel-hydrazine complex) in the above-described reaction, the particle size of the fine nickel particles may be different depending on the concentration of NaOH, looking at the embodiment for this.
First, the raw material for basic nickel supply as described above using 1.5M NiCl 2 , 6M N 2 H 4 , but proceeded to the secondary reduction by dividing into 4.5M and 6.0M NaOH, the reaction time is maintained for 90 minutes Experiment with.
12 and 13 are SEM pictures showing the form of nickel powder formed according to the precursor reducing agent concentration conditions of the fine nickel powder production method according to the present invention, Figure 14 is a precursor reducing agent concentration conditions of the fine nickel powder production method according to the present invention It is a graph showing the nickel powder XRD pattern formed along.
12 is a SEM image showing a nickel powder prepared according to a concentration of 4.5 M NaOH. Referring to the XRD result of FIG. 14, the particle size of the powder is 0.18 μm, and Ni (OH) 2 is mostly reduced to the nickel powder. It can be seen that.
Next, FIG. 13 is an SEM image of nickel powder prepared according to a concentration of 6.0 M NaOH. Referring to the XRD result of FIG. 14, the particle diameter of the powder is 0.17 μm and is mixed with a small amount of Ni (OH) 2 . It can be seen that.
Here, in the case of proceeding to the concentration of 4.5M NaOH of FIG. 12, in the process of reducing Ni (OH) 2 (green) to nickel (black) powder in the nickel-hydrazine complex, it took about 10 minutes, but the concentration of 6.0M NaOH In case of proceeding, the reaction time was shortened to about 5 minutes.
It can be seen that the average particle size of the synthesized nickel powder decreases as the concentration of NaOH increases, and the solubility of Ni (OH) 2 increases as the concentration of NaOH increases.
As described above, in the method for producing fine nickel powder using the slurry reduction method according to the present invention, the reaction retention time of reducing the precursor to the nickel powder is controlled between 90 minutes and 120 minutes, thereby obtaining 0.1-0.2 μm spherical nickel powder. Can be.
In addition, the precursor was not reduced when the concentration of the precursor is less than 1.5M, it can be seen that the nickel powder reduction is activated at 1.5M or more, and the concentration of Ni (OH) 2 when the concentration of NaOH is 4.5 ~ 6.0M. Nickel powder can be obtained with minimal.
While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
110: dielectric 120: electrode
130: terminal electrode 200: reactor
210: heating device 220: thermometer
230: stirrer 240: drop-wiser
300: nickel source 310: primary reducing agent
320: secondary reducing agent
Claims (14)
A drop-wiser for supplying a primary reducing agent and a secondary reducing agent to the reactor;
A stirrer capable of mixing the contents of the reactor to induce uniform mixing and uniform particle size distribution of the primary reducing agent for forming a nickel powder precursor; And
And a heating mantle (Heating mantle) maintained at a temperature of 60 to 80 ° C. for 90 to 120 minutes while the precursor reduction reaction is maintained in the reactor.
The drop-wiser monitors when the concentration of the nickel powder precursor is less than 1.5 M, maintains the concentration at 1.5 M, and adjusts the concentration of the secondary reducing agent to 4.5 to 6.0 M, characterized in that the apparatus .
The heater is
Nickel powder manufacturing apparatus comprising a thermometer connected into the reactor.
The powder manufacturing apparatus
A nickel powder manufacturing apparatus comprising a washing apparatus for washing nickel powder using distilled water and alcohol and an oven for drying the washed nickel powder.
The oven
Nickel powder production apparatus characterized in that the drying is carried out for at least 8 hours at a temperature of 80 ℃ or more.
(a) injecting a solution containing a nickel compound into the reactor;
(b) injecting a primary reducing agent into the solution to form a nickel powder precursor;
(c) injecting 4.5 to 6.0 M of a secondary reducing agent into the reactor to reduce the precursor to nickel powder;
(d) washing the nickel powder obtained through step (c); And
(e) drying the washed nickel powder; and
The nickel powder production method of maintaining a concentration of the nickel powder precursor to 1.5M.
The nickel compound is
A method for producing nickel powder, comprising at least one of NiCl 2 · 6H 2 O, Ni (OH) 2 and NiSO 4 · 6H 2 O.
The primary reducing agent
A nickel powder production method comprising at least one of N 2 H 4 H 2 O and NH 4 OH.
The secondary reducing agent
Nickel powder production method comprising NaOH.
The reaction time for reducing the nickel powder of the step (c) is 90 to 120 minutes, characterized in that the nickel powder production method.
Nickel powder particle size of the step (c) is 0.1 ~ 0.2㎛, nickel powder manufacturing method, characterized in that formed in a spherical shape.
Drying nickel powder of the step (e)
Nickel powder production method characterized in that performed for more than 8 hours at a temperature of 80 ℃ or more.
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| KR20100127146A KR101324527B1 (en) | 2010-12-13 | 2010-12-13 | Apparatus for manufacturing fine nickel powders and method of manufacturing fine nickel powders using the same |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040047101A (en) * | 2002-11-29 | 2004-06-05 | (주)창성 | Method for manufacturing nano-scale nickel powders by wet reducing process |
| KR20120055020A (en) * | 2010-11-22 | 2012-05-31 | 한국지질자원연구원 | Apparatus for manufacturing cupper powders using slurry and wet chemical reduction and method of manufacturing cupper powders for electronic materials using the method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040047101A (en) * | 2002-11-29 | 2004-06-05 | (주)창성 | Method for manufacturing nano-scale nickel powders by wet reducing process |
| KR20120055020A (en) * | 2010-11-22 | 2012-05-31 | 한국지질자원연구원 | Apparatus for manufacturing cupper powders using slurry and wet chemical reduction and method of manufacturing cupper powders for electronic materials using the method |
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| 논문1 * |
| 논문2 * |
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