US20090025510A1 - Method for manufacturing nickel nanoparticles - Google Patents
Method for manufacturing nickel nanoparticles Download PDFInfo
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- US20090025510A1 US20090025510A1 US12/081,274 US8127408A US2009025510A1 US 20090025510 A1 US20090025510 A1 US 20090025510A1 US 8127408 A US8127408 A US 8127408A US 2009025510 A1 US2009025510 A1 US 2009025510A1
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- Prior art keywords
- nickel
- mixture solution
- nickel nanoparticles
- nanoparticles
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 52
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 150000002815 nickel Chemical class 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 7
- 150000003077 polyols Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- NQXGLOVMOABDLI-UHFFFAOYSA-N sodium oxido(oxo)phosphanium Chemical compound [Na+].[O-][PH+]=O NQXGLOVMOABDLI-UHFFFAOYSA-N 0.000 claims description 4
- MXRGSJAOLKBZLU-UHFFFAOYSA-N 3-ethenylazepan-2-one Chemical compound C=CC1CCCCNC1=O MXRGSJAOLKBZLU-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 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
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- FYUWIEKAVLOHSE-UHFFFAOYSA-N ethenyl acetate;1-ethenylpyrrolidin-2-one Chemical compound CC(=O)OC=C.C=CN1CCCC1=O FYUWIEKAVLOHSE-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- VBOFDBONKAERAE-UHFFFAOYSA-M sodium;sulfenatooxymethanol Chemical compound [Na+].OCOS[O-] VBOFDBONKAERAE-UHFFFAOYSA-M 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
- 238000005406 washing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000003985 ceramic capacitor Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 208000012868 Overgrowth Diseases 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 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
- -1 alcohol compound Chemical class 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000008569 process Effects 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
- ZXQOBTQMLMZFOW-UHFFFAOYSA-N 2-methylhex-2-enamide Chemical compound CCCC=C(C)C(N)=O ZXQOBTQMLMZFOW-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
- 239000003513 alkali Substances 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
- 230000008901 benefit Effects 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process 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
- 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
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 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
- 229920005903 polyol mixture Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance 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
- 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
-
- 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
-
- 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
Definitions
- the present invention related to a method for manufacturing nickel nanoparticles and more particularly, to a method for manufacturing nickel nanoparticles having uniform size and high dispersibility.
- the multi layer ceramic capacitor has been widely used as a capacitor having a miniaturized size and high capacity.
- Highly expensive materials such as Pd, Pt, etc. have been used for the internal electrode of the multi layer ceramic capacitor but they are recently replaced with nickel particles for a cost matter.
- nickel As a material of the internal electrode of the multi layer ceramic capacitor having high capacity has been greatly increased.
- nickel electrode layer of the multi layer ceramic capacitor has a lower packing density than that of a nickel molding obtained by the powder metallurgy and much larger shrinkage than a dielectric substance during the sintering process, the defect rate is high with shorten-turn and broken phenomena.
- nickel particles should not contain large size particles but have narrow and uniform particle distribution and good dispersibility without coagulation.
- nickel chloride is carried for the gas phase reduction with hydrogen at a high temperature of about 1000° C.
- the particle distribution is wide and the size of particles is large, larger than 1.0 ⁇ m, since nucleation and growth are occurred at the same time. Thus, these particles are insufficient for thinning layers of the internal electrode.
- a wet reduction for manufacturing nickel powders which reduces a solution of nickel chloride and nickel sulfate with a reducing agent of hydrazine and hydrazine hydrate in the presence of a strong alkali. Even if this method provides a narrower particle distribution compared to the gas phase reduction, the surface of particles is not smooth and thus it is not suitable for the internal electrode.
- a metal precursor and an alcohol compound are added and then acetone and ethylene glycol are added to produce metal nanoparticles.
- the reaction temperature is increased before the metal precursor is added. This method is not simple.
- An aspect of the present invention is to provide a method for manufacturing nickel nanoparticles which have uniform particle distribution and high dispersibility and allows mass production with a simple process.
