CN102811829B - Nickel-cobalt nanometer particle and manufacture method thereof - Google Patents
Nickel-cobalt nanometer particle and manufacture method thereof Download PDFInfo
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- CN102811829B CN102811829B CN201180014315.6A CN201180014315A CN102811829B CN 102811829 B CN102811829 B CN 102811829B CN 201180014315 A CN201180014315 A CN 201180014315A CN 102811829 B CN102811829 B CN 102811829B
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- 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
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Abstract
Nickel-cobalt nanometer particle of the present invention comprises the core that formed by nickel in fact and covers in fact whole of core and the shell formed by cobalt in fact.The manufacture method of nickel-cobalt nanometer particle of the present invention has following operation: the mixture heating containing nickel salt or nickel particle, cobalt salt and primary amine is obtained the operation of reactant liquor or the mixture of cobalt salt and primary amine is heated the operation obtaining reactant liquor; With operation reactant liquor heating being obtained nickel-cobalt nanometer particle slurry.
Description
Technical field
The present invention relates to the nano particle with the nucleocapsid structure formed by dissimilar metal.
Background technology
Cobalt nanometer particle is more cheap compared with Nano silver grain, chemically more stable compared with copper nano-particle, with nickel particles phase specific catalytic activity and magnetic saturation higher, utilize desirable therefore in its electrode in various catalyst, magnetic material, fuel cell, laminated ceramic capacitor etc.But cobalt is rare metal, also more expensive than nickel particles, therefore wish to develop cobalt particle and the method for making thereof that can play the performance of cobalt with less amount.In order to play the performance of cobalt well, its particle diameter and particle shape must control evenly.
Generally speaking, the manufacture method of metal nanoparticle is broadly divided into Physical and chemical method.Physical is that the method (comminuting method) manufacturing nano particle is pulverized in reguline metal, and chemical method metallic atom is produced and the method (agglutination) controlling its aggegation to make.When utilizing Physical to pulverize, the reduction of particle diameter is limited, and the shape of particle also becomes uneven, is difficult to form uniform particle.Therefore, more favourable for controlling chemical method for the shape of particle or particle diameter.
In addition, the manufacture method of the metal nanoparticle of chemical method is utilized can be divided into damp process and dry process.For the dry process of chemical method, there will be a known CVD (chemical vapour deposition (CVD)) method, evaporation deposition in gas, laser method, sputtering method, molten drop spray-on process etc., because the particle generated is spherical through high-temperature process, good crystallinity, but then, the distribution of particle diameter is wide, productivity ratio is also low is shortcoming.And for taking chemical reduction method as the damp process of representative, there is compared with dry process the advantage of high, the easy control particle diameter of productivity ratio, large quantity research has been carried out in the development therefore along with nanometer technology in recent years.
In addition, can expect compared with single metal nanoparticle that the research of the binary system nano particle (metal composite nano particle) that physical property embodies is carried out widely further.In addition, be conceived to according to the purposes of nano particle need there is specific character metal as the coating metal of particle, as binary system nano particle, the binary system nano particle forming core and shell with dissimilar metal is also studied.
As such metal nanoparticle with nucleocapsid structure, such as, disclose and comprise copper core and copper core surrounded and there is the metal nanoparticle (patent document 1) of the thin layer of the metal such as silver, palladium, platinum, gold of the reduction potential higher than copper.The manufacture method of this metal nanoparticle comprises following steps: tert-butyl hydroxy toluene, ascorbic acid, flavonoids etc. are used for reducing agent in containing the solution of primary amine and from the copper precursors be made up of copper complexs such as copper nitrate, copper chloride, copper formates to form the step of copper nano-particle; With the step in the formation of the surface of copper nano-particle with the thin layer of the metal of the reduction potential higher than copper.The metal nanoparticle with nucleocapsid structure of gained has such as the following advantage: owing to being core with copper particle and it being coated to noble metal, thus the containing ratio of copper can be improved while the oxidation preventing copper, therefore economy is excellent, and, due to metals such as the silver containing Conductivity Ratio copper excellence in thin layer, the distribution of Conductivity Ratio copper excellence therefore can be formed.
In addition, such as also disclose following method: dissolve containing the metal precursor as the 1st metal (such as cobalt) of nano particle and reduction potential the 2nd metal (such as platinum) higher than the 1st metal respectively with suitable organic solvent, by formed each solution mixing, manufactured the metal nanoparticle (patent document 2) of nucleocapsid structure by the 1st metal and the 2nd intermetallic metal substitution reaction.
Patent document 1,2 realizes the metal nanoparticle with the core formed by the metal that reduction potential is low and the shell formed by the metal that reduction potential is high by diverse ways.But, for the metal nanoparticle using the manufacture method of patent document 1,2 suitably can obtain the nucleocapsid structure formed by other dissimilar metal, it be unclear that.Particularly for the dissimilar metal that the oxidation-reduction potential that such as nickel and cobalt are such is close, be difficult to think applicable with patent document 1,2 identical methods.
On the other hand, the present inventor is to being core with copper and the Cu-Ni alloy in shell with the reduction potential nickel lower than copper is studied and has done report (non-patent literature 1,2).According to by non-patent literature 2 deep further for the research of non-patent literature 1, the method for making of Cu-Ni alloy is as follows: copper formate and nickel formate are mixed with oleyl amine separately respectively, by at room temperature heating the mixed liquor of copper formate, heating being carried out under 393K to the mixed liquor of nickel formate carry out complexing (namely forming complex compound) thus prepare precursor, mix with 1-octanol, then, nano particle is obtained by carrying out Fast Heating with microwave.Because copper is different from the oxidation-reduction potential of nickel and occur at different temperature to reduce and particle generates (Cu
2+for 433K, Ni
2+for 463K), therefore thinking and first generate copper nano-particle, take copper nano-particle as core and at the shell of its Surface Creation nickel along with temperature raises.Through confirming, the nano particle obtained is the nano particle that nickel concentration is high near particle surface.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-224420 publication
Patent document 2: Japanese Unexamined Patent Publication 2003-055703 publication
Non-patent literature
Non-patent literature 1: the former Baode of intelligence Yang, mound and field hero two, " employing synthesis and the magnetic property (マ イ Network ロ ripple adds Hot The い Cu-Ni alloy Na ノ particle synthesis と magnetic mood Quality) of the Cu-Ni alloy nano particle of heating using microwave ", Japanization association the 89th Spring Meeting (2009) preliminary draft collection, 2D2-34 in mountain
Non-patent literature 2: intelligence centre in mountain, the former Baode of mound and field hero two, another 1, " employing synthesis and the magnetic property (the property Quality of マ イ Network ロ ripple The い Cu core-Nishell Na ノ particle synthesis と magnetic mood) of the Cu core-Ni core/shell nanoparticles of microwave ", the 3rd Japanese electromagnetic wave energy application association forum preliminary draft collection, P190,18 ~ 20 November in 2009
Summary of the invention
The technical problem that invention will solve
The object of the present invention is to provide a kind of that can be applicable to the purposes such as such as catalyst, magnetic material, electrode, that nickel forms core, cobalt forms shell nickel-cobalt nanometer particle and manufacture method thereof.
