CN102811829A - Nickel-cobalt nanoparticle and manufacturing method therefor - Google Patents
Nickel-cobalt nanoparticle and manufacturing method therefor Download PDFInfo
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Abstract
The disclosed nickel-cobalt nanoparticle includes a core, which essentially comprises nickel, and a shell, which essentially completely covers the core and essentially comprises cobalt. The disclosed method for manufacturing said nanoparticle includes: either a step in which a mixture containing a nickel salt or nickel microparticles, a cobalt salt, and a primary amine is heated to produce a reaction solution, or a step in which a mixture containing a cobalt salt and a primary amine is heated to produce a reaction solution; and a step in which the reaction solution is heated to produce a nickel-cobalt nanoparticle slurry.
Description
Technical field
The present invention relates to have the nano particle of the nucleocapsid structure that forms by dissimilar metal.
Background technology
That cobalt nanometer particle is compared with Nano silver grain is more cheap, it is chemically more stable to compare with copper nano-particle, specific catalytic activity and magnetic saturation are higher mutually with nickel particles, so utilizes desirable in its electrode in various catalyst, magnetic material, fuel cell, laminated ceramic capacitor etc.Yet cobalt is a rare metal, and is also more expensive than nickel particles, therefore hopes to develop cobalt particle and the method for making thereof that can bring into play the performance of cobalt with amount still less.In order to bring into play the performance of cobalt well, its particle diameter and particle shape must be controlled evenly.
Generally speaking, the manufacturing approach of metal nanoparticle is broadly divided into physics method and chemical method.The physics method is that the method (comminuting method) of making nano particle is pulverized in the reguline metal, and chemical method is to make metallic atom produce and control the method (agglutination) that its aggegation is made.When utilizing the physics method to pulverize, reducing of particle diameter is limited, and the shape of particle also becomes uneven, is difficult to form uniform particle.Therefore, chemical method is more favourable for the shape of controlling particle or particle diameter.
In addition, utilize the manufacturing approach of the metal nanoparticle of chemical method can be divided into damp process and dry process.Dry process for chemical method; Known have evaporation, laser method, sputtering method, a molten drop spray-on process etc. in CVD (chemical vapour deposition (CVD)) method, the gas, owing to the particle that generates is spherical through high-temperature process, and good crystallinity; But then, the distribution of particle diameter is wide, productivity ratio is also low is shortcoming.And, compare the advantage that has the productivity ratio height, controls particle diameter easily with dry process for being the damp process of representative with the chemical reduction method, therefore being accompanied by the development of nanometer technology has in recent years carried out big quantity research.
In addition, the research of comparing the binary system nano particle (metal composite nano particle) that can expect further that rerum natura embodies with single metal nanoparticle is carried out widely.In addition, be conceived to purposes according to nano particle and need metal with specific character top layer metal,, also study for the binary system nano particle that constitutes nuclear and shell with dissimilar metal as the binary system nano particle as particle.
As such metal nanoparticle with nucleocapsid structure, the metal nanoparticle (patent documentation 1) of thin layer that comprises copper nuclear and copper nuclear surrounded and have the metals such as silver, palladium, platinum, gold of the reduction potential higher than copper is for example disclosed.The manufacturing approach of this metal nanoparticle comprises following steps: in containing the solution of primary amine, tert-butyl group hydroxy-methylbenzene, ascorbic acid, flavonoids etc. are used for reducing agent and form the step of copper nano-particle from the copper precursors that is made up of copper complexs such as copper nitrate, copper chloride, copper formates; With the step that forms the thin layer of metal on the surface of copper nano-particle with reduction potential higher than copper.The metal nanoparticle with nucleocapsid structure of gained has with inferior advantage: owing to be nuclear with the copper particle and it is covered with noble metal; Thereby can in the oxidation that prevents copper, improve the containing ratio of copper; Therefore economy is excellent; And, owing to contain the electrical conductivity metals such as silver more excellent in the thin layer, therefore can form the electrical conductivity distribution more excellent than copper than copper.
In addition; For example also disclose following method: the metal precursor that will contain the 1st metal (for example cobalt) and reduction potential as nano particle 2nd metal (for example platinum) higher than the 1st metal dissolves respectively with suitable organic solvent; Formed each solution is mixed, make the metal nanoparticle (patent documentation 2) of nucleocapsid structure through the 1st metal and the 2nd intermetallic metal substitution reaction.
Patent documentation 1,2 realizes having the nuclear that formed by the low metal of reduction potential through diverse ways and the metal nanoparticle of the shell that formed by the high metal of reduction potential.But can the metal nanoparticle of the nucleocapsid structure that suitably obtain for the manufacturing approach of using patent documentation 1,2 being formed by other dissimilar metal it be unclear that.Particularly for the such close dissimilar metal of oxidation-reduction potential of for example nickel and cobalt, be difficult to think the method that applicable and patent documentation 1,2 are identical.
