CN101352760A - Method for manufacturing nickel nanoparticles - Google Patents
Method for manufacturing nickel nanoparticles Download PDFInfo
- Publication number
- CN101352760A CN101352760A CNA2008100932956A CN200810093295A CN101352760A CN 101352760 A CN101352760 A CN 101352760A CN A2008100932956 A CNA2008100932956 A CN A2008100932956A CN 200810093295 A CN200810093295 A CN 200810093295A CN 101352760 A CN101352760 A CN 101352760A
- Authority
- CN
- China
- Prior art keywords
- mixed solution
- nickel
- nickel salt
- group
- reducing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000002105 nanoparticle Substances 0.000 title abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 54
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- NQXGLOVMOABDLI-UHFFFAOYSA-N sodium oxido(oxo)phosphanium Chemical compound [Na+].[O-][PH+]=O NQXGLOVMOABDLI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 241000080590 Niso Species 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- -1 propyl methyl acid amides Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 239000003985 ceramic capacitor Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HNJJXZKZRAWDPF-UHFFFAOYSA-N methapyrilene Chemical compound C=1C=CC=NC=1N(CCN(C)C)CC1=CC=CS1 HNJJXZKZRAWDPF-UHFFFAOYSA-N 0.000 description 1
- 229960001869 methapyrilene Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention relates to a method for manufacturing nickel nanoparticles and more particularly to a method including preparing a mixture solution by adding a reducing agent, a dispersing agent and a nickel salt to a polyol; stirring and heating the mixture solution; and producing nickel nanoparticles by reacting the mixture solution, so that it allows mass production of nickel nanoparticles having uniformity of size 30 to 50 nm and high dispersibility.
Description
Related application
The application requires to be committed on July 23rd, 2007 priority of the korean patent application No.10-2007-0073598 of Korea S Department of Intellectual Property, and its content is all incorporated this paper into reform.
Technical field
The present invention relates to a kind of method that is used to produce nano nickel particles, more specifically, the present invention relates to a kind of method that is used to produce nano nickel particles with single-size and polymolecularity.
Background technology
For adapting to the needs to littler electronic unit, multilayer ceramic capacitor has been widely used as having the capacitor of microminiaturized size and high power capacity.Very Ang Gui material such as Pd, Pt etc. has been used for the interior electrode of multilayer ceramic capacitor, but because cost, they are replaced by the nickel particle at present.Especially, use nickel to increase greatly as the research of the inner electrode of multilayer ceramic capacitor with high power capacity.
Because the bulk density (packing density) of the nickel electrode layer of multilayer ceramic capacitor is less than the bulk density of the nickel mechanograph that obtains by powder metallurgy, and its shrinkage factor is much larger than dielectric material in sintering process, therefore the ratio of defects height has the phenomenon of layer short circuit and short-term.For fear of such defective, the nickel particle should not comprise large-sized particle and should have than the distribution of particles of close limit and homogeneous and do not have coalescent good dispersibility.
The various methods that are used to produce as the nickel by powder of multilayer ceramic capacitor inner electrode have been proposed, but up to now, any method all can not satisfy and produces the requirement have less than the nickel powder of the single-size of 100nm (this size is suitable for multilayer and high capacity capacitor).
Particularly, by existing method, carry out vapour phase reduction with the hydrogen carrier band nickel chloride of about 1000 ℃ of high temperature.Yet even because the cause of thermal history (thermalhistory) of reaction at high temperature, particle surface is smooth, and distribution of particles is broad and particle size big (greater than 1.0 μ m) also, this be take place simultaneously by nucleation and growth due to.Therefore, these particles layer of electrode in the thinning fully.
In addition, the someone has introduced a kind of wet reducing that is used to produce nickel by powder, and it is reducing agent that this method adopts hydrazine and hydrazine hydrate, reduction nickel chloride and nickel sulfate solution in the presence of highly basic.Provide the more distribution of particles of close limit although this method is compared with gas phase reduction process, therefore particle rough be not suitable for interior electrode.
In addition, after adding ethylene glycol, end-cap molecule (capping molecule) and reducing agent, adding metal precursor and alcoholic compound, thus add acetone then and ethylene glycol obtains metal nanoparticle.In this method, before adding this metal precursor, reaction temperature is raised.This method is simple and easy inadequately.