For the means of technical solution problem
Nickel-cobalt nanometer particle of the present invention possesses the core that formed by nickel in fact and covers in fact whole of this core and the shell formed by cobalt in fact.
In addition, the feature of nickel-cobalt nanometer particle of the present invention is, preferably: nickel content is in the scope of 30 ~ 90 quality %, and cobalt content is in the scope of 10 ~ 70 quality %, average grain diameter is in the scope of 10 ~ 200nm, and the thickness of above-mentioned shell is in the scope of 1 ~ 50nm.
In addition, the manufacture method of nickel-cobalt nanometer particle of the present invention possesses following operation: the operation mixture heating containing nickel salt, cobalt salt and primary amine being obtained complex reaction liquid; With the operation above-mentioned complex reaction liquid heating being obtained nickel-cobalt nanometer particle slurry.
In addition, the manufacture method of nickel-cobalt nanometer particle of the present invention possesses following operation: the operation mixture heating containing nickel particle, cobalt salt and primary amine being obtained complex reaction liquid; With the operation above-mentioned complex reaction liquid heating being obtained nickel-cobalt nanometer particle slurry.
In addition, the manufacture method of nickel-cobalt nanometer particle of the present invention possesses following operation: the operation mixture heating containing cobalt salt and primary amine being obtained complex reaction liquid; With in above-mentioned complex reaction liquid, add nickel particle after carry out heating the operation obtaining nickel-cobalt nanometer particle slurry.
In addition, the feature of the manufacture method of nickel-cobalt nanometer particle of the present invention is, preferably: above-mentioned nickel salt and cobalt salt have any one in the straight-chain carboxylic acid's base or the group shown in following structural formula (1) that carbon number is 1 ~ 3 respectively.
(wherein, substituent R a ~ Rc is selected from the group in methyl, ethyl, phenyl and halogen, and substituent R a ~ Rc can be identical, also can be different.)
In addition, the manufacture method of nickel-cobalt nanometer particle of the present invention is preferred: above-mentioned carboxylic acid group is formyl or acetoxy group, and the group shown in structure above (1) is acetylacetone,2,4-pentanedione dentate.
In addition, the manufacture method of nickel-cobalt nanometer particle of the present invention is preferred: in the operation obtaining above-mentioned nickel-cobalt nanometer particle slurry, use microwave as heater means.
Invention effect
Nickel-cobalt nanometer particle of the present invention is made up of the core of nickel and the shell of cobalt, is therefore suitable for the purposes such as such as catalyst, magnetic material, electrode.In addition, by regulating cobalt content according to these purposes, cost can be made reasonable, in addition, in above-mentioned each purposes, the performance of cobalt can also be played to greatest extent.
In addition, according to the manufacture method of nickel-cobalt nanometer particle of the present invention, nickel-cobalt nanometer particle of the present invention compatibly can be obtained.
Accompanying drawing explanation
Fig. 1 is the figure of the structure representing each nickel acetate complex compound, and (a) represents that two nibble coordination, and (b) expression singly nibbles coordination, and (c) represents the state of Carboxylic Acid Ions coordination in outer ring.
Fig. 2 A is transmission electron microscope (the TEM:Transmission Electron Microscope) photo about the nickel-cobalt nanometer particle obtained in embodiment 1.
Fig. 2 B is the figure of electronic diffraction (ED:Electron diffraction) pattern represented from the TEM photo region of Fig. 2 A.
Fig. 3 is the figure of the map image utilizing STEM-EDS to obtain representing the nickel-cobalt nanometer particle obtained in embodiment 1.
Fig. 4 is the figure of the result of the line analysis utilizing STEM-EDS to obtain representing the nickel-cobalt nanometer particle obtained in embodiment 1.
Fig. 5 is the figure of the result of the SQUID Magnetisability determination representing the nickel-cobalt nanometer particle of embodiment 1,2, the nickel particles of comparative example 8 and commercially available cobalt particle.
Fig. 6 is the figure of the map image utilizing STEM-EDS to obtain representing the nickel-cobalt nanometer particle obtained in embodiment 2.
Fig. 7 is the figure of the map image utilizing STEM-EDS to obtain representing the nickel-cobalt nanometer particle obtained in embodiment 4.
Detailed description of the invention
Below embodiments of the present invention are described.
[nickel-cobalt nanometer particle]
Nickel-the cobalt nanometer particle of present embodiment (below sometimes by it referred to as " nano particle ") comprises the core that formed by nickel in fact and covers in fact whole of core and the shell formed by cobalt in fact.Here, nano particle is not got rid of core and is contained a small amount of cobalt and shell contains a small amount of nickel fractions.Namely, " core formed by nickel in fact " refers to the existence allowing a small amount of cobalt inevitably contained in core, but major part is formed by nickel, " shell formed by cobalt in fact " refers to the existence allowing a small amount of nickel inevitably contained in shell, but major part is formed by cobalt.In addition, the shell of nano particle preferably covers whole of core, but is not limited to this, does not get rid of the form that a part of nickel exposes.That is, " cover in fact the whole face of core " and not only refer to that shell fully covers the form of core, also allow to be formed discontinuously and the form exposed of core local at the scope inner casing not damaging effect of the present invention (function of nano particle), but the major part on the surface of nickel-cobalt nanometer particle is become by hull shape.In addition, nano particle also can be the formation between the shell and nickel of cobalt with inner casing.
