CN104439278B - A kind of preparation method of nanometer spherical nikel powder - Google Patents
A kind of preparation method of nanometer spherical nikel powder Download PDFInfo
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- CN104439278B CN104439278B CN201410712512.0A CN201410712512A CN104439278B CN 104439278 B CN104439278 B CN 104439278B CN 201410712512 A CN201410712512 A CN 201410712512A CN 104439278 B CN104439278 B CN 104439278B
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Abstract
The present invention relates to a kind of preparation method of nanometer spherical nikel powder, comprises the following steps：Ni will be contained2+Solution mix with reducing solution after reaction prepare the solution containing nikel powder；M will be contained2+Solution and contain R2‑Solution add to the solution containing nikel powder in fully reaction obtain the nikel powder for being coated with covering, wherein M2+It is selected from Mg2+、Ca2+And Zn2+In at least one, R2‑It is selected from C2O4 2‑And CO3 2‑In at least one；The nikel powder of covering vacuum bakeout 1 hour～5 hours at 600 DEG C～1100 DEG C will be coated with；And the nikel powder for being coated with covering is carried out pickling remove covering post-drying obtain nanometer spherical nikel powder.The preparation method of above-mentioned nanometer spherical nikel powder, simple to operate, low for equipment requirements, it is suitable for industrialized production；Surfactant control pattern need not be added and nucleating agent and stabilizer control reaction need not be added；After tested, nanometer spherical nikel powder degree of crystallinity height, epigranular, good sphericity and the good dispersion for obtaining.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer spherical nikel powder.
Background technology
Nano-nickel powder has that surface energy is high, specific surface area is big, electric conductivity, heat conductivity are good, and it is a series of that oxidation resistance is strong etc.
Unique physicochemical properties, show many exceptional functions at aspects such as magnetic, thermal resistance, intrinsic pressure, light absorbs, chemisms,
Therefore have broad application prospects in fields such as electrocondution slurry, effective catalyst, additive and light absorbing materials, be domestic and international
The application focus of functional material.
The main production method of nano-nickel powder has spray pyrolysis, plasma method, chemical vapour deposition technique, electrochemistry at present
Method, liquid phase reduction etc..Liquid phase reduction is to prepare extra-fine nickel powder most common method, and liquid phase reduction is existed using reducing agent
Nickel is restored in liquid phase and be gathered into extra-fine nickel powder.Nikel powder degree of crystallinity prepared by existing liquid phase reduction is low and granularity is uneven
Even.
Content of the invention
It is based on this, it is necessary to provide that a kind of degree of crystallinity is high and the preparation method of even-grained nanometer spherical nikel powder.
A kind of preparation method of nanometer spherical nikel powder, comprises the following steps：
Ni will be contained2+Solution mix with reducing solution after reaction prepare the solution containing nikel powder；
M will be contained2+Solution and contain R2-Solution add to the solution containing nikel powder in fully reaction wrapped
The nikel powder of covering is covered with, wherein described M2+It is selected from Mg2+、Ca2+And Zn2+In at least one, the R2-It is selected from C2O4 2-And
CO3 2-In at least one；
By the nikel powder for being coated with covering at 600 DEG C～1100 DEG C vacuum bakeout 1 hour～5 hours；And
The pickling removing covering post-drying is carried out to the nikel powder for being coated with covering obtains nanometer spherical nickel
Powder..
Wherein in one embodiment, described contain Ni2+Solution in also contain dispersant, the dispersant be selected from second
At least one in alcohol, polyvinylpyrrolidone and Polyethylene Glycol, the dispersant and the Ni2+Mol ratio be 10：1～
50:1.
Wherein in one embodiment, in the reducing solution, contain BH4 -And dispersant, the dispersant is selected from second
At least one in alcohol, polyvinylpyrrolidone and Polyethylene Glycol, the dispersant and the BH4 -Mol ratio be 10：1～
50:1.
Wherein in one embodiment, the Ni2+With NH4 -Mol ratio be 1:2～1:5.
Wherein in one embodiment, Ni will be contained2+Solution mix with reducing solution after react preparation contain nikel powder
Solution the step of in, react pH value be 8-10, at 30 DEG C～80 DEG C react 1 hour～2 hours.
Wherein in one embodiment, using sodium carbonate, sodium hydroxide and ammonia at least one adjust pH value.
Wherein in one embodiment, described contain M2+Solution in M2+Contain Ni with described2+Solution in Ni2+
Mol ratio be 1.2:1～2:1.