On the other hand, the inventor is to being that the Cu-Ni alloy that has the reduction potential nickel lower than copper in nuclear and the shell has carried out research and done report (non-patent literature 1,2) with copper.According to the further deep non-patent literature 2 of the research of non-patent literature 1; The method for making of Cu-Ni alloy is following: copper formate and nickel formate are mixed with oleyl amine respectively separately; Mixed liquor through to copper formate at room temperature heats, the mixed liquor of nickel formate is heated under 393K carry out complexing (promptly forming complex compound) thereby the preparation precursor; Mix with the 1-octanol, then, obtain nano particle through carrying out Fast Heating with microwave.Reduction and particle generation (Cu take place under different temperature because the oxidation-reduction potential of copper and nickel is different
2+Be 433K, Ni
2+Be 463K), therefore think to generate copper nano-particle earlier, be nuclear and generate the shell of nickel on its surface along with temperature raises with the copper nano-particle.Through confirming that the nano particle that obtains is near the high nano particle of nickel concentration particle surface.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-224420 communique
Patent documentation 2: TOHKEMY 2003-055703 communique
Non-patent literature
Patent Document 1: Yamauchi Chilean central, Tsukahara Baldor, Wada Yuji, "Use of microwave heating Cu-Ni alloy nanoparticles synthesis and magnetic properties (ma イ black wave heating を with Kei ta Cu-Ni alloy Nano Particles Synthesis and Magnetic's nature), "Chemical Society of Japan 89th Spring Meeting (2009) Preliminary draft set, 2D2-34
Non-patent literature 2: intelligence centre, the former Baode of mound and field male two, 1 in addition, " having used the synthetic and magnetic property (マ イ Network ロ ripple The with the character of the synthetic と magnetic mood of い Cu core-Nishell Na ノ particle) of the Cu nuclear-Ni core/shell nanoparticles of microwave ", the 3rd Japanese electromagnetic wave energy application learn forum preliminary draft collection, P190,18～20 November in 2009 in the mountain
Summary of the invention
The technical problem that invention will solve
The object of the present invention is to provide a kind of can be applicable to purposes such as catalyst, magnetic material, electrode for example, nickel forms nickel-cobalt nanometer particle and the manufacturing approach thereof that nuclear, cobalt form shell.
The means that are used for the technical solution problem
Nickel-cobalt nanometer particle of the present invention possesses in fact nuclear that is formed by nickel and the shell that covers whole of this nuclear in fact and formed by cobalt in fact.
In addition; Nickel-cobalt nanometer particle of the present invention is characterised in that preferred: 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 manufacturing approach of nickel-cobalt nanometer particle of the present invention possesses following operation: the mixture that will contain nickel salt, cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With above-mentioned complex reaction liquid is heated the operation that obtains nickel-cobalt nanometer particle slurry.
In addition, the manufacturing approach of nickel-cobalt nanometer particle of the present invention possesses following operation: the mixture that will contain nickel particle, cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With above-mentioned complex reaction liquid is heated the operation that obtains nickel-cobalt nanometer particle slurry.
In addition, the manufacturing approach of nickel-cobalt nanometer particle of the present invention possesses following operation: the mixture that will contain cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With in above-mentioned complex reaction liquid, add nickel particle after heat the operation that obtains nickel-cobalt nanometer particle slurry.
In addition, the manufacturing approach of nickel-cobalt nanometer particle of the present invention is characterised in that, and is preferred: it is 1～3 straight-chain carboxylic acid's base or in the group shown in the following structural formula (1) any that above-mentioned nickel salt and cobalt salt have carbon number respectively.
(wherein, substituent R a～Rc is the group that is selected from methyl, ethyl, phenyl and the halogen, and substituent R a～Rc can be identical, also can be different.)
In addition, the manufacturing approach 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 the said structure formula (1) is the acetylacetone,2,4-pentanedione dentate.
In addition, the manufacturing approach of nickel-cobalt nanometer particle of the present invention is preferred: in the operation that obtains above-mentioned nickel-cobalt nanometer particle slurry, use microwave as heater means.
The invention effect
Nickel-cobalt nanometer particle of the present invention is made up of the nuclear of nickel and the shell of cobalt, therefore is suitable for for example purposes such as catalyst, magnetic material, electrode.In addition,, can make cost reasonable, in addition, can also in above-mentioned each purposes, bring into play the performance of cobalt to greatest extent through regulating cobalt content according to these purposes.
In addition, according to the manufacturing approach of nickel-cobalt nanometer particle of the present invention, can compatibly obtain nickel-cobalt nanometer particle of the present invention.
Description of drawings
Fig. 1 is the figure of the structure of each nickel acetate complex compound of expression, and (a) coordination is nibbled in expression two, and (b) coordination is singly nibbled in expression, and (c) expression carboxylic acid ion coordination is at the state of outer ring.
Fig. 2 A is about the transmission electron microscope of the nickel-cobalt nanometer particle that obtains among the embodiment 1 (TEM:Transmission Electron Microscope) photo.
Fig. 2 B is the figure of expression from electronic diffraction (ED:Electron diffraction) pattern in the TEM photo zone of Fig. 2 A.
Fig. 3 is the figure that utilizes the map image that STEM-EDS obtains of nickel-cobalt nanometer particle of obtaining among the embodiment 1 of expression.
Fig. 4 is the result's who utilizes the line analysis that STEM-EDS obtains of nickel-cobalt nanometer particle of obtaining among the embodiment 1 of expression figure.
Fig. 5 is the result's that measures of the SQUID magnetic susceptibility of nickel particles and commercially available cobalt particle of nickel-cobalt nanometer particle, the comparative example 8 of expression embodiment 1,2 figure.
Fig. 6 is the figure that utilizes the map image that STEM-EDS obtains of nickel-cobalt nanometer particle of obtaining among the embodiment 2 of expression.
Fig. 7 is the figure that utilizes the map image that STEM-EDS obtains of nickel-cobalt nanometer particle of obtaining among the embodiment 4 of expression.