The nano particle such as nickel content of present embodiment is 30 ~ 90 quality % and cobalt content is 10 ~ 70 quality %.About the cobalt content of nano particle, can consider that characteristic, cost etc. required in the purposes be suitable for suitably set, but when lower than 10 quality %, such as likely core greatly can expose and fully cannot obtain the effect of catalytic performance, magnetic characteristic from shell, and when more than 70 quality %, cost can improve.
The average grain diameter of nano particle is such as 10 ~ 200nm, is preferably 10 ~ 150nm.When the average grain diameter of nano particle is lower than 10nm, aggegation is violent and dispersiveness is deteriorated, and is likely not suitable as the Paste Materials of such as catalyst or electrode etc.On the other hand, when the average grain diameter of nano particle is more than 200nm, specific area can diminish, and likely cannot play such as high catalytic performance.In addition, the preferred Cv value of the nano particle [coefficient of variation; Ratio σ/the d of average grain diameter (d) and standard deviation (σ)] be 0.01≤σ/d≤0.5.
The thickness of the shell of nano particle is such as 1 ~ 50nm, is preferably 5 ~ 20nm.About the thickness of the shell of nano particle, when lower than 1nm, cobalt amount is very few, likely cannot play catalytic activity and magnetic characteristic that cobalt itself has fully.And when more than 50nm, cost can improve.
The shape of nano particle can be such as spherical, intend spherical, the various shape such as long ball shape, cube sample, truncated tetrahedron sample, suspension shape, regular octahedron sample, decahedra sample, regular dodecahedron sample, but from the view point of the packed density improved when such as nickel nano particle being used for the electrode of electronic device, preferably spherical or intend spherical, more preferably spherical.Here, the shape of nano particle is by being undertaken observing confirming by SEM (SEM).
The nano particle of present embodiment described above can regulate cobalt content according to purposes such as catalyst, magnetic material, electrodes thus make cost reasonable, in addition, compatibly can also play the performance of cobalt.
[manufacture method of nickel-cobalt nanometer particle]
Then, the manufacture method of the nickel-cobalt nanometer particle for compatibly obtaining nickel-cobalt nanometer particle is described.As the manufacture method (below sometimes referred to as " manufacture method of nano particle ") of the nickel-cobalt nanometer particle of present embodiment, enumerate first case ~ three example.
< first case >
The first case of the manufacture method of nano particle has following operation: the operation mixture heating containing nickel salt, cobalt salt and primary amine being obtained complex reaction liquid; With the operation heating of complex reaction liquid being obtained nickel-cobalt nanometer particle slurry.
< second case >
The second case of the manufacture method of nano particle has following operation: the operation mixture heating containing nickel particle, cobalt salt and primary amine being obtained complex reaction liquid; With the operation heating of complex reaction liquid being obtained nickel-cobalt nanometer particle slurry.That is, nickel particle is used to replace the nickel salt of first case.
The routine > of < the 3rd
3rd example of the manufacture method of nano particle has following operation: the operation mixture heating containing cobalt salt and primary amine being obtained complex reaction liquid; With in complex reaction liquid, add nickel particle after carry out heating the operation obtaining nickel-cobalt nanometer particle slurry.That is, not the nickel particle adding second case in complex reaction liquid generative process, but add in nickel-cobalt nanometer particle slurry generative process.
Second case and the 3rd example are all preferred embodiment, but when adding nickel particle, need to make nickel particle high dispersive in complex reaction liquid, when disperseing insufficient, likely cannot carry out the uniform formation of crust of cobalt.It means, does not need the first case of high dispersive process to be most preferred method.
[obtaining the operation of complex reaction liquid]
In this operation, by the mixture containing nickel salt, cobalt salt and primary amine being carried out heat (first case), the mixture containing nickel particle, cobalt salt and primary amine being carried out heat (second case), maybe the mixture containing cobalt salt and primary amine carried out heat (the 3rd example), thus the complex compound of generating nickel and/or cobalt, obtain complex reaction liquid.Here, complex reaction liquid refers to reaction by nickel salt and/or cobalt salt and primary amine and the reaction solution (product) generated.Think complex reaction liquid in first case containing nickel complex and cobalt complex as complex compound, in second case and the 3rd example containing cobalt complex as complex compound.By heating complex reaction liquid, nickel ion and/or the cobalt ions of nickel complex and/or cobalt complex are reduced, the Carboxylic Acid Ions of coordination on this ion decomposes simultaneously, the final generation Ni of 0 valency and/or the Co of 0 valency, thus generates the nano particle of nucleocapsid structure.
(nickel salt, cobalt salt)
Nickel salt and cobalt salt are all not particularly limited, and preferably have any one or two kinds of in the straight-chain carboxylic acid's base or the group shown in following structural formula (1) that carbon number is 1 ~ 3.Group shown in following structural formula (1) is 1,3-diketo (beta-diketon polymerization of olefin using catalyst base).The salt of nickel salt and cobalt salt can be salt of the same race also can be xenogenesis.In addition, nickel salt and cobalt salt can be all anhydrides, also can be hydrates.
(wherein, substituent R a ~ Rc is selected from the group in methyl, ethyl, phenyl and halogen.Substituent R a ~ Rc can be identical, also can be different.)