In addition, proposed to be used to produce the several different methods of metal nanoparticle, in these methods, the wet reducing ratio is easier to control coating of particles and size, and the fine particle with submicron-scale is provided.Yet, because to have a plurality of response variables, this reaction in course of reaction may be uneven, and be difficult to make have homogeneity, size is at 200nm to 1 μ m, less than the fine particle of 100nm.In addition, it needs extra reduction step, so it is not suitable for a large amount of productions of homogeneous nano nickel particles.
Summary of the invention
One aspect of the present invention provides a kind of method that is used to produce the nano nickel particles with homogeneous distribution of particles and polymolecularity, and can use simple process to produce in a large number.
In order to solve the problems referred to above that existing method is brought, a kind of method that is used to produce nano nickel particles is provided, this method comprises: prepare a kind of mixed solution by add reducing agent, dispersant and nickel salt in polyalcohol; Stirring is also heated this mixed solution; And, this mixed solution produces nano nickel particles by being reacted.
According to a kind of specific embodiment of the present invention, this reducing agent can be to be selected from sodium hypophosphite (NaH
2PO
2), hydrazine (N
2H
4), hydrochloride, sodium borohydride (NaBH
4) and rongalite (NaHSO
2CH
2O2H
2O) at least a in.
According to a kind of specific embodiment of the present invention, this dispersant can be to be selected from least a in cationic surfactant, anion surfactant, cellulose derivative, polymer, copolymer and the terpolymer.
According to a kind of specific embodiment of the present invention, this dispersant can be to be selected from least a in softex kw (CTAB), dodecyl sodium sulfate (SDS), sodium carboxymethylcellulose (Na-CMC), polyvinylpyrrolidone (PVP), vinylpyrrolidone-vinyl acetate copolymer (PVP/VA) and the caprolactam-vinyl pyrrolidone-propyl methyl amide copolymer.
According to a kind of specific embodiment of the present invention, this nickel salt can add with respect to the concentration of this mixed solution with 0.001M to 1M.
According to a kind of specific embodiment of the present invention, this reducing agent can add with 2 to 10 mol ratio with respect to this nickel salt.
According to a kind of specific embodiment of the present invention, this dispersant can be added into 1 to 20 mol ratio with respect to this nickel salt.
According to a kind of specific embodiment of the present invention, this nickel salt can be to be selected from NiCl
2, Ni (NO
3)
2, NiSO
4And (CH
3COO)
2At least a among the Ni.
According to a kind of specific embodiment of the present invention, this polyalcohol can be selected from ethylene glycol, diethylene glycol, triethylene glycol and the polyethylene glycol at least a.
According to a kind of specific embodiment of the present invention, this mixed solution can be heated to 80 ℃ to 160 ℃.
According to a kind of specific embodiment of the present invention, this method may further include washs, separates and dry step the nano nickel particles that makes.
Description of drawings
Fig. 1 is the SEM photo of the nano nickel particles that makes in embodiments of the invention 1.
Fig. 2 is the XRD figure of the nano particle that makes in embodiments of the invention 1.
Fig. 3 is the SEM photo of the nano nickel particles that makes in comparative example 1.
Fig. 4 is the XRD figure of the nano nickel particles that makes in comparative example 1.
The specific embodiment
Hereinafter, will the method that be used to produce nano nickel particles according to of the present invention be described in more detail.
The preparation of nano nickel particles: prepare mixed solution by in polyalcohol, adding reducing agent, dispersant and nickel salt; Stirring is also heated this mixed solution; Produce the nickel particle by reaction temperature and in check reduction reaction of reaction time; And washing, separation and drying.
This nickel salt can be such as NiCl
2, Ni (NO
3)
2, NiSO
4And (CH
3COO)
2The water soluble salt of Ni, it can use separately or at least two kinds be used in combination.This nickel salt can be NiCl
2This nickel salt can add with the concentration of 0.001M to 1M.When the concentration of nickel salt during less than 0.001M, because nickel concentration is low, efficient is undesirable, and when the concentration of nickel salt during above 1M, causes the undue growth of particle coalescent.In this article, the amount of the nickel precursor of use is few more, and the nano nickel particles of production is more little.
Polyalcohol such as ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol can use or use at least two kinds combination separately, preferably makes spent glycol separately.