The specific embodiment
Below embodiment of the present invention is described.
[nickel-cobalt nanometer particle]
Nickel-the cobalt nanometer particle of this embodiment (following sometimes it is abbreviated as " nano particle ") comprises in fact nuclear that is formed by nickel and whole and the shell that is formed by cobalt in fact that covers nuclear in fact.Here, nano particle is not got rid of nuclear and is contained the form that a spot of cobalt and shell contain a spot of nickel.Promptly; The existence of a spot of cobalt that " nuclear that is formed by nickel in fact " contains in being meant and allowing to examine inevitably; But major part is formed by nickel, and " shell that is formed by cobalt in fact " is meant the existence of a spot of nickel that contains inevitably in the permission shell, but major part is formed by cobalt.In addition, the shell of nano particle preferably covers whole of nuclear, but is not limited to this, does not get rid of the form that a part of nickel exposes.That is to say; " cover the whole face of nuclear in fact " and be meant that not only shell fully covers the form of nuclear; Also allow to form discontinuously and examine the form that expose the part, but the major part on the surface of nickel-cobalt nanometer particle is become by hull shape at the scope inner casing that does not damage effect of the present invention (function of nano particle).In addition, nano particle also can be the formation that between the shell of cobalt and nickel, has inner casing.
The nano particle of this embodiment for example nickel content is that 30～90 quality % and cobalt content are 10～70 quality %.Cobalt content about nano particle; Desired characteristic, cost wait suitably and set in the purposes that can consider to be suitable for; But when being lower than 10 quality %; For example might nuclear can from shell, expose greatly and can't fully obtain the effect of catalytic performance, magnetic characteristic, and when surpassing 70 quality %, cost can improve.
The average grain diameter of nano particle is 10～200nm for example, is preferably 10～150nm.When the average grain diameter of nano particle was lower than 10nm, the violent and dispersed variation of aggegation might be not suitable for as the for example paste material of catalyst or electrode etc.On the other hand, when the average grain diameter of nano particle surpassed 200nm, specific area can diminish, and might can't bring into play for example 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 1～50nm for example, is preferably 5～20nm.About the thickness of the shell of nano particle, when being lower than 1nm, the cobalt amount is very few, might bring into play catalytic activity and the magnetic characteristic that cobalt itself has fully.And when surpassing 50nm, cost can improve.
The shape of nano particle for example can be spherical, different shapes such as plan is spherical, long ball shape, cube appearance, truncated tetrahedron appearance, suspension shape, regular octahedron appearance, positive decahedron appearance, regular dodecahedron appearance; But the viewpoint of the packed density when nickel nano particle being used for the electrode of electronic device from for example improving; Preferred spherical or intend spherical, more preferably spherical.Here, the shape of nano particle can be confirmed through observing with SEM (SEM).
Make cost reasonable thereby the nano particle of this embodiment of more than explaining can be regulated cobalt content according to purposes such as catalyst, magnetic material, electrodes, in addition, can also compatibly bring into play the performance of cobalt.
[manufacturing approach of nickel-cobalt nanometer particle]
Then, the manufacturing approach to nickel-cobalt nanometer particle of being used for compatibly obtaining nickel-cobalt nanometer particle describes.As the manufacturing approach (following abbreviate as sometimes " manufacturing approach of nano particle ") of the nickel-cobalt nanometer particle of this embodiment, enumerate first example～the 3rd example.
< first example >
First example of the manufacturing approach of nano particle has following operation: the mixture that will contain nickel salt, cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With complex reaction liquid is heated the operation that obtains nickel-cobalt nanometer particle slurry.
< second example >
Second example of the manufacturing approach of nano particle has following operation: the mixture that will contain nickel particle, cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With complex reaction liquid is heated the operation that obtains nickel-cobalt nanometer particle slurry.That is, use nickel particle to replace the nickel salt of first example.
< the 3rd example >
The 3rd example of the manufacturing approach of nano particle has following operation: the mixture that will contain cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With in complex reaction liquid, add nickel particle after heat the operation that obtains nickel-cobalt nanometer particle slurry.That is, not in complex reaction liquid generative process, to add the nickel particle of second example, but in nickel-cobalt nanometer particle slurry generative process, add.
Second example and the 3rd example all are preferred embodiment, but when adding nickel particle, need make the nickel particle high dispersive in complex reaction liquid, when dispersion is insufficient, might can't carry out the uniform formation of crust of cobalt.It means that first example that does not need high dispersive to handle is most preferred method.
[obtaining the operation of complex reaction liquid]
In this operation; The mixture that the mixture that mixture through containing nickel salt, cobalt salt and primary amine heats (first example), will contain nickel particle, cobalt salt and primary amine heats (second example), maybe will contain cobalt salt and primary amine heats (the 3rd example); Thereby generate the complex compound of nickel and/or cobalt, obtain complex reaction liquid.Here, complex reaction liquid is meant the reaction solution (product) that the reaction through nickel salt and/or cobalt salt and primary amine generates.Think that complex reaction liquid contains nickel complex and cobalt complex as complex compound, in second example and the 3rd example, contain cobalt complex as complex compound in first example.Through complex reaction liquid is heated; The nickel ion and/or the cobalt ions of nickel complex and/or cobalt complex are reduced; The carboxylic acid ion of coordination on this ion decomposes simultaneously, finally generates the Ni of 0 valency and/or the Co of 0 valency, thereby generates the nano particle of nucleocapsid structure.