Having carbon number is that the nickel salt of straight-chain carboxylic acid's base of 1 ~ 3 is specially nickel formate, nickel acetate or propionic acid nickel, particularly preferably uses nickel formate or nickel acetate.In addition, having carbon number is that the cobalt salt of straight-chain carboxylic acid's base of 1 ~ 3 is specially cobaltous formate, cobalt acetate or Cobaltous propionate, particularly preferably uses cobaltous formate or cobalt acetate.These nickel carboxylates and carboxylic acid cobalt can be anhydrides, also can be hydrates.In addition, it is also conceivable to use the inorganic salts such as nickel chloride (cobalt chloride), nickel nitrate (cobalt nitrate), nickelous sulfate (cobaltous sulfate), nickelous carbonate (cobalt carbonate), nickel hydroxide (cobalt hydroxide) to replace nickel carboxylate or carboxylic acid cobalt, but when inorganic salts, owing to dissociating, (decomposition) is high temperature, therefore need to heat at higher temperatures in the process of reducing to the nickel ion (or nickel complex) after dissociating or cobalt ions (or cobalt complex), thus not preferred.
As the group shown in structure above (1), such as can enumerate 2,4-pentadione (another name: acetylacetone,2,4-pentanedione dentate), 2,4-acetyl butyryl base, 3,5-heptadione base, 1-phenyl-1, chloro-1, the 3-diacetyl bases of 3-diacetyl base, 1-etc., wherein preferably use acetylacetone,2,4-pentanedione dentate.
About the use level of nickel salt, cobalt salt, such as convert in metal, relative to total amount 100 mass parts of the nickel in complex reaction liquid and cobalt, be preferably set to that nickel is 30 ~ 90 mass parts, cobalt is 10 ~ 70 mass parts, be more preferably set to that nickel is 50 ~ 80 mass parts, cobalt is 20 ~ 50 mass parts.The use level of cobalt can consider that characteristic, cost etc. required in the purposes of nano particle suitably set, but when total amount 100 mass parts relative to nickel and cobalt that converts in metal is lower than 10 mass parts, such as likely core can greatly expose from shell and fully cannot obtain the effect of catalytic performance and magnetic characteristic, and when more than 70 mass parts, cost can improve.
(nickel particle)
About the nickel particle used in the second case of the manufacture method of nano particle and the 3rd example, the not size of defined particle size, but the nickel particle preferably using the particle diameter of such as 5 ~ 200nm.When particle diameter is lower than 5nm, aggegation is violent, is likely also difficult to dispersion in a liquid.And when particle diameter is more than 200nm, the specific area of particle becomes too small, likely cannot react fully.In addition, the shape preference of nickel particle is as spherical, sphaeroid etc., but most preferably spherical.
About the addition of nickel particle, convert in metal, relative to total amount 100 mass parts of the nickel in complex reaction liquid and cobalt, be preferably set to 30 ~ 90 mass parts, be more preferably set as 50 ~ 80 mass parts.
(primary amine)
Primary amine can form complex compound with nickel ion or cobalt ions, effectively plays the reducing power to nickel complex (or nickel ion).On the other hand, secondary amine, due to greatly sterically hindered, likely can hinder the good formation of nickel complex or cobalt complex, and tertiary amine, owing to not having the reducing power of nickel ion or cobalt ions, therefore all can not use.
As long as primary amine can form the primary amine of complex compound with nickel ion or cobalt ions, be not particularly limited, the primary amine at normal temperatures for solid or liquid can be used.Here, normal temperature refers to 20 DEG C ± 15 DEG C.For the primary amine of liquid also plays the effect of organic solvent when forming nickel complex or cobalt complex under normal temperature.In addition, even under normal temperature be the primary amine of solid, as long as by the primary amine being heated to be liquid or with an organic solvent dissolving of more than 100 DEG C, there is no special problem.
Primary amine also plays the effect of dispersant, nickel complex or cobalt complex can be made to disperse well in reactant liquor, therefore, it is possible to suppress the aggegation between particle when carrying out heat resolve to obtain nano particle to nickel complex or cobalt complex after complex compound is formed.Primary amine can be primary aromatic amine, but from the view point of the easiness that the nickel complex in reactant liquor is formed or cobalt complex is formed, preferred aliphat primary amine.The particle diameter of Armeen such as by regulating the length of its carbochain can control generated nano particle is particularly favourable when manufacture average grain diameter is the nano particle of 10 ~ 200nm.From the view point of controlling the particle diameter of nano particle, Armeen preferably from its carbon number be choice for use the primary amine of about 6 ~ 20.Carbon number is more, and the particle diameter of the nano particle obtained becomes less.As such amine, such as, can enumerate octylame, trioctylamine, dioctylamine, cetylamine, lauryl amine, tetradecy lamine, stearylamine, oleyl amine, nutmeg amine, lauryl amine etc.Such as oleyl amine, owing to existing with liquid condition under the temperature conditions in nano particle generative process, therefore can carry out the reaction in homogeneous solution effectively.
Primary amine, owing to playing the effect of coating material when the generation of nano particle, also can suppress secondary aggegation even if therefore remove after primary amine.In addition, the easiness of the process operation from the view point of the solid constituent of nano particle and the washing procedure of solvent or unreacted primary amine etc. of the rear generation of separating reducing reaction, primary amine is also preferred.In addition, the easiness of reaction controlling when obtaining nano particle from the view point of reduced nickel complex compound or cobalt complex, the preferred boiling point of primary amine is higher than the primary amine of reduction temperature.That is, in Armeen, the Armeen of preferred boiling point more than 200 DEG C, preferred carbon number is more than 9.Here, such as carbon number is the aliphatic amine C of 9
9h
21the boiling point of N (nonyl amine) is 201 DEG C.About the amount of primary amine, convert in metal, relative to the total amount 1mol of nickel and cobalt, preferably use more than 2mol, more preferably use more than 2.5mol, preferably use more than 4mol.The upper limit of the amount of primary amine is not particularly limited, but such as from the view point of productivity ratio, is preferably set to the total amount 1mol that converts relative to nickel and cobalt in metal for below 20mol left and right.
The nickel ion of divalent replaces spike and known as dentate, and the dentate of the complex compound of formation may according to temperature, concentration and easily exchanged by dentate and make complexing change.Such as obtain in the operation of reactant liquor heating the mixture of nickel carboxylate and primary amine, if consider, the carbon chain lengths of the amine used etc. is sterically hindered, then such as Carboxylic Acid Ions (R as shown in Figure 1
1cOO, R
2cOO) likely nibble coordination (a) with two or singly nibble coordination (b) any one carry out coordination, and then also may take the structure (c) that there is Carboxylic Acid Ions in outer ring when the concentration excess of amine.In order to make homogeneous solution under the reaction temperature (reduction temperature) of target, at least one place coordination at least in the dentate of A, B, C, D, E, F is needed to have primary amine.In order to take this state, in reaction solution, needing excessively there is primary amine, preferably at least there is more than 2mol relative to nickel ion 1mol, more preferably there is more than 2.5mol, preferably there is more than 4mol.