Wherein in one embodiment, the operation of the pickling is specially：First with 2 minutes～10 points of hydrochloric acid or sulfuric acid scrubbing
Clock, then with Fructus Citri Limoniae acid elution 30 minutes～60 minutes, be washed with water to neutrality afterwards, then filtered with ethanol.
Wherein in one embodiment, the mass concentration of the hydrochloric acid or the sulphuric acid is 1%～20%, the citric acid
Mass concentration be 0.5%～10%.
Wherein in one embodiment, the temperature of the drying is 60 DEG C～100 DEG C, and when drying, vacuum is less than 10Pa.
The preparation method of above-mentioned nanometer spherical nikel powder, simple to operate, low for equipment requirements, it is suitable for industrialized production；Need not
Add surfactant control pattern and nucleating agent and stabilizer control reaction need not be added；After tested, the nanosphere for obtaining
Shape nikel powder degree of crystallinity height, epigranular, good sphericity and good dispersion.
Description of the drawings
Fig. 1 is the XRD figure of the nanometer spherical nikel powder that embodiment 1 is obtained；
Fig. 2 is the SEM figures of the nanometer spherical nikel powder that embodiment 1 is obtained.
Specific embodiment
Understandable for enabling the above objects, features and advantages of the present invention to become apparent from, with reference to embodiment to this
Bright specific embodiment is described in detail.Elaborate a lot of details in order to fully understanding this in the following description
Invention.But the present invention can be to be much different from alternate manner described here implementing, and those skilled in the art can be
Without prejudice to similar improvement is done in the case of intension of the present invention, therefore the present invention is not embodied as being limited by following public.
The preparation method of the nanometer spherical nikel powder of one embodiment, comprises the following steps：
Step S110, Ni will be contained2+Solution mix with reducing solution after reaction prepare the solution containing nikel powder.
Preferably, containing Ni2+Solution in also contain dispersant.Dispersant is selected from ethanol, polyvinylpyrrolidone (PVP)
And at least one in Polyethylene Glycol (PEG).Dispersant and Ni2+Mol ratio be 10：1～50:1.
Preferably, containing Ni2+Solution in Ni2+Concentration be 0.5mol/L～1mol/L.
Preferably, containing Ni2+Solution be at least one in nickel sulfate solution and nickel chloride solution.
Preferably, contain BH in reducing solution4 -And dispersant, dispersant is selected from ethanol, polyvinylpyrrolidone and poly-
At least one in ethylene glycol, dispersant and the BH4 -Mol ratio be 10：1～50:1.
Preferably, reducing solution is containing BH4- solution.Further, containing Ni2+Solution in Ni2+With reduction
BH in property solution4 -Mol ratio be 1:2～1:5.Further, containing BH4 -Solution in BH4 -Concentration be 0.05mol/L
～0.1mol/L.
Preferably, reducing solution is selected from NaBH4Or KBH4At least one in solution.
Preferably, reaction is 8-10 in pH value, reacts 1 hour～2 hours at 30 DEG C～80 DEG C.Further, using carbon
At least one regulation pH value in sour sodium, sodium hydroxide and ammonia.
Step S120, M will be contained2+Solution and contain R2-Solution add to the solution containing nikel powder in fully react
Obtain the nikel powder for being coated with covering, wherein M2+It is selected from Mg 2+、Ca2+And Zn2+In at least one, R2-It is selected from C2O4 2-And CO3 2-
In at least one.
Preferably, containing M2+Solution in M2+Contain Ni with described2+Solution in Ni2+Mol ratio be 1.2:1～
2:1.
Preferably, containing M2+Solution be MCl2Solution.
Preferably, containing M2+Solution in M2+Concentration be 1mol/L～10mol/L.
Preferably, containing R2-Solution be (NH4)2R solution.Further, R2-Concentration be 1mol/L～10mol/L.
Preferably, the response time is 20 minutes～60 minutes.
Preferably, M will be contained2+Solution and contain R2-Solution be simultaneously introduced to the solution containing nikel powder.
Preferably, reaction terminates the nikel powder that rear filtration drying obtains being coated with covering.Further, dry temperature is
200 DEG C～280 DEG C.
Step S130, the nikel powder of covering vacuum bakeout 1 hour～5 hours at 600 DEG C～1100 DEG C will be coated with.
Preferably, the vacuum of vacuum bakeout is less than 10Pa.
Preferably, 600 DEG C～1000 DEG C are heated to the heating rate of 3 DEG C/min～10 DEG C/min.
Step S140, the nikel powder for being coated with covering is carried out pickling remove covering post-drying obtain nanometer spherical nickel
Powder.