(nickel salt, cobalt salt)
Nickel salt and cobalt salt all limit less than special, preferably have carbon number and be straight-chain carboxylic acid's base of 1～3 or any or two kinds in the group shown in the following structural formula (1).Group shown in the following structural formula (1) is 1,3-diketo (beta-diketon polymerization of olefin using catalyst base).Nickel salt and cobalt salt can be that salt of the same race also can be the salt of xenogenesis.In addition, nickel salt and cobalt salt all can be anhydrides, also can be hydrates.
(wherein, substituent R a～Rc is the group that is selected from methyl, ethyl, phenyl and the halogen.Substituent R a～Rc can be identical, also can be different.)
The nickel salt that has carbon number and be straight-chain carboxylic acid's base of 1～3 is specially nickel formate, nickel acetate or propionic acid nickel, especially preferably uses nickel formate or nickel acetate.In addition, the cobalt salt that has carbon number and be straight-chain carboxylic acid's base of 1～3 is specially cobaltous formate, cobalt acetate or Cobaltous propionate, especially 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 that and use nickel chloride (cobalt chloride), nickel nitrate (cobalt nitrate), nickelous sulfate (cobaltous sulfate), nickelous carbonate (cobalt carbonate), nickel hydroxide inorganic salts such as (cobalt hydroxides) to replace nickel carboxylate or carboxylic acid cobalt; But under the situation of inorganic salts; (decompositions) is high temperature owing to dissociate, so in the process that the nickel ion after dissociating (or nickel complex) or cobalt ions (or cobalt complex) are reduced, need under higher temperature, heat, thereby not preferred.
The acetylacetone,2,4-pentanedione dentate), 2 as the group shown in the said structure formula (1), for example can enumerate 2,4-pentadione (another name:; 4-acetyl butyryl base, 3,5-heptadione base, 1-phenyl-1,3-diacetyl base, 1-chloro-1; 3-diacetyl bases etc. wherein preferably use the acetylacetone,2,4-pentanedione dentate.
Use level about nickel salt, cobalt salt; For example convert in metal; With respect to total amount 100 mass parts of nickel in the complex reaction liquid and cobalt, preferably setting into nickel is that 30～90 mass parts, cobalt are 10～70 mass parts, and more preferably setting nickel for is that 50～80 mass parts, cobalt are 20～50 mass parts.The use level of cobalt can consider that desired characteristic, cost wait suitably and set in the purposes of nano particle; But when total amount 100 mass parts with respect to nickel and cobalt of converting in metal are lower than 10 mass parts; For example might nuclear can expose greatly from shell and can't fully obtain the effect of catalytic performance and magnetic characteristic; And when surpassing 70 mass parts, cost can improve.
(nickel particle)
About the nickel particle that uses in second example of the manufacturing approach of nano particle and the 3rd example, the size of defined particle size not, but the preferred for example nickel particle of the particle diameter of 5～200nm that uses.When particle diameter was lower than 5nm, aggegation was violent, might in liquid, also be difficult to disperse.And when particle diameter surpassed 200nm, the specific area of particle became too small, might can't react fully.In addition, the shape preference of nickel particle is like sphere, sphaeroid etc., but most preferably spherical.
About the addition of nickel particle, convert in metal, total amount 100 mass parts with respect to nickel in the complex reaction liquid and cobalt are preferably set to 30～90 mass parts, more preferably are set at 50～80 mass parts.
(primary amine)
Primary amine can form complex compound with nickel ion or cobalt ions, brings into play the reducing power to nickel complex (or nickel ion) effectively.On the other hand, secondary amine might hinder the good formation of nickel complex or cobalt complex owing to sterically hindered big, and therefore tertiary amine all can not use owing to do not have the reducing power of nickel ion or cobalt ions.
Primary amine is so long as can get final product with the primary amine that nickel ion or cobalt ions form complex compound, and not special qualification can be used at normal temperatures the primary amine as solid or liquid.Here, normal temperature is meant 20 ℃ ± 15 ℃.The effect of the organic solvent when normal temperature also plays formation nickel complex or cobalt complex for the primary amine of liquid down.In addition, even normal temperature is the primary amine of solid down,, there is not special problem so long as get final product through the primary amine that is heated to be liquid or dissolving with an organic solvent more than 100 ℃.
Primary amine also plays the effect of dispersant; Nickel complex or cobalt complex are disperseed in reactant liquor well, therefore can be suppressed at complex compound and form the back nickel complex or cobalt complex are carried out the aggegation between the particle of heating and decomposition when obtaining nano particle.Primary amine can be a primary aromatic amine, but the nickel complex from reactant liquor forms or the viewpoint of the easy property that cobalt complex forms, the aliphatic primary amine.Armeen for example can be controlled the particle diameter of the nano particle that is generated through the length of regulating its carbochain, be favourable making under the situation of nano particle that average grain diameter is 10～200nm particularly.From the viewpoint of particle diameter of control nano particle, Armeen is preferably selected to use from its carbon number is about 6～20 primary amine.Carbon number is many more, and the particle diameter of the nano particle that obtains becomes more little.As such amine, for example can enumerate octylame, trioctylamine, dioctylamine, cetylamine, lauryl amine, tetradecy lamine, stearylamine, oleyl amine, nutmeg amine, lauryl amine etc.For example oleyl amine owing to exist with liquid condition under the temperature conditions in the nano particle generative process, therefore can carry out the reaction in the homogeneous solution effectively.