Think that cobalt ions also takes the behavior similar with nickel ion to form complex compound.Therefore, primary amine also needs excessive existence relative to cobalt ions, preferably at least there is more than 2mol relative to cobalt ions 1mol, more preferably there is more than 2.5mol, preferably there is more than 4mol.
Complex reaction at room temperature also can be carried out, but in order to reliably and more effectively react, heats at the temperature preferably more than 100 DEG C.This heating is such as using the hydrate of the hydrate of the nickel carboxylate of nickel acetate tetrahydrate and so on or carboxylic acid cobalt as advantageous particularly when nickel salt or cobalt salt.Heating-up temperature is by being preferably set to temperature more than 100 DEG C, being more preferably set as the temperature of more than 105 DEG C, the dentate substitution reaction of the water of coordination of coordination on nickel carboxylate or carboxylic acid cobalt and primary amine is carried out effectively, this hydrone as complex ligand base can be made to dissociate, and then can this water be discharged to outside system, thus can form complex compound efficiently.Such as, nickel acetate tetrahydrate is owing at room temperature taking 2 waters of coordination and there is the complex structure of 2 hydrones as two 2 acetic acid ions nibbling dentate, outer ring, therefore complexing is carried out efficiently to be replaced by the dentate of these 2 waters of coordination and primary amine, preferably by carrying out heating at the temperature higher than 100 DEG C thus making this hydrone as complex ligand base dissociate.In addition, be reliably separated, complete the complex reaction of leading portion from the view point of the process of the heat reduction with follow-up nickel complex (or nickel ion) and cobalt complex (or cobalt ions), heating-up temperature is preferably less than 175 DEG C.Therefore, heating when being formed about complex compound, such as preferably carries out at 105 ~ 175 DEG C.More preferably heating-up temperature is 125 ~ 160 DEG C.
Heat time suitably can determine according to the content of heating-up temperature, each raw material, but from the view point of making complex reaction reliably complete, is preferably set to more than 15 minutes.The upper limit of heat time is not particularly limited, but from the view point of saving energy consumption and activity time, long-time heating is unhelpful.In addition, the method for this heating is not particularly limited, such as, can be the heating utilizing the thermal mediums such as oil bath, also can be the heating utilizing microwave irradiation.
Complex reaction confirms by the change of solution colour after heating solution nickel salt and/or cobalt salt and primary amine are mixed to get.In addition, this complex reaction can also confirm by the following method: such as use uv-visible absorption spectra determinator, the wavelength that the absorption of the absorption spectrum that the wavelength region being determined at 300nm ~ 750nm observes is maximum, confirmed relative to the displacement of the reactant liquor of the maximum absorption wavelength (such as nickel acetate tetrahydrate, its maximum absorption wavelength is 710nm) of raw material by observation.
After having carried out the complexing of nickel salt and/or cobalt salt and primary amine, by utilizing the methods such as microwave irradiation to heat as will be explained later the reactant liquor obtained, the nickel ion of nickel complex and/or the cobalt ions of cobalt complex are reduced, on nickel ion or cobalt ions, the Carboxylic Acid Ions of coordination decomposes simultaneously, and final to generate containing oxidation number is the nickel of 0 valency and/or the nano particle of cobalt.Usually, nickel carboxylate and carboxylic acid cobalt are slightly solubility under taking water as the condition beyond solvent, and as the last stage utilizing the heat reduction of microwave irradiation to react, the solution containing nickel carboxylate or carboxylic acid cobalt needs to make homogeneous reaction solution.On the other hand, think that the primary amine used in present embodiment is liquid under serviceability temperature condition, and liquefied by coordination on nickel ion or cobalt ions, thus form homogeneous reaction solution.
(organic solvent)
In order to more effectively carry out the reaction in homogeneous solution, also can newly add the organic solvent different from primary amine.Time with an organic solvent, organic solvent and nickel salt or cobalt salt and primary amine can be mixed simultaneously, but add organic solvent after carrying out complexing if first nickel salt or cobalt salt mixed with primary amine, then primary amine can effectively coordination on nickel ion or cobalt ions, thus more preferably.As spendable organic solvent, as long as do not hinder the organic solvent of the complexing of primary amine and nickel ion or cobalt ions, be not particularly limited, such as can use carbon number be 4 ~ 30 ether system organic solvent, the carbon number saturated or undersaturated hydrocarbon system organic solvent that is 7 ~ 30, the carbon number alcohol system organic solvent etc. that is 8 ~ 18.In addition, also can use from the view point of under the heating condition utilizing microwave irradiation etc., the organic solvent used preferably selects boiling point to be the organic solvent of more than 170 DEG C, more preferably selects boiling point to be organic solvent in the scope of 200 ~ 300 DEG C.As the object lesson of such organic solvent, such as, TEG, octyl ether etc. can be enumerated.
[obtaining the operation of nickel-cobalt nanometer particle slurry]
In this operation, by heating complex reaction liquid, nickel complex and/or cobalt complex (nickel ion and/or cobalt ions) are reduced into metal and generate nano particle.Such as, in first case, think that the mixture of nickel complex and cobalt complex is reduced, when there is thermal decomposition, nickel complex first at a lower temperature thermal decomposition occurs and reduced by amine compared with cobalt complex, nickel particles forms core, and the surface of this core is formed the shell of cobalt.Usually, cobalt complex by thermal decomposition dentate dissociate, by Co
2+complex compound formed Co (0 valency) nano particle.On the other hand, in the present invention, under excessive oleyl amine exists, take Ni as catalyst, cobalt complex at than usually low temperature by Co
2+be reduced into Co (0 valency) (complex compound dissociates).