Preferably, the operation of pickling is specially：First with hydrochloric acid or sulfuric acid scrubbing 2 minutes～10 minutes, then use Fructus Citri Limoniae pickling
Wash 30 minutes～60 minutes, be washed with water to neutrality afterwards, then filtered with ethanol.Further, the quality of hydrochloric acid or sulphuric acid is dense
Spend for 1%～20%, the mass concentration of citric acid is 0.5%～10%.
Preferably, the hydrochloric acid or the amount of sulphuric acid that pickling is used is the 110%～150% of theoretical amount, and theoretical amount refers to manage
Amount required for dissolving by the covering for above making nikel powder surface.
Preferably, the temperature of drying is 60 DEG C～100 DEG C, and when drying, vacuum is less than 10Pa.
The preparation method of above-mentioned nanometer spherical nikel powder, simple to operate, low for equipment requirements, it is suitable for industrialized production；Need not
Add surfactant control pattern and nucleating agent and stabilizer control reaction need not be added；After tested, the nanosphere for obtaining
Shape nikel powder degree of crystallinity height, epigranular, good sphericity and good dispersion.
The preparation method of nanometer spherical nikel powder is described in further details below in conjunction with specific embodiment.
Embodiment 1
60 DEG C are at the uniform velocity added to contain 60 DEG C of mixed aqueous solution 100ml containing 0.5mol/L Nickel dichloride .s, 120g/L ethanol
0.05mol/L NaBH4, 120g/LPVP mixed aqueous solution 2000ml in, in stirring reactor, (speed of agitator is
150rpm), adopt saturated aqueous sodium carbonate pH value to be adjusted for 10, after reacting 60 minutes, obtain the solution containing nikel powder.
Then, the magnesium chloride brine and the ammonium oxalate water of 1.0mol/L of the 5mol/L of 1.5 times of mole will be measured with nickel
Solution presses the mol ratio 1 of magnesium and oxalate:1 at the uniform velocity adds in stirring-type reaction vessel, reacts 30min, then with pure after adding
Water cyclic washing 3 times, after in electric oven 250 DEG C drying, obtain the nickel for being enclosed with magnesium oxalate.
Then, the nickel of magnesium oxalate will be enclosed with the conditions of vacuum (vacuum ＜ 6Pa) with the heating rate of 10 DEG C/min
800 DEG C of insulation 5h are warmed up to, room temperature are cooled to and are come out of the stove, with the chlorohydric acid pickling that mass concentration is 1% 10 minutes, acid amount was theoretical amount
150%, acid solution is outwelled after pickling, then adopt mass concentration for 1% citric acid solution wash 60 minutes, outwell acid solution,
With pure water lotion to PH=7, subsequently filtered with ethanol, by lotion after nikel powder through 80 DEG C, after 8Pa vacuum dryings, obtain nearly ball
The nanometer spherical nikel powder of shape.
Fig. 1 is referred to, Fig. 1 is the XRD figure of the nanometer spherical nikel powder that embodiment 1 is obtained, from figure 1 it appears that nikel powder
Better crystallinity degree, crystal size 42.3nm.
Fig. 2 is referred to, Fig. 2 is the SEM figures of the nanometer spherical nikel powder that embodiment 1 is obtained, from figure 2 it can be seen that nikel powder
Soap-free emulsion polymeization between granule, good dispersion.Absorption method is adopted to measure nikel powder particle diameter for 80nm.
Embodiment 2
By 80 DEG C of mixed aqueous solution 200ml containing 1mol/L nickel sulfate, 50g/L PEG, at the uniform velocity add 5000ml, 80 DEG C
Containing 0.1mol/L KBH4, 80g/L ethanol mixed aqueous solution stirring reactor in (speed of agitator is 200rpm), adopt
PH to 9 is adjusted with sodium hydroxide, after reacting 1.5 hours, nikel powder is obtained.
Then, will be water-soluble for the ammonium oxalate for measuring the calcium chloride water and 1.0mol/l of the 2mol/l of 2 times of mole with nickel
Liquid presses calcium and oxalate mol ratio 1:1, than at the uniform velocity adding in stirring-type reaction vessel, reacts 50min after adding, then uses pure water
Cyclic washing 2 times, then 250 DEG C of drying in electric oven, obtains the nikel powder for being enclosed with calcium oxalate.