Primary amine is owing to the effect of when the generation of nano particle, playing coating material, even also can suppress the secondary aggegation after therefore removing primary amine.In addition, the viewpoint of the easy property of the processing operation the solid constituent of the nano particle that after separating reduction reaction, generates and the washing procedure of solvent or unreacted primary amine etc., primary amine also is preferred.In addition, the viewpoint of the easy property of the reaction control when reduced nickel complex compound or cobalt complex obtain nano particle, the preferred boiling point of primary amine is higher than the primary amine of reduction temperature.That is, in Armeen, preferred boiling point is at the Armeen more than 200 ℃, and preferred carbon number is more than 9.Here, for example carbon number is 9 aliphatic amine C
9H
21The boiling point of N (nonyl amine) is 201 ℃.About the amount of primary amine, convert in metal, with respect to the total amount 1mol of nickel and cobalt, preferably use more than the 2mol, more preferably use more than the 2.5mol, preferably use more than the 4mol.The upper limit of the amount of primary amine is not special to be limited, but for example from the viewpoint of productivity ratio, preferably set in metal convert total amount 1mol with respect to nickel and cobalt be below the 20mol about.
The nickel ion of divalent replaces spike as dentate and known, and the dentate of the complex compound of formation may easily change complexing through the dentate exchange according to temperature, concentration.For example heat in the operation that obtains reactant liquor at mixture to nickel carboxylate and primary amine; If the carbon chain lengths of the employed amine of consideration etc. are sterically hindered; Then for example the carboxylic acid ion of that kind shown in Figure 1 (R1COO, R2COO) might with two nibble coordination (a) or singly nibble coordination (b) any carry out coordination, and then when the concentration of amine is superfluous, also possibly take to exist the structure (c) of carboxylic acid ion in the outer ring.In order under the reaction temperature (reduction temperature) of target, to process homogeneous solution, need at least one place coordination in the dentate of A, B, C, D, E, F at least that primary amine is arranged.In order to take this state, in reaction solution, need excessively there be primary amine, preferably exist more than the 2mol with respect to nickel ion 1mol at least, more preferably exist more than the 2.5mol, preferably exist more than the 4mol.
Think that cobalt ions also takes to form complex compound with the similar behavior of nickel ion.Therefore, primary amine also needs excessive existence with respect to cobalt ions, preferably exists more than the 2mol with respect to nickel ion 1mol at least, more preferably exists more than the 2.5mol, preferably exists more than the 4mol.
Complex reaction at room temperature also can be carried out, but in order reliably and more effectively to react, preferably under the temperature more than 100 ℃, heats.This heating is at the hydrate of the hydrate of the nickel carboxylate that for example uses nickel acetate tetrahydrate and so on or carboxylic acid cobalt advantageous particularly during as nickel salt or cobalt salt.Heating-up temperature surpasses 100 ℃ temperature through being preferably set to, more preferably is set at temperature more than 105 ℃; Water of coordination and the dentate substitution reaction of primary amine of coordination on nickel carboxylate or carboxylic acid cobalt carried out effectively; This hydrone as the complex compound dentate is dissociated; And then can this water be discharged to outside the system, thereby can form complex compound efficiently.For example; The nickel acetate tetrahydrate is owing at room temperature take 2 waters of coordination and nibble 2 acetic acid ions of dentate, the complex structure that there are 2 hydrones in the outer ring as two; Therefore carry out complexing efficiently for the dentate through these 2 waters of coordination and primary amine replaces to come, thereby preferably this hydrone as the complex compound dentate is dissociated through heating under than 100 ℃ of high temperature.In addition, from separating, accomplish the viewpoint of the complex reaction of leading portion reliably with the process that adds thermal reduction of follow-up nickel complex (or nickel ion) and cobalt complex (or cobalt ions), heating-up temperature is preferably below 175 ℃.Therefore, the heating when forming about complex compound is for example preferably carried out under 105～175 ℃.More preferably heating-up temperature is 125～160 ℃.
Can come according to the content of heating-up temperature, each raw material suitably to determine heat time heating time, but the viewpoint from complex reaction is accomplished reliably be preferably set to more than 15 minutes.The upper limit of heat time heating time is not special to be limited, and still from the viewpoint of energy efficient and activity time, long-time heating is unhelpful.In addition, the not special restriction of the method for this heating for example can be the heating that utilizes thermal medium such as oil bath, also can be the heating that utilizes microwave irradiation.
Complex reaction can be through confirming nickel salt and/or cobalt salt and primary amine being mixed the variation that the solution that obtains heats the back solution colour.In addition; This complex reaction can also be confirmed through following method: for example use the uv-visible absorption spectra determinator; Be determined at the maximum wavelength of absorption of the absorption spectrum that the wavelength region may of 300nm～750nm observes; Confirm with respect to the displacement of the reactant liquor of the maximum absorption wavelength of raw material (for example nickel acetate tetrahydrate, its maximum absorption wavelength is 710nm) through observation.
After having carried out the complexing of nickel salt and/or cobalt salt and primary amine; Through the reactant liquor that obtains being utilized methods such as microwave irradiation heat as illustrated later; The nickel ion of nickel complex and/or the cobalt ions of cobalt complex are reduced; The carboxylic acid ion of coordination on nickel ion or the cobalt ions decomposes simultaneously, and it is the nickel of 0 valency and/or the nano particle of cobalt that final generation contains oxidation number.Usually, nickel carboxylate and carboxylic acid cobalt are being to be slightly solubility under the condition beyond the solvent with water, and as the last stage that adds thermal reduction reaction of utilizing microwave irradiation, the solution that contains nickel carboxylate or carboxylic acid cobalt need be processed homogeneous reaction solution.Relative therewith, think that the primary amine that uses in this embodiment is liquid under the serviceability temperature condition, and liquefy, thereby form homogeneous reaction solution through coordination on nickel ion or cobalt ions.