By heating complex reaction liquid, complex reaction liquid is reduced, and complex compound is thermal decomposited.From the view point of effectively carrying out reduction reaction, heating-up temperature is preferably more than 200 DEG C, is more preferably more than 220 DEG C.From the view point of effectively processing, heating-up temperature is preferably less than 270 DEG C, is more preferably about less than 250 DEG C.Such as be described for nickel, in order to generate the nano particle with uniform grading, needing to make nickel complex evenly in the operation obtaining complex reaction liquid and generate fully and occur simultaneously at core complex reaction liquid being heated to the Ni (0 valency) obtaining being generated by the reduction of nickel ion in the operation of nickel-cobalt nanometer particle slurry and grow.That is, by regulating the heating-up temperature of the operation obtaining complex reaction liquid in above-mentioned specific scope, make it lower than the heating-up temperature of the operation obtaining nickel-cobalt nanometer particle slurry effectively, thus easily generate particle diameter and the unified particle of shape.Such as, when in the operation obtaining complex reaction liquid, heating-up temperature is too high, then the generation of nickel complex is carried out with the reduction reaction to Ni (0 valency) simultaneously, is likely difficult to generate the unified particle of shape of particle in the operation obtaining nickel-cobalt nanometer particle slurry.In addition, when the heating-up temperature of the operation obtaining nickel-cobalt nanometer particle slurry is too low, owing to slowing to the reduction reaction of Ni (0 valency), the generation of core reduces, therefore not only particle becomes large, and also not preferred from the viewpoint of the yield of nano particle.
In this operation, heating source can also be other except oil bath, but is preferably microwave.When to complex reaction liquid irradiating microwaves, microwave infiltrates in complex reaction liquid, is heated and heat up fast and homogeneous heating by inside.Thus, complex reaction liquid entirety can be made to reach required temperature equably, the reduction of nickel or cobalt particle, karyogenesis, each process of nucleus growth are produced in solution entirety simultaneously, and result is the monodispersed particle that easily can manufacture narrow diameter distribution at short notice.In addition, the use wavelength of microwave is not particularly limited, such as, be 2.45GHz.
The nano particle slurry heating of complex reaction liquid obtained, such as by after standing separation removing supernatant, uses suitable solvent to carry out washing and carries out drying, can obtain nano particle.
In the operation obtaining nickel-cobalt nanometer particle slurry, as required, above-mentioned organic solvent can also be added in complex reaction liquid.In addition, as described above, directly being used as organic solvent by the primary amine used in complex reaction is the preferred embodiment of the present invention.In the operation that complex reaction liquid is carried out heating as required and add solvent be not particularly limited, such as can use alcohol or the non-polar solvens etc. such as octanol (octyl group alcohol).As described above, when using oleyl amine as primary amine, solvent can omit.
The manufacture method of the nano particle of present embodiment can also comprise arbitrary operation except above-mentioned operation.In addition, the arbitrary process such as the interpolation of coating material can also such as be carried out as described later.In addition, the manufacture method of the nano particle of present embodiment utilizes microwave etc. to carry out the method for reducing heated owing to adopting in the operation obtaining nickel-cobalt nanometer particle slurry, does not therefore need to use powerful reducing agent.But in the scope not damaging invention effect, there is the material with reduction in complex reaction liquid is that it doesn't matter.
(interpolation of coating material)
In the manufacture method of the nano particle of present embodiment, as the coating material of the particle diameter for controlling nano particle, such as, can add long-chain carboxylic acid or the carboxylates etc. such as macromolecule resin, myristic acid, oleic acid such as PVP (PVP), polymine, polyacrylamide.But when the finishing amount of the nano particle obtained is many, likely can cause harmful effect as impurity according to purposes, the finishing amount after therefore being washed by the nano particle obtained is preferably the least possible.Such as when conductive paste for nickel electrode, if nickel particles made paste and at high temperature burn till, then can cause the minimizing of packed density, likely can produce splitting or crackle.Therefore, about the addition of coating material, relative to total amount 100 mass parts of nickel element, be preferably set to more than 0.1 and in scope below 100 mass parts.Coating material can add in stage of mixture of nickel carboxylate in complex reaction liquid formation process and primary amine, add in the complex reaction liquid that also can obtain in complex reaction liquid formation process, but interpolation be preferably complex reaction opportunity after or nickel nano particle generation after.
According to the manufacture method of the nickel-cobalt nanometer particle of present embodiment discussed above, average grain diameter can be obtained and be 10 ~ 200nm, there is nickel-cobalt nanometer particle that Cv value [coefficient of variation: the ratio σ/d of average grain diameter (d) and standard deviation (σ)] is the narrow domain size distribution of 0.01≤σ/d≤0.5, that be made up of the core of nickel and the shell of cobalt.
Embodiment
Enumerate embodiment and comparative example to further illustrate the present invention, but the present invention is not limited to the embodiment of following explanation.
About the particle diameter of nano particle, utilizing transmission electron microscope (TEM) to take the photo of nanoparticle powder, from wherein randomly drawing 200, obtaining its average grain diameter and standard deviation.In addition, result obtains Cv value (=σ/d) value thus.In addition, utilize the sweep type transmission electron microscope (STEM-EDS) possessing energy dispersion type x-ray analysis equipment, confirm the nickel of the particle obtained, the existence of cobalt or respective concentration by surface analysis, line analysis.About the thickness of crust of cobalt layer, as shown in Figure 4, calculated the nickel on the line of 1 particle crosscut, cobalt atom concentration by STEM-EDS.According to this provision of on-line analysis methodology, the atomic concentration in the only core portion of generated spherical particle cannot be calculated.That is, the concentration of simple particle surface can be shown by the analysis near particle surface, but the analysis result near particle central authorities is the summation of the concentration of the metallic element of particle surface and inner (core).Therefore, in the result of this analysis, using the thickness of the mean value of the thickness of layer higher for the intensity of cobalt compared with nickel as crust of cobalt layer.About the composition of obtained particle, analyzed by inductively coupled plasma luminescence spectrometer method (ICP-AES:Inductively Coupled Plasma-Atomic Emission Spectrometry).