Then, will be enclosed with the nickel of calcium oxalate in vacuum atmosphere (vacuum ＜ 6Pa) with the heating rate liter of 3 DEG C/min
Temperature is subsequently cooled to room temperature and comes out of the stove to 1100 DEG C of insulation 1h.With the sulfuric acid washing that mass concentration is 10% 3 minutes, acid amount was
Acid solution is outwelled after pickling by the 120% of theoretical amount, then adopts mass concentration for for 30 points of 10% citric acid acid solution wash
Clock, outwells acid solution, with pure water lotion to PH=7, is subsequently filtered with ethanol, is 90 DEG C of bakings in 6Pa vacuum drying ovens in vacuum
Dry, obtain spherical nanometer spherical nikel powder.
The mean diameter of the nanometer spherical nikel powder for adopting adsorption method testing example 2 to prepare is for 63nm.
The crystal size 43.1nm of the nanometer spherical nikel powder prepared using XRD method testing example 2.
Embodiment 3
By 30 DEG C of mixed aqueous solution 200ml containing 1mol/L Nickel dichloride .s, 180g/L ethanol at the uniform velocity add 4000ml, 30 DEG C
In the stirring reactor of the mixed aqueous solution containing 0.1mol/L NaBH4,180g/LPEG (speed of agitator is 200rpm), adopt
It is 8 that pH value is adjusted with ammonia spirit, after reacting 30 minutes, obtains the solution containing nikel powder.
Then, the calcium chloride water and the ammonium carbonate water of 1.0mol/L of the 5mol/L of 1.2 times of mole will be measured with nickel
Solution presses the mol ratio 1 of magnesium and carbonate:1 at the uniform velocity adds in stirring-type reaction vessel, reacts 40min, then with pure after adding
Water cyclic washing 3 times, after in electric oven 200 DEG C drying, obtain the nickel for being enclosed with Calcium Carbonate.
Then, the nickel of magnesium oxalate will be enclosed with the conditions of vacuum (vacuum ＜ 6Pa) with the heating rate liter of 5 DEG C/min
Temperature is cooled to room temperature and comes out of the stove to 800 DEG C of insulation 3h, and with the chlorohydric acid pickling that mass concentration is 5% 5 minutes, acid amount was theoretical amount
130%, acid solution is outwelled after pickling, then adopt mass concentration for washing 40 minutes for 0.7% citric acid solution, outwell acid
Liquid, with pure water lotion to PH=7, is subsequently filtered with ethanol, by lotion after nikel powder through 70 DEG C, after 5Pa vacuum dryings, obtain near
Spherical nanometer spherical nikel powder.
The mean diameter of the nanometer spherical nikel powder for adopting adsorption method testing example 3 to prepare is for 70nm.
The crystal size 43.7nm of the nanometer spherical nikel powder prepared using XRD method testing example 3.
Embodiment 4
By 60 DEG C of mixed aqueous solution 100ml containing 0.5mol/L Nickel dichloride .s, 120g/L ethanol at the uniform velocity add 2000ml, 60
DEG C contain 0.05mol/L NaBH4, 120g/L PVP mixed aqueous solution stirring reactor in (speed of agitator is
150rpm), adopt saturated aqueous sodium carbonate pH value to be adjusted for 10, after reacting 60 minutes, obtain the solution containing nikel powder.
Then, the magnesium chloride and calcium chloride mixed aqueous solution of 1.5 times of mole will be measured, magnesium calcium mol ratio is 1 with nickel:1,
The mol ratio 1 of magnesium and calcium total amount and oxalate is pressed with the oxalic acid aqueous ammonium of 1.0mol/L:1 at the uniform velocity adds stirring-type reaction vessel
In, react 30min after adding, then with pure water cyclic washing 3 times, after 250 DEG C of drying in electric oven, obtain being enclosed with oxalic acid
Magnesium and the nickel of calcium oxalate.
Then, the nickel of magnesium oxalate and calcium oxalate will be enclosed with the conditions of vacuum (vacuum ＜ 6Pa) with 10 DEG C/min's
Heating rate is warmed up to 600 DEG C of insulation 5h, is cooled to room temperature and comes out of the stove, and with the chlorohydric acid pickling 8 minutes of quality 1%, acid amount is theory
Acid solution is outwelled after pickling by the 110% of amount, then adopts concentration for 10% citric acid solution of mass concentration washing 30 minutes,
Fall acid solution, with pure water lotion to PH=7, subsequently filtered with ethanol, by lotion after nikel powder through 80 DEG C, after 8Pa vacuum dryings, obtain
Arrive subglobose nanometer spherical nikel powder.
The mean diameter of the nanometer spherical nikel powder for adopting adsorption method testing example 3 to prepare is for 90nm.
The degree of crystallinity of the nanometer spherical nikel powder for adopting XRD method testing example 3 to prepare is 42.5nm for crystal size.