(organic solvent)
In order more effectively to carry out the reaction in the homogeneous solution, also can newly add the organic solvent different with primary amine.In the time of with an organic solvent, can organic solvent and nickel salt or cobalt salt and primary amine be mixed simultaneously, but if nickel salt or cobalt salt are mixed with primary amine carry out adding organic solvent after the complexing earlier, then primary amine effectively coordination on nickel ion or cobalt ions, thereby more preferably.As spendable organic solvent; Do not get final product so long as do not hinder the organic solvent of the complexing of primary amine and nickel ion or cobalt ions; Not special the qualification, for example can use carbon number is that 4～30 ether is that organic solvent, carbon number are that 7～30 saturated or undersaturated hydrocarbon system organic solvent, carbon number are that 8～18 alcohol is organic solvent etc.In addition, from utilizing the viewpoint that also can use under the heating condition of microwave irradiation etc., it is the organic solvent more than 170 ℃ that employed organic solvent is preferably selected boiling point, and more preferably selecting boiling point is the organic solvent in 200～300 ℃ the scope.As the object lesson of such organic solvent, for example can enumerate TEG, octyl ether etc.
[obtaining the operation of nickel-cobalt nanometer particle slurry]
In this operation,, nickel complex and/or cobalt complex (nickel ion and/or cobalt ions) are reduced into metal and generate nano particle through complex reaction liquid is heated.For example; In first example, think that the mixture of nickel complex and cobalt complex is reduced, when thermal decomposition takes place, nickel complex is compared with cobalt complex and thermal decomposition takes place under lower temperature earlier and is reduced by amine; Nickel particles forms nuclear, on the surface of this nuclear, forms the shell of cobalt.Usually, cobalt complex through thermal decomposition dentate dissociate, by Co
2+Complex compound form the nano particle of Co (0 valency).Relative therewith, in the present invention, in the presence of excessive oleyl amine, be catalyst with Ni, cobalt complex under than usually low temperature by Co
2+Be reduced into Co (0 valency) (complex compound dissociates).
Through complex reaction liquid is heated, complex reaction liquid is reduced, and complex compound is by thermal decomposition.From carrying out the viewpoint of reduction reaction effectively, heating-up temperature is preferably more than 200 ℃, more preferably more than 220 ℃.From the viewpoint of handling effectively, heating-up temperature is preferably below 270 ℃, more preferably below 250 ℃ about.For example be that example describes with nickel; In order to generate nano particle, nickel complex is generated evenly and fully and the nuclear of the Ni (0 valency) that generates in the reduction of complex reaction liquid being heated in the operation that obtains nickel-cobalt nanometer particle slurry through nickel ion takes place simultaneously and grows with uniform grading.That is, regulate through the heating-up temperature to the operation that obtains complex reaction liquid in above-mentioned specific scope, heating-up temperature than the operation that obtains nickel-cobalt nanometer particle slurry is low effectively to make it, thereby generates particle diameter and the unified particle of shape easily.For example, when heating-up temperature is too high in the operation that obtains complex reaction liquid, then the generation of nickel complex with carry out simultaneously to the reduction reaction of Ni (0 valency), might be difficult in the operation that obtains nickel-cobalt nanometer particle slurry to generate the unified particle of shape of particle.In addition, cross when low when the heating-up temperature of the operation that obtains nickel-cobalt nanometer particle slurry, because slack-off to the reduction reaction speed of Ni (0 valency), the generation of nuclear reduces, and therefore not only particle becomes big, and also not preferred from the viewpoint of the yield of nano particle.
In this operation, heating source can also be other except that oil bath, but is preferably microwave.When to complex reaction liquid irradiating microwaves, microwave infiltrates in the complex reaction liquid, heats up fast and evenly heating through the inside heating.Thus; Can make complex reaction liquid integral body reach required temperature equably; Reduction, karyogenesis, each process of nucleus growth of nickel or cobalt particle are produced in solution integral body simultaneously, and the result can easily make the monodispersed particle of narrow diameter distribution at short notice.In addition, the use wavelength of microwave is not special to be limited, and for example is 2.45GHz.
After the nano particle slurry that the heating of complex reaction liquid is obtained was for example removed supernatant through standing separation, the use appropriate solvent was washed and is carried out drying, can obtain nano particle.
In the operation that obtains nickel-cobalt nanometer particle slurry, as required, can also in complex reaction liquid, add above-mentioned organic solvent.In addition, as above-mentioned, it is preferred implementation of the present invention that the primary amine that will in complex reaction, use directly uses as organic solvent.The solvent that in the operation that complex reaction liquid is heated, adds as required is not special to be limited, and for example can use octanol alcohol such as (octyl group alcohol) or non-polar solven etc.As above-mentioned, when using oleyl amine as primary amine, solvent can omit.