(embodiment 1)
In cobaltous formate dihydrate 12.5mmol and nickel acetate tetrahydrate 12.5mmol, add oleyl amine 275mmol, heat 20 minutes under nitrogen flowing, at 120 DEG C, thus obtain complex reaction liquid.Then, by this complex reaction liquid heating using microwave to 225 DEG C, this temperature is kept 30 minutes, thus obtains nano particle slurry.By nano particle slurry standing separation, after removing supernatant, with hexanes wash 3 times.Afterwards, within 6 hours, nano particle is obtained with the vacuum drier drying maintaining 60 DEG C.
TEM (Transmission Electron Microscope, the transmission electron microscope) photo of the nano particle obtained is shown in Fig. 2 A, ED (electronic diffraction: Electron diffraction) pattern is shown in Fig. 2 B.Define the spherical uniform particle that average grain diameter is 82nm.In addition, by the known nano particle of ED pattern be the metal of fcc structure of oxide-free.In addition, by ICP-AES, the metal composition of the particle obtained is confirmed, result Ni, Co are respectively 47.6 quality %, 47.3 quality %, and therefore mol is than being Ni/Co=1.0, very consistent with feed ratio (rate of charge (mol%) of Ni salt and Co salt).The photo of STEM-EDS map image is shown in Fig. 3 equally.Nickel is distributed in the central authorities of nano particle and cobalt is distributed in the surface of nano particle in a large number, it can thus be appreciated that be the nano particle with Ni (core)-Co (shell) structure.
In addition, the result of the line analysis of particle is as shown in Figure 4 known, and the thickness of crust of cobalt layer (shell) is approximately 13nm.In addition, the result of the magnetic saturation obtained by SQUID Magnetisability determination (unit: emu/g) is shown in Fig. 5.Compared with known with commercially available cobalt nanometer particle (particle diameter is below 50nm, Aldrich system), magnetic saturation is lower, but magnetic saturation significantly increases compared with the nano particle of comparative example 8 described later.
(embodiment 2 ~ 7, comparative example 1 ~ 8)
In embodiment 2 ~ 7 and comparative example 1 ~ 8, except changing the kind of nickel salt and cobalt salt and the kind obtaining the heating source in the operation of nano particle slurry and reaction temperature (heating-up temperature), prepare nano particle according to embodiment 1.Its result is shown in table 1 together with embodiment 1.In addition, in each embodiment and each comparative example, the mol ratio of oleyl amine/(Ni salt+Co salt) is 10.In addition, about the heating means of complex reaction liquid, except using the embodiment 3 of oil bath, all carry out with heating using microwave.
In addition, the result of the SQUID Magnetisability determination of the nickel-cobalt nanometer particle of embodiment 1,2, the nickel particles of comparative example 8 and commercially available cobalt particle is shown in Fig. 5, the TEM photo of the nickel-cobalt nanometer particle obtained in embodiment 2 is shown in Fig. 6, the TEM photo of the nickel-cobalt nanometer particle obtained in embodiment 4 is shown in Fig. 7.
Confirmed by table 1, by using formic acid, acetate or acetylacetonate as nickel salt and cobalt salt, average grain diameter can be obtained and be 10 ~ 200nm and crust of cobalt layer is the nickel-cobalt nanometer particle of 1 ~ 50nm.In addition, confirmed by Fig. 5, the nickel-cobalt nanometer particle of embodiment 1 and 2 is close to the magnetic saturation of cobalt.
Table 1
(embodiment 8)
Be 100nm and the nickel particles 25mmol that Cv value is 0.14 (does not use cobalt salt, obtains complex reaction liquid according to above-mentioned first case from nickel acetate tetrahydrate, carried out heating and the particle obtained at cobaltous formate dihydrate 12.5mmol and average grain diameter; Comparative example 8) in add oleyl amine 125mmol, heat 20 minutes under nitrogen flowing, at 120 DEG C, thus obtain complex reaction liquid.Then, by this complex reaction liquid heating using microwave to 225 DEG C, this temperature is kept 30 minutes, thus obtain nickel-cobalt nanometer particle slurry.
By above-mentioned nickel-cobalt nanometer particle slurry standing separation, after removing supernatant, with hexanes wash 3 times.Afterwards, with the vacuum drier maintaining 60 DEG C dry 6 hours, nickel-cobalt nanometer particle is obtained.The average grain diameter of the nickel-cobalt nanometer particle of gained is 120nm, and the Cv value of size distribution is 0.15, and the thickness of crust of cobalt layer is 17nm.
(embodiment 9)
In cobaltous formate dihydrate 12.5mmol, add oleyl amine 125mmol, heat 20 minutes under nitrogen flowing, at 120 DEG C, thus obtain complex reaction liquid.Then, in this complex reaction liquid, add average grain diameter be 100nm and the nickel particles 25mmol that Cv value is 0.14 (does not use cobalt salt, obtains complex reaction liquid by nickel acetate tetrahydrate, be heated and obtained particle; Comparative example 8) and after fully stirring, with heating using microwave to 225 DEG C, this temperature is kept 30 minutes, thus obtain nickel-cobalt nanometer particle slurry.
By above-mentioned nickel-cobalt nanometer particle slurry standing separation, after removing supernatant, with hexanes wash 3 times.Afterwards, with the vacuum drier maintaining 60 DEG C dry 6 hours, nickel-cobalt nanometer particle is obtained.The average grain diameter of the nickel-cobalt nanometer particle of gained is 117nm, and the Cv value of size distribution is 0.15, and the thickness of crust of cobalt layer is 15nm.
Above, for illustrative purposes embodiments of the present invention have been described in detail, but the present invention is not limited to above-mentioned embodiment.This international application advocates the priority based on No. 2010-60773, the Japanese patent application of filing an application on March 17th, 2010, and is incorporated herein by its full content.
Claims (9)
1. a manufacture method for nickel-cobalt nanometer particle, described nickel-cobalt nanometer particle possesses the core that formed by nickel in fact and covers in fact whole of described core and the shell formed by cobalt in fact, and described manufacture method possesses following operation:
Mixture heating containing nickel salt, cobalt salt and primary amine is obtained the operation of complex reaction liquid; With the operation described complex reaction liquid heating being obtained nickel-cobalt nanometer particle slurry.
