CN1299862C - Technological method for preparating ultrafine nickel powder - Google Patents
Technological method for preparating ultrafine nickel powder Download PDFInfo
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- CN1299862C CN1299862C CNB2004100071164A CN200410007116A CN1299862C CN 1299862 C CN1299862 C CN 1299862C CN B2004100071164 A CNB2004100071164 A CN B2004100071164A CN 200410007116 A CN200410007116 A CN 200410007116A CN 1299862 C CN1299862 C CN 1299862C
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Abstract
The present invention discloses a process method for preparing ultrafine nickel powder. In the method, firstly, anhydrous sodium carbonate is dissolved in distilled water; hydrazine hydrate is added as a reductant, and polyvinyl pyrrolidone (PVP) is added to regulate pH value for 9 to 10; the solution is heated up, and then hexahydrate nickel chloride is dissolved in the distilled water to prepare a solution which is sprayed into a reactor by a spray pistol to react. After a little, reaction liquid flowing out from an outlet of the reactor is processed with procedures of magnetic separation, water washing, alcohol washing, vacuum drying and sieve analysis to obtain the grey black ultrafine nickel powder. The nickel powder prepared by the present invention has the advantages of good sphericity, narrow grain size distribution, small crystal grain and grain size of 40 to 60 nm with favorable effect.
Description
Technical Field
The present invention belongs to a technological method and a device for directly preparing ultramicro nickel powder by a liquid phase reduction method.
Background
As a nano metal material, the ultrafine nickel powder has wide application prospect in many fields such as catalysts, battery materials, hard alloy binders and the like due to high surface activity, good electrical conductivity and good thermal conductivity. Among various preparation methods of the ultrafine nickel powder, the solution reduction method has become a hot spot of scientific and technological work research at home and abroad in recent years due to the simple process, high purity of the obtained powder, small particle size and uniform distribution. Liao Rong et al published in "inorganic chemistry journal" Vol.19.NO.10 OCT.2003, 1047- "liquid phase reduction method for preparing superfine spherical nickel powder", by NiSO4·5H2O is used as raw material, NaOH is used for adjusting the pH value of the solution, andNi (OH) is formed2The reducing agent is N2H4·5H2And O, adding a crystal nucleus initiator and a surfactant in the reduction process. And (3) finding out precipitation conditions by adopting an orthogonal test to prepare the spherical nickel powder for the conductive paste. "research on the preparation of ultrafine nickel powder by microemulsion method" is described in "inorganic chemistry journal of Vol.17.NO.4 JULY, 2001, 491-495", by Highe Baojiao et al, wherein a water (solution)/xylene/SDS/normal alcohol reverse microemulsion system is adopted, and hydrazine hydrate is used to reduce nickel sulfate to prepare nickel particles. The product is identified and characterized by XRD, TEM and other methods.
Disclosure of Invention
The invention aims to provide a process method for preparing ultrafine nickel powder. Dissolving anhydrous sodium carbonate in distilled water, adding hydrazine hydrate as a reducing agent, adding polyvinylpyrrolidone (PVP), adjusting the pH value of the solution, dissolving nickel chloride hexahydrate in distilled water, preparing a solution formed by dissolving the nickel chloride hexahydrate in water, spraying the solution into a reactor by using a spray gun for reaction, and carrying out magnetic separation, water washing, alcohol washing, vacuum drying and screen analysis on reaction liquid flowing out of the reactor to obtain the ultrafine metal nickel powder.
Another object of the present invention is to provide a reaction apparatus for preparing ultrafine nickel powder.
The purpose of the invention can be realized by the following technical scheme
A method for preparing superfine nickel powder, its step is in the reaction kettle, dissolve 120g anhydrous carbonic acid in 7000ml distilled waterfirst, add 300 and 500ml hydrazine hydrate as reducing agent, add 5g polyvinylpyrrolidone (PVP) additionally, get solution A, heat up to 85-105 deg.C, make pH value of solution A9-10, then dissolve 47.6g nickel chloride hexahydrate in 2000ml distilled water and make solution B that nickel chloride hexahydrate dissolves in water, spray gun spray solution B into reaction kettle take place and react, and let in nitrogen gas constantly in the reaction; and after the reaction is carried out for 20-25min, discharging reaction liquid from the reactor, magnetically separating out most of water, repeatedly washing with distilled water to be neutral, taking out washing water with absolute ethyl alcohol, carrying out vacuum drying at 40-60 ℃, and screening out a dried product to obtain gray black powder, namely the ultrafine metallic nickel powder.