The manufacturing approach of the nano particle of this embodiment can also comprise operation arbitrarily except that above-mentioned operation.In addition, for example can also as after carry out coating material stating interpolation etc. handle arbitrarily.In addition, therefore the method for reducing that the manufacturing approach of the nano particle of this embodiment owing in the operation that obtains nickel-cobalt nanometer particle slurry, adopt utilizes microwave etc. to heat need not use powerful reducing agent.But in the scope of not damaging the invention effect, in complex reaction liquid, having the material with reduction is that it doesn't matter.
(interpolation of coating material)
In the manufacturing approach of the nano particle of this embodiment; Coating material as the particle diameter that is used to control nano particle for example can add long-chain carboxylic acids such as macromolecule resin, myristic acid, oleic acid such as PVP (PVP), polymine, polyacrylamide or carboxylate etc.But, when the finishing amount of the nano particle that obtains for a long time, might cause harmful effect as impurity according to purposes, therefore that the finishing amount after the nano particle washing that obtains is preferably the least possible.For example when being used for the conductive paste that nickel electrode uses, if nickel particles is processed paste and at high temperature burnt till, then can cause the minimizing of packed density, might produce splitting or crackle.Therefore, about the addition of coating material, with respect to total amount 100 mass parts of nickel element, be preferably set to more than 0.1 and 100 mass parts below scope in.Coating material can add in the stage that complex reaction liquid forms the mixture of nickel carboxylate and primary amine in the operation; Add in the complex reaction liquid that also can in complex reaction liquid forms operation, obtain, but interpolation is preferably after the complex reaction opportunity or the generation of nickel nano particle after.
According to the manufacturing approach of the nickel-cobalt nanometer particle of discussed above embodiment, can to obtain average grain diameter be 10～200nm, have the Cv value [coefficient of variation: the ratio σ/d of average grain diameter (d) and standard deviation (σ)] is nickel-cobalt nanometer particle that the narrow particle diameter of 0.01≤σ/d≤0.5 distributes, that be made up of the shell of the nuclear of nickel and cobalt.
Embodiment
Enumerate embodiment and comparative example further specifies the present invention, but the present invention is not limited to following illustrated example.
About the particle diameter of nano particle, utilize transmission electron microscope (TEM) to take the photo of nanoparticle powder, from wherein randomly drawing 200, obtain its average grain diameter and standard deviation.In addition, the result obtains the Cv value (value of=σ/d) thus.In addition, utilize the sweep type transmission electron microscope (STEM-EDS) possess energy dispersion type x-ray analysis equipment, nickel, the existence of cobalt or the concentration separately of the particle of confirming through surface analysis, line analysis to obtain.About the thickness of crust of cobalt layer, that kind as shown in Figure 4 is calculated the nickel on the line of 1 particle crosscut, cobalt atom concentration through STEM-EDS.According to this provision of on-line analysis methodology, can't calculate the atomic concentration of the only nuclear portion of the spherical particle that is generated.That is, the concentration of simple particle surface can be shown, but near the analysis result the particle central authorities is the summation of concentration of the metallic element of particle surface and inside (nuclear) through near the analysis the particle surface.Therefore, in the result of this analysis, the average thickness value of will be with the intensity of nickel treatment higher layer is as the thickness of crust of cobalt layer.About the composition of resulting particle, (ICP-AES:Inductively Coupled Plasma-Atomic Emission Spectrometry) analyzes through the luminous optical spectroscopy of inductively coupled plasma.
(embodiment 1)
In cobaltous formate dihydrate 12.5mmol and nickel acetate tetrahydrate 12.5mmol, add oleyl amine 275mmol, flow down at nitrogen, heated 20 minutes down, thereby obtain complex reaction liquid in 120 ℃.Then, this complex reaction liquid with heating using microwave to 225 ℃, is kept this temperature 30 minutes, thereby obtains the nano particle slurry.With nano particle slurry standing separation, remove supernatant after, with hexane wash 3 times.Afterwards, obtained nano particle in dry 6 hours with the vacuum drier that maintains 60 ℃.
TEM (Transmission Electron Microscope, the transmission electron microscope) photo of the nano particle that obtains is shown in Fig. 2 A, and (electronic diffraction: Electron diffraction) pattern is shown in Fig. 2 B with ED.Having formed average grain diameter is the uniform particle of the sphere of 82nm.In addition, can know that by the ED pattern nano particle is the metal of the fcc structure of oxide-free.In addition, through ICP-AES the metal of the particle that obtains formed and to be confirmed that Ni, Co are respectively 47.6 quality %, 47.3 quality % as a result, so mol is than being Ni/Co=1.0 that (rate of charge of Ni salt and Co salt (mol%)) is very consistent with feed ratio.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, and hence one can see that is the nano particle with Ni (nuclear)-Co (shell) structure.
In addition, the result by the line analysis of particle shown in Figure 4 can know that the thickness of crust of cobalt layer (shell) is approximately 13nm.In addition, (unit: result emu/g) is shown in Fig. 5 will to measure the magnetic saturation that obtains through SQUID magnetic susceptibility.Can know that to compare magnetic saturation lower with commercially available cobalt nanometer particle (particle diameter be below the 50nm, Aldrich system), but with after the nano particle of the comparative example 8 stated compare magnetic saturation and significantly increase.
(embodiment 2～7, comparative example 1～8)
In embodiment 2～7 and comparative example 1～8, the kind of the heating source in the kind that changes nickel salt and cobalt salt and the operation that obtains the nano particle slurry and the reaction temperature (heating-up temperature) prepares nano particle according to embodiment 1.Its result is shown in table 1 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 that the embodiment 3 that uses oil bath, all carry out with heating using microwave.