- a method for manufacturing nickel nanoparticles 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.
- the reducing agent may be at least one chosen from sodium hypophosphite (NaH 2 PO 2 ), hydrazine (N 2 H 4 ), hydrochloride, sodium borohydride (NaBH 4 ), and sodium hydroxymethylsulfoxylate (NaHSO 2 ⁇ CH 2 O ⁇ 2H 2 O).
- the dispersing agent may be at least one chosen from a cationic surfactant, an anionic surfactant, an analogue of cellulose, a polymer, a copolymer and a terpolymer.
- the dispersing agent may be at least one chosen from cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), sodium carboxymethyl cellulose (Na-CMC), polyvinylpyrrolidone (PVP), vinylpyrrolidone/vinylacetate (PVP/VA), and vinylcaprolactam/vinylpyrrolidone/propylmethacylamide.
- CTAB cetyltrimethylammonium bromide
- SDS sodium dodecyl sulfate
- Na-CMC sodium carboxymethyl cellulose
- PVP polyvinylpyrrolidone
- PVP/VA vinylpyrrolidone/vinylacetate
- vinylcaprolactam/vinylpyrrolidone/propylmethacylamide vinylcaprolactam/vinylpyrrolidone/propylmethacylamide.
- the nickel salt may be added in a concentration of 0.001 to 1M with respect to the mixture solution.
- the reducing agent may be added in a mole ratio of 2 to 10 with respect to the nickel salt.
- the dispersing agent may be added in a mole ratio of 1 to 20 with respect to the nickel salt.
- the nickel salt may be at least one chosen from NiCl 2 , Ni(NO 3 ) 2 , NiSO 4 and (CH 3 COO) 2 Ni.
- the polyol may be at least one chosen from ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
- the mixture solution may be heated to 80 to 160° C.
- the method may further include washing, isolating, and drying the produced nickel nanoparticles.
- FIG. 1 is a SEM image of nickel nanoparticles produced in Example 1 of the present invention.
- FIG. 2 is a XRD graph of nickel nanoparticles produced in Example 1 of the present invention.
- FIG. 3 is a SEM image of nickel nanoparticles produced in Comparison Example 1.
- FIG. 4 is a XRD graph of nickel nanoparticles produced in Comparison Example 1
- Nickel nanoparticles are produced by preparing a mixture solution by adding a reducing agent, a dispersing agent, a nickel salt to a polyol, stirring and heating the mixture solution, producing nickel particles through a reducing reaction under control of a reaction temperature and a reaction time, and washing, isolating, and drying.
- the nickel salt may be a water soluble salt such as NiCl 2 , Ni(NO 3 ) 2 , NiSO 4 , and (CH 3 COO) 2 Ni and it may be used alone or a combination of at least two.
- the nickel salt may be NiCl 2 .
- the nickel salt may be added in a concentration of 0.001 to 1M. When the concentrating of the nickel salt is less than 0.001M, the efficiency is not preferable due to low concentration of nickel ions, while when it exceeds more than 1M, it causes overgrowth coagulation of particles. Here, the less amount of a nickel precursor is used the smaller the nickel nanoparticles are produced.
- the polyol such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol may be used alone or as a combination of at least two, preferably ethylene glycol alone.
- Ethylene glycol reduces the metal precursor along with the reducing agent by preventing remaining of unreacted compounds, so that it increases the yield of manufacturing. Further, ethylene glycol may not only be used as a solvent to dissolve the metal precursor but also removes unreacted PVP with addition of excess amount of acetone and completes the reaction.
- Examples of the reducing agent include dimethylformamide (DMF), glucose, ascorbic acid, tannic acid, tetrabutyl ammonium borohydride, sodium hypophosphite (NaH 2 PO 2 ), hydrazine (N 2 H 4 ), hydrochloride, sodium borohydride (NaBH 4 ), sodium hydroxymethylsulfoxylate (NaHSO 2 ⁇ CH 2 O ⁇ 2H 2 O), etc., preferably sodium hypophosphite (NaH 2 PO 2 ).