Ethylene glycol comes the reducing metal precursor with reducing agent by the residue that prevents unreacted compound, thereby improves yield.In addition, ethylene glycol not only can be used as the solvent of dissolution of metals precursor, can also remove unreacted PVP and finish this reaction by adding excessive acetone.
The example of reducing agent comprises dimethyl formamide (DMF), glucose, ascorbic acid, tannic acid, tetrabutyl ammonium borohydride, sodium hypophosphite (NaH
2PO
2), hydrazine (N
2H
4), hydrochloride, sodium borohydride (NaBH
4) and rongalite (NaHSO
2CH
2O2H
2O) etc., preferred sodium hypophosphite (NaH
2PO
2).
Can be that 2 to 10 mol ratio adds reducing agent with respect to nickel salt.When fashionable to add less than 2 mol ratio, nickel ion can not be reduced fully, and when fashionable to add greater than 10 mol ratio, then produces excessive accessory substance, and since the amount of the reducing agent that uses much larger than the amount of reduction 100% nickel ion, this also is uneconomic.
This dispersant can be cationic surfactant or anion surfactant, for example softex kw (CTAB) or dodecyl sodium sulfate (SDS), cellulose derivative such as sodium carboxymethylcellulose (Na-CMC), polymer such as polyvinylpyrrolidone (PVP), copolymer such as vinylpyrrolidone-vinyl acetate copolymer (PVP/VA), such as terpolymer of caprolactam-vinyl pyrrolidone-propyl methyl acid amides etc., it can use or use at least two kinds combination separately, the preferred PVP that uses separately, and more preferably using molecular weight separately is 40,000 PVP.
In addition, can use with respect to the nickel salt mol ratio is 1 to 20 dispersant.When its mol ratio less than 1 the time, the gained particle that may be difficult to control coating of particles and size and therefore enough dispersivenesses can not be provided, and when its mol ratio greater than 20 the time, the viscosity of precursor solution increases sharply, may be difficult to mix equably, reaction can not be carried out equably, produces excessive unreacted compound or accessory substance, and a large amount of solvent of needs washs and separates, and is uneconomic therefore.
The polyalcohol mixed solution that has wherein dissolved reducing agent, dispersant and nickel salt can be heated to 80 ℃ to 160 ℃.When temperature was higher than 160 ℃, reaction can be carried out rapidly, so the particle heterogeneity of stability decreases and generation, and when temperature was lower than 80 ℃, reduction reaction can not be carried out fully.
When mixed solution was heated as mentioned above, reduction reaction was the temperature at 100 ℃ to 140 ℃, carries out according to the mol ratio of nickel salt and reducing agent.Reaction time is in 1 minute to 1 hour scope.When the reaction time was within 1 minute, reduction reaction can not be carried out fully, and yield reduces.On the other hand, when the reaction time greater than 1 hour, can cause the undue growth and the inhomogeneity of particle.
When reduction reaction is finished and when producing nano nickel particles, made reaction cooling fast by using frozen water, thereby prevent the undue growth of particle, and the nano nickel particles that produces is separated by centrifugal etc.Water and the separated nano nickel particles of acetone washing are to remove accessory substance and any remaining compound.Nano nickel particles after will washing subsequently in vacuum drying chamber with 30 ℃-80 ℃ temperature drying 2 to 8 hours.
Although described the present invention in conjunction with the specific specific embodiment, should be appreciated that, those skilled in the art can carry out various changes and modification, and do not deviate from the spirit and scope of the present invention, and scope of the present invention is limited by claims and their equivalents.When the description for a certain technology is determined is that relevant detailed description will be omitted when breaking away from inventive point of the present invention.
Embodiment 1: the preparation of nano nickel particles
In beaker, mix the nickel chloride of 95.04g (0.4M), the sodium hypophosphite of 106g (1.2M), the PVP of 444g (4M), the ethylene glycol of 500ml.Stirring and temperature slowly is increased to the speed of 2 ℃/min in 120 ℃ the process, mixed solution is dissolved.Owing to reduce under 120 ℃ temperature, reactant mixture becomes black, and makes reaction proceed 30 minutes.With frozen water reactant mixture is cooled off fast subsequently, and by the centrifugal nano nickel particles that from reactant mixture, reclaims black.With acetone and distilled water with the nano nickel particles washing that generates 3 times, thereby and in vacuum drying chamber under 50 ℃ temperature the dry target nano nickel particles that obtained 12g in 3 hours.