The invention can also be realized by the following measures
A reaction device for preparing ultrafine nickel powder comprises a reaction kettle, a probe and a temperature control box. The reaction kettle is provided with a feed inlet, a nitrogen inlet and a temperature measuring port, the bottom of the reaction kettle is provided with an outlet, and a probe is led out from the temperature control box and enters the solution of the reaction kettle from the temperature measuring port.
The reaction process is expressed by the following chemical equation
The raw material and reagent used in the invention are nickel chloride NiCl hexahydrate2·6H2O (Shantou gold chemical industry plant), anhydrous sodium carbonate Na2CO3(chemical reagent works Fuchen, Tianjin) hydrazine hydrate (N)2H4·H2Taixing reagent factory O Tianjin), polyvinylpyrrolidone (imported and packaged PVP, Shanghai chemical reagent Co., China medicine) and ethanol C2H5OH (Laiyang chemical laboratory), other reagents are commercially available.
The invention adopts X-ray diffraction and transmission electron microscope observation to characterize the ultrafine nickel powder.
1. Diffraction by X-ray
And (4) carrying out XRD (X-ray diffraction) pattern determination on a dried product sample. According to the X-ray diffraction patterns of fig. 3, 5, 7, 9, and 11, the broadened diffraction peaks at 2 θ of 56.99 ° and 66.79 ° correspond to the (111) and (200) planes on the Ni standard card plane, respectively, and the corresponding interplanar spacings are 2.03A and 1.76A, respectively. The diffraction peak of the Ni oxide is not seen in the figure, indicating that the prepared sample is phase-pure elemental nickel.
2. Transmission electron microscopy analysis
Dispersing the prepared powder sample in absolute ethyl alcohol, carrying out ultrasonic treatment for 5min, dipping the dispersion liquid by using a copper net, taking out and drying the dispersion liquid for TEM observation, wherein as can be seen from a figure 4, the ultrafine nickel powder is spherical, has narrow particle size distribution and fine grains, and the average particle size is 40nm, and as can be seen from figures 8, 10 and 12, the phenomena of irregular shape, agglomeration, narrow particle size distribution, increased particle size andthe like of the nickel powder appear along with the change of reaction conditions.
Compared with the prior art, the invention has the advantages that
1. The superfine nickel powder prepared by the invention is spherical particles, the surface is smooth, the particle size range is between 40nm and 100nm, and 40nm to 60nm is the optimal particle size of the nickel powder. The actual yield of the nickel powder is higher (more than 90%), compared with the result of preparing the superfine spherical nickel powder by a liquid phase reduction method, the particle size is smaller and the distribution is more uniform, and a crystal nucleus initiator and a surfactant are not required to be added; compared with the results of the research on the preparation of the superfine nickel powder by the microemulsion method, the reaction speed is higher, the required time is short, and the reaction time is almost reduced by half;
2. the solution formed by dissolving nickel chloride hexahydrate in water is sprayed into a reactor by a spray gun to react, so that the dilution effect is achieved, and the further growth of nickel crystal grains generated by the reaction can be prevented. In the reaction process, nitrogen is continuously introduced into the reaction kettle to play two roles, wherein one role is stirring to uniformly mix reaction liquid, so that the normal reaction is facilitated, and the other role is maintaining the reaction system in a reducing atmosphere, so that the quality of the product is ensured;
3. the method has no strict requirements on raw materials and reaction conditions, the cost of the organic dispersion medium is low, the problem of difficult solid-liquid separation is solved by utilizing magnetic separation, and high-speed separation equipment is not needed;
4. by using the existing equipment, 50g of nickel powder can be obtained if the feeding amount at one time is increased by five times. Because the operation time for one reaction is 4.5 hours, the operation can be carried out five times a day, the daily nickel powder yield can reach 250g, and a new way is opened up for preparing the ultrafine nickel powder.