- The may be added in a mole ratio of 2 to 10 with respect to the nickel salt.
- the nickel ions cannot be sufficiently reduced, while when it is added more than 10 mole ratio, excess amount of byproducts are produced and thus it is not economical since the reducing agent is used much more than the amount to reduce 100% of the nickel ions.
- the dispersing agent may be a cationic or anionic surfactant such as cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS), an analogue of cellulose such as sodium carboxymethyl cellulose (Na-CMC), a polymer such as polyvinylpyrrolidone (PVP), a copolymer such as vinylpyrrolidone/vinylacetate (PVP/VA), a terpolymer such as vinylcaprolactam/vinylpyrrolidone/propylmethacrylamide, etc., and it can be used alone or a combination of at least two, preferably PVP alone, and more preferably PVP having a molecular weight of 40,000 alone.
- CTAB cetyltrimethylammonium bromide
- SDS sodium dodecyl sulfate
- an analogue of cellulose such as sodium carboxymethyl cellulose (Na-CMC)
- a polymer such as poly
- the dispersing agent may be used in a mole ratio of 1 to 20 with respect to the nickel salt.
- the viscosity of the precursor solution is rapidly increased, it may be difficult to mix uniformly, the reaction cannot be performed uniformly, it produces excess amount of unreacted compounds or byproducts, and it requires large amount of a solvent to wash and isolate which is then uneconomical.
- the polyol mixture solution in which the reducing agent, the dispersing agent and the nickel salt are dissolved, may be heated to 80 to 160° C.
- the temperature is higher than 160° C., the reaction may proceed rapidly and thus the stability gets decreased and the produced particles are not uniform, while it is lower than 80° C., the reduction is not sufficiently performed.
- the reduction is performed at a temperature of 100 to 140° C. according the mole ratio of the nickel salt and the reducing agent.
- the reaction time is in a range of 1 minute to 1 hour. When the reaction time is within 1 minute, the reduction is not performed sufficiently and the yield thus becomes lowered. On the other hand, when the reaction time is more than 1 hour, it causes overgrowth of particles and ununiformity.
- the reaction is quickly cooled by using ice-water to prevent overgrowth of particles and the nickel nanoparticles produced are isolated by centrifuge, etc.
- the isolated nickel nanoparticles are washed with water and acetone to remove byproducts and any remained compound.
- the washed nickel nanoparticles are then dried in a vacuum oven at a temperature of 30 to 80° C. for 2 to 8 hours.
- Nickel chloride 95.04 g (0.4M), sodium hypophosphite 106 g (1.2M), PVP 444 g (1.2M), ethylene glycol 500 ml were mixed in a beaker.
- the mixture solution was dissolved while stirring and the temperature was slowly increased up to 120° C. at a rate of 2° C./min.
- the reaction mixture was turned to black due to the reduction at a temperature of 120° C. and preceded for 30 min.
- the reaction mixture was then cooled down quickly by using ice-water and black nickel nanoparticles were recovered from the reaction mixture by centrifuge.
- the produced nickel nanoparticles were washed with acetone and distilled water 3 times and dried in a vacuum oven at a temperature of 50° C. for 3 hours to provide target nickel nanoparticles 12 g.
- FIG. 1 A SEM image of the nickel nanoparticles produced in Example 1 is shown in FIG. 1 . According to FIG. 1 , it is noted that the nickel nanoparticles have a size of 30 to 50 nm and are uniform.
- FIG. 2 A XRD graph of the nickel nanoparticles produced in Example 1 is shown in FIG. 2 .
- FCC structure face-centered cubic lattice structure
- 3 distinctive peaks are appeared at 111, 200, and 220 corresponding to each FCC structure as shown in FIG. 2 .
- Sodium hypophosphite 106 g, PVP 444 g, ethylene glycol 400 g were mixed in a beaker and the mixture solution was dissolved while stirring and increasing the temperature up to 120° C. at a rate of 2° C./min.