The SEM photo of the nano nickel particles that makes in embodiment 1 is shown among Fig. 1.According to Fig. 1 as can be seen this nano nickel particles have the size of 30nm to 50nm and be homogeneous.
The XRD figure of the nano nickel particles that makes in embodiment 1 is shown among Fig. 2.According to Fig. 2 as can be seen: formed have centroid cubic lattice structure (FCC structure) the pure nickel crystalline solid and without any impurity and oxidized compound.When formation has the pure nickel particle of FCC structure, as shown in Figure 2, at 111,200 and 220 places corresponding to each FCC structure 3 characteristic peaks appear.
Comparative example 1
For the result with embodiment 1 compares, the reaction that adds slaine after the rising reaction temperature is performed as follows.
In beaker, mix the sodium hypophosphite of 106g, the PVP of 444g, the ethylene glycol of 400ml.Stirring and temperature is increased to the speed of 2 ℃/min in 120 ℃ the process, mixed solution is dissolved.The nickel chloride of 95.04g is dissolved in the ethylene glycol of 150ml, mixed solution is heated to 120 ℃ subsequently.The mixed solution of nickel chloride is added in the mixed solution of sodium hypophosphite, PVP, ethylene glycol at once, temperature is remained on 120 ℃ then, use agitator that it is mixed up hill and dale.Reactant mixture become lentamente black go forward side by side one the step carried out 60 minutes.With frozen water reactant mixture is cooled off apace subsequently and by the centrifugal nano nickel particles that from reactant mixture, reclaims black.With acetone and distilled water with the nano nickel particles washing that makes 3 times, thereby and in vacuum drying chamber under 50 ℃ temperature the dry target nano nickel particles that obtained 8g in 3 hours.
The SEM photo of the nano nickel particles that makes in comparative example 1 is shown among Fig. 3.Can see according to Fig. 3: nano nickel particles is inhomogenous, has serious coalescent.
The XRD figure of the nano nickel particles that makes in comparative example 1 is shown among Fig. 4.Can see according to Fig. 4: the nickel crystal is not centroid cubic lattice structure (a FCC structure).Also can see: the existing method (shown in comparative example 1) according to the back adding slaine that raises in temperature can not form the nickel crystal well.
Claims (11)
1. method that is used to produce nano nickel particles comprises:
In polyalcohol, add reducing agent, dispersant and nickel salt with the preparation mixed solution;
Stirring is also heated described mixed solution; And
Described mixed solution is reacted to produce nano nickel particles.
2. according to the process of claim 1 wherein, described reducing agent is to be selected from by sodium hypophosphite (NaH
2PO
2), hydrazine (N
2H
4), hydrochloride, sodium borohydride (NaBH
4) and rongalite (NaHSO
2CH
2O2H
2O) at least a in the group of Zu Chenging.
3. according to the process of claim 1 wherein, described dispersant is to be selected from least a in the group of being made up of cationic surfactant, anion surfactant, cellulose derivative, polymer, copolymer and terpolymer.
4. according to the method for claim 1, wherein, described dispersant is to be selected from least a by in softex kw (CTAB), dodecyl sodium sulfate (SDS), sodium carboxymethylcellulose (Na-CMC), polyvinylpyrrolidone (PVP), vinylpyrrolidone-vinyl acetate copolymer (PVP/VA) and the group that caprolactam-vinyl pyrrolidone-the propyl methyl acid amides is formed.
5. according to the process of claim 1 wherein, described nickel salt adds with the concentration with respect to described mixed solution 0.001M to 1M.
6. according to the process of claim 1 wherein, described reducing agent is to add with the mol ratio with respect to described nickel salt 2 to 10.
7. according to the process of claim 1 wherein, described dispersant is to add with the mol ratio with respect to described nickel salt 1 to 20.
8. according to the process of claim 1 wherein, described nickel salt is selected from by NiCl
2, Ni (NO
3)
2, NiSO
4(CH
3COO)
2At least a in the group that Ni forms.
9. according to the process of claim 1 wherein, described polyalcohol is selected from least a in the group of being made up of ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol.