2. a manufacture method for nickel-cobalt nanometer particle, described nickel-cobalt nanometer particle possesses the core that formed by nickel in fact and covers in fact whole of described core and the shell formed by cobalt in fact, and described manufacture method possesses following operation:
Mixture heating containing nickel particle, cobalt salt and primary amine is obtained the operation of complex reaction liquid; With the operation described complex reaction liquid heating being obtained nickel-cobalt nanometer particle slurry.
3. a manufacture method for nickel-cobalt nanometer particle, described nickel-cobalt nanometer particle possesses the core that formed by nickel in fact and covers in fact whole of described core and the shell formed by cobalt in fact, and described manufacture method possesses following operation:
Mixture heating containing cobalt salt and primary amine is obtained the operation of complex reaction liquid; With in described complex reaction liquid, add nickel particle after carry out heating the operation obtaining nickel-cobalt nanometer particle slurry.
4. the manufacture method of the nickel-cobalt nanometer particle according to any one of claims 1 to 3, wherein, the nickel content of described nickel-cobalt nanometer particle is in the scope of 30 ~ 90 quality %, cobalt content is in the scope of 10 ~ 70 quality %, average grain diameter is in the scope of 10 ~ 200nm, and the thickness of described shell is in the scope of 1 ~ 50nm.
5. the manufacture method of nickel-cobalt nanometer particle according to claim 1, wherein, described nickel salt has any one in the straight-chain carboxylic acid's base and the group shown in following structural formula (1) that carbon number is 1 ~ 3,
Wherein, substituent R a ~ Rc is selected from the group in methyl, ethyl, phenyl and halogen, and substituent R a ~ Rc can be identical, also can be mutually different.
6. the manufacture method of the nickel-cobalt nanometer particle according to any one of claims 1 to 3, wherein, described cobalt salt has any one in the straight-chain carboxylic acid's base and the group shown in following structural formula (1) that carbon number is 1 ~ 3,
Wherein, substituent R a ~ Rc is selected from the group in methyl, ethyl, phenyl and halogen, and substituent R a ~ Rc can be identical, also can be mutually different.
7. the manufacture method of nickel-cobalt nanometer particle according to claim 5, wherein, described carbon number be 1 ~ 3 straight-chain carboxylic acid's base be formyl or acetoxy group, the group shown in described structural formula (1) is acetylacetone,2,4-pentanedione dentate.
8. the manufacture method of nickel-cobalt nanometer particle according to claim 6, wherein, described carbon number be 1 ~ 3 straight-chain carboxylic acid's base be formyl or acetoxy group, the group shown in described structural formula (1) is acetylacetone,2,4-pentanedione dentate.
9. the manufacture method of the nickel-cobalt nanometer particle according to any one of claims 1 to 3, wherein, in the operation obtaining described nickel-cobalt nanometer particle slurry, uses microwave as heater means.
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| PCT/JP2011/056408 WO2011115214A1 (en) | 2010-03-17 | 2011-03-17 | Nickel-cobalt nanoparticle and manufacturing method therefor |
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| RU2568858C2 (en) * | 2013-10-24 | 2015-11-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Кемеровский государственный университет" (КемГУ) | Nanostructured powder of solid cobalt-nickel solution and method of its production |
| JP2015138915A (en) * | 2014-01-23 | 2015-07-30 | 住友金属鉱山株式会社 | Nickel-based alloy fine particle for laminate capacitors, and method for manufacturing the same |
| JP6608378B2 (en) * | 2014-09-30 | 2019-11-20 | 日鉄ケミカル＆マテリアル株式会社 | Method for producing nickel particles |
| CN106141171B (en) * | 2015-04-27 | 2018-06-05 | 中国科学院宁波材料技术与工程研究所 | Hud typed superstructure nano material, its preparation method and application |
| JP6958995B2 (en) * | 2015-09-30 | 2021-11-02 | 日鉄ケミカル＆マテリアル株式会社 | Copper-nickel-cobalt ternary nanoparticles and their manufacturing method, sintered body, current collector and fuel cell |
| CN106834763B (en) * | 2017-01-05 | 2018-06-19 | 东南大学 | A kind of blacker-than-black nanometer column Co and preparation method thereof |
| CN110899718B (en) * | 2018-09-14 | 2022-11-15 | 上海铁路通信有限公司 | Preparation method of large-particle-size cobalt particles with shell-core structures |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101379639A (en) * | 2005-08-01 | 2009-03-04 | 布鲁克哈文科学协会 | Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof |
| JP2009270146A (en) * | 2008-05-02 | 2009-11-19 | Shoei Chem Ind Co | Method for producing silver hyperfine particle |
| JP2009293126A (en) * | 2008-06-05 | 2009-12-17 | Xerox Corp | Method for forming core-shell metal nanoparticle |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003013103A (en) * | 2001-06-26 | 2003-01-15 | Murata Mfg Co Ltd | Method for manufacturing electroconductive powder, electroconductive powder, electroconductive paste and laminated ceramic electronic component |
| JP5063003B2 (en) * | 2006-01-25 | 2012-10-31 | 株式会社日本触媒 | Method for producing copper nanoparticles, copper nanoparticles, conductive composition, and electronic device |
| JP5045015B2 (en) * | 2006-07-28 | 2012-10-10 | セイコーエプソン株式会社 | Method for producing copper formate, method for producing copper particles, and method for producing wiring board |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101379639A (en) * | 2005-08-01 | 2009-03-04 | 布鲁克哈文科学协会 | Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof |
| JP2009270146A (en) * | 2008-05-02 | 2009-11-19 | Shoei Chem Ind Co | Method for producing silver hyperfine particle |
| JP2009293126A (en) * | 2008-06-05 | 2009-12-17 | Xerox Corp | Method for forming core-shell metal nanoparticle |
Non-Patent Citations (1)
| Title |
|---|
| 单分散磁性金属纳米粒子的液相法合成与表征;罗晓华;《中国优秀硕士学位论文全文数据库》;20091215;B020-162 * |
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