- Nickel chloride 95.04 g was dissolved in ethylene glycol 150 g and the mixture solution was then heated to 120° C.
- the mixture solution of nickel chloride was added at once to the mixture solution of sodium hypophosphite, PVP, ethylene glycol and then thoroughly mixed using a stirrer while keeping the temperature at 120° C.
- the reaction mixture was turned slowly to black and further preceded for 60 minutes.
- the reaction mixture was then cooled down quickly by using ice-water and black nickel nanoparticles were recovered from the reaction mixture by centrifuge.
- the produced nickel nanoparticles were washed with acetone and distilled water 3 times and dried at a vacuum oven at a temperature of 50° C. for 3 hours to provide target nickel nanoparticles 8 g.
- FIG. 3 A SEM image of the nickel nanoparticles produced in Comparison Example 1 is shown in FIG. 3 . According to FIG. 3 , it is noted that the nickel nanoparticles are ununiform with heavy coagulation.
- FIG. 4 A XRD graph of the nickel nanoparticles produced in Comparison Example 1 is shown in FIG. 4 .
- the nickel crystalline is not a face-centered cubic lattice structure (FCC structure). It is also noted that nickel crystalline is not formed smoothly according to the conventional method which adds a metal salt after the temperature is increased as shown in Comparison Example 1.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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
- This application claims the benefit of Korean Patent Application No. 10-2007-0073598 filed on Jul. 23, 2007, with the Korea Intellectual Property Office, the contents of which are incorporated here by reference in their entirety.
- 1. Technical Field
- The present invention related to a method for manufacturing nickel nanoparticles and more particularly, to a method for manufacturing nickel nanoparticles having uniform size and high dispersibility.
- 2. Description of the Related Art
- In response to demands for much smaller electronic components, the multi layer ceramic capacitor has been widely used as a capacitor having a miniaturized size and high capacity. Highly expensive materials such as Pd, Pt, etc. have been used for the internal electrode of the multi layer ceramic capacitor but they are recently replaced with nickel particles for a cost matter. Particularly, researches using nickel as a material of the internal electrode of the multi layer ceramic capacitor having high capacity has been greatly increased.
- Since a nickel electrode layer of the multi layer ceramic capacitor has a lower packing density than that of a nickel molding obtained by the powder metallurgy and much larger shrinkage than a dielectric substance during the sintering process, the defect rate is high with shorten-turn and broken phenomena. In order to avoid such defects nickel particles should not contain large size particles but have narrow and uniform particle distribution and good dispersibility without coagulation.
- Various methods for manufacturing nickel powders to be used as a material of the internal electrode of the multi layer ceramic capacitors have been introduced but any method until now has not satisfied to manufacture nickel powders having uniform size of less than 100 nm which is suitable for multi-layered and high capacity capacitors.
- Particularly, conventionally nickel chloride is carried for the gas phase reduction with hydrogen at a high temperature of about 1000° C. However, even if the surface of particles is smooth due to thermal history of the reaction at a high temperature, the particle distribution is wide and the size of particles is large, larger than 1.0 μm, since nucleation and growth are occurred at the same time. Thus, these particles are insufficient for thinning layers of the internal electrode.
- Further, a wet reduction for manufacturing nickel powders is introduced which reduces a solution of nickel chloride and nickel sulfate with a reducing agent of hydrazine and hydrazine hydrate in the presence of a strong alkali. Even if this method provides a narrower particle distribution compared to the gas phase reduction, the surface of particles is not smooth and thus it is not suitable for the internal electrode.
- Further, after adding ethylene glycol, a capping molecule and a reducing agent, a metal precursor and an alcohol compound are added and then acetone and ethylene glycol are added to produce metal nanoparticles. In this method, the reaction temperature is increased before the metal precursor is added. This method is not simple.