10. according to the process of claim 1 wherein, described mixed solution is heated to 80 ℃ to 160 ℃.
11., also comprise washing, separation and dry prepared nano nickel particles according to the method for claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070073598 | 2007-07-23 | ||
| KR1020070073598A KR20090010477A (en) | 2007-07-23 | 2007-07-23 | Method for manufacturing nickel nanoparticles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101352760A true CN101352760A (en) | 2009-01-28 |
Family
ID=40294077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100932956A Pending CN101352760A (en) | 2007-07-23 | 2008-05-21 | Method for manufacturing nickel nanoparticles |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20090025510A1 (en) |
| JP (1) | JP5047064B2 (en) |
| KR (1) | KR20090010477A (en) |
| CN (1) | CN101352760A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101869989A (en) * | 2010-06-03 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Method for preparing water dispersible metal nano-particles |
| CN101879604A (en) * | 2010-06-02 | 2010-11-10 | 浙江大学 | Preparation method and application of metallic indium nanometer particle ink |
| CN101890504A (en) * | 2010-07-07 | 2010-11-24 | 江苏技术师范学院 | Method for preparing flaky nano copper powder |
| CN103028739A (en) * | 2013-01-05 | 2013-04-10 | 河北工业大学 | Preparation method of long-range ordered, layered and self-assembled nano-structure superlattice copper |
| CN103586481A (en) * | 2013-10-19 | 2014-02-19 | 南昌大学 | Preparation method for Fe100-xNix nanometer powder |
| CN103706804A (en) * | 2013-12-25 | 2014-04-09 | 南昌航空大学 | Environment-friendly preparing method of nickel nanocrystalline |
| CN104039688A (en) * | 2011-12-09 | 2014-09-10 | 韩化石油化学株式会社 | Phosphorus-doped nickel nanoparticle and method of manufacturing the same |
| CN105642903A (en) * | 2016-03-01 | 2016-06-08 | 河海大学 | Dispersion method for surface non-covalent modification of nickel nanowire |
| CN107684909A (en) * | 2017-09-30 | 2018-02-13 | 陕西科技大学 | A kind of preparation method of the flower-shaped nickel nano catalytic material of high activity |
| CN110253032A (en) * | 2019-07-16 | 2019-09-20 | 浙江大学 | A kind of method that high yield prepares flower-shaped nano nickel particles under normal temperature and pressure |
| CN114130067A (en) * | 2021-12-16 | 2022-03-04 | *** | Nickel-based oil-water separation membrane and preparation method thereof |
| CN115609000A (en) * | 2020-12-24 | 2023-01-17 | 赵伟 | Preparation method of high-dispersion nickel nano dispersion liquid |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102892533B (en) | 2010-03-17 | 2014-12-10 | 新日铁住金化学株式会社 | Process for production of nickel nanoparticles |
| KR101239386B1 (en) * | 2010-12-13 | 2013-03-05 | 한국지질자원연구원 | METHOD OF MANUFACTURING DIRECTLY NICKEL POWDERS USING hydrothermal process |
| JP5126862B1 (en) | 2011-03-14 | 2013-01-23 | エム・テクニック株式会社 | Method for producing metal fine particles |
| US20130202909A1 (en) * | 2012-02-06 | 2013-08-08 | Lg Chem, Ltd. | Method of producing metal nanoparticles |
| CN104411428B (en) | 2012-09-12 | 2017-05-03 | M技术株式会社 | Method for manufacturing nickel microparticles |
| EP2896474B1 (en) * | 2012-09-12 | 2019-01-16 | M Technique Co., Ltd. | Method for manufacturing metal microparticles |
| JP5376483B1 (en) * | 2012-09-12 | 2013-12-25 | エム・テクニック株式会社 | Method for producing nickel fine particles |
| US9827613B2 (en) | 2012-09-12 | 2017-11-28 | M. Technique Co., Ltd. | Method for producing metal microparticles |
| JP5261780B1 (en) * | 2012-09-12 | 2013-08-14 | エム・テクニック株式会社 | Method for producing metal fine particles |
| KR101445375B1 (en) * | 2013-01-28 | 2014-10-07 | 순천대학교 산학협력단 | manufacturing method of nickel nano fluid using liquid phase plasma reaction |
| KR101593748B1 (en) * | 2013-06-18 | 2016-02-12 | 주식회사 엘지화학 | Method for preparing nickel particle and nickel particle prepared by thereof |