Drawings
FIG. 1 is a flow chart of a process for preparing ultrafine nickel powder
FIG. 2 is a schematic diagram of a reactor and a temperature control device for preparing ultrafine nickel powder
FIG. 3 is a 40nm XRD diagram of particle size of the prepared ultrafine nickel powder
FIG. 4 is transmission electron microscope image of the prepared ultrafine nickel powder with particle size of 40nmTEM
FIG. 5 is an XRD pattern of particle size of 60nm obtained from the ultrafine nickel powder
FIG. 6 is transmission electron microscope image of prepared ultrafine nickel powder with particle size of 60nmTEM
FIG. 7 is an XRD pattern of particle size 87nm obtained from the preparation of ultrafine nickel powder
FIG. 8 is a transmission electron microscope image of the prepared ultrafine nickel powder with a particle size of 87nmTEM
FIG. 9 is an XRD pattern of particle size of 85nm obtained from ultrafine nickel powder
FIG. 10 is a transmission electron microscope image of the prepared ultrafine nickel powder with a particle size of 85nmTEM
FIG. 11 is an XRD pattern of particle size 94nm for ultrafine nickel powder
FIG. 12 is a transmission electron microscope image of the prepared ultrafine nickelpowder with a particle size of 94nmTEM
Detailed Description
The invention will be further described with reference to the accompanying drawings
In example 1, 120g of anhydrous carbonic acid was dissolved in 7000ml of distilled water, 500ml of hydrazine hydrate was added as a reducing agent, 5g of polyvinylpyrrolidone (PVP) was added and placed in a reaction vessel 1 to obtain a solution a, the temperature was raised to 92 ℃, a probe 5 led out from a temperature control box 6 was introduced into the reaction vessel 1 through a temperature measuring port 4 to maintain the solution a at a certain temperature. Adjusting the pH value of the solution A to 9.5, dissolving 47.6g of nickel chloride hexahydrate in 2000ml of distilled water to prepare a solution B formed by dissolving nickel chloride hexahydrate in water, spraying the solution B into the reaction kettle 1 from the feed inlet 2 by using a spray gun for reaction, and continuously introducing nitrogen in the reaction; and after the reaction is carried out for 20min, carrying out magnetic separation on reaction liquid flowing out of an outlet 7 of the reaction kettle by virtue of magnet attraction, washing the reaction liquid to be neutral by virtue of distilled water, carrying out vacuum drying at the temperature of 40 ℃ after carrying out a small amount of washing water with absolute ethyl alcohol, and carrying out screen separation on a dried product to obtain the grey-black ultrafine nickel powder. The particles are spherical, the surface is smooth, the particle size distribution is narrow, the crystal grains are fine, two diffraction peaks 2 theta are 59.98 degrees and 66.80 degrees, and the particle size is 40nm (see figures 3 and 4).
Example 2, dissolving 120g of anhydrous carbonic acid in 7000ml of distilledwater, adding 500ml of hydrazine hydrate as a reducing agent, adding 5g of polyvinylpyrrolidone (PVP) and placing in a reaction kettle 1 to obtain a solution A, heating to 85 ℃, adjusting the pH value of the solution A to 9.4, dissolving 47.6g of nickel chloride hexahydrate in 2000ml of distilled water to prepare a solution B formed by dissolving nickel chloride hexahydrate in water, spraying the solution B into the reaction kettle 1 from a feed inlet 2 by using a spray gun for reaction, and continuously introducing nitrogen gas into the reaction; after the reaction is carried out for 20min, carrying out magnetization separation on reaction liquid flowing out of an outlet 7 of the reaction kettle, washing the reaction liquid to be neutral by using distilled water, carrying out vacuum drying at 55 ℃ by using absolute ethyl alcohol, and carrying out sieving on a dried product to obtain gray black ultrafine nickel powder, wherein an X-ray powder diffraction pattern shown in figure 5 has two diffraction peaks of 2 theta-57.04 degrees and 66.78 degrees; TEM transmission electron microscopy is shown in FIG. 6. The superfine nickel powder is spherical, has narrow particle size distribution, and has an average particle size of 60 nm.