- In addition, various methods for manufacturing metal nanoparticles have been introduced and among these methods the wet reduction is relatively easy to control shape and size of particles and provides fine particles having a sub-micron size. However, since there are several reaction variables during the reaction process, the reaction can be ununiform and it is difficult to manufacture fine particles having uniformity of a size of 200 nm to 1 μm which is less than 100 nm. Further, it requires an additional reduction step, so that it is not suitable for mass production of uniform nickel nanoparticles.
- An aspect of the present invention is to provide a method for manufacturing nickel nanoparticles which have uniform particle distribution and high dispersibility and allows mass production with a simple process.
- In order to resolve the aforementioned problems associated with the conventional methods, is a method for manufacturing nickel nanoparticles provided, the 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.
- According to an embodiment of the present invention, the reducing agent may be at least one chosen from sodium hypophosphite (NaH2PO2), hydrazine (N2H4), hydrochloride, sodium borohydride (NaBH4), and sodium hydroxymethylsulfoxylate (NaHSO2◯CH2O◯2H2O).
- According to an embodiment of the present invention, the dispersing agent may be at least one chosen from a cationic surfactant, an anionic surfactant, an analogue of cellulose, a polymer, a copolymer and a terpolymer.
- According to an embodiment of the present invention, the dispersing agent may be at least one chosen from cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), sodium carboxymethyl cellulose (Na-CMC), polyvinylpyrrolidone (PVP), vinylpyrrolidone/vinylacetate (PVP/VA), and vinylcaprolactam/vinylpyrrolidone/propylmethacylamide.
- According to an embodiment of the present invention, the nickel salt may be added in a concentration of 0.001 to 1M with respect to the mixture solution.
- According to an embodiment of the present invention, the reducing agent may be added in a mole ratio of 2 to 10 with respect to the nickel salt.
- According to an embodiment of the present invention, the dispersing agent may be added in a mole ratio of 1 to 20 with respect to the nickel salt.
- According to an embodiment of the present invention, the nickel salt may be at least one chosen from NiCl2, Ni(NO3)2, NiSO4 and (CH3COO)2Ni.
- According to an embodiment of the present invention, the polyol may be at least one chosen from ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
- According to an embodiment of the present invention, the mixture solution may be heated to 80 to 160° C.
- According to an embodiment of the present invention, the method may further include washing, isolating, and drying the produced nickel nanoparticles.
-
FIG. 1 is a SEM image of nickel nanoparticles produced in Example 1 of the present invention. -
FIG. 2 is a XRD graph of nickel nanoparticles produced in Example 1 of the present invention. -
FIG. 3 is a SEM image of nickel nanoparticles produced in Comparison Example 1. -
FIG. 4 is a XRD graph of nickel nanoparticles produced in Comparison Example 1 - Hereinafter, the method for manufacturing nickel nanoparticles according to the invention will be described in more detail.
- Nickel nanoparticles are produced by preparing a mixture solution by adding a reducing agent, a dispersing agent, a nickel salt to a polyol, stirring and heating the mixture solution, producing nickel particles through a reducing reaction under control of a reaction temperature and a reaction time, and washing, isolating, and drying.
- The nickel salt may be a water soluble salt such as NiCl2, Ni(NO3)2, NiSO4, and (CH3COO)2Ni and it may be used alone or a combination of at least two. The nickel salt may be NiCl2. The nickel salt may be added in a concentration of 0.001 to 1M. When the concentrating of the nickel salt is less than 0.001M, the efficiency is not preferable due to low concentration of nickel ions, while when it exceeds more than 1M, it causes overgrowth coagulation of particles. Here, the less amount of a nickel precursor is used the smaller the nickel nanoparticles are produced.
- The polyol such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol may be used alone or as a combination of at least two, preferably ethylene glycol alone.
- Ethylene glycol reduces the metal precursor along with the reducing agent by preventing remaining of unreacted compounds, so that it increases the yield of manufacturing. Further, ethylene glycol may not only be used as a solvent to dissolve the metal precursor but also removes unreacted PVP with addition of excess amount of acetone and completes the reaction.