| KR101627372B1 (en) * | 2014-07-17 | 2016-06-08 | 한국세라믹기술원 | Nanosheet-shaped nickel metal by mechanochemical reduction, and fabrication method of positive electrode of Ni-based alkaline storage battery using the same |
| US10378446B2 (en) * | 2015-11-17 | 2019-08-13 | Delavan Inc | Thermal management for injectors |
| JP6898619B2 (en) * | 2016-01-15 | 2021-07-07 | 日本ゼオン株式会社 | Composition for thermoelectric conversion element and its manufacturing method, molded body for thermoelectric conversion element and its manufacturing method, and thermoelectric conversion element |
| JP6573563B2 (en) | 2016-03-18 | 2019-09-11 | 住友金属鉱山株式会社 | Nickel powder, nickel powder manufacturing method, internal electrode paste using nickel powder, and electronic component |
| KR101712503B1 (en) * | 2016-05-02 | 2017-03-13 | 한국세라믹기술원 | The manufacturing method of nanosheet-shaped nickel metal by mechanochemical reduction |
| KR20190043277A (en) * | 2017-10-18 | 2019-04-26 | 현대자동차주식회사 | Battery module having cooling channel and battery system comprising the same |
| KR102022936B1 (en) * | 2018-12-28 | 2019-09-20 | 에이치플러스에코 주식회사 | Preparation method of nano zero-valent Iron modified with PVP-VA |
| GB202009513D0 (en) * | 2020-06-22 | 2020-08-05 | Univ Of Stellenbosch | An enzyme-polymer matrix |
| CN114260462A (en) * | 2020-09-16 | 2022-04-01 | 南京理工大学 | Method for preparing nickel nano-particles |
| CN112520740A (en) * | 2020-11-13 | 2021-03-19 | 中科合成油技术有限公司 | Co3Preparation method of material C |
| CN112958780B (en) * | 2021-02-01 | 2023-05-09 | 中科南京绿色制造产业创新研究院 | Flake nano metal nickel and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4474810B2 (en) * | 2001-07-06 | 2010-06-09 | 株式会社村田製作所 | Metal powder manufacturing method, metal powder, conductive paste, multilayer ceramic electronic component |
| TWI399254B (en) * | 2004-12-10 | 2013-06-21 | Mitsui Mining & Smelting Co | Nickel powder and its manufacturing method and conductive paste |
| WO2006076611A2 (en) * | 2005-01-14 | 2006-07-20 | Cabot Corporation | Production of metal nanoparticles |
| KR100716201B1 (en) * | 2005-09-14 | 2007-05-10 | 삼성전기주식회사 | Metal nanoparticles and method for manufacturing thereof |
| US7625637B2 (en) * | 2006-05-31 | 2009-12-01 | Cabot Corporation | Production of metal nanoparticles from precursors having low reduction potentials |
-
2007
- 2007-07-23 KR KR1020070073598A patent/KR20090010477A/en not_active Application Discontinuation
-
2008
- 2008-04-14 US US12/081,274 patent/US20090025510A1/en not_active Abandoned
- 2008-05-21 CN CNA2008100932956A patent/CN101352760A/en active Pending
- 2008-06-06 JP JP2008148847A patent/JP5047064B2/en active Active
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101879604A (en) * | 2010-06-02 | 2010-11-10 | 浙江大学 | Preparation method and application of metallic indium nanometer particle ink |
| CN101869989A (en) * | 2010-06-03 | 2010-10-27 | 中国林业科学研究院林产化学工业研究所 | Method for preparing water dispersible metal nano-particles |
| CN101890504A (en) * | 2010-07-07 | 2010-11-24 | 江苏技术师范学院 | Method for preparing flaky nano copper powder |
| CN104039688A (en) * | 2011-12-09 | 2014-09-10 | 韩化石油化学株式会社 | Phosphorus-doped nickel nanoparticle and method of manufacturing the same |
| US9339870B2 (en) | 2011-12-09 | 2016-05-17 | Hanwha Chemical Corporation | Phosphorus-doped nickel nanoparticle and method of manufacturing the same |
| CN104039688B (en) * | 2011-12-09 | 2016-05-04 | 韩化石油化学株式会社 | Mix nano nickel particles and the manufacture method thereof of phosphorus |
| CN103028739A (en) * | 2013-01-05 | 2013-04-10 | 河北工业大学 | Preparation method of long-range ordered, layered and self-assembled nano-structure superlattice copper |
| CN103586481A (en) * | 2013-10-19 | 2014-02-19 | 南昌大学 | Preparation method for Fe100-xNix nanometer powder |