Each technical characteristic of embodiment described above arbitrarily can be combined, for making description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Therefore can not be construed as limiting the scope of the patent.It should be pointed out that for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (5)
1. a kind of preparation method of nanometer spherical nikel powder, it is characterised in that comprise the following steps：
Ni will be contained2+Solution mix with reducing solution after reaction prepare the solution containing nikel powder, described contain Ni2+Solution
In also contain dispersant, at least one of the dispersant in ethanol, polyvinylpyrrolidone and Polyethylene Glycol, described point
Powder and the Ni2+Mol ratio be 10：1～50:1, contain BH in the reducing solution4 -And dispersant, the dispersant
At least one in ethanol, polyvinylpyrrolidone and Polyethylene Glycol, the dispersant and the BH4 -Mol ratio be
10：1～50:1, Ni will be contained2+Solution mix with reducing solution after reaction prepare the solution containing nikel powder the step of in, instead
Should be 8-10 in pH value, react 1 hour～2 hours at 30 DEG C～80 DEG C, the Ni2+With BH4 -Mol ratio be 1:2～1:5,
At least one regulation pH value in using sodium carbonate, sodium hydroxide and ammonia；
M will be contained2+Solution and contain R2-Solution add to the solution containing nikel powder in fully reaction be coated with
The nikel powder of covering, wherein described M2+It is selected from Mg2+、Ca2+And Zn2+In at least one, the R2-It is selected from C2O4 2-And CO3 2-In
At least one；
By the nikel powder for being coated with covering at 600 DEG C～1100 DEG C vacuum bakeout 1 hour～5 hours；And
The pickling removing covering post-drying is carried out to the nikel powder for being coated with covering obtains nanometer spherical nikel powder.
2. the preparation method of nanometer spherical nikel powder according to claim 1, it is characterised in that described contain M2+Solution in
M2+Contain Ni with described2+Solution in Ni2+Mol ratio be 1.2:1～2:1.
3. the preparation method of nanometer spherical nikel powder according to claim 1, it is characterised in that the operation of the pickling is concrete
For：First with hydrochloric acid or sulfuric acid scrubbing 2 minutes～10 minutes, then with Fructus Citri Limoniae acid elution 30 minutes～60 minutes, wash with water afterwards
To neutrality, then filtered with ethanol.
4. the preparation method of nanometer spherical nikel powder according to claim 3, it is characterised in that the hydrochloric acid or the sulphuric acid
Mass concentration be 1%～20%, the mass concentration of the citric acid is 0.5%～10%.
5. the preparation method of nanometer spherical nikel powder according to claim 1, it is characterised in that the temperature of the drying is 60
DEG C～100 DEG C, when drying, vacuum is less than 10Pa.
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|---|---|---|---|---|
| CN102814158A (en) * | 2012-07-20 | 2012-12-12 | 安徽师范大学 | Preparation method and application of porous magnetic superstructure nanocomposite |
| CN103567437A (en) * | 2013-10-11 | 2014-02-12 | 国家钽铌特种金属材料工程技术研究中心 | Preparation method of nickel powder with high tap density and degree of crystallinity |
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| JP2005023394A (en) * | 2003-07-04 | 2005-01-27 | Murata Mfg Co Ltd | Conductive powder, production method thereof and conductive paste |
| EP1825265A4 (en) * | 2004-12-10 | 2008-08-27 | Univ Maryland | Serum amyloid a protein in inflammation and obesity |
| JP4957172B2 (en) * | 2005-10-20 | 2012-06-20 | 住友金属鉱山株式会社 | Nickel powder and method for producing the same |
| CN102699338B (en) * | 2012-05-18 | 2014-06-04 | 国家钽铌特种金属材料工程技术研究中心 | Method for preparing spherical nickel powder |
| CN102728852B (en) * | 2012-07-10 | 2014-11-12 | 国家钽铌特种金属材料工程技术研究中心 | Preparation method of oxide or meta-coated nickel ultrafine powder |
| CN103894623B (en) * | 2014-03-19 | 2016-08-17 | 深圳航天科技创新研究院 | A kind of preparation method of antioxidant ultrafine nickel powder |
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| CN102814158A (en) * | 2012-07-20 | 2012-12-12 | 安徽师范大学 | Preparation method and application of porous magnetic superstructure nanocomposite |
| CN103567437A (en) * | 2013-10-11 | 2014-02-12 | 国家钽铌特种金属材料工程技术研究中心 | Preparation method of nickel powder with high tap density and degree of crystallinity |
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