- Examples of the reducing agent include dimethylformamide (DMF), glucose, ascorbic acid, tannic acid, tetrabutyl ammonium borohydride, sodium hypophosphite (NaH2PO2), hydrazine (N2H4), hydrochloride, sodium borohydride (NaBH4), sodium hydroxymethylsulfoxylate (NaHSO2◯CH2O◯2H2O), etc., preferably sodium hypophosphite (NaH2PO2).
- The may be added in a mole ratio of 2 to 10 with respect to the nickel salt. When it is added less than 2 mole ratio, the nickel ions cannot be sufficiently reduced, while when it is added more than 10 mole ratio, excess amount of byproducts are produced and thus it is not economical since the reducing agent is used much more than the amount to reduce 100% of the nickel ions.
- The dispersing agent may be a cationic or anionic surfactant such as cetyltrimethylammonium bromide (CTAB) or sodium dodecyl sulfate (SDS), an analogue of cellulose such as sodium carboxymethyl cellulose (Na-CMC), a polymer such as polyvinylpyrrolidone (PVP), a copolymer such as vinylpyrrolidone/vinylacetate (PVP/VA), a terpolymer such as vinylcaprolactam/vinylpyrrolidone/propylmethacrylamide, etc., and it can be used alone or a combination of at least two, preferably PVP alone, and more preferably PVP having a molecular weight of 40,000 alone.
- Further, the dispersing agent may be used in a mole ratio of 1 to 20 with respect to the nickel salt. When it is less than 1 mole ratio, it can be difficult to control the shape and size of particles and thus cannot provide sufficient dispersibility of the produced particles, while when it is more than 20 mole ratio, the viscosity of the precursor solution is rapidly increased, it may be difficult to mix uniformly, the reaction cannot be performed uniformly, it produces excess amount of unreacted compounds or byproducts, and it requires large amount of a solvent to wash and isolate which is then uneconomical.
- The polyol mixture solution, in which the reducing agent, the dispersing agent and the nickel salt are dissolved, may be heated to 80 to 160° C. When the temperature is higher than 160° C., the reaction may proceed rapidly and thus the stability gets decreased and the produced particles are not uniform, while it is lower than 80° C., the reduction is not sufficiently performed.
- When the mixture solution is heated as described above, the reduction is performed at a temperature of 100 to 140° C. according the mole ratio of the nickel salt and the reducing agent. The reaction time is in a range of 1 minute to 1 hour. When the reaction time is within 1 minute, the reduction is not performed sufficiently and the yield thus becomes lowered. On the other hand, when the reaction time is more than 1 hour, it causes overgrowth of particles and ununiformity.
- When the reduction completes to produce nickel nanoparticles, the reaction is quickly cooled by using ice-water to prevent overgrowth of particles and the nickel nanoparticles produced are isolated by centrifuge, etc. The isolated nickel nanoparticles are washed with water and acetone to remove byproducts and any remained compound. The washed nickel nanoparticles are then dried in a vacuum oven at a temperature of 30 to 80° C. for 2 to 8 hours.
- While the present invention has been described with reference to particular embodiments, it is to be appreciated that various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the present invention, as defined by the appended claims and their equivalents. Throughout the description of the present invention, when describing a certain technology is determined to evade the point of the present invention, the pertinent detailed description will be omitted.
- Nickel chloride 95.04 g (0.4M), sodium hypophosphite 106 g (1.2M), PVP 444 g (1.2M), ethylene glycol 500 ml were mixed in a beaker. The mixture solution was dissolved while stirring and the temperature was slowly increased up to 120° C. at a rate of 2° C./min. The reaction mixture was turned to black due to the reduction at a temperature of 120° C. and preceded for 30 min. The reaction mixture was then cooled down quickly by using ice-water and black nickel nanoparticles were recovered from the reaction mixture by centrifuge. The produced nickel nanoparticles were washed with acetone and distilled water 3 times and dried in a vacuum oven at a temperature of 50° C. for 3 hours to provide target nickel nanoparticles 12 g.