In addition; The result that the SQUID magnetic susceptibility of the nickel particles of nickel-cobalt nanometer particle of embodiment 1,2, comparative example 8 and commercially available cobalt particle is measured is shown in Fig. 5; The TEM photo of the nickel-cobalt nanometer particle that obtains among the embodiment 2 is shown in Fig. 6, the TEM photo of the nickel-cobalt nanometer particle that obtains among the embodiment 4 is shown in Fig. 7.
Confirmed that by table 1 through using formic acid, acetate or acetylacetonate as nickel salt and cobalt salt, can obtain average grain diameter is that 10～200nm and crust of cobalt layer are nickel-cobalt nanometer particle of 1～50nm.In addition, confirmed that embodiment 1 and nickel-cobalt nanometer particle of 2 are near the magnetic saturation of cobalt by Fig. 5.
Table 1
(embodiment 8)
In cobaltous formate dihydrate 12.5mmol and average grain diameter is that 100nm and Cv value are that 0.14 nickel particles 25mmol (does not use cobalt salt, obtains complex reaction according to above-mentioned first example from the nickel acetate tetrahydrate, it is heated and the particle that makes; Comparative example 8) adds oleyl amine 125mmol in, flow down at nitrogen, heated 20 minutes down, thereby obtain complex reaction liquid in 120 ℃.Then, this complex reaction liquid with heating using microwave to 225 ℃, is kept this temperature 30 minutes, thereby obtains nickel-cobalt nanometer particle slurry.
With above-mentioned nickel-cobalt nanometer particle slurry standing separation, remove supernatant after, with hexane wash 3 times.Afterwards, with the vacuum drier that maintains 60 ℃ dry 6 hours, obtain nickel-cobalt nanometer particle.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, flow down at nitrogen, heated 20 minutes down, thereby obtain complex reaction liquid in 120 ℃.Then, in this complex reaction liquid, adding average grain diameter and be 100nm and Cv value and be 0.14 nickel particles 25mmol (does not use cobalt salt, obtains complex reaction by the nickel acetate tetrahydrate, be heated and the particle that makes; Comparative example 8) and fully after stirring,, this temperature was kept 30 minutes, thereby obtain nickel-cobalt nanometer particle slurry with heating using microwave to 225 ℃.
With above-mentioned nickel-cobalt nanometer particle slurry standing separation, remove supernatant after, with hexane wash 3 times.Afterwards, with the vacuum drier that maintains 60 ℃ dry 6 hours, obtain nickel-cobalt nanometer particle.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.
More than, for illustrative purposes embodiment of the present invention is specified, but the present invention is not limited to above-mentioned embodiment.The application of this world is advocated based on Japanese patent application 2010-60773 number the priority of filing an application on March 17th, 2010, and its full content is incorporated herein.
Claims (9)
1. nickel-cobalt nanometer particle, it possesses in fact nuclear that is formed by nickel and the shell that covers whole of said nuclear in fact and formed by cobalt in fact.
2. nickel-cobalt nanometer particle according to claim 1, wherein, nickel content is in the scope of 30～90 quality %, and cobalt content is in the scope of 10～70 quality %, and average grain diameter is in the scope of 10～200nm, and the thickness of said shell is in the scope of 1～50nm.
3. the manufacturing approach of a nickel-cobalt nanometer particle, it possesses following operation:
The mixture that will contain nickel salt, cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With said complex reaction liquid is heated the operation that obtains nickel-cobalt nanometer particle slurry.
4. the manufacturing approach of a nickel-cobalt nanometer particle, it possesses following operation:
The mixture that will contain nickel particle, cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With said complex reaction liquid is heated the operation that obtains nickel-cobalt nanometer particle slurry.
5. the manufacturing approach of a nickel-cobalt nanometer particle, it possesses following operation:
The mixture that will contain cobalt salt and primary amine heats the operation that obtains complex reaction liquid; With in said complex reaction liquid, add nickel particle after heat the operation that obtains nickel-cobalt nanometer particle slurry.
6. according to the manufacturing approach of each described nickel-cobalt nanometer particle in the claim 3～5, wherein, it is 1～3 straight-chain carboxylic acid's base and in the group shown in the following structural formula (1) any that said nickel salt has carbon number,
Wherein, substituent R a～Rc is the group that is selected from methyl, ethyl, phenyl and the halogen, and substituent R a～Rc can be identical, also can be different each other.
7. according to the manufacturing approach of each described nickel-cobalt nanometer particle in the claim 3～6, wherein, it is 1～3 straight-chain carboxylic acid's base and in the group shown in the following structural formula (1) any that said cobalt salt has carbon number,
Wherein, substituent R a～Rc is the group that is selected from methyl, ethyl, phenyl and the halogen, and substituent R a～Rc can be identical, also can be different each other.
8. according to the manufacturing approach of claim 6 or 7 described nickel-cobalt nanometer particles, wherein, said carbon number is that straight-chain carboxylic acid's base of 1～3 is formyl or acetoxy group, and the group shown in the said structural formula (1) is the acetylacetone,2,4-pentanedione dentate.
9. according to the manufacturing approach of each described nickel-cobalt nanometer particle in the claim 3～5, wherein, in the operation that obtains said nickel-cobalt nanometer particle slurry, use 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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| CN106834763A (en) * | 2017-01-05 | 2017-06-13 | 东南大学 | A kind of blacker-than-black nanometer column Co and preparation method thereof |
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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 |
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