Example 3, the procedure was as in example 1. In the experiment, 120g of anhydrous sodium carbonate is dissolved in 7000ml of distilled water, then 500ml of hydrazine hydrate is added as a reducing agent, 5g of polyvinylpyrrolidone (PVP) is added and placed in a reaction kettle 1 to obtain a solution A, the temperature is raised to 95 ℃, the pH value of the solution A is adjusted to 9.6, then 47.6g of nickel chloride hexahydrate is dissolved in 2000ml of distilled water to prepare a solution B formed by dissolving nickel chloride hexahydrate in water, the solution B is sprayed into the reaction kettle 1 from a feed inlet 2 by a spray gun for reaction, and nitrogen is continuously introduced in the reaction; after the reaction is carried out for 20min,carrying out magnetic separation, water washing, alcohol washing, vacuum drying and screening on reaction liquid flowing out from an outlet 7 of the reaction kettle to obtain gray black ultrafine nickel powder, wherein an X-ray powder diffraction pattern shown in figure 7 has two diffraction peaks of 2 theta (56.96 degrees) and 66.74 degrees; the TEM is shown in FIG. 8. The ultrafine nickel powder has irregular particle shape, narrow particle size distribution and average particle size of 87 nm.
Example 4, the procedure was as in example 1. In the experiment, 120g of anhydrous sodium carbonate is dissolved in 7000ml of distilled water, then 500ml of hydrazine hydrate is added as a reducing agent, 5g of polyvinylpyrrolidone (PVP) is added and placed in a reaction kettle 1 to obtain a solution A, the temperature is raised to 100 ℃, the pH value of the solution A is adjusted to 9.8, then 47.6g of nickel chloride hexahydrate is dissolved in 2000ml of distilled water to prepare a solution B formed by dissolving nickel chloride hexahydrate in water, the solution B is sprayed into the reaction kettle 1 from a feed inlet 2 by a spray gun for reaction, and nitrogen is continuously introduced in the reaction; after the reaction is carried out for 20min, the reaction solution flowing out from the outlet 7 of the reaction kettle is subjected to magnetic separation, water washing, alcohol washing, vacuum drying and screen analysis to obtain gray black ultrafine nickel powder, as shown in fig. 9, the gray black ultrafine nickel powder has two diffraction peaks, namely 2 theta 57.02 degrees and 66.88 degrees; as can be seen from FIG. 10, the extra-fine nickel powder has irregular particle shape, slight agglomeration, broad particle size distribution, and an average particle size of 85 nm.
Example 5, the procedure was as in example 1. In the experiment, 120g of anhydrous sodium carbonate is dissolved in 7000ml of distilled water, then 500ml of hydrazine hydrate is added as a reducing agent, 5g of polyvinylpyrrolidone (PVP) is added and placed in a reaction kettle 1 to obtain a solution A, the temperature is raised to 92 ℃, the pH value of the solution A is adjusted to 9.3, then 47.6g of nickel chloride hexahydrate is dissolved in 2000ml of distilled water to prepare a solution B formed by dissolving nickel chloride hexahydrate in water, the solution B is sprayed into the reaction kettle 1 from a feed inlet 2 by a spray gun for reaction, and nitrogen is continuously introduced in the reaction; after the reaction is carried out for 25min, the reaction solution flowing out from the outlet 7 of the reaction kettle is subjected to magnetic separation, water washing, alcohol washing, vacuum drying and screen analysis to obtain the gray black ultrafine nickel powder, as shown in fig. 11, the 2 theta of two diffraction peaks is respectively 56.98 degrees and 66.76 degrees. As can be seen from FIG. 12, the ultrafine nickel powders had irregular particle shapes, some agglomeration, wide particle size distribution range, and an average particle size of 94 nm.