- A SEM image of the nickel nanoparticles produced in Example 1 is shown in
FIG. 1 . According toFIG. 1 , it is noted that the nickel nanoparticles have a size of 30 to 50 nm and are uniform. - A XRD graph of the nickel nanoparticles produced in Example 1 is shown in
FIG. 2 . According toFIG. 2 , it is noted that pure nickel crystalline having face-centered cubic lattice structure (FCC structure) is formed without any impurity and oxidized compound. When pure nickel particles having FCC structure are formed, 3 distinctive peaks are appeared at 111, 200, and 220 corresponding to each FCC structure as shown inFIG. 2 . - In order to compare with the result of Example 1, a reaction in which a metal salt was added after increasing the reaction temperature was performed as follows.
- Sodium hypophosphite 106 g, PVP 444 g, ethylene glycol 400 g were mixed in a beaker and the mixture solution was dissolved while stirring and increasing the temperature up to 120° C. at a rate of 2° C./min. Nickel chloride 95.04 g was dissolved in ethylene glycol 150 g and the mixture solution was then heated to 120° C. The mixture solution of nickel chloride was added at once to the mixture solution of sodium hypophosphite, PVP, ethylene glycol and then thoroughly mixed using a stirrer while keeping the temperature at 120° C. The reaction mixture was turned slowly to black and further preceded for 60 minutes. The reaction mixture was then cooled down quickly by using ice-water and black nickel nanoparticles were recovered from the reaction mixture by centrifuge. The produced nickel nanoparticles were washed with acetone and distilled water 3 times and dried at a vacuum oven at a temperature of 50° C. for 3 hours to provide target nickel nanoparticles 8 g.
- A SEM image of the nickel nanoparticles produced in Comparison Example 1 is shown in
FIG. 3 . According toFIG. 3 , it is noted that the nickel nanoparticles are ununiform with heavy coagulation. - A XRD graph of the nickel nanoparticles produced in Comparison Example 1 is shown in
FIG. 4 . According toFIG. 4 , it is noted that the nickel crystalline is not a face-centered cubic lattice structure (FCC structure). It is also noted that nickel crystalline is not formed smoothly according to the conventional method which adds a metal salt after the temperature is increased as shown in Comparison Example 1.
Claims (11)
1. A method for manufacturing nickel nanoparticles, comprising:
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.
2. The method of claim 1 , wherein the reducing agent is at least one selected from the group consisting of sodium hypophosphite (NaH2PO2), hydrazine (N2H4), hydrochloride, sodium borohydride (NaBH4), and sodium hydroxymethylsulfoxylate (NaHSO2◯CH2O◯H2O).
3. The method of claim 1 , wherein the dispersing agent is at least one selected from the group consisting of a cationic surfactant, an anionic surfactant, an analogue of cellulose, a polymer, a copolymer and a terpolymer.
4. The method of claim 1 , wherein the dispersing agent is at least one selected from the group consisting of cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), sodium carboxymethyl cellulose (Na-CMC), polyvinylpyrrolidone (PVP), vinylpyrrolidone/vinylacetate (PVP/VA), and vinylcaprolactam/vinylpyrrolidone/propylmethacylamide.
5. The method of claim 1 , wherein the nickel salt is added in a concentration of 0.001 to 1M with respect to the mixture solution.
6. The method of claim 1 , wherein the reducing agent is added in a mole ratio of 2 to 10 with respect to the nickel salt.
7. The method of claim 1 , wherein the dispersing agent is added in a mole ratio of 1 to 20 with respect to the nickel salt.
8. The method of claim 1 , wherein the nickel salt is at least one selected from the group consisting of NiCl2, Ni(NO3)2, NiSO4 and (CH3COO)2Ni.
9. The method of claim 1 , wherein the polyol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol.
10. The method of claim 1 , wherein the mixture solution is heated to 80 to 160° C.
11. The method of claim 1 , further comprising washing, isolating, and drying the produced nickel nanoparticles.
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