| CN103706804A (en) * | 2013-12-25 | 2014-04-09 | 南昌航空大学 | Environment-friendly preparing method of nickel nanocrystalline |
| CN105642903A (en) * | 2016-03-01 | 2016-06-08 | 河海大学 | Dispersion method for surface non-covalent modification of nickel nanowire |
| CN107684909A (en) * | 2017-09-30 | 2018-02-13 | 陕西科技大学 | A kind of preparation method of the flower-shaped nickel nano catalytic material of high activity |
| CN110253032A (en) * | 2019-07-16 | 2019-09-20 | 浙江大学 | A kind of method that high yield prepares flower-shaped nano nickel particles under normal temperature and pressure |
| CN110253032B (en) * | 2019-07-16 | 2020-11-13 | 浙江大学 | Method for preparing flower-like nickel nanoparticles at normal temperature and normal pressure in high yield |
| CN115609000A (en) * | 2020-12-24 | 2023-01-17 | 赵伟 | Preparation method of high-dispersion nickel nano dispersion liquid |
| CN114130067A (en) * | 2021-12-16 | 2022-03-04 | *** | Nickel-based oil-water separation membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20090010477A (en) | 2009-01-30 |
| US20090025510A1 (en) | 2009-01-29 |
| JP5047064B2 (en) | 2012-10-10 |
| JP2009024254A (en) | 2009-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101352760A (en) | Method for manufacturing nickel nanoparticles | |
| KR101398821B1 (en) | Method of manufacturing metal nano-particle, conductive ink composition having the metal nano-particle and method of forming conductive pattern using the same | |
| CN100569418C (en) | The metal nanoparticle of making method of metal nanoparticles and making thus | |
| CN101104205B (en) | Method for manufacturing copper nano granule | |
| KR101789213B1 (en) | Method of Manufacturing Silver-Coated Copper Nano Wire Having Core-Shell Structure by Chemical Reduction Method | |
| US20070180954A1 (en) | Copper nano-particles, method of preparing the same, and method of forming copper coating film using the same | |
| WO2019113993A1 (en) | Carbon nanotube and method for fabrication thereof | |
| CN108788175B (en) | Spherical silver particles, method for producing same, conductive paste, and device comprising same | |
| KR20080035315A (en) | Silver nano-particles and preparation method thereof | |
| WO2012123442A1 (en) | Manufacture of base metal nanoparticles using a seed particle method | |
| WO2006069513A1 (en) | Spherical ultrafine nickel powder with high tap density and its wet processes preparing mothod | |
| Bornamehr et al. | Prussian blue and its analogues as functional template materials: control of derived structure compositions and morphologies | |
| JP5421339B2 (en) | Nickel powder direct manufacturing method using hydrothermal synthesis method | |
| CN111515408B (en) | NiTi alloy powder and preparation method and application thereof | |
| JP6872099B2 (en) | Manufacturing method of hollow structure | |
| KR20130121422A (en) | Fabrication method of lithium complex oxide | |
| JP2012224885A (en) | Method for producing metal porous body | |
| KR101283984B1 (en) | Silver nanowire having protuberance and Method for preparing the same | |
| JP2013040358A (en) | Method for manufacturing metal porous body | |
| KR20200060184A (en) | Silver nano wire ink and manufacturing method thereof | |
| CN116003116B (en) | ZnFe2O 4-based composite wave-absorbing material and preparation method thereof | |
| CN111448162B (en) | Fibrous carbon nanostructures | |
| KR102210660B1 (en) | Silver nano wire ink and manufacturing method thereof | |
| KR102002853B1 (en) | Method for manufacturing germanium nano particles coated by ZnO nano particles, germanium nano particles manufactured by the method and a lithium ion battery comprising the ZnO coated germanium nano particles | |
| KR20170061659A (en) | Method for producing nickel particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090128 |