A large number of test results show that:
1. the pH value range suitable for preparing the pure ultrafine nickel powder is 9-10. When the pH value is more than 11, pure nickel powder cannot be obtained; when the pH is less than 8, the above reaction is impossible and the grayish black ultrafine nickel powder cannot be obtained. Thus in the above test, anhydrous sodium carbonate was dissolved in distilled water to adjust the pH of the solution between 9 and 10;
2. in the preparation process, the temperature and the hydrazine hydrate are timed, the pH value is between 9 and 10, and the stirring is sufficient, so that the product quality can be better ensured. As can be seen from the XRD diffraction pattern and the TEM transmission electron micrograph, the examples 1 and 2 have good effect, spherical particles and narrow particle size distribution. The results of example 1 are better, good sphericity, narrow particle size distribution, fine grains and an average particle size of 40 nm.
Claims (2)
1. A method for preparing superfine nickel powder is characterized in that: dissolving 120g of anhydrous carbonic acid in 7000ml of distilled water in a reaction kettle, adding 300-500ml of hydrazine hydrate as a reducing agent, adding 5g of polyvinylpyrrolidone (PVP) to obtain a solution A, heating to 85-105 ℃ to ensure that the pH value of the solution A is 9-10, dissolving 47.6g of nickel chloride hexahydrate in 2000ml of distilled water to prepare a solution B formed by dissolving nickel chloride hexahydrate in water, spraying the solution B into the reaction kettle by using a spray gun for reaction, and continuously introducing nitrogen in the reaction kettle; and after the reaction is carried out for 20-25min, discharging reaction liquid from the reactor, magnetically separating out most of water, repeatedly washing with distilled water to be neutral, taking out washing water with absolute ethyl alcohol, carrying out vacuum drying at 40-60 ℃, and screening out a dried product to obtain gray black powder, namely the ultrafine metallic nickel powder.
2. A reaction device for the method of claim 1, which comprises a reaction kettle (1), a probe (5) and a temperature control box (6), and is characterized in that the reaction kettle (1) is provided with a feed inlet (2), a nitrogen inlet (3) and a temperature measurement port (4), the bottom of the reaction kettle is provided with an outlet (7), and the probe (5) is led out from the temperature control box (6) and enters the solution in the reaction kettle (1) from the temperature measurement port (4).
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| CN100509220C (en) * | 2006-03-17 | 2009-07-08 | 金川集团有限公司 | Method for preparing round nickel powder in submicro |
| CN100581693C (en) * | 2006-12-31 | 2010-01-20 | 中国科学技术大学 | Method for making polycrystalline uniform nickel microball and line-shape nickel chain |
| CN102327806B (en) * | 2011-06-20 | 2014-03-26 | 宁波广博纳米新材料股份有限公司 | Method taking organic solvent as medium for grading nano-nickel powder for MLCC (multilayer ceramic capacitor) |
| CN102554259B (en) * | 2012-02-07 | 2015-03-18 | 宇辰新能源材料科技无锡有限公司 | Method for preparing spherical submicron nickel powder with controllable particle size |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6120576A (en) * | 1997-09-11 | 2000-09-19 | Mitsui Mining And Smelting Co., Ltd. | Method for preparing nickel fine powder |
| CN1280044A (en) * | 1999-07-08 | 2001-01-17 | 中国科学技术大学 | Chemicalpreparing method for nanometre metal iron powder |
| JP2001192710A (en) * | 2000-01-07 | 2001-07-17 | Osaki Industry Co Ltd | Method for producing nickel powder |
| US6503291B2 (en) * | 2000-04-27 | 2003-01-07 | Murata Manufacturing Co. Ltd. | Method for manufacturing a metal powder, a metal powder, an electroconductive paste using the same, and a multilayer ceramic electronic component using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6120576A (en) * | 1997-09-11 | 2000-09-19 | Mitsui Mining And Smelting Co., Ltd. | Method for preparing nickel fine powder |
| CN1280044A (en) * | 1999-07-08 | 2001-01-17 | 中国科学技术大学 | Chemicalpreparing method for nanometre metal iron powder |
| JP2001192710A (en) * | 2000-01-07 | 2001-07-17 | Osaki Industry Co Ltd | Method for producing nickel powder |
| US6503291B2 (en) * | 2000-04-27 | 2003-01-07 | Murata Manufacturing Co. Ltd. | Method for manufacturing a metal powder, a metal powder, an electroconductive paste using the same, and a multilayer ceramic electronic component using